CN1331589C - Layer-by-layer microcapsule assembling process based on mutual covalent action - Google Patents
Layer-by-layer microcapsule assembling process based on mutual covalent action Download PDFInfo
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Abstract
本发明公开的基于共价键相互作用层-层组装微胶囊的方法，是采用将两种可反应的聚合物在氨基化的二氧化硅颗粒表面进行反应，获得具有多层结构的聚合物超薄膜；然后采用氢氟酸去除无机粒子，得到囊壁为共价交联多层膜结构的中空微胶囊。采用本发明方法组装微胶囊具有囊壁厚度在纳米或亚纳米范围内可调、强度高、稳定性好、耐酸碱盐腐蚀的特点，并容易进行功能化。原材料易得，制备工艺简单、稳定、可控性强。所得微胶囊可用于医药、染料、化妆品、传感器等领域。The method for assembling microcapsules based on covalent bond interaction layer-layer disclosed by the present invention is to react two kinds of reactive polymers on the surface of aminated silica particles to obtain a polymer superstructure with a multilayer structure. thin film; and then use hydrofluoric acid to remove inorganic particles to obtain hollow microcapsules whose walls are covalently cross-linked multilayer membrane structures. The microcapsules assembled by the method of the invention have the characteristics of adjustable capsule wall thickness in the range of nanometer or subnanometer, high strength, good stability, resistance to acid, alkali and salt corrosion, and are easy to be functionalized. The raw materials are easy to obtain, and the preparation process is simple, stable and highly controllable. The obtained microcapsules can be used in medicine, dyes, cosmetics, sensors and other fields.
Description
Technical field
The present invention relates to a kind of preparation method of polymer hollow microcapsule.Be the interaction that utilizes covalent bond specifically, but, form thin polymer film with sandwich construction by of the layer-layer assembling reaction of two kinds of reactive polymeric things at the silicon dioxide colloid particle surface; Then the silicon dioxide colloid particle is removed, obtained the microcapsules that cyst wall is the multi-layer film structure of covalent cross-linking.
Background technology
Microcapsules are by film forming matter the space in the capsule and the capsule external space to be kept apart to form the material of particular geometric configuration, and its inside can be filled, and also can be hollow.The shape of microcapsules also can be oval, square or rectangular, polygonal and various irregularly shaped based on spherical structure.Tradition microcapsules size usually at micron to the millimeter level, wall thickness in sub-micron to the hundreds of micron.According to the principle that cyst wall forms, the traditional preparation process technology of microcapsules cardinal principle can be divided three classes: the physical method of the chemical method of utilization reaction generation cyst wall, the physico-chemical process that utilizes the formation cyst wall that is separated and utilization machinery or other physical action formation cyst wall.Cyst wall is made up of natural or synthetic macromolecular material usually, also inorganic compound.In recent years, developed the preparation method of many new microcapsules again, as template assembling, matrix polymerization, surface grafting polymerization, dispersin polymerization etc.Wherein, has structure based on the microcapsules of the layer-layer self-assembling technique of weak interaction preparation and performance is controlled, easily give characteristics such as various unique functions.These weak interactions comprise electrostatic force, hydrogen bond, hydrophobic force etc.Yet these are usually not enough based on stability of the polymer microcapsule of weak interaction, can not resist comparatively harsh external environment condition and destroyed.These external environment conditions comprise the dissolving of organic solvent, the erosion of soda acid salt, the decomposition of high temperature etc.Obtain structure and stable performance, can resist the environment harsh conditions, the microcapsules of functionalization have become an important problem easily.Like this, can expand the application of micro-capsule, satisfy some specific requirement.
The intensity of covalent bond is bigger than weak interactions such as static and hydrogen bonds.If prepare the cyst wall of hollow microcapsule by the method for covalent bond, then can obtain more stable polymer microcapsules of structure.This is because two big intermolecular reactable groups that lean on mutually combine, and forms highly cross-linked polymer network structure.Therefore, in case reaction is finished, just can not can not be destroyed by the acid of general concentration, alkali and salt by organic solvent dissolution, resistance to elevated temperatures also can be improved greatly.Simultaneously, still can keep the advantages such as facility of layer-layer package technique, still can on nanometer and Ya Nami level, control growth as the thickness of film in the controlling diaphragm configuration aspects.
By covalent bond interaction preparation polymer hollow microcapsule, can be divided into two kinds technically.A kind of is to adopt the assembling of layer-layer earlier, obtains polymer wall through further crosslinking Treatment then.Typical case's representative is that the multilayer film that contains diazo resin forms cross-linked structure under UV-irradiation.In addition, polyacrylic acid and PAH multilayer film also can form the microcapsule wall of cross-linked structure through after high-temperature process or the carbodiimide treatment.Another is promptly to utilize two kinds of chemical reactions between polymer in preparation process, forms covalently cross-linked layer-layer assembling microcapsule wall.Under latter event, select for use the polymer of high reaction activity to carry out that the covalent bond assembling is easier to be accepted by actual production, because can form the microcapsule wall of stable performance at short notice, the shortening preparation time, enhance productivity, and can keep the quality of cyst wall.At present, Shang Weijian has the bibliographical information of this respect.
Summary of the invention
The purpose of this invention is to provide a kind of stable performance, wall thickness is controlled, is easy to the method based on covalent bond interplay layer-layer assembling microcapsules of functionalization.
Method based on covalent bond interplay layer-layer assembling microcapsules of the present invention, may further comprise the steps: with silicon dioxide granule by stirring or ultrasound suspending in the toluene solution that contains the silane coupling agent at least 3 hours, centrifugal then, with toluene or the solvent wash that dissolves each other with toluene, oven dry obtains amidized silicon dioxide granule;
1) amidized silicon dioxide granule is passed through stirring or ultrasound suspending in the tetrahydrofuran solution of poly (glycidylmethacrylate--co-ethylene dimethacrylate) or poly (glycidylmethacrylate--co-ethylene dimethacrylate)-co-methyl methacrylate, remove oxygen and filling nitrogen, stir down at 20～60 ℃, centrifugal then, use organic solvent washing;
2) with step 2) the gained particle by stir or ultrasound suspending in the aqueous solution of PAH, remove oxygen and filling nitrogen, stir down at 20～80 ℃, centrifugal then, wash with water;
3) repeating step 1) and 2), up to the required number of plies, remove silica with hydrofluoric acid then, obtain the hollow microcapsule that cyst wall is the covalent cross-linking multi-layer film structure.
Among the present invention, said silane coupler can be gamma-aminopropyl-triethoxy-silane or γ-An Bingjisanjiayangjiguiwan.The said solvent that dissolves each other with toluene can adopt methyl alcohol, ethanol, acetone or their mixture.Step 2) organic solvent used in can be oxolane, acetone, chloroform, carrene or dioxane.
The present invention is based upon on the addition reaction basis of amino and epoxy radicals, and interacting by covalent bond obtains the microcapsules of hollow structure, and its cyst wall is made up of the polymer ultra-thin film with sandwich construction.
The present invention selects poly (glycidylmethacrylate--co-ethylene dimethacrylate) or poly (glycidylmethacrylate--co-ethylene dimethacrylate)-co-methyl methacrylate and the PAH unit as covalency assembling microcapsules for use.All contain a large amount of amino or epoxy radicals on the side chain of these two kinds of polymer.Reactivity between these two kinds of groups is very high, and therefore prepared layer-layer is assembled polymer microcapsule at short notice; The cyst wall of gained microcapsules also has highly cross-linked structure.Simultaneously, utilize amino or epoxy radicals on a small amount of side chain, can be coupled to functional group in the module units in advance; Also can utilize in the cyst wall remaining amino or epoxy radicals to come the coupling function group.
Because the intensity of covalent bond is more much bigger than the intensity of electrostatic force, hydrogen bond etc., and two big intermolecular mutual couplings of reactable functional group of leaning on the side chain, will form highly cross-linked polymer network structure, this can make the intensity of highly cross-linked system of formation very big.
Beneficial effect of the present invention is:
1) addition reaction process and assembling process are finished simultaneously, need not post processing and just have highly cross-linked structure.
2) amino and epoxy reaction speed are fast, need not extra catalyst.
3) cyst wall of resulting polymers is controlled on nanometer and Ya Nami level.
4) polymer wall of Xing Chenging is stable, and is stable to organic solvent, soda acid salt, high temperature etc.
5) still contain amino and the epoxy radicals that to react on the polymer wall, realize functionalization easily.The microcapsules that the present invention makes can be used for fields such as medicine, dyestuff, cosmetics, sensor.
Description of drawings
Fig. 1 is an atomic force picture after the stoning of covalency assembling microcapsules a); B) be the amplification after the stoning of covalency assembling microcapsules the atomic force image (on) and tangent plane height distribution curve (descending);
Fig. 2 is the preceding transmission electron microscope photo of covalency assembling microcapsules stoning a); B) be transmission electron microscope photo after the stoning of covalency assembling microcapsules;
Fig. 3 is the stereoscan photograph after the stoning of covalency assembling microcapsules;
Fig. 4 is a laser confocal microscope photo after the microcapsules stoning of covalency assembling preparation on 1 micron the silicon dioxide colloid particle a); B) be laser confocal microscope photo after the microcapsules stoning of covalency assembling preparation on 4 microns the silicon dioxide colloid particle;
Fig. 5 is to be the AFM photo of construction material prepared microcapsule with the copolymer;
Fig. 6 is the laser confocal microscope photo of the covalency assembling microcapsules that soaked in alkali lye.
The specific embodiment
Embodiment 1:
The silicon dioxide microparticle that with the 4g diameter is 1 micron spends the night in containing the toluene solution of 5% gamma-aminopropyl-triethoxy-silane by stirring suspension, and is centrifugal then, with toluene wash twice, uses the ethanol washed twice then earlier, oven dry.The amidized silicon dioxide microparticle of 1g is suspended in the tetrahydrofuran solution of poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 4mg/ml, logical nitrogen 10 minutes stirred 3 hours down at 60 ℃, and is centrifugal then, with tetrahydrofuran solvent washing three times; Again with these particles by stirring suspension in the aqueous solution of the PAH of 4mg/ml, logical nitrogen 10 minutes stirred 3 hours down at 80 ℃, and is centrifugal then, washes with water three times.Repeat said process, reach 7 layers, remove silicon dioxide microparticle with the hydrofluoric acid of 0.4mol/L then, on mica sheet, do the AFM test up to the number of plies of assembling.Fig. 1 a is the atomic force microscope images of microcapsules, Fig. 1 b be the atomic force microscope images that amplifies (on) and tangent plane height distribution curve (descending).As seen from the figure, obtained hollow microcapsule later on having removed silica, and microcapsules keep good integrality.
Embodiment 2:
The silicon dioxide microparticle that with the 4g diameter is 1 micron spends the night in containing the toluene solution of 5% γ-An Bingjisanjiayangjiguiwan by ultrasound suspending, and is centrifugal then, with toluene wash twice, uses methanol wash twice then earlier, oven dry.With the amidized silicon dioxide microparticle of 1g by ultrasound suspending in the tetrahydrofuran solution of the poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 8mg/ml, logical nitrogen 20 minutes stirred 10 hours down at 20 ℃, and is centrifugal then, with acetone washing three times; Again with these particles by ultrasound suspending in the aqueous solution of the PAH of 2mg/ml, logical nitrogen 20 minutes stirred 1 hour down at 80 ℃, and is centrifugal then, washes with water three times.Repeat said process, the number of plies up to assembling reaches 7 layers, Fig. 2 a is the images of transmissive electron microscope when not removing silica, Fig. 2 b is with the images of transmissive electron microscope behind the hydrofluoric acid removal silica of 0.1mol/L, prove the existence of silica particle surface processing of ultra-thin polymeric film respectively, and obtained the microcapsules of hollow behind the removal silica.
Embodiment 3:
The silicon dioxide microparticle that with the 4g diameter is 1 micron spends the night in containing the toluene solution of 10% γ-An Bingjisanjiayangjiguiwan by stirring suspension, and is centrifugal then, with toluene wash 5 times, and oven dry.With the amidized silicon dioxide microparticle of 1g by stirring suspension in the tetrahydrofuran solution of the poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 1mg/ml, logical nitrogen 30 minutes stirred 4 hours down at 60 ℃, and is centrifugal then, with chloroform washing three times; These particles are suspended in the aqueous solution of PAH of 1mg/ml, logical nitrogen 10 minutes stirred 10 hours down at 20 ℃, and is centrifugal then, washes with water 5 times again.Repeat said process, reach 7 layers, remove silica with the hydrofluoric acid of 0.4mol/L then, microcapsule suspension is dripped to the enterprising line scanning electron microscopic observation of mica sheet, prove that the gained microcapsules have hollow structure (Fig. 3) up to the number of plies of assembling.
Embodiment 4:
The silicon dioxide microparticle that with the 4g diameter is 1 micron was by ultrasound suspending in containing the toluene solution of 2% gamma-aminopropyl-triethoxy-silane 10 hours, and is centrifugal then, with acetone washing 4 times, oven dry.With the amidized silicon dioxide microparticle of 1g by ultrasound suspending in the tetrahydrofuran solution of the poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 5mg/ml, logical nitrogen 30 minutes stirred 3 hours down at 50 ℃, and is centrifugal then, with washed with dichloromethane three times; Again with these particles by stirring suspension in the aqueous solution of the PAH of 2mg/ml, logical nitrogen 15 minutes stirred 3 hours down at 50 ℃, and is centrifugal then, washes with water three times.Repeat said process, reach 7 layers, remove silica with the hydrofluoric acid of 0.2mol/L then up to the number of plies of assembling.After dripping a spot of rhodamine solution, under laser confocal microscope, observe.Fig. 4 a proof gained microcapsules have hollow structure.
Embodiment 5:
The silicon dioxide microparticle that with the 1g diameter is 4 microns spends the night in containing the toluene solution of 3% gamma-aminopropyl-triethoxy-silane by stirring suspension, and is centrifugal then, with methanol wash 3 times, and oven dry.With the amidized silicon dioxide microparticle of 0.5g by stirring suspension in the tetrahydrofuran solution of the poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 3mg/ml, logical nitrogen 20 minutes stirred 7 hours down at 40 ℃, and is centrifugal then, with dioxane washing three times; Again with these particles by ultrasound suspending in the aqueous solution of the PAH of 3mg/ml, logical nitrogen 15 minutes stirred 7 hours down at 40 ℃, and is centrifugal then, washes with water three times.Repeat said process, reach 7 layers, remove silica with the hydrofluoric acid of 0.3mol/L then up to the number of plies of assembling.After dripping a spot of rhodamine solution, under laser confocal microscope, observe.Fig. 4 b proof gained microcapsules have hollow structure.
Embodiment 6:
The silicon dioxide microparticle that with the 4g diameter is 1 micron spends the night in containing the toluene solution of 7% gamma-aminopropyl-triethoxy-silane by ultrasound suspending, and is centrifugal then, with ethanol washing 5 times, oven dry.With the amidized silicon dioxide microparticle of 1g by stirring suspension in the tetrahydrofuran solution of poly (glycidylmethacrylate--co-ethylene dimethacrylate)-co-methyl methacrylate of 2mg/ml, logical nitrogen 30 minutes, stirred 4 hours down at 30 ℃, centrifugal then, with tetrahydrofuran solvent washing three times; Again with these particles by stirring suspension in the aqueous solution of the PAH of 2mg/ml, logical nitrogen 15 minutes stirred 1 hour down at 70 ℃, and is centrifugal then, washes with water 4 times.Repeat said process, reach 8 layers, remove silica with the hydrofluoric acid of 0.2mol/L then up to the number of plies of assembling.The later microcapsules of stoning are done the AFM test, prove to have hollow structure (Fig. 5).
Embodiment 7:
The silicon dioxide microparticle that with the 4g diameter is 1 micron spends the night in containing the toluene solution of 4% gamma-aminopropyl-triethoxy-silane by stirring suspension, and is centrifugal then, with acetone washing 5 times, oven dry.With the amidized silicon dioxide microparticle of 1g by stirring suspension in the tetrahydrofuran solution of the poly (glycidylmethacrylate--co-ethylene dimethacrylate) of 1mg/ml, logical nitrogen 15 minutes stirred 8 hours down at 30 ℃, and is centrifugal then, with tetrahydrofuran solvent washing three times; Again with these particles by ultrasound suspending in the aqueous solution of the PAH of 1mg/ml, logical nitrogen 15 minutes stirred 8 hours down at 30 ℃, and is centrifugal then, washes with water 2 times.Repeating said process, reach 7 layers up to the number of plies of assembling, is that immersion is after 11 hours in 12 the alkali lye in pH value, and centrifuge washing is removed silica with hydrofluoric acid then.After rhodamine dyeing, laser confocal microscope is observed the proof microcapsules and is still had intact structure (Fig. 6).
Claims (3)
1. based on the method for covalent bond interplay layer-layer assembling microcapsules, this method may further comprise the steps:
1) with silicon dioxide granule by stirring or ultrasound suspending in the toluene solution that contains the silane coupling agent at least 3 hours, centrifugal then, with toluene or the solvent wash that dissolves each other with toluene, oven dry, said silane coupler is gamma-aminopropyl-triethoxy-silane or γ-An Bingjisanjiayangjiguiwan;
2) step 1) gained particle is passed through stirring or ultrasound suspending in the tetrahydrofuran solution of poly (glycidylmethacrylate--co-ethylene dimethacrylate) or poly (glycidylmethacrylate--co-ethylene dimethacrylate)-co-methyl methacrylate, remove oxygen and filling nitrogen, stir down at 20～60 ℃, centrifugal then, use organic solvent washing;
3) with step 2) the gained particle by stir or ultrasound suspending in the aqueous solution of PAH, remove oxygen and filling nitrogen, stir down at 20～80 ℃, centrifugal then, wash with water;
4) repeating step 2) and 3), up to the required number of plies, remove silica with hydrofluoric acid then, obtain the hollow microcapsule that cyst wall is the covalent cross-linking multi-layer film structure.
2. by the described method of claim 1, it is characterized in that the said solvent that dissolves each other with toluene is methyl alcohol, ethanol, acetone or their mixture based on covalent bond interplay layer-layer assembling microcapsules.
3. by the described method of assembling microcapsules of claim 1, it is characterized in that step 2 based on covalent bond interplay layer-layer) used organic solvent is oxolane, acetone, chloroform, carrene or dioxane.
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| CN100463713C (en) * | 2006-10-13 | 2009-02-25 | 东南大学 | Multilayer hollow nanofiber for cell culture and preparation method thereof |
| CN100462135C (en) * | 2007-01-31 | 2009-02-18 | 四川大学 | Polyethyleneimine derivative nano hollow microspheres and preparation method thereof |
| CN101564668B (en) * | 2009-05-26 | 2011-07-20 | 浙江理工大学 | Preparation method of microcapsule |
| CN101773813B (en) * | 2010-03-12 | 2011-12-21 | 浙江大学 | Method for preparing hollow micro-capsules on basis of specific interaction between concanavalin and glycogen |
| US10034819B2 (en) * | 2012-09-24 | 2018-07-31 | Firmenich Sa | Multilayered core/shell microcapsules |
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| CN1125337C (en) * | 2001-03-09 | 2003-10-22 | 中国科学院大连化学物理研究所 | Ammonia-type inverse bonded stationary phase and its prepn |
| US20050147594A1 (en) * | 2003-10-17 | 2005-07-07 | Francois Leblond | Semi-permeable microcapsule with covalently linked layers and method for producing same |
| CN1687202A (en) * | 2005-03-24 | 2005-10-26 | 武汉理工大学 | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine |
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| CN1125337C (en) * | 2001-03-09 | 2003-10-22 | 中国科学院大连化学物理研究所 | Ammonia-type inverse bonded stationary phase and its prepn |
| US20050147594A1 (en) * | 2003-10-17 | 2005-07-07 | Francois Leblond | Semi-permeable microcapsule with covalently linked layers and method for producing same |
| CN1687202A (en) * | 2005-03-24 | 2005-10-26 | 武汉理工大学 | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine |
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| Core-Shell Colloids and Hollow PolyelectrolyteCapsules Based on Diazoresins Isabel Pastoriza.Santos et al,ADNANCED FUNCTIONAL MATERIALS,Vol.11 No.2 2001;层-层组装聚合物中空微胶囊 高长有，沈家骢，自然科学进展，第14卷第5期 2004 * |
| 层-层组装聚合物中空微胶囊 高长有，沈家骢，自然科学进展，第14卷第5期 2004 * |
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