CN101519472A - Composition for preparing capsule wall of hollow micro-capsule and preparation method thereof - Google Patents
Composition for preparing capsule wall of hollow micro-capsule and preparation method thereof Download PDFInfo
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- CN101519472A CN101519472A CN200910038260A CN200910038260A CN101519472A CN 101519472 A CN101519472 A CN 101519472A CN 200910038260 A CN200910038260 A CN 200910038260A CN 200910038260 A CN200910038260 A CN 200910038260A CN 101519472 A CN101519472 A CN 101519472A
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Abstract
The invention provides a composition for preparing the capsule wall of a hollow micro-capsule and a preparation method thereof. The composition consists of the following components in portion by weight: 5 to 15 portions of single-functionality monomer, 1 to 10 portions of di-functionality monomer, 0.1 to 1 portion of cross-linking agent, and 0.1 to 2 portions of foaming type thermal initiator. The preparation method provided by the invention is to prepare the composition into the hollow micro-capsule. The method for preparing the hollow micro-capsule comprises the following steps of: dissolving an emulsifying agent into water, adding the composition for preparing the capsule wall of the hollow micro-capsule with stirring, and obtaining an emulsion or a suspension through homogeneous emulsification; and heating the prepared emulsion or suspension to react, solidifying the composition in the emulsion or the suspension into a film, and capturing bubbles produced during the reaction to form the hollow micro-capsule. The capsule prepared by the method has the advantages of regular sphericity, high degree of hollowness, narrower particle size distribution, smooth surface, good heat resistance, low density, large specific surface area, and good surface permeation capability.
Description
Technical field
The present invention relates to a kind of composition that is used to prepare the hollow microcapsule cyst wall and, belong to the microcapsulary field with the method for described preparation of compositions hollow microcapsule.
Background technology
Hollow microcapsule is meant the material with special construction of a class size between nanometer is to hundreds of microns, and its hollow space can hold a large amount of guest molecules or large-sized object; In addition, it is low that hollow capsules has density, and specific surface area is big, good stability and the characteristics with surface seepage ability.The character of the special construction of hollow capsules and various materials self combines, to give material new performance, therefore in fields such as chemistry, biology and Materials science important use is arranged all, as be applied to fields such as sustained release capsule (medicine, pigment, makeup, printing ink), artificial cell, electricity component, filler, catalysis, parting material, coating and Accoustical sound proofing material.
Of many uses in view of hollow microcapsule, also deep day by day to the research of its preparation method and processing condition.The preparation method of hollow microcapsule mainly contains self-assembly method, template synthesis method and emulsion method three classes at present.Self-assembly method can obtain the hollow structure polymer microcapsule of nano-scale, but this method is tighter to the system requirement, and need carry out under extremely low polymer concentration, thereby their practical application is subjected to very big restriction.Emulsion method is to utilize the innovative techniques synthetic hollow microcapsule of emulsion in synthetic, though widened the range of application of hollow microcapsule greatly, preparation process is loaded down with trivial details.The template synthesis method need be removed made " nuclear-shell " type capsular " nuclear " template by physics or chemical process, except that time consumption and energy consumption, also can cause destruction in various degree to the integrity of cyst wall.In addition, existing cyst material is by above-mentioned three kinds of prepared hollow capsules of method, be difficult to functional modification is carried out on the surface of shell, the incompatibility hollow capsules is to multiple demands of applications (as the load to the difference in functionality material), and the structure of Capsules cyst wall and character are difficult for regulating easily on demand.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of composition that is used to prepare the hollow microcapsule cyst wall is provided, the microcapsule cyst wall character that composition of the present invention is made is easy to regulate, and stopping property and thermostability are all very good.
Another object of the present invention provides above-mentioned composition and prepares method in the hollow microcapsule, a kind of method for preparing hollow microcapsule by original position emulsion or suspension free-radical copolymerization film forming of more specifically saying so.
Purpose of the present invention is achieved through the following technical solutions:
A kind of composition that is used to prepare the hollow microcapsule cyst wall, form by the component of following parts by weight:
5～15 parts of single functionality monomers;
1～10 part of difunctionality monomer;
0.1～1 part of linking agent;
0.1～2 part of expansion type thermal initiator.
Described single functionality monomer is one or more the mixture in the sulfonated bodies of methyl acrylate (MA), acrylamide (Ann), acrylamide propane sulfonic acid sodium salt (AMPS), N hydroxymethyl acrylamide (NMA), allyloxy hydroxide sodium dimercaptosulphanatein (HAPS), sodium vinyl sulfonate (SVS), allyloxy nonyl phenolic ether or allyloxy nonyl phenolic ether.
Described difunctionality monomer is one or more the mixture in dimethacrylate TEG ester (TEGDMA), pentanediol diacrylate, neopentylglycol diacrylate, Ethylene glycol dimethacrylate (EGDMA), dimethacrylate triglycol ester or the allyl methacrylate(AMA).
Described linking agent is one or more the mixture in trimethylolpropane trimethacrylate (TMPTMA), ethoxylated trimethylolpropane triacrylate or the Viscoat 295 (TMPTA).
The preferred Diisopropyl azodicarboxylate of described expansion type thermal initiator, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl or 2, the mixture of one or more in the 2-azo two (2-methylbutyronitrile).
The application of composition of the present invention in the preparation hollow microcapsule is that described composition is passed through original position emulsion or suspension free-radical copolymerization film forming, and then is prepared into hollow microcapsule.
The method of utilizing the present composition to prepare hollow microcapsule comprises the steps:
(1) with emulsifiers dissolve in water, under agitation add the composition of above-mentioned preparation hollow microcapsule cyst wall, homogenizing emulsifying gets emulsion or suspension;
(2) with the emulsion or the suspension reacting by heating that make, the composition film-forming in emulsion or the suspension, and the bubble that is produced in the capture reaction process form hollow microcapsule.
Emulsifying agent described in the step (1) can be the conventional emulsion polymerization emulsifying agent, the mixture of one or more in preferred Sodium dodecylbenzene sulfonate, polyoxyethylene nonylphenol ether (NP-30), sodium lauryl sulphate (SDS), gelatin, gum arabic, styrene-maleic anhydride copolymer sodium salt (SMA), ethene-copolymer-maleic anhydride sodium salt, sulfo-succinic acid decyl polyoxyethylene ether-ester disodium or the sulfo-succinic acid double tridecyl ester sodium; Preferred 3-10min of the time of described homogenizing emulsifying.
The preferred 50-90 of temperature of reacting by heating described in the step (2) ℃, preferred 1-3 of reaction times hour, cyst wall constituent polymerizing curable film forming was also captured the bubble that is produced in the microballoon, has formed the hollow microcapsule structure.
The also further optimization process of hollow microcapsule that step (2) forms specifically is to add big water gaging to wash repeatedly, with hollow microcapsule floating matter vacuum lyophilization, obtains more purified hollow microcapsule product; The mean diameter of gained microcapsule is 1～45 μ m.Made capsule is that regular spherical, degree of hollowness height, size distribution are narrower, smooth surface, thermotolerance is good, density is low, specific surface area is big, have the characteristics of excellent surface penetrating power, its hollow space can hold a large amount of guest molecules or large-sized object, therefore in fields such as chemistry and Materials science important application is arranged all, as be applied to fields such as sustained release capsule (pigment, makeup, printing ink), filler, catalysis, parting material, coating and Accoustical sound proofing material, self-repair material.
Compared with prior art, the present invention has following beneficial effect:
The bubble that the present invention is emitted with initiator is a template, select the monomer of different functionality to capture the gas template in bubble surface copolymerization film forming, therefore, it need not take other chemistry or physical method to remove template, prevent to remove the damage of template procedure to cyst wall, and can be according to application, choosing monomer of different nature easily is the wall material, regulates and control the cyst wall character of hollow capsules.
The hollow microcapsule that the present invention makes is regular spherical, smooth surface, narrow diameter distribution, has that density is little, characteristics such as specific surface area is big, perviousness and good heat stability.
The original position emulsion of the present invention design or suspension free-radical copolymerization film forming and prepare the method for hollow microcapsule, technology is simple, the production efficiency height, do not need solvent, no coupling product, easily realize mass preparation, this method can regulate and control capsule size and cyst wall is formed, and regulate and control the surface properties of hollow capsules by different needs, help the load function material.
Description of drawings
Fig. 1 is the sem photograph of hollow microcapsule;
Fig. 2 is the sem photograph of hollow microcapsule of breaking.
Embodiment
Below further specify technical scheme of the present invention by specific embodiment.
Embodiment 1
(1) with 9 parts of (parts by weight of polystyrene-maleic anhydride multipolymer sodium salt, down with) join in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 9 parts of capsule wall material allyloxy hydroxide sodium dimercaptosulphanateins, 9 parts of dimethacrylate TEG esters, 0.6 part of trimethylolpropane trimethacrylate, 0.8 part of Diisopropyl azodicarboxylate, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 2 hours generates hollow microcapsule, add big water gaging and wash repeatedly, collect the hollow microcapsule floating matter, through vacuum lyophilization, obtain the hollow microcapsule product, the mean diameter 10 μ m of hollow microcapsule, wall thickness 200nm.The sem photograph of microcapsule such as Fig. 1, the sem photograph of the microcapsule that break such as Fig. 2.
Embodiment 2
(1) 5 parts of 5 parts of Sodium dodecylbenzene sulfonatees and polyoxyethylene nonylphenol ethers is joined in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 12 parts of capsule wall material methyl acrylates, 6 parts of Ethylene glycol dimethacrylate, 0.6 part of Viscoat 295,1 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 1 hour generates hollow microcapsule, add big water gaging and wash repeatedly, collect the hollow microcapsule floating matter, through vacuum lyophilization, obtain the hollow microcapsule product, the mean diameter 8 μ m of hollow microcapsule, wall thickness 150nm.
Embodiment 3
(1) 5 parts of 5 parts of sodium lauryl sulphate and gum arabics is joined in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 6 parts of capsule wall material acrylamide propane sulfonic acid sodium salts, 6 parts of dimethacrylate triglycol esters, 0.6 part of ethoxylated trimethylolpropane triacrylate, 0.5 part of azo-bis-iso-dimethyl, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 80 ℃, stirring reaction 1.5 hours generates hollow microcapsule, add big water gaging and wash repeatedly, the hollow microcapsule floating matter obtains the hollow microcapsule product through vacuum lyophilization, the mean diameter 10 μ m of hollow microcapsule, wall thickness 150nm.
Embodiment 4
(1) 5 parts of 5 parts of polystyrene-maleic anhydride multipolymer sodium salts and polyoxyethylene nonylphenol ethers is joined in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 6 parts of capsule wall material sodium vinyl sulfonates, 4 parts of pentanediol diacrylates, 2 parts of neopentylglycol diacrylates, 0.6 part of Viscoat 295,0.6 part of Diisopropyl azodicarboxylate, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 2 hours generates hollow microcapsule, add big water gaging and wash repeatedly, the hollow microcapsule floating matter obtains the hollow microcapsule product through vacuum lyophilization, the mean diameter 15 μ m of hollow microcapsule, wall thickness 150nm.
Embodiment 5
(1) 6 parts of gum arabics is joined in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 6 parts of capsule wall material acrylamide propane sulfonic acid sodium salts, 4 parts of methyl acrylates, 2 parts of Ethylene glycol dimethacrylate, 0.6 part of trimethylolpropane trimethacrylate, 0.8 part of Diisopropyl azodicarboxylate, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 2 hours generates hollow microcapsule, add big water gaging and wash repeatedly, the hollow microcapsule floating matter obtains the hollow microcapsule product through vacuum lyophilization, the mean diameter 5 μ m of hollow microcapsule, wall thickness 150nm.
Embodiment 6
(1) 6 parts of gum arabics is joined in 300 parts of the deionized waters, the mixture that under clarifixator stirs, adds 6 parts of capsule wall material acrylamide propane sulfonic acid sodium salts, 4 parts of methyl acrylates, 2 parts of Ethylene glycol dimethacrylate, 0.6 part of trimethylolpropane trimethacrylate, 0.8 part of Diisopropyl azodicarboxylate, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 2 hours generates hollow microcapsule, add big water gaging and wash repeatedly, the hollow microcapsule floating matter obtains the hollow microcapsule product through vacuum lyophilization, the mean diameter 5 μ m of hollow microcapsule, wall thickness 150nm.
Embodiment 7
(1) 6 parts of gum arabics is joined in 100 parts of the deionized waters, the mixture that under clarifixator stirs, adds 6 parts of capsule wall material sodium vinyl sulfonates, 4 parts of methyl acrylates, 2 parts of dimethacrylate triglycol esters, 0.6 part of Viscoat 295,0.8 part of Diisopropyl azodicarboxylate, emulsification 5min obtains monomer emulsion.
(2) step (1) gained emulsion is warming up to 70 ℃, stirring reaction 2 hours generates hollow microcapsule, add big water gaging and wash repeatedly, the hollow microcapsule floating matter obtains the hollow microcapsule product through vacuum lyophilization, the mean diameter 15 μ m of hollow microcapsule, wall thickness 150nm.
Claims (9)
1. a composition that is used to prepare the hollow microcapsule cyst wall is characterized in that being made up of the component of following parts by weight: 5～15 parts of single functionality monomers; 1～10 part of difunctionality monomer; 0.1～1 part of linking agent; 0.1～2 part of expansion type thermal initiator.
2. composition as claimed in claim 1 is characterized in that described single functionality monomer is one or more the mixture in the sulfonated bodies of methyl acrylate, acrylamide, acrylamide propane sulfonic acid sodium salt, N hydroxymethyl acrylamide, allyloxy hydroxide sodium dimercaptosulphanatein, sodium vinyl sulfonate, allyloxy nonyl phenolic ether or allyloxy nonyl phenolic ether.
3. composition as claimed in claim 1 is characterized in that described difunctionality monomer is one or more the mixture in dimethacrylate TEG ester, pentanediol diacrylate, neopentylglycol diacrylate, Ethylene glycol dimethacrylate, dimethacrylate triglycol ester or the allyl methacrylate(AMA).
4. composition as claimed in claim 1 is characterized in that described linking agent is one or more the mixture in trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate or the Viscoat 295.
5. composition as claimed in claim 1 is characterized in that described expansion type thermal initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl or 2, the mixture of one or more in the 2-azo two (2-methylbutyronitrile).
6. the method for the described preparation of compositions hollow microcapsule of claim 1 is characterized in that comprising the steps:
(1) with emulsifiers dissolve in water, under agitation add the described composition of claim 1, homogenizing emulsifying gets emulsion or suspension;
(2) with the emulsion or the suspension reacting by heating that make, the composition film-forming in emulsion or the suspension, and the bubble that is produced in the capture reaction process form hollow microcapsule.
7. as preparing the method for hollow microcapsule as described in the claim 6, it is characterized in that the emulsifying agent described in the step (1) is one or more the mixture in Sodium dodecylbenzene sulfonate, polyoxyethylene nonylphenol ether, sodium lauryl sulphate, gelatin, gum arabic, styrene-maleic anhydride copolymer sodium salt, ethene-copolymer-maleic anhydride sodium salt, sulfo-succinic acid decyl polyoxyethylene ether-ester disodium or the sulfo-succinic acid double tridecyl ester sodium.
8. as preparing the method for hollow microcapsule as described in the claim 7, the time that it is characterized in that homogenizing emulsifying described in the step (1) is 3-10min.
9. as preparing the method for hollow microcapsule as described in the claim 7, the temperature that it is characterized in that reacting by heating described in the step (2) is 50-90 ℃, and the reaction times is 1-3 hour.
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| CN2009100382607A CN101519472B (en) | 2009-03-27 | 2009-03-27 | Composition for preparing capsule wall of hollow micro-capsule and preparation method thereof |
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| CN101519472B CN101519472B (en) | 2012-05-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702449A (en) * | 2012-06-13 | 2012-10-03 | 福建省锦浪精细化工有限公司 | Preparation method of heat-resistant foamed microcapsule |
| CN104707580A (en) * | 2015-03-13 | 2015-06-17 | 惠州学院 | Method for preparing heavy metal extraction agent microcapsule and application of heavy metal extraction agent microcapsule to heavy metal wastewater treatment |
| CN105683456A (en) * | 2013-05-09 | 2016-06-15 | 声学空间有限公司 | A sound insulating sheet material with a cellular structure including gelatine and/or a process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6288171B2 (en) * | 1998-07-01 | 2001-09-11 | Advanced Elastomer Systems, L.P. | Modification of thermoplastic vulcanizates using random propylene copolymers |
| CN1562456A (en) * | 2004-04-14 | 2005-01-12 | 浙江大学 | Method for embedding water-soluble matter into microcapsule |
| CN1290604C (en) * | 2004-12-29 | 2006-12-20 | 浙江大学 | Process for preparing organic-inorganic hybrid nano microcapsule using polymer as core |
| CN100354039C (en) * | 2005-01-26 | 2007-12-12 | 浙江大学 | Preparation of organic-inorganic hybridized nanometer microcapsule with organic micromolecular hydrocarbon as model plate |
| CN100395014C (en) * | 2005-07-28 | 2008-06-18 | 同济大学 | Hollow microcapsules of polymer in multi-layers, and preparation method |
| CN100484618C (en) * | 2006-08-15 | 2009-05-06 | 浙江大学 | Method for preparing microcapsule by using doping porous calcium carbonate mould plates |
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- 2009-03-27 CN CN2009100382607A patent/CN101519472B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702449A (en) * | 2012-06-13 | 2012-10-03 | 福建省锦浪精细化工有限公司 | Preparation method of heat-resistant foamed microcapsule |
| CN105683456A (en) * | 2013-05-09 | 2016-06-15 | 声学空间有限公司 | A sound insulating sheet material with a cellular structure including gelatine and/or a process for producing the same |
| CN104707580A (en) * | 2015-03-13 | 2015-06-17 | 惠州学院 | Method for preparing heavy metal extraction agent microcapsule and application of heavy metal extraction agent microcapsule to heavy metal wastewater treatment |
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| CN101519472B (en) | 2012-05-23 |
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