CN101543756B - Controlled polymer/inorganic compound hollow microsphere and method for preparing same - Google Patents
Controlled polymer/inorganic compound hollow microsphere and method for preparing same Download PDFInfo
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- CN101543756B CN101543756B CN200910048261XA CN200910048261A CN101543756B CN 101543756 B CN101543756 B CN 101543756B CN 200910048261X A CN200910048261X A CN 200910048261XA CN 200910048261 A CN200910048261 A CN 200910048261A CN 101543756 B CN101543756 B CN 101543756B
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Abstract
The invention belongs to the technical fields of compound materials and functional polymer materials, and particularly relates to a controlled polymer/inorganic compound hollow microsphere and a method for preparing the same. The preparation method comprises the following steps that: the surface of a silicon dioxide hollow microsphere is modified by KH-550; and a nitrogen-oxygen free radical is inoculated to the surface of silicon dioxide, and the nitrogen-oxygen free radical is used for triggering the active free radical polymerization on the surface of a monomer to form a controlled polymer layer. The microsphere prepared by the method has the advantages of uniform size, good size stability, big mechanical strength, good compatibility with an organic substrate, difficult falling-off of the polymer layer, controllable thickness of an inorganic layer and the polymer layer, quite strong designability and wide application prospect.
Description
Technical field
The invention belongs to composite and technical field of function materials, be specifically related to a kind of controlled polymer/inorganic compound hollow microballoon and preparation method thereof.
Background technology
Tiny balloon is a kind of functional material with special construction, and its hollow space can be that gas, liquid or other have the active component of specific function, and skin is the shell that inorganic matter or polymer are formed.Particle size has small size, hollow and feature that spheroid capsule three be integrated in one to the polymer hollow Nano microballoon between micron because of it in nanometer, be with a wide range of applications in fields such as biology, catalysis, electronics, optics and magnetics, become hot research in recent years gradually.
The method for preparing polymer hollow microsphere mainly contains self-assembly method, 3 kinds of template and emulsion methods.The method for preparing SiO 2 hollow microsphere is a lot, [Li Yong is superfine comprising template/self assembly layer by layer/ablation method, template/sol-gel/ablation method, surfactant/ultrasonic dispersion and one-step method etc., the composite journal, 2005,22 (2): 21].And hollow polymer or inorganic matter microballoon all have the limitation of self, and polymer hollow microsphere and organic matrix compatibility are fine, but bad mechanical property easily caves in; Inorganic hollow microballoon mechanicalness and dimensional stability are fine, but poor with the organic matrix compatibility, make overall performance descend.
At inorganic particulate such as white carbon, graft polymers can improve surface nature effectively on carbon black and the ferrite, because the polymers grafted chain has hindered the gathering of these particles on the surface, and the affinity [Ren Li etc. of surface and solvent and polymeric matrix have been increased, polymer material science and engineering, 2004,20 (6): 60].Reported in the document and various polymer grafts have been arrived its surface [Norio T., etal.Progress in Organic Coating, 2002,44:69] by the peroxide of silica particle surface or the initator initiated polymerization of azo class.
Summary of the invention
The objective of the invention is to propose a kind of good mechanical property, with good controlled polymer/inorganic compound hollow microballoon of organic matrix compatibility and preparation method thereof.
The polymer/inorganic compound hollow microballoon that the present invention proposes, be with gamma-aminopropyl-triethoxy-silane (KH-550) modification on the hollow silicon dioxide surface, make its surface have amino, utilize amino reaction that NO free radical is received silica surface with epoxy radicals, and utilize the NO free radical trigger monomer at its surface aggregate, form controlled polymeric layer, its raw material is formed and is comprised:
2 parts of hollow silicon dioxide microballoons (mass number)
0.5～2 part of gamma-aminopropyl-triethoxy-silane (KH-550) (mass number)
0.5～3 part of the NO free radical (mass number) that contains epoxy radicals
1～50 part of monomer (mass number)
Among the present invention, described monomer is a styrene or derivatives thereof etc., as styrene, vinyl benzyl chloride, sulfonated phenylethylene, p-methylstyrene, phosphonate group styrene etc., or the polymer monomer of the active free radical polymerization that can cause by NO free radical arbitrarily.The cinnamic structural formula of phosphonate group is as follows:
Among the present invention, described NO free radical is that an end has NO free radical, and other end end group is an epoxide group, as 2,2,6, and 6-tetramethyl pyridine-1-oxygen (Tempo).The NO free radical that contains epoxy radicals is a 4-glycidol ether-2,2,6,6-tetramethyl pyridine-1-oxygen (GTEMPO).The structural formula of GTEMPO is as follows:
The preparation method of the controlled polymer/inorganic compound hollow microballoon that the present invention proposes, concrete steps are as follows:
(1) according to document (Z.F.Jia, Q.Fu, J.L.Huang.Journal of Polymer Science:Part A:PolymerChemistry, 44 (2006): 3836-3842) make the NO free radical that contains epoxy radicals.
(2) the 2g hollow silicon dioxide microballoon ultrasonic dispersion of polar organic solvent A, add in the reaction vessels, logical nitrogen, condensing reflux, 80～120 ℃ of control temperature, add 0.5～2g KH-550, magnetic agitation was reacted 8～20 hours, cooling, centrifugal, and clean for several times (as 3-6 time) repeatedly with organic solvent A;
(3) with the silica spheres of step (2) gained modification with the ultrasonic dispersion of organic solvent A, the NO free radical that contains epoxy radicals that adds 0.5～3g step (1) gained, under the nitrogen atmosphere, stirring at room 12～72 hours, question response is complete, centrifugal, and clean for several times (as 3-6 time) repeatedly with organic solvent A, guarantee that the unreacted NO free radical that contains epoxy radicals all eliminates;
(4) the hollow silicon dioxide microballoon that will connect NO free radical under the nitrogen protection, adds monomer with the ultrasonic dispersion of organic solvent B; under 80～120 ℃ of temperature, reacted 18～36 hours cooling, high speed centrifugation; and clean for several times (as 3-6 time) repeatedly with organic solvent B, promptly get required product.
Among the present invention, described hollow silicon dioxide microballoon is for being rich in the SiO 2 hollow microsphere of hydroxyl by the synthetic surface of modes such as template/self assembly layer by layer/ablation method, template/sol-gel/ablation method, surfactant/ultrasonic dispersion and one-step method.
Among the present invention, described organic solvent A is that alcohols or ester class etc. can make the polar solvent of silicon dioxide microsphere favorable dispersibility, but does not contain amino.
Among the present invention, described organic solvent B is the higher boilings such as toluene, benzene or dimethyl formamide and the solvent of dissolved monomer and its homopolymers simultaneously.
Advantage of the present invention is: the big or small homogeneous of microballoon, and dimensional stability is good, Heat stability is good, chemical stability is good, and mechanical strength is big, and is good with the compatibility of organic matrix.Because between the organic and inorganic layer is chemical bonding, the polymeric layer difficult drop-off, and the thickness of inorganic layer and polymeric layer is all controlled, has very strong designability, has broad application prospects and use value in nanometer technology, composite, interface tech, filed of functional.
Description of drawings
Fig. 1 is SiO
2The TEM photo of tiny balloon.
Fig. 2 is SiO
2The TEM photo of/PS hollow compound microsphere (the hollow silicon dioxide microballoon is 2: 1 with the monomer mass ratio).
Fig. 3 is SiO
2The TEM photo of/PS hollow compound microsphere (the hollow silicon dioxide microballoon is 1: 1 with the monomer mass ratio).
Fig. 4 is SiO
2The TEM photo of/PS hollow compound microsphere (the hollow silicon dioxide microballoon is 2: 5 with the monomer mass ratio).
Fig. 5 is SiO
2The TEM photo of/PVBPA hollow compound microsphere.
The specific embodiment
Following examples are only for further specifying the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following example is specifically expressed.
Raw materials used as follows:
Hollow silicon dioxide microballoon (according to document Chen M., et al.Adv.Mater., 2006, the preparation of 18:801. template);
Gamma-aminopropyl-triethoxy-silane (KH-550), Chemical Reagent Co., Ltd., Sinopharm Group;
2,2,6,6-tetramethyl pyridine-1-oxygen (Tempo), rich Anhua, Wuxi factory;
Epoxychloropropane, Chemical Reagent Co., Ltd., Sinopharm Group;
Styrene, Chemical Reagent Co., Ltd., Sinopharm Group;
Embodiment 1
Raw materials used proportioning is as follows:
2 parts of hollow silicon dioxide microballoons (mass number)
1 part of KH-550 (mass number)
4-glycidol ether-2,2,6,6-tetramethyl pyridine-0.5 part of 1-oxygen (GTEMPO) (mass number)
1 part of styrene (mass number)
2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of ethanol, logical nitrogen, and condensing reflux, 80 ℃ of control temperature add 1gKH-550, and magnetic agitation was reacted 12 hours, and cooling is centrifugal, and cleans repeatedly for several times with ethanol.Use the ultrasonic dispersion of ethanol again, add 0.5gGTEMPO, under the nitrogen atmosphere, stirring at room 36 hours, centrifugal, and clean repeatedly for several times with ethanol, guarantee that unreacted GTEMPO all eliminates.Disperse to connect the hollow silicon dioxide microballoon of NO free radical with toluene, under the nitrogen protection, add 1g styrene, 120 ℃ of reactions of control temperature 24 hours.Cooling, high speed centrifugation, and clean repeatedly for several times with toluene, promptly get polymer/inorganic composite Nano hollow microsphere.
Embodiment 2
Raw materials used proportioning is as follows:
2 parts of hollow silicon dioxide microballoons (mass number)
1 part of KH-550 (mass number)
0.5 part of GTEMPO (mass number)
0.1 part of azodiisobutyronitrile (AIBN) (mass number)
1 part of styrene (mass number)
2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of ethanol, logical nitrogen, and condensing reflux, 80 ℃ of control temperature add 1gKH-550, and magnetic agitation was reacted 12 hours, and cooling is centrifugal, and cleans repeatedly for several times with ethanol.Use the ultrasonic dispersion of ethanol again, add 0.5gGTEMPO, under the nitrogen atmosphere, stirring at room 36 hours, centrifugal, and clean repeatedly for several times with ethanol, guarantee that unreacted GTEMPO all eliminates.Disperse to connect the hollow silicon dioxide microballoon of NO free radical with toluene, under the nitrogen protection, add 1g styrene and 0.1gAIBN, 80 ℃ of reactions of control temperature 12 hours.Cooling, high speed centrifugation, and clean repeatedly for several times with toluene, promptly get polymer/inorganic composite Nano hollow microsphere, as shown in Figure 2, as can be seen from the figure, it is thin slightly to have made wall, dispersed reasonable PS/SiO
2Compound hollow microballoon.
Embodiment 3
Raw materials used proportioning is as follows:
2 parts of hollow silicon dioxide microballoons (mass number)
1 part of KH-550 (mass number)
0.5 part of GTEMPO (mass number)
0.1 part of azodiisobutyronitrile (AIBN) (mass number)
2 parts of styrene (mass number)
2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of ethanol, logical nitrogen, and condensing reflux, 80 ℃ of control temperature add 1gKH-550, and magnetic agitation was reacted 12 hours, and cooling is centrifugal, and cleans repeatedly for several times with ethanol.Use the ultrasonic dispersion of ethanol again, add 0.5gGTEMPO, under the nitrogen atmosphere, stirring at room 36 hours, centrifugal, and clean repeatedly for several times with ethanol, guarantee that unreacted GTEMPO all eliminates.Disperse to connect the hollow silicon dioxide microballoon of NO free radical with toluene, under the nitrogen protection, add 1g styrene and 0.1g AIBN, 80 ℃ of reactions of control temperature 12 hours.Cooling, high speed centrifugation, and clean repeatedly for several times with toluene, promptly get polymer/inorganic composite Nano hollow microsphere, as shown in Figure 3.As can be seen from the figure, made thicker slightly than Fig. 2 mesospore, finely dispersed PS/SiO
2Compound hollow microballoon.
Embodiment 4
Raw materials used proportioning is as follows:
2 parts of hollow silicon dioxide microballoons (mass number)
1 part of KH-550 (mass number)
0.5 part of GTEMPO (mass number)
0.1 part of azodiisobutyronitrile (AIBN) (mass number)
5 parts of styrene (mass number)
2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of ethanol, logical nitrogen, and condensing reflux, 80 ℃ of control temperature add 1gKH-550, and magnetic agitation was reacted 12 hours, and cooling is centrifugal, and cleans repeatedly for several times with ethanol.Use the ultrasonic dispersion of ethanol again, add 0.5gGTEMPO, under the nitrogen atmosphere, stirring at room 36 hours, centrifugal, and clean repeatedly for several times with ethanol, guarantee that unreacted GTEMPO all eliminates.Disperse to connect the hollow silicon dioxide microballoon of NO free radical with toluene, under the nitrogen protection, add 1g styrene and 0.1gAIBN, 80 ℃ of reactions of control temperature 12 hours.Cooling, high speed centrifugation, and clean repeatedly for several times with toluene promptly get polymer/inorganic composite Nano hollow microsphere, as scheming shown in the .4, as can be seen from the figure, made thicker slightly than Fig. 3 mesospore, finely dispersed PS/SiO
2Compound hollow microballoon.
Embodiment 5
Raw materials used proportioning is as follows:
2 parts of hollow silicon dioxide microballoons (mass number)
1 part of KH-550 (mass number)
0.5 part of GTEMPO (mass number)
0.1 part of azodiisobutyronitrile (AIBN) (mass number)
2 parts of phosphonate group styrene (VBPA) (mass number)
2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of ethanol, logical nitrogen, and condensing reflux, 80 ℃ of control temperature add 1gKH-550, and magnetic agitation was reacted 12 hours, and cooling is centrifugal, and cleans repeatedly for several times with ethanol.Use the ultrasonic dispersion of ethanol again, add 0.5gGTEMPO, under the nitrogen atmosphere, stirring at room 36 hours, centrifugal, and clean repeatedly for several times with ethanol, guarantee that unreacted GTEMPO all eliminates.Disperse to connect the hollow silicon dioxide microballoon of NO free radical with toluene, under the nitrogen protection, add 1g styrene and 0.1gAIBN, 80 ℃ of reactions of control temperature 12 hours.Cooling, high speed centrifugation, and clean repeatedly for several times with toluene, promptly get polymer/inorganic composite Nano hollow microsphere, as shown in Figure 5.As can be seen from the figure, made dispersed reasonable PVBPA/SiO
2Compound hollow microballoon.
In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part institute restricted portion, all can obtain the similar compound hollow microballoon of the foregoing description.
Claims (3)
1. controlled polymer/inorganic compound hollow microballoon, it is characterized in that in the gamma-aminopropyl-triethoxy-silane modification of hollow silicon dioxide surface, make its surface have amino, utilize amino reaction that NO free radical is received silica surface with epoxy radicals, and utilize the NO free radical trigger monomer at its surface aggregate, form controlled polymeric layer, its raw material is formed and is comprised:
2 parts of hollow silicon dioxide microballoons, in mass number,
0.5～2 part of gamma-aminopropyl-triethoxy-silane, in mass number,
0.5～3 part of the NO free radical that contains epoxy radicals, in mass number,
1～50 part of monomer is in mass number;
Wherein: described monomer is the styrene or derivatives thereof, or the polymer monomer of the active free radical polymerization that is caused by NO free radical; Described NO free radical is 2,2,6,6-tetramethyl pyridine-1-oxygen, and the described NO free radical that contains epoxy radicals is a 4-glycidol ether-2,2,6,6-tetramethyl pyridine-1-oxygen, its structural formula is as follows:
2. the preparation method of a controlled polymer/inorganic compound hollow microballoon as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) preparation contains the NO free radical of epoxy radicals;
(2) 2g hollow silicon dioxide microballoon adds in the reaction vessels with the ultrasonic dispersion of polar organic solvent A, logical nitrogen, condensing reflux, 80～120 ℃ of control temperature add 0.5～2g gamma-aminopropyl-triethoxy-silane, and magnetic agitation was reacted 8～20 hours, cooling, centrifugal, and clean with organic solvent A;
(3) with the silica spheres of step (2) gained modification with the ultrasonic dispersion of organic solvent A, the NO free radical that contains epoxy radicals that adds 0.5～3g step (1) gained, under the nitrogen atmosphere, stirring at room 12～72 hours, question response is complete, centrifugal, and clean to the NO free radical that contains epoxy radicals with organic solvent A and all to eliminate;
(4) the hollow silicon dioxide microballoon that will connect NO free radical under the nitrogen protection, adds monomer with the ultrasonic dispersion of organic solvent B, under 80～120 ℃ of temperature, reacted 18～36 hours, and cooling, centrifugation, and, promptly get required product with the organic solvent B cleaning;
Wherein: described organic solvent A is alcohols or ester class polar solvent, but does not contain amino; Described organic solvent B is toluene, benzene or dimethyl formamide.
3. the preparation method of controlled polymer/inorganic compound hollow microballoon according to claim 2 is characterized in that described hollow silicon dioxide microballoon is for being rich in the SiO 2 hollow microsphere of hydroxyl by the synthetic surface of template/self assembly layer by layer/ablation method, template/sol-gel/ablation method, surfactant/ultrasonic dispersion or one-step method mode.
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| CN101733052B (en) * | 2010-01-25 | 2011-09-28 | 吉林大学 | Preparation method of heterogeneous binary asymmetric particles |
| CN102451772B (en) * | 2010-10-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Dual-functional hollow nanocomposite oxide material and preparation and application thereof |
| CN102764616B (en) * | 2011-05-03 | 2014-07-16 | 中国科学院化学研究所 | Hollow microsphere and its preparation method |
| CN105944694B (en) * | 2016-05-24 | 2018-06-12 | 南京理工大学 | A kind of preparation method of aminated polymer hollow nanometer material |
| CN112159515A (en) * | 2020-09-10 | 2021-01-01 | 贵州师范大学 | Based on SiO2Method for preparing TEMPO free radical functionalized hollow conjugated microporous polymer by using template and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983369A (en) * | 1989-11-22 | 1991-01-08 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
| CN1631906A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Method for preparing monodisperse core/shell composite particle emulsion by using polystyrene coated nano silicon dioxide microspheres |
| CN101172609A (en) * | 2007-10-25 | 2008-05-07 | 同济大学 | Method of producing hollow silicon dioxide microsphere with mercapto on internal and external surfaces |
| CN101318660A (en) * | 2008-07-12 | 2008-12-10 | 太原理工大学 | Method of preparing hollow silicon dioxide ball |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983369A (en) * | 1989-11-22 | 1991-01-08 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
| CN1631906A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Method for preparing monodisperse core/shell composite particle emulsion by using polystyrene coated nano silicon dioxide microspheres |
| CN101172609A (en) * | 2007-10-25 | 2008-05-07 | 同济大学 | Method of producing hollow silicon dioxide microsphere with mercapto on internal and external surfaces |
| CN101318660A (en) * | 2008-07-12 | 2008-12-10 | 太原理工大学 | Method of preparing hollow silicon dioxide ball |
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