CN103554325B - A kind of preparation method of functional hollow polymer microballoon - Google Patents
A kind of preparation method of functional hollow polymer microballoon Download PDFInfo
- Publication number
- CN103554325B CN103554325B CN201310518323.5A CN201310518323A CN103554325B CN 103554325 B CN103554325 B CN 103554325B CN 201310518323 A CN201310518323 A CN 201310518323A CN 103554325 B CN103554325 B CN 103554325B
- Authority
- CN
- China
- Prior art keywords
- shell
- monomer
- microsphere
- functional
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The preparation method that the invention discloses a kind of functional hollow polymer microballoon.The shell of described functional hollow polymer microballoon is prepared through precipitation polymerization by functional monomer and the cross-linking agent of different proportion, and the crosslinking shell formed has meso-hole structure.Specifically: first, monodisperse polymer micro-sphere template is prepared by self-stabilization precipitation polymerization；Reaction system is not separated, is directly added into shell and forms required functional monomer and cross-linking agent, prepares, by precipitation polymerization, the core-shell polymer microsphere that shell is cross-linked mesoporous structure；Finally micro polymer ball is removed by the mode that solvent dissolves and can obtain functional hollow polymer microballoon.Present invention process is simple, easy-to-operate, reaction condition is gentle, do not need special equipment, preparation efficiency is significantly high, microsphere separates easily and size is controlled, and the functional groups content of polymer microballoon is very high simultaneously, and the large-scale industrial production for functional hollow polymer microballoon is laid a good foundation.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related to polymeric hollow microsphere of a kind of functional excellence and preparation method thereof.It is cross-linked mesoporous structure that the method can be used for preparing shell, and nucleocapsid structure polymer microballoon containing the functional groups such as a large amount of anhydride, acid imide or carboxylate in shell, and the functional hollow polymer microballoon that the core removing of prepared functional core shell polymer microsphere is formed by the mode dissolved by solvent.
Technical background
Polymeric hollow microsphere is the polymeric material that a class morphosis is unique; there is inside it one or more cavity; therefore there is the characteristics such as density is low, specific surface is high, optical property is unique; have broad application prospects as a kind of new function material; can be used for the protection of medicine, enzyme, albumen, gene and catalyst, embedding, transmission and controllable release; it is used as to absorb the functional coating of sound wave and microwave, is used for the preparation etc. of nano-device as capsule of nano and microreactor.
From Kowalski et al. (USPatent4427836 in a series of patents eighties in 20th century, USPatent4594363, USPatent4970241) reported since Permeation Swelling method prepares polymeric hollow microsphere, the excellent properties of polymeric hollow microsphere arouses widespread concern, and the research of its preparation method and process conditions is also day by day deep.At present, the method preparing hollow microsphere mainly has: suspend and emulsion polymerization, template, self-assembly method, Core-Shell Polymer Particles precursor process.
nullSuspension polymerisation law system is simple，Polymerization process is easy to control easily，But limited by suspension polymerization system shortcoming，Prepared particle is micron order，And it is difficult to the effective control to particle diameter，It is mainly suitable for the preparation (OkuboM to the less demanding micron order polymeric hollow microsphere of appearance and size,KonishiY,InoharaT,MinamiH.Productionofhollowpolymerparticlesbysuspensionpolymerizationsforethyleneglycoldimethacrylate/toluenedropletsdissolvingstyrene–methylmethacrylatecopolymers.J.Appl.Polym.Sci.2002,86:1087 91)；Although emulsion polymerization can directly prepare nanometer-sized monodisperse polymeric hollow microsphere, but complicated process of preparation needs to adopt special emulsifying agent, and the more difficult control (JangJ of condition, HaH.Fabricationofhollowpolystyrenenanospheresinmicroemul sionpolymerizationusingtriblockcopolymers.Langmuir2002,18:5613-8).
Template ratio juris is based on microsphere template as core, polymeric shell layer is formed by modes such as surface deposition, self assembly, surface initiation polymerization on the surface of core, then again through the mode such as extracting or etching, mould material is removed, thus obtaining the polymer microballoon with hollow structure.Template can prepare the polymeric hollow microsphere that size is homogeneous, and size tunable.Such as publication number has been the patent disclosure of CN1631951A, and one passes through microemulsion method at inorganic nanometer microballoon surface keyed jointing one layer of polymeric, form the nucleocapsid complex microsphere of polymer inorganic nanoparticle, then with strong acid, inorganic nano-particle etching is removed, be finally prepared for the polymeric hollow microsphere that size uniformity, chemical stability are good.But template synthesis process needs certain moduli panel material, template removes process to use special solvent, it is easy to pollute prepared polymeric hollow microsphere, and template removes and is easily caused shell breakage, so template application is very restricted.
Although self-assembly method can accurately control the pattern of polymeric hollow microsphere, size, and it is relatively stable to form tiny balloon, and even without enucleation step, preparation process is relatively simple.Such as Wooley et al. adopts polyisoprene-polyacrylic acid (PI-PAA) to be system, be prepared for PI be core, PAA be shell micelle, then with the polyethylene glycol crosslinked PAA shell of amine end-blocking and by ozone oxidation degraded removing PI core, can obtain that there is PAA and cross-link the polymeric hollow microsphere (HuangHY of shell structurre, RemsenEE, KowalewskiT, WooleyKL.Nanocagesderivedfromshellcross-linkedmicelletem plates.J.Am.Chem.Soc.1999,121:3805-3806.).nullJiang Ming etc. utilize the two ends of rigidity all with the polyimides oligomer of carboxyl and flexible poly-(4-vinyl gives a tongue-lashing pyridine)-mix in chloroformic solution，Hollow polymer microsphere (WangM can be formed by self aggregation immediately,JiangM,NingFL,ChenDY,LinSY,DuanHW.Block-copolymer-freestrategyforpreparingmicellesandhollowspheres:·self-assemblyofpoly(4-vinylpyridine)andmodifiedpolystyrene.Macromolecules,2002,35:5980-5989.).But self-assembly method needs the polymer of special construction, material relatively costly, it is impossible to high-volume puts into commodity production.
Core-Shell Polymer Particles precursor process is the classical method preparing hollow microsphere, its preparation process is as follows: first prepare the polymer particle presoma of nucleocapsid structure, again the core of Core-Shell Polymer Particles is removed, and then obtain hollow polymer particle, Hollow Latex Particles even particle size distribution prepared by this method, size are controlled, shell thickness can be regulated easily by change polymer core size, is the focus of current Hollow Latex Particles preparation research.Caruso is core with surface with the template particles of electric charge, different composition and the Core-Shell Polymer Particles of different shell thickness it is prepared for by the mode of electrostatic self-assembled, remove polymer core by modes such as solvent dissolving, etchings further and can prepare polymeric hollow microsphere (CarusoF.Hollowcapsuleprocessingthroughcolloidaltemplatin gandself-assembly.Chem.Eur.J., 2000,6:413-9).But the preparation method of Core-Shell Polymer Particles is generally complex, operation is required higher by preparation process, production concentration not high yield is relatively low, and is easily caused the fall damage of shell in core subtractive process, and therefore this preparation method not yet reaches the degree of practical application at present.
In sum, also lack suitable in what commercially produce at present, the preparation method containing the single dispersing polymeric hollow microsphere of a large amount of functional groups in the large-scale producing method of single dispersing polymeric hollow microsphere, particularly shell.
In conventional research process, the applicant, in a series of patents, discloses self-stabilization precipitation polymerization and prepares monodisperse copolymerization thing micro-sphere method.nullThe such as patent No. is the Chinese patent disclosed " method of maleic anhydride and vinyl acetate copolymerized reaction " of ZL200310115329.4，The patent No. is the Chinese patent disclosed " a kind of method of phenylethylene/maleic anhydride copolyreaction " of ZL200810101948.0，Application number is the Chinese patent disclosed " a kind of method that α-methyl styrene and maleic anhydride react " of 200910087181.5，Application number is the Chinese patent disclosed " synthetic method of a kind of high molecular weight styrene and maleic anhydride alternate copolymer " of 200910087177.9，The patent No. is the Chinese patent disclosed " synthetic method of a kind of low molecular weight phenylethylene/maleic anhydride alternate copolymer " of ZL200910079490.8，The patent No. is the Chinese patent disclosed " a kind of method preparing itaconic anhydride and styrene monomer alternate copolymer " of ZL201010522333.2，Aforementioned patents disclose the method preparing a series of size monodisperse polymer micro-sphere different with composition by self-stabilization precipitation polymerization.Based on above-mentioned patent, the applicant it is further proposed that add cross-linking agent in self-stabilization precipitation polymerization system, the single dispersing functional copolymer microsphere of cross-linked structure the preparation method disclosing cross-linked structure copolymer microsphere in a series of patents can be prepared.nullSuch as application number is the Chinese patent disclosed " preparation method of a kind of cross-linking maleic anhydride-vinyl acetate copolymer " of 200810118553.1，Application number is the Chinese patent disclosed " preparation method of a kind of cross-linking maleic anhydride-styrene copolymer " of 200810118552.7，Application number is the Chinese patent disclosed " prepared by a kind of C5 mixture-maleic anhydride the copolymer containing functional groups and preparation method " of 201210138133.6，The patent No. is the Chinese patent disclosed " a kind of method that dicyclopentadiene and maleic anhydride react " of ZL201110115705.4，The patent No. is the Chinese patent disclosed " method of a kind of maleic anhydride/conjugated diolefin copolymer reaction " of ZL201010130571.9.
In above-mentioned monodisperse copolymerization thing microsphere and cross-linked structure copolymer microsphere preparation process, polyalcohol microspherulite diameter increases along with the rising of response time prolongation and monomer conversion, and this shows that the growth of copolymer particle size is owing to formed polymer causes in the constantly deposition on copolymer microsphere surface.
nullBased on above-mentioned analysis，Applicant proposed a kind of method (DengJP preparing hollow polymer microsphere,YuY,DunS,YangWT.Hollowpolymerparticleswithnanoscaleporesandreactivegroupsontheirrigidshells:preparationandapplicationasnanoreactors.J.Phys.Chem.B,2010,114:2593 2601)，Preparation process is broadly divided into three steps: first passes through self-stabilization precipitation polymerization process and prepares single dispersing vinylacetate-maleic anhydride alternate copolymer particle (PMV)，Using prepared PMV separate particles washing purification the preparation being used for Core-Shell Polymer Particles as mould material，PMV template particles is dispersed in butyl acetate/normal heptane mixed solvent by second step again，In system, add MAH simultaneously、DVB and initiator，Initiator causes the alternating copolymerization of MAH-DVB thus obtaining shell-crosslinked Core-Shell Polymer Particles；Finally PMV core solvent such as acetone eluting can be obtained polymeric hollow microsphere.
The shortcoming that this method can overcome customary preparation methods to a certain extent, and prepared polymeric hollow microsphere is with anhydride functional groups, but preparation process is still complex, especially need PMV template particles purification, with the unreacted Vinyl Acetate Monomer of thorough eluting.It is therefore desirable to exploitation more simplifies and practical functional hollow method for preparing polymer micro.
For the deficiency that foregoing is mentioned, the present invention proposes a kind of method preparing nucleocapsid and hollow polymer microspheres by Multistep feeding one kettle way, it is therefore intended that the preparation method providing a kind of simple, quick, mild condition, functional hollow polymer microballoon efficient, lower-cost.
Summary of the invention
The concrete thought of the present invention is: first prepare monodisperse copolymerization thing microsphere (such as single dispersing PMS, PMV copolymer microsphere etc.)；The not separated purification of reaction system, it is directly added into shell to form required functional monomer, cross-linking agent, solvent and initiator (wherein functional monomer can be the excessive portion of functional monomer in copolymer microsphere template preparation process, or form required cross-linking agent with shell to add to reaction system), polymerization is prepared with copolymer microsphere for core further, and shell is the Core-Shell Polymer Particles of cross-linked mesoporous structure；Finally, the mode dissolved by solvent removes copolymer microsphere core, can obtain polymeric hollow microsphere.
Specifically, preparing monodisperse copolymerization thing microsphere for template core with self-stabilization precipitation polymerization, the functional hollow polymer microballoon preparation that shell is cross-linked mesoporous structure includes three steps of following continuous print:
(1) preparation of monodisperse copolymerization thing microsphere
Monodisperse copolymerization thing microsphere is prepared by self-stabilization precipitation polymerization process, and described self-stabilization precipitation polymerization system is made up of monomer, initiator and solvent.
The monomer of self-stabilization precipitation polymerization system is by collectively forming to electron donating monomer with by electron donating monomer, wherein include to electron donating monomer: styrene monomer (St, ±-methyl styrene, ±-ethyl styrene, p-methylstyrene, to methoxy styrene, 4-ethyl styrene, 3,4-dimethyl styrene etc.), vinylacetate one or several, included by electron donating monomer: MAH, maleimide and derivant thereof, itaconic anhydride, ±-methylene-3One or several of-butyrolactone；Mol ratio to electron donating monomer with by electron donating monomer is 1:1-1:4, it is preferable that 1:2-1:3；The monomer concentration of reaction system is 5-40wt%.Owing to charge transfer complex can be formed to electron donating monomer with by electron donating monomer, it is only capable of when general polymerization obtaining preparing linear alternating copolymer.By electron donating monomer, be there is special reactivity, it is easy to and other monomer copolymerizations, but itself is difficult to autohemagglutination, when to electron donating monomer and by the mol ratio of electron donating monomer less than 1:1 time, unnecessary can be retained in reaction system by electron donating monomer, in next step nucleocapsid structure forming process, participate in the formation of shell as shell compositing monomer.
Initiator used by self-stabilization precipitation polymerization system is the conventional oil soluble radical initiator known by professional and technical personnel, can be azo-initiator or peroxide initiator, in system, initiator content is 0.05～2.5wt% of monomer mass, it is preferable that 0.5～1.5wt%.Described azo-initiator includes: azo-bis-isobutyl cyanide, azo two cyanogen in different heptan etc.；Described peroxide initiator includes: dibenzoyl peroxide, cumyl peroxide, peroxidating two (2,4 dichloro-benzoyl), di-tert-butyl peroxide, dilauroyl peroxide, perbenzoic acid spy's butyl ester, diisopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate etc..
The solvent of self-stabilization precipitation polymerization system can be organic acid alkylester did or the mixed solution of ketone and alkane.The general structure of wherein said organic acid alkylester did is
Wherein R1It is the alkyl of 1-8, benzyl, phenyl or substituted-phenyl for H, C atomic number, R2It is the alkyl of 1-5 for C atomic number.Organic acid alkylester did includes Ethyl formate, propyl formate, Tetryl formate., amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, phenylacetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl n-butyrate., propyl butyrate, butyl butyrate, isobutyl isobutyrate (IBIB), isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, iso-amyl iso-valeriate, essence of Niobe, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, the esters solvents such as isoamyl phenylacetate；Ketone is 5%-65% with the volume fraction of ketone in alkane mixed solution, described ketone is selected from acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, and described alkane is selected from alkane solvents such as pentane, normal hexane, hexamethylene, normal heptane, normal octane and isobutyltrimethylmethane .s.
Self-stabilization precipitation polymerization is the free radical precipitation polymerization process that a class is novel, relatively more special, and macromolecule chemical industry technical professional can understand its process characteristic by Literature Consult.
The reason that self-stabilization Precipitation Polymerization Process prepares copolymer particle is adopted to be in that, compared with common precipitation polymerization system, self-stabilization precipitation polymerization system need not add cross-linking agent, without stirring, and products pure, can be easily separated, can obtain particle size distribution is monodispersed polymer particle, polymerization rate is fast simultaneously, and productivity is high, and the particle diameter of product can carry out adjustment (particle size range 200-2000nm) easily by the adjustment of monomer concentration, solvent composition.
(2) preparation of functional nucleocapsids structural polymer microsphere
Core-Shell Polymer Particles precursor process is classical way prepared by hollow microsphere, the present invention proposes the monodisperse polymer particle prepared by self-stabilization precipitation polymerization as template core, being directly added into shell in reaction system and form required monomer, initiator and solvent, one kettle way preparation has the Multifunctional Aids for Paper--Core-shell Structure Polymer Particles of crosslinking shell structurre.Specifically comprise the following steps that
First, the monodisperse polymer micro-sphere suspension system prepared by above-mentioned self-stabilization precipitation polymerization is cooled to 20-60 DEG C, it is preferable that 20-45 DEG C, and stirring makes monodisperse polymer micro-sphere dispersed in suspension system；
Secondly, under agitation by appropriate alkane solvents, shell forms required functional monomer and cross-linking agent joins in above-mentioned reaction system, dissolving is uniformly dispersed.Wherein, the promotion that is added to of alkane solvents cross-links the formation of shell and prevents secondary nucleation phenomenon from occurring, described alkane solvents can be made up of one or several of pentane, normal hexane, hexamethylene, normal heptane, normal octane or isobutyltrimethylmethane., it is preferable that normal heptane；In the alkane solvents added and above-mentioned self-stabilization precipitation polymerization reaction system, the volume ratio of solvent for use is between 1:5～1:1.5, it is preferable that 1:3.5～1:2.Shell formed functional monomer by MAH, maleimide and derivant thereof, itaconic anhydride, ±-methylene-3One or several compositions of-butyrolactone, described functional monomer can be the excessive portion in micro polymer ball template preparation process by electron donating monomer, it is also possible to forms required cross-linking agent with shell and adds to reaction system.Shell formed required cross-linking agent can by divinyl aromatic compound, bifunctionality or polyfunctionality (methyl) acrylate, (methyl) allyl acrylate, conjugated diene one or several form；Described divinyl aromatic compound be between position, para-position divinyl benzene mixtures (DVB), wherein DVB can be divinyl benzene content be 55% the DVB-80 of DVB-55 or 80%；nullDescribed bifunctionality or polyfunctionality (methyl) acrylate include such as two (methyl) acrylic acid glycol ester、Diethylene glycol two (methyl) acrylate、2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate、Two terminal hydroxyl acrylic or methacrylic acid of the ethylene glycol such as tetraethylene glycol (TEG) two (methyl) propylene or its oligomer carry out the product being esterified，Two terminal hydroxyl acrylic or methacrylic acid of propylene glycol or its oligomer carry out the product being esterified，Two (methyl) acrylic acid DOPCP、Two (methyl) acrylic acid hexanediol ester、The hydroxyl acrylic or methacrylic acid of 2 yuan of alcohol such as two (methyl) acrylic acid butanediol ester carries out the product being esterified，Bisphenol-A、The ethylene oxide of bisphenol-A or epoxychloropropane addition product、Or two terminal hydroxyl acrylic or methacrylic acid of their halogen substituents carry out the product that is esterified，Trimethylolpropane、The Esterification product of acrylic or methacrylic of the polyhydric alcohol such as tetramethylolmethane，There is the hydroxyl of 2 and above hydroxyl or amino-compound or the addition compound product (epoxy ring-opening addition) of amido and glycidyl acrylate or glycidyl methacrylate，Glycidyl acrylate or glycidyl methacrylate are by epoxy ring-opening addition and succinic acid、Adipic acid、P-phthalic acid、Phthalic acid、The ethylene glycol addition compound product of above-mentioned binary acid or the product of halogen substituents；Described conjugated diene includes 1,4 butadiene, isoprene, C 5 fraction, dicyclopentadiene etc.；Wherein, it is preferred to use DVB-55, DVB-80, Ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate and neopentyl glycol dimethacrylate.In order to ensure the crosslinking degree of shell and prevent generation offspring in system, it is between 1:0.8～1:1.5 that shell forms the vinyl mol ratio of required functional monomer and cross-linking agent, it is preferable that 1:1.0～1:1.2.
Finally, reaction system is warmed up to 60-90 DEG C gradually, keeps constant temperature polyase 13-6 hours, can obtain the core-shell polymer microsphere that shell is cross-linked mesoporous structure, and in polymerization process, initiator is residue initiator in monodisperse polymer micro-sphere template preparation process；In order to ensure response speed, it is possible to add appropriate initiator in system, added initiator is conventional oil soluble radical initiator, and the consumption of initiator is functional monomer and 0.05～2.5wt% of cross-linking agent gross mass, it is preferable that 0.8～1.5wt%.Described initiator can be made up of one or several of azo or peroxide radical initiator, and azo-initiator includes: azo-bis-isobutyl cyanide, azo two cyanogen in different heptan etc.；Described peroxide initiator includes: dibenzoyl peroxide, cumyl peroxide, peroxidating two (2,4 dichloro-benzoyl), di-tert-butyl peroxide, dilauroyl peroxide, perbenzoic acid spy's butyl ester, diisopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate etc..
In the size of nucleocapsid structure polymer microballoon of the contained preparation of said process, shell thickness, shell-crosslinked degree and shell, the kind of functional groups and content all simply can be controlled by the change that polymerization system forms.
(3) preparation of polymeric hollow microsphere
For prepared by said process with monodisperse copolymerization thing microsphere for core, shell is the Core-Shell Polymer Particles of cross-linked structure, wherein copolymer microsphere template core is by list monomer and the preparing linear alternating copolymer that formed through radical polymerization by electron donating monomer, it is absent from cross-linked structure, can be removed by the mode that solvent dissolves, the dissolving of preparing linear alternating copolymer can adopt acetone, oxolane, butanone, the low boiling point solvents such as Ketohexamethylene, and the shell formed has meso-hole structure, aperture is about 2-100nm, preparing linear alternating copolymer dissolve after can easily from microsphere diffusion inside to solution in；Meanwhile, the shell of Core-Shell Polymer Particles is formed by precipitation polymerization by functional monomer and cross-linking agent, has dimensionally stable and the cross-linked structure of high rigidity, processes without the change that shape and size occur even across solvent；Finally, the polymeric hollow microsphere that can obtain that there is crosslinking shell structurre is processed by simple solvent, in the size of polymeric hollow microsphere, shell thickness, shell-crosslinked degree and shell, the kind of functional groups and content are determined by core-shell polymer microsphere presoma, the difference of functional monomer is formed, containing functional groups such as anhydride, acid imide or carboxylates in shell according to shell.
DVB-MAH functional hollow polymer microballoon of the present invention can be realized by the synthetic route shown in accompanying drawing 1.Specifically, PMS particle is core, DVB-MAH is the core-shell polymer microsphere of crosslinking shell, and the synthetic route of corresponding polymeric hollow microsphere and reaction system formula following (for nucleocapsid mol ratio for 1:1).
1.PMS polymer particle template core:
Monomer: styrene 1.30g (12.5mmol), maleic anhydride 2.45g (25mmol)；
Solvent: isoamyl acetate 25mL；
Initiator: AIBN/BPO0.040g (1.0wt% of monomer)
2.DVB-MAH shell:
Monomer: 1.225g (12.5mmol) (MAH for remaining in PMS polymer particle preparation process)；
Cross-linking agent: DVB-551.15g (contents of ethylene 13.0mmol)
Initiator: AIBN/BPO0.010g (1.0wt%)
Solvent: normal heptane 12.5mL,
Operating procedure is as follows:
(1) the monomer styrene 1.30g (12.5mmol) of accurate weight, maleic anhydride 2.45g (25mmol) and initiator A IBN0.040g (1.0wt%) are dissolved in 25mL isoamyl acetate, logical nitrogen deoxygenation in 20 minutes；
(2) above-mentioned reaction system is heated to 60-100 degree Celsius, it is preferable that 65-80 DEG C, react 1.5-3.0 hour, obtain PMS polymer microballoon suspension system；
(3) PMS polymer microballoon suspension system is cooled to 20-60 DEG C, and stirring makes PMS polymer microballoon be uniformly dispersed in system；
(4) joining in above-mentioned PMS dispersion liquid by 12.5mL alkane solvents (can be made up of one or several of normal hexane, normal heptane, octane etc., it is preferable that normal heptane), 1.15gDVB under agitation, dissolving is uniformly dispersed；
(5) 0.010g initiator (oil-soluble azo-initiator or peroxide initiator) is joined in above-mentioned reaction system, reaction system is warmed up to 60-90 DEG C gradually, keep constant temperature polyase 13-4 hours, PMS particle can be obtained to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell；
(6) in above-mentioned Core-Shell Polymer Particles dispersion, add 20mL acetone solvent, stir 30 minutes, centrifugation, obtain the DVB-MAH polymeric hollow microsphere of the present invention；
(7) above-mentioned polymeric hollow microsphere is dispersed in water, 50 DEG C are reacted 1 hour, anhydride group can be converted into hydroxy-acid group, obtain carboxylic acid functional polymeric hollow microsphere, similarly, anhydride conversion can be amine groups by anhydride and polyamines reaction (polyamines such as diethylenetriamine, triethylene tetramine), obtains functional amido polymeric hollow microsphere.
Sample from the dispersion of hollow polymerizing microballoons, observe the pattern of microsphere, the SEM photograph according to gained sample with scanning electron microscope (SEM), use at least 100 microspherulite diameters of software measurement, calculate via formula below, the size of microsphere mean diameter (Dn) represent, the particle size distribution coefficient of dispersion (U) represents, formula is as follows:
U=Dw/Dn
Wherein DiFor the diameter of i-th microsphere, N is microsphere sum, DwMathematic(al) mean particle diameter for definition.
The shell thickness of polymeric hollow microsphere is determined by transmission electron microscope (TEM), the TEM photo according to gained sample, uses the shell thickness of at least 100 microspheres of software measurement, calculates via formula below, and the size of shell thickness is with average shell thickness (dn) represent,
Wherein diFor the diameter of i-th microsphere, N is microsphere sum.
The mean diameter of the polymeric hollow microsphere prepared by the present invention is 500-1000nm, and average shell thickness is 50-250nm, and the coefficient of dispersion of particle size distribution is 1.004-1.1, for single dispersing or close to monodispersity.In the size of polymeric hollow microsphere, shell thickness, shell-crosslinked degree and shell, functional groups content all simply can be controlled by the change that polymerization system forms.
The method of the invention has the advantage that
1. reaction condition is gentle, and course of reaction is one kettle way, it is not necessary to template polymer particle is easily separated purification, and preparation process is fairly simple, it is easy to large-scale production；
2. adopt self-stabilization precipitation polymerization, it is not necessary to any stabilizer and firmly stabilizer, preparation efficiency is higher, and resulting polymers particle can be easily separated, and solvent is easily recycled to be reused, and solvent for use is organic acid alkylester did, ketone and alkane, and toxicity is relatively low；
3. by the adjustment of the optimization of reaction condition and reaction system composition, the core-shell polymer microsphere that single dispersing, nuclear shell size are controlled, shell-crosslinked can be prepared, and stratum nucleare polymer can be removed simply by the mode that solvent dissolves, thus obtaining polymeric hollow microsphere；
4. the polymeric hollow microsphere shell prepared by is cross-linked mesoporous structure, wherein the addition of cross-linking agent causes the formation of cross-linked structure, improve the intensity of hollow polymer shell, make polymer microballoon have higher size and chemically stable, meso-hole structure is beneficial to transmission and the absorption of material；
5. in shell, functional groups can be converted into the group such as carboxyl, amido by simple chemical modification, is with a wide range of applications in the field such as elimination of the absorption of Acidity of Aikalinity dyestuff, metal ion.
Compared with prior art, method of the present invention can reduce energy consumption and solvent uses, process simplification, improve the preparation efficiency of polymeric hollow microsphere, and prepared polymeric hollow microsphere has the cross-linked mesoporous structure of uniqueness and the functional of excellence, is therefore more suitable for commercial Application.
Accompanying drawing illustrates:
Fig. 1 is: PMS micro polymer ball, PMSDVB-MAH Multifunctional Aids for Paper--Core-shell Structure Polymer Particles and DVB-MAH Hollow Latex Particles prepare schematic diagram.
The stereoscan photograph of the polymer microballoon of the nucleocapsid prepared by Fig. 2 (a) Multistep feeding one kettle way.
The stereoscan photograph of the polymer microballoon of hollow structure prepared by Fig. 2 (b) Multistep feeding one kettle way.Scale is 1 μm.
The transmission electron microscope picture (a) 20000 times (b) 40000 times of the polymeric hollow microsphere difference enlargement ratio prepared by Fig. 3 (a) Multistep feeding one kettle way.
Fig. 4 is: the carboxylated modified polymeric hollow microsphere saturation curve to basic stain methylene blue.
Fig. 5 is: the aminated modified polymeric hollow microsphere saturation curve to acid stain methyl blue.
Detailed description of the invention
Below by way of example, technical scheme is described, but these examples are not limiting as the present invention.Following nucleocapsid ratio refers in particular to the molar ratio of monomer MAH in nuclear shell.
Self-stabilization precipitation polymerization prepares monodisperse copolymerization thing microsphere
The concrete monomer ratio of embodiment 1(, solvent, formula of initiator are in Table 1)
Monomer vinylacetate 2.15g, maleic anhydride 4.90g, AIBN0.070g initiator are joined in reaction bulb, add butyl acetate 25mL to dissolve, stir, after mix homogeneously, within 30 minutes, except dissolved oxygen, reaction system is gradually heating to reaction temperature 75 DEG C to logical nitrogen afterwards, and condensing tube condensation refluxes.Reaction, to the setting time, stops heating, obtains single dispersing PMV copolymer microsphere 1# after cooling.For styrene, monomer styrene 1.30g, maleic anhydride 2.45g, AIBN0.040g initiator are joined in reaction bulb, add isoamyl acetate 25mL to dissolve, stir, after mix homogeneously, logical nitrogen removes dissolved oxygen in 30 minutes, reaction system is gradually heating to reaction temperature 75 DEG C afterwards, and condensing tube condensation refluxes.Reaction, to the setting time, stops heating, obtains single dispersing PMS copolymer microsphere 5# after cooling.The monodisperse polymer particle template core of different copolymer thing composition and different-grain diameter is prepared respectively according to formula in table 1.
Table 1 self-stabilization precipitation polymerization system formulation
The preparation of nucleocapsid and hollow polymer microspheres
Embodiment 2
nullThe suspension/dispersion of single dispersing PMV microsphere 1# is cooled to 30 DEG C，Starting stirring makes PMV polymer microballoon be uniformly dispersed in system，Under agitation by 12.5mL normal heptane、MAH2.45g and DVB2.3g joins in above-mentioned PMV dispersion liquid，Dissolving adds BPO initiator 0.025g in above-mentioned reaction system after being uniformly dispersed，Reaction system is warmed up to 85 DEG C gradually，Keep constant temperature polyase 13 hour，Can obtain PMV particle is core、DVB-MAH is the Core-Shell Polymer Particles of crosslinking shell，Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL，Stir 30 minutes，Centrifugation，Dry，Obtain the DVB-MAH polymeric hollow microsphere of the present invention，Conversion ratio is more than 99%，The nucleocapsid ratio of this polymeric hollow microsphere is the 1:1(thing mass ratio refering in particular to functional monomer MAH in nuclear shell，As follows)，Particle diameter is 530nm，Particle size distribution coefficient is 1.04，Shell thickness is 60nm.
Embodiment 3
The suspension/dispersion of single dispersing PMV microsphere 2# is cooled to 30 DEG C, starting stirring makes PMV polymer microballoon be uniformly dispersed in system, under agitation by 12.5mL normal hexane with 1,4-butadiene 0.675g joins in PMV dispersion liquid, AIBN initiator 0.0150g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMV particle to be core, butadiene-maleic anhydride be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the butadiene-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 630nm, particle size distribution coefficient is 1.05, and shell thickness is 60nm.
Embodiment 4
The suspension/dispersion of single dispersing PMV copolymer microsphere 3# is cooled to 20 DEG C, starting stirring makes PMV polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and C 5 fraction 3.66g are joined in above-mentioned PMV dispersion liquid, dissolving adds AIBN initiator 0.025g in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMV particle to be core, C 5 fraction-maleic anhydride be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the C 5 fraction-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.5, and particle diameter is 790nm, particle size distribution coefficient is 1.06, and shell thickness is 65nm.
Embodiment 5
The suspension/dispersion of methoxy styrene-copolymer-maleic anhydride microsphere 4# is cooled to 25 DEG C by single dispersing, starting stirring makes polymer microballoon be uniformly dispersed in system, under agitation the normal octane of 10mL and isoprene 0.425g are joined in above-mentioned dispersion liquid, dissolving adds AIBN initiator 0.010g in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain methoxy styrene-maleic anhydride particle is core, isoprene-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the isoprene-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 620nm, particle size distribution coefficient is 1.03, and shell thickness is 85nm.
Embodiment 6
The suspension/dispersion of single dispersing ±-methyl styrene-copolymer-maleic anhydride microsphere 5# is cooled to 40 DEG C, starting stirring makes polymer microballoon be uniformly dispersed in system, under agitation the normal heptane of 10mL and ethylene glycol diacrylate 1.063g are joined in above-mentioned dispersion liquid, dissolving adds AIBN initiator 0.010g in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain ±-methyl styrene-maleic anhydride particle is core, ethylene glycol diacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the ethylene glycol diacrylate-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 580nm, particle size distribution coefficient is 1.05, and shell thickness is 75nm.
Embodiment 7
The suspension/dispersion of single dispersing PMS copolymer microsphere 6# is cooled to 40 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 7.5mL normal heptane, MAH1.225g and DVB1.15g are joined in PMS dispersion liquid, AIBN initiator 0.010g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 620nm, particle size distribution coefficient is 1.15, and shell thickness is 60nm.
Embodiment 8
The suspension/dispersion of single dispersing PMS microsphere 7# is cooled to 20 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 10.0mL normal heptane and DVB1.15g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.005g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 760nm, particle size distribution coefficient is 1.004, and shell thickness is 90nm.
Embodiment 9
The suspension/dispersion of single dispersing PMS microsphere 7# is cooled to 30 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and Ethylene glycol dimethacrylate 1.238g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.008g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, Ethylene glycol dimethacrylate-maleic anhydride be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stirs 30 minutes, centrifugation, dry, obtain the polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, particle diameter is 790nm, and particle size distribution coefficient is 1.09, and shell thickness is 110nm.
Embodiment 10
The suspension/dispersion of single dispersing PMS microsphere 7# is cooled to 30 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and trimethylol-propane trimethacrylate 1.408g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.010g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain with PMS particle for core, trimethylol-propane trimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stirs 30 minutes, centrifugation, dry, obtain the polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, particle diameter is 800nm, and particle size distribution coefficient is 1.15, and shell thickness is 100nm.
Embodiment 11
The suspension/dispersion of single dispersing PMS copolymer microsphere 8# is cooled to 20 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and DVB0.88g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.005g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain with PMS particle be core, DVB-MAH be crosslinking shell Core-Shell Polymer Particles, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 675nm, particle size distribution coefficient is 1.01, and shell thickness is 75nm.
Embodiment 12
The suspension/dispersion of single dispersing PMS copolymer microsphere 9# is cooled to 35 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 12.5mL hexamethylene and DVB0.60g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.005g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:0.5, and particle diameter is 590nm, particle size distribution coefficient is 1.10, and shell thickness is 65nm.
Embodiment 13
The suspension/dispersion of single dispersing PMS copolymer microsphere 10# is cooled to 45 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and neopentyl glycol dimethacrylate 1.875g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.005g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is core, neopentyl glycol dimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the neopentyl glycol dimethacrylate-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.0, and particle diameter is 890nm, particle size distribution coefficient is 1.12, and shell thickness is 105nm.
Embodiment 14
The suspension/dispersion of single dispersing PMS microsphere 11# is cooled to 30 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation the alkane solvents normal octane of 10.0mL and DVB1.96g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.015g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.5, and particle diameter is 835nm, particle size distribution coefficient is 1.02, and shell thickness is 110nm.
Embodiment 15
The suspension/dispersion of single dispersing PMS microsphere 12# is cooled to 30 DEG C, starting stirring makes PMS polymer microballoon be uniformly dispersed in system, under agitation the alkane solvents isobutyltrimethylmethane. of 12.5mL and DVB2.60g are joined in above-mentioned PMS dispersion liquid, AIBN initiator 0.015g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtaining PMS particle to be core, DVB-MAH be the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the DVB-MAH polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:2, and particle diameter is 990nm, particle size distribution coefficient is 1.08, and shell thickness is 70nm.
Embodiment 16
The suspension/dispersion of single dispersing styrene-maleimide copolymer microsphere 13# is cooled to 30 DEG C, starting stirring makes polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and DVB-801.0g are joined in above-mentioned styrene-maleimide dispersion liquid, AIBN initiator 0.015g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain styrene-maleimide particle is core, diethylene glycol dimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the diethylene glycol dimethacrylate-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, and particle diameter is 770nm, particle size distribution coefficient is 1.05, and shell thickness is 75nm.
Embodiment 17
The suspension/dispersion of single dispersing styrene-itaconic anhydride microsphere 14# is cooled to 30 DEG C, starting stirring makes polymer microballoon be uniformly dispersed in system, under agitation the alkane solvents normal heptane of 10mL and dimethyl allene acid propylene glycol ester 1.325g are joined in above-mentioned styrene-itaconic anhydride dispersion liquid, AIBN initiator 0.005g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain styrene-itaconic anhydride particle is core, dimethyl allene acid propylene glycol ester-maleic anhydride is the Core-Shell Polymer Particles of crosslinking shell, monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtaining the dimethyl allene acid propylene glycol ester-maleic anhydride polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.0, and particle diameter is 750nm, particle size distribution coefficient is 1.09, and shell thickness is 80nm.
Embodiment 18
By single dispersing styrene-±-methylene-3The suspension/dispersion of-butyrolactone microsphere 15# is cooled to 30 DEG C, starting stirring makes polymer microballoon be uniformly dispersed in system, under agitation 12.5mL normal heptane and diethylene glycol dimethacrylate 1.513g are joined in above-mentioned dispersion liquid, AIBN initiator 0.015g is added in above-mentioned reaction system after being uniformly dispersed, reaction system is warmed up to 75 DEG C gradually, keep constant temperature polyase 13 hour, can obtain styrene-±-methylene-3-butyrolactone particle be core, diethylene glycol dimethacrylate-±-methylene-3-butyrolactone is the Core-Shell Polymer Particles of crosslinking shell, and monomer conversion is more than 99%；Above-mentioned Core-Shell Polymer Particles dispersion adds solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain the diethylene glycol dimethacrylate-±-methylene of the present invention-3-butyrolactone polymeric hollow microsphere, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.0, and particle diameter is 830nm, and particle size distribution coefficient is 1.12, and shell thickness is 95nm.
Modifiying of polymeric hollow microsphere
Embodiment 19
Take DVB-MAH hollow polymer microspheres powder (3.0g) obtained by appropriate embodiment 11, add 50mL water, and ultrasonic so as to be uniformly dispersed, 60 DEG C of reaction 3h；Or add NaOH (1.4g) under room temperature condition, add excessive dilute hydrochloric acid after reacting 2 hours and be neutralized to pH=3, then by polymer particle suspension at 8000rad min-1Centrifugation under rotating speed.After removing the supernatant, it is washed with water and washs, centrifugation, repeats 2 times, is dried by resulting polymers particle room temperature in vacuo afterwards, can obtain carboxylated modified polymeric hollow microsphere.The carboxylated modified polymeric hollow microsphere of gained can be used for the selective absorption of basic stain, for methylene blue, its saturation curve is as shown in Figure 4, its pH is that under 10 conditions, saturated extent of adsorption is 1428mg/g, and time of equilibrium adsorption is short, when methylene blue concentration is relatively low, adsorption equilibrium in 5 minutes, can be reached, when methylene blue concentration is higher, within 15 minutes, adsorption equilibrium can be reached.What obtain under two kinds of conditions is all carboxylated modified polymeric hollow microsphere, and the effect of water and (NaOH+HCl) is just as.
Embodiment 20
Take a small amount of obtained nucleocapsid structure polymer microballoon powder (2.0g), add 50mL oxolane (THF), ultrasonic so as to be uniformly dispersed, add excessive triethylene tetraamine (TETA10.0g) after 30min is stirred at room temperature, room temperature reaction after 3 hours reaction system be warming up to 60 DEG C continue reaction 3h.After reaction system is cooled to room temperature, at 10000rad min-1Centrifugation under rotating speed.After removing the supernatant, again add 25mLTHF and soak, centrifugation, repeat 3 times, remove excessive TETA, room temperature in vacuo dries the crosslinking polymeric hollow microsphere that can obtain amino modified.This aminated modified polymeric hollow microsphere can be used for the field such as elimination and carbon dioxide adsorption of the selective absorption of acid stain, metallic.For acid stain methyl blue, as shown in Figure 5, its pH is that under 4 conditions, saturated extent of adsorption is 955mg/g to its saturation curve, and time of equilibrium adsorption is shorter, when methyl blue concentration is relatively low, adsorption equilibrium in 5 minutes, can be reached, when methylene blue concentration is relatively low, within 10 minutes, adsorption equilibrium can be reached.
Claims (9)
1. the preparation method of a functional hollow polymer microballoon, it is characterised in that include three steps of continuous print:
First, preparing monodisperse polymer micro-sphere template by self-stabilization precipitation polymerization, self-stabilization precipitation polymerization system is made up of monomer, solvent and initiator；
Secondly, above-mentioned self-stabilization precipitation polymerization system is not separated, it is directly added into shell and forms desired function monomer, cross-linking agent, alkane solvents and initiator, with prepared monodisperse polymer micro-sphere for template core, functional monomer occurs precipitation polymerization to react under the existence of initiator and cross-linking agent, and adsorbed by micro polymer ball template, being gradually deposited at polymer microballoon template core surface and form the core-shell polymer microsphere that shell is cross-linked mesoporous structure, the concrete preparation process of nucleocapsid structure functional polymer microsphere is as follows:
1) above-mentioned self-stabilization precipitation polymerization system is cooled to 20-60 DEG C, and stirring makes prepared monodisperse polymer micro-sphere be dispersed in reaction system；
2) add alkane solvents, functional monomer, cross-linking agent and initiator under agitation, dissolve dispersion mix homogeneously；
3) reaction system is warmed up to 60-90 DEG C gradually, keeps constant temperature polyase 13-6 hours, can obtain the core-shell polymer microsphere that shell is cross-linked mesoporous structure；
Finally, the mode that the core of core-shell polymer microsphere is dissolved by solvent is removed, functional hollow polymer microballoon can be obtained.
2. method according to claim 1; it is characterized in that; described monodisperse polymer micro-sphere template is prepared by self-stabilization precipitation polymerization process; under inert gas shielding, monomer is dissolved dispersion in a solvent; oleosoluble radical initiators is adopted to cause polymerization; reaction temperature 50-100 DEG C, reacting 1-6 hour and can obtain monodisperse polymer micro-sphere template, prepared polymer microballoon is stably dispersed in reaction system.
3. method according to claim 2, it is characterized in that, preparing copolymer microsphere template by self-stabilization precipitation polymerization, in reaction system, monomer is by collectively constituting to electron donating monomer with by electron donating monomer, wherein give electron donating monomer by styrene monomer, vinylacetate one or several form；By electron donating monomer by MAH, maleimide and derivant thereof, itaconic anhydride, alpha-methylene-gamma-butyrolactone one or several collectively constitute, obtained the copolymer microsphere template of different composition by self-stabilization precipitation polymerization；The monomer mass percent concentration of reaction system is 5-60%；To electron donating monomer and by the mol ratio of electron donating monomer between 1:1～1:5, excessive in reaction system can be participated in shell as functional monomer by electron donating monomer and formed.
4. method according to claim 2, it is characterised in that prepare copolymer microsphere template by self-stabilization precipitation polymerization, in reaction system, solvent is organic acid alkylester did or the mixed solution of ketone and alkane；The general structure of wherein said organic acid alkylester did is
Wherein R1It is the alkyl of 1-8, benzyl, phenyl or substituted-phenyl for H, C atomic number, R2It is the alkyl of 1-5 for C atomic number；Ketone is 5%-65% with the volume fraction of ketone in alkane mixed solution, described ketone is selected from acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK) or methyl isopropyl Ketone, and described alkane is selected from pentane, normal hexane, hexamethylene, normal heptane, normal octane or isobutyltrimethylmethane..
5. method according to claim 2, it is characterized in that, copolymer microsphere template is prepared by self-stabilization precipitation polymerization, in reaction system, initiator is made up of one or several of azo or peroxide radical initiator, and in system, initiator content is 0.05～2.5wt% of monomer mass.
6. method according to claim 1, it is characterised in that need to add in reaction system alkane solvents in shell forming process；In the alkane solvents added and described self-stabilization precipitation polymerization system, the volume ratio of solvent for use is between 1:5～1:1.5；The described alkane solvents added is made up of one or several of pentane, normal hexane, hexamethylene, normal heptane, normal octane and isobutyltrimethylmethane..
7. method according to claim 1, it is characterized in that, described shell formed desired function monomer by MAH, maleimide and derivant thereof, itaconic anhydride, alpha-methylene-gamma-butyrolactone one or several form, described functional monomer is by the excessive portion of electron donating monomer in micro polymer ball template preparation process, or forms required cross-linking agent with shell and add to reaction system.
8. method according to claim 1, it is characterised in that described shell formed required cross-linking agent by divinyl aromatic compound, bifunctionality or polyfunctionality (methyl) acrylate, conjugated diene one or several form；Described nucleocapsid structure its shell of functional polymer microsphere is made up of functional monomer and the cross-linking agent of different proportion, and the vinyl mol ratio of functional monomer and cross-linking agent is between 1:0.8～1:1.5；The amount ratio of described nucleocapsid structure functional polymer microsphere preparation process center shell matter is between 1:0.5-1:3, and nucleocapsid amount of substance is than the thing mass ratio refering in particular to functional monomer in nuclear shell.
9. method according to claim 1, it is characterized in that, carboxyl or the polymeric hollow microsphere of functional amido that prepared functional hollow polymer microballoon is formed after modified are respectively applied to the absorption of Acidity of Aikalinity dyestuff or the elimination field of metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518323.5A CN103554325B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of functional hollow polymer microballoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518323.5A CN103554325B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of functional hollow polymer microballoon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554325A CN103554325A (en) | 2014-02-05 |
| CN103554325B true CN103554325B (en) | 2016-07-06 |
Family
ID=50008708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310518323.5A Active CN103554325B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of functional hollow polymer microballoon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554325B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933911B (en) * | 2014-05-06 | 2016-02-03 | 河北工业大学 | A kind of preparation method of Polymers hierarchical porous structure interlocking micro-capsule |
| CN104940145B (en) * | 2015-06-11 | 2017-12-22 | 武汉纺织大学 | A kind of method for improving drug bearing microsphere controlled release ability |
| US10058844B2 (en) * | 2015-06-19 | 2018-08-28 | 3M Innovative Properties Company | Divinylbenzene/maleic anhydride polymeric sorbents for carbon dioxide |
| US10464045B1 (en) * | 2015-06-19 | 2019-11-05 | 3M Innovative Properties Company | Hydrolyzed divinylbenzene/maleic anhydride polymeric sorbents for carbon dioxide |
| CN105949388B (en) * | 2016-05-23 | 2019-03-29 | 北京化工大学 | A kind of functional copolymer directly prepared by higher carbon number hydrocarbon class mixture and 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 |
| CN108129602B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer elastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN108129599B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer plastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN108126634B (en) * | 2016-12-01 | 2020-08-21 | 广州蓝月亮实业有限公司 | Hollow polymer brittle microsphere with micro-channels on surface and preparation method and application thereof |
| CN110760032B (en) * | 2017-07-24 | 2021-11-09 | 苏州大学 | Preparation method of degradable monodisperse polymer microspheres |
| CN107417841B (en) * | 2017-08-10 | 2020-04-17 | 北京化工大学 | Method for preparing small-particle-size functional polymer nano microspheres with high yield |
| CN111194239B (en) | 2017-09-04 | 2021-09-21 | 诺力昂化学品国际有限公司 | Thermally expandable microspheres made from bio-based monomers |
| CN107522894B (en) * | 2017-10-13 | 2020-06-02 | 西南大学 | Preparation method of hollow polymer nano-microsphere with mesopores and product thereof |
| CN108129596B (en) * | 2018-01-12 | 2019-11-26 | 浙江东太新材料有限公司 | A kind of hollow porous micro sphere and preparation method thereof of compound organic uv absorbers |
| CN108714420A (en) * | 2018-05-08 | 2018-10-30 | 宁波工程学院 | The preparation method of optomagnetic response hollow microsphere |
| CN108727628B (en) * | 2018-06-14 | 2021-03-02 | 常州大学 | Nano-silver hollow microsphere/PVDF ultrafiltration membrane and preparation method thereof |
| CN109593164B (en) * | 2018-12-10 | 2021-08-17 | 南开大学 | Active polymer microsphere with hollow structure and preparation method thereof |
| CN112708034B (en) * | 2019-10-24 | 2022-11-18 | 中国石油化工股份有限公司 | Composite microsphere containing alpha-methylstyrene polymer and preparation method and application thereof |
| CN112708029B (en) * | 2019-10-25 | 2022-11-18 | 中国石油化工股份有限公司 | Polymer composite microsphere containing vinyl acetate-maleic anhydride and preparation method and application thereof |
| CN113086963B (en) * | 2019-12-23 | 2022-10-25 | 中国科学院青岛生物能源与过程研究所 | Monodisperse hollow-structure carbon mesoporous microsphere material and induced assembly preparation method using organic-inorganic hybrid salt as template |
| CN114479262B (en) * | 2020-10-23 | 2023-02-28 | 中国石油化工股份有限公司 | Flame-retardant photodiffusion polypropylene composition and application thereof, flame-retardant photodiffusion polypropylene and preparation method and application thereof |
| CN114797697B (en) * | 2021-01-27 | 2024-04-12 | 北京化工大学 | Hollow polymer microsphere of bismaleimide resin, preparation method thereof and method for modifying cyanate resin |
| CN113649069B (en) * | 2021-08-02 | 2022-10-25 | 青海大学 | Photocatalytic material sulfur-doped polyimide hollow sphere and preparation method thereof |
| CN114621380A (en) * | 2022-03-10 | 2022-06-14 | 北京化工大学 | Method for preparing poly (styrene-maleic anhydride) special-shaped functional microspheres by miniemulsion polymerization |
| CN115138347B (en) * | 2022-07-25 | 2023-08-22 | 杭州师范大学 | Preparation method of strong-acid hollow nanospheres and application of strong-acid hollow nanospheres in urea adsorption |
| CN115386132B (en) * | 2022-08-12 | 2023-06-20 | 华南理工大学 | Low dielectric polyimide film taking electrostatic spinning high molecular organic porous film as pore-forming sacrificial template and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101550213A (en) * | 2009-05-13 | 2009-10-07 | 北京化工大学 | A metal/ polymer composite particle and method of preparing the same |
-
2013
- 2013-10-28 CN CN201310518323.5A patent/CN103554325B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101550213A (en) * | 2009-05-13 | 2009-10-07 | 北京化工大学 | A metal/ polymer composite particle and method of preparing the same |
Non-Patent Citations (3)
| Title |
|---|
| Hollow Polymer Particles with Nanoscale Pores and Reactive Groups on Their Rigid Shells:Preparation and Application as Nanoreactors;Jianping Deng,et.al;《J.Phys.Chem.B》;20100205;第114卷(第8期);第2593-2601页 * |
| 一锅法制备核壳结构聚合物微球;陈冬等;《2013年全国高分子学术论文报告会》;20131012;第101页 * |
| 邢长民.马来酸酐电荷转移络合物体系表面接枝聚合研究及"自分散"聚合制备高分子微球.《中国知网博士学位论文全文数据库》.2005,第B016-7页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554325A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554325B (en) | A kind of preparation method of functional hollow polymer microballoon | |
| JP5717766B2 (en) | Thermoplastic nanocomposite materials based on nanocrystalline cellulose (NCC) | |
| CN107417840A (en) | A kind of multiple copolymer micro-and nano-particles and preparation method thereof | |
| CN100579995C (en) | Copolymerization reaction method for styrene/maleic anhydride | |
| CN103570946B (en) | A kind of preparation method of polyimide microsphere | |
| CN109985584B (en) | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres | |
| JP5793577B2 (en) | Polyvinyl acetal fine particles for aqueous dispersions | |
| CN107417841A (en) | A kind of method for preparing small particle functional polymer nano microballoon in high yield | |
| CN102653580A (en) | Preparation method of Janus-structure composite emulsion particle | |
| Huang et al. | Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization‐Induced Self‐Assembly | |
| CN106478904A (en) | A kind of preparation method of the segmented copolymer material with temperature and pH-sensitivity | |
| CN109053960A (en) | A kind of preparation method of temperature sensitive beta-cyclodextrin nanoparticle | |
| JP2006257139A (en) | Core-shell type polymer particulate and method for producing the same | |
| Cao et al. | Synthesis of nanogels of poly (ε-caprolactone)-b-poly (glycidyl methacrylate) by click chemistry in direct preparation | |
| CN110775981A (en) | Silica microspheres and process for producing the same | |
| CN110511313A (en) | A kind of preparation method of acrylamide monomers multiple copolymer microballoon | |
| JP4494473B2 (en) | Method and apparatus for producing polyvinyl alcohol having a high degree of polymerization | |
| Yu et al. | A facile approach preparing PMMA nanospheres through in-situ surfactant miniemulsion photopolymerization under green LED irradiation | |
| JP4192245B2 (en) | Process for producing irregular polymer particles | |
| JP2020514423A5 (en) | ||
| CN111171220A (en) | Preparation method of water-based pigment dispersion and water-based ink | |
| Zhang et al. | A Giant Capsule from the Self‐Assembly of a Penta‐Telechelic Hybrid Poly (acrylic acid) Based on Polyhedral Oligomeric Silsesquioxane | |
| CN114456326A (en) | Carboxylated polystyrene nano-microsphere and preparation method and application thereof | |
| JP2006137951A (en) | Polymer particle and method of producing the same | |
| Yang et al. | Facile synthesis of monodisperse poly (styrene-co-acrylonitrile) microspheres using redox initiator in ethanol/water: Special formation mechanism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |