CN103554325A - Preparation method of functional hollow polymer microspheres - Google Patents
Preparation method of functional hollow polymer microspheres Download PDFInfo
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Abstract
The invention discloses a preparation method of functional hollow polymer microspheres. The shell of the functional hollow polymer microspheres is prepared by carrying out precipitation polymerization on a functional monomer and a crosslinking agent in different ratios; and the formed crosslinked shell has a mesoporous structure. The preparation method comprises the following steps: preparing a monodisperse polymer microsphere template by self-stabilization precipitation polymerization; directly adding the reaction system into the shell without separation to form the required functional monomer and crosslinking agent, and preparing core-shell polymer microspheres of which the shell has a crosslinked mesoporous structure by precipitation polymerization; and finally, removing the polymer microsphere core by solvent dissolution to obtain the functional hollow polymer microspheres. The technique is simple, and safe and convenient to operate, has the advantages of mild reaction conditions, no need of special equipment, high preparation efficiency, easy microsphere separation, controllable size, and very high functional group content in the polymer microspheres, and lays a foundation for large-scale industrial production of the functional hollow polymer microspheres.
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 in shell, contain the nucleocapsid structure polymer microballoon of the functional groups such as a large amount of acid anhydrides, imide or carboxylicesters, and by the mode of dissolution with solvents, the core of prepared functional core-shell polymer microballoon is removed to formed functional hollow polymer microballoon.
Technical background
Polymeric hollow microsphere is the polymer materials of a class morphological structure uniqueness; its inside has one or more cavity; therefore there is the characteristics such as density is low, specific surface is high, optical property is unique; as a kind of new function material, have broad application prospects; the protection, embedding, transmission and the controllable release that can be used for medicine, enzyme, albumen, gene and catalyzer; as the functional coating that absorbs sound wave and microwave, as capsule of nano and microreactor for the preparation of nano-device etc.
From people (US Patent 4427836 in a series of patents such as Kowalski eighties in 20th century, US Patent 4594363, US Patent 4970241) since having reported that Permeation Swelling legal system is for polymeric hollow microsphere, the excellent properties of polymeric hollow microsphere arouses widespread concern, also day by day deep to the research of its preparation method and processing condition.At present, the method for preparing hollow microsphere mainly contains: suspension and emulsion polymerization, template, self-assembly method, Core-Shell Polymer Particles precursor process.
Suspension polymerization law system is simple, polymerization process is controlled easily convenient, but be subject to suspension polymerization system drawbacks limit, prepared particle is micron order, and be difficult to realize the effective control to particle diameter, main being applicable to the preparation of the less demanding micron order polymeric hollow microsphere of appearance and size (Okubo M, Konishi Y, Inohara T, Minami H.Production of hollow polymer particles by suspension polymerizations for ethylene glycol dimethacrylate/toluene droplets dissolving styrene – methyl methacrylate copolymers.J.Appl.Polym.Sci.2002, 86:1087 – 91), although emulsion polymerization can directly be prepared nano level list disperse, hollow polymer microballoon, but complicated process of preparation need to adopt special emulsifying agent, and the more difficult control of condition (Jang J, Ha H.Fabrication of hollow polystyrene nanospheres in microemulsion polymerization using triblock copolymers.Langmuir2002,18:5613-8).
Template ratio juris is as core based on microsphere template, surface at core forms polymkeric substance shell by modes such as surface deposition, self-assembly, surperficial initiated polymerizations, and then by modes such as extracting or etchings, mould material is removed, thereby obtain the polymer microballoon with hollow structure.Template can the uniform polymeric hollow microsphere of preparation size, and particle diameter is controlled.The patent that for example publication number is CN1631951A disclose a kind of by microemulsion method at inorganic nanometer microballoon surface keyed jointing one layer of polymeric, form the nucleocapsid complex microsphere of polymkeric substance@inorganic nano-particle, then with strong acid, inorganic nano-particle etching is removed, finally prepared size homogeneous, the good polymeric hollow microsphere of chemical stability.But the mould material that template synthesis process need is special, template removes process will use special solvent, easily pollutes prepared polymeric hollow microsphere, and template removes and easily cause shell damaged, so template application is very restricted.
Although self-assembly method can accurately be controlled pattern, the size of polymeric hollow microsphere, and it is comparatively stable to form tiny balloon, and even without stoning step, preparation process is comparatively simple.Such as people such as Wooley, adopt polyisoprene-polyacrylic acid (PI-PAA) for system, prepared and take the micella that PI is shell as core, PAA, then with the polyethylene glycol crosslinked PAA shell of amine end-blocking and degrade and remove PI core by ozone oxidation, can obtain having polymeric hollow microsphere (the Huang H Y of the crosslinked shell structure of PAA, Remsen E E, Kowalewski T, Wooley K L.Nanocages derived from shell cross-linked micelle templates.J.Am.Chem.Soc.1999,121:3805-3806.).The two ends that Jiang Ming etc. utilize rigidity are all with the polyimide oligomer of carboxyl and flexible poly-(4-vinyl is given a tongue-lashing pyridine)-mix in chloroformic solution, self aggregation forms hollow polymer microsphere (Wang M immediately, Jiang M, Ning F L, Chen D Y, Lin S Y, Duan H W.Block-copolymer-free strategy for preparing micelles and hollow spheres:self-assembly of poly (4-vinylpyridine) and modified polystyrene.Macromolecules, 2002,35:5980-5989.).But self-assembly method needs the polymkeric substance of special construction, the cost of material is higher, cannot drop in enormous quantities commercial production.
Core-Shell Polymer Particles precursor process is the classical method of preparing hollow microsphere, its preparation process is as follows: the polymer particle presoma of first preparing nucleocapsid structure, again the core of Core-Shell Polymer Particles is removed, and then obtain hollow polymer particle, the prepared Hollow Latex Particles size distribution of this method is even, size is controlled, shell thickness can regulate easily by changing polymer core size, is the focus of current Hollow Latex Particles preparation research.It is core with the template particles of electric charge that Caruso be take surface, the Core-Shell Polymer Particles of having prepared different compositions and different shell thicknesses by the mode of electrostatic self-assembled, further by modes such as dissolution with solvents, etchings, remove polymer core and can prepare polymeric hollow microsphere (Caruso F.Hollow capsule processing through colloidal templating and self-assembly.Chem.Eur.J., 2000,6:413-9).But the preparation method of Core-Shell Polymer Particles is generally comparatively complicated, preparation process is higher to operational requirement, production concentration not high yield is lower, and in core subtractive process, easily causes the destruction of caving in of shell, so this preparation method not yet reaches the degree of practical application at present.
In sum, current also shortage is applicable to commercially produce, and contains the preparation method of single disperse, hollow polymer microballoon of a large amount of functional groups in the large-scale producing method of single disperse, hollow polymer microballoon, particularly shell.
In research process in the past, the applicant, in a series of patents, discloses self stabilization precipitation polymerization and has prepared monodisperse copolymerization thing micro-sphere method.For example the patent No. is the Chinese patent disclosed " maleic anhydride and vinyl acetate copolymerized method of reacting " of ZL 200310115329.4, the patent No. is a kind of Chinese patent of ZL200810101948.0 disclosed " method of phenylethylene/maleic anhydride copolyreaction ", application number is 200910087181.5 Chinese patent disclosed " a kind of method of alpha-methyl styrene and maleic anhydride copolyreaction ", application number is 200910087177.9 Chinese patent disclosed " synthetic method of a kind of high molecular weight styrene and maleic anhydride alternate copolymer ", the patent No. is the Chinese patent of ZL 200910079490.8 disclosed " a kind of synthetic method of low molecular weight phenylethylene/maleic anhydride alternate copolymer ", the patent No. is a kind of Chinese patent of ZL201010522333.2 disclosed " method of preparing itaconic anhydride and styrene monomer alternating copolymer ", above-mentioned patent discloses by self stabilization precipitation polymerization prepares a series of sizes and the method that forms different monodisperse polymer micro-spheres.Take above-mentioned patent as basis, the applicant further proposes to add linking agent in self stabilization precipitation polymerization system, can prepare single divergent function copolymer microsphere of crosslinking structure, and in a series of patents, disclose the preparation method of crosslinking structure copolymer microsphere.The Chinese patent disclosed " a kind of preparation method of cross-linking maleic anhydride-vinyl acetate copolymer " that for example application number is 200810118553.1, application number is 200810118552.7 Chinese patent disclosed " a kind of preparation method of cross-linking maleic anhydride-styrene copolymer ", application number is 201210138133.6 Chinese patent disclosed " multipolymer that contains functional groups and preparation method prepared by a kind of C5 mixture-maleic anhydride ", the patent No. is the Chinese patent of ZL201110115705.4 disclosed " a kind of method of dicyclopentadiene and maleic anhydride copolyreaction ", the patent No. is the Chinese patent of ZL 201010130571.9 disclosed " method of a kind of maleic anhydride/conjugated diolefin copolymer reaction ".
In above-mentioned monodisperse copolymerization thing microballoon and crosslinking structure copolymer microsphere preparation process, polyalcohol microspherulite diameter increases along with the rising of reaction times prolongation and monomer conversion, and this shows that the growth of copolymer particle size is because the continuous deposition of formed polymkeric substance on copolymer microsphere surface causes.
Based on above-mentioned analysis, applicant has proposed a kind of method (Deng J P for preparing hollow polymer microsphere, Yu Y, Dun S, Yang W T.Hollow polymer particles with nanoscale pores and reactive groups on their rigid shells:preparation and application as nanoreactors.J.Phys.Chem.B, 2010, 114:2593 – 2601), preparation process is mainly divided into three steps: first by the single vinyl acetate-maleic anhydride alternate copolymer particle (PMV) that disperses of self stabilization precipitation polymerization process preparation, using prepared PMV separate particles washing purifying the preparation for Core-Shell Polymer Particles as mould material, second step is dispersed in PMV template particles in butylacetate/normal heptane mixed solvent again, in system, add MAH simultaneously, DVB and initiator, thereby initiator causes the alternative copolymerization of MAH-DVB has obtained shell-crosslinked Core-Shell Polymer Particles, finally PMV core can be obtained to polymeric hollow microsphere with solvent as acetone wash-out.
This method can overcome conventional preparation method's shortcoming to a certain extent, and prepared polymeric hollow microsphere is with acid anhydrides functional groups, but preparation process is still comparatively complicated, especially needs PMV template particles purifying, with the unreacted Vinyl Acetate Monomer of thorough wash-out.Therefore be necessary exploitation more simplification and practical functional hollow method for preparing polymer micro.
The deficiency of mentioning for foregoing, the present invention proposes a kind of method of preparing nucleocapsid and hollow polymer microspheres by Multistep feeding one kettle way, object is to provide the preparation method of a kind of simple, quick, mild condition, efficient, lower-cost functional hollow polymer microballoon.
Summary of the invention
Concrete thought of the present invention is: first prepare monodisperse copolymerization thing microballoon (such as single PMS of dispersion, PMV copolymer microsphere etc.); Reaction system is without separation and purification, (wherein functional monomer can be the excessive part of functional monomer in copolymer microsphere template preparation process directly to add shell to form required functional monomer, linking agent, solvent and initiator, or with shell, forming required linking agent adds to reaction system), further polymerization is prepared and be take copolymer microsphere as core, the Core-Shell Polymer Particles that shell is cross-linked mesoporous structure; Finally, by the mode of dissolution with solvents, remove copolymer microsphere core, can obtain polymeric hollow microsphere.
Particularly, it is template core that the self stabilization precipitation polymerization of take is prepared monodisperse copolymerization thing microballoon, and the functional hollow polymer microballoon preparation that shell is cross-linked mesoporous structure comprises following three continuous steps:
(1) preparation of monodisperse copolymerization thing microballoon
Monodisperse copolymerization thing microballoon is prepared by self stabilization precipitation polymerization process, and described self stabilization precipitation polymerization system is by monomer, initiator and solvent composition.
The monomer of self stabilization precipitation polymerization system is by giving electronics monomer and jointly formed by electronics monomer, comprise wherein to electronics monomer: styrene monomer (St, ±-vinyl toluene, ±-ethyl styrene, p-methylstyrene, to methoxy styrene, 4-ethyl styrene, 3,4-dimethyl styrene etc.), vinyl acetate one or several, comprised by electronics monomer: MAH, maleimide and derivative thereof, itaconic anhydride, ±-methylene radical-
3one or several of-butyrolactone; Giving electronics monomer and being subject to the mol ratio of electronics monomer is 1:1-1:4, preferably 1:2-1:3; The monomer concentration of reaction system is 5-40wt%.Owing to giving electronics monomer and being subject to electronics monomer can form charge transfer complex, under general polymerization condition, only can obtain preparing linear alternating multipolymer.Be subject to electronics monomer to there is special reactive behavior, be easy to and other monomer copolymerizations, but itself is difficult to autohemagglutination, when being less than 1:1 with the mol ratio that is subject to electronics monomer to electronics monomer, the unnecessary electronics monomer that is subject to can be retained in reaction system, in next step nucleocapsid structure forming process, as shell compositing monomer, participate in the formation of shell.
Self stabilization precipitation polymerization system initiator used is the known conventional oil dissolubility of professional and technical personnel radical initiator, can be azo-initiator or peroxide initiator, 0.05～2.5wt% that in system, initiator content is monomer mass, preferably 0.5～1.5wt%.Described azo-initiator comprises: azo-bis-isobutyl cyanide, azo two cyanogen in different heptan etc.; Described peroxide initiator comprises: dibenzoyl peroxide, dicumyl peroxide, peroxidation two (2,4 dichloro-benzoyl), di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of benzoyl peroxide formic acid, peroxy dicarbonate diisopropyl ester and di-cyclohexylperoxy dicarbonate etc.
The solvent of self stabilization precipitation polymerization system can be the mixing solutions of organic acid alkyl ester or ketone and alkane.The general structure of wherein said organic acid alkyl ester is
R wherein
1for H, C atomicity be 1-8 alkyl, benzyl, phenyl or substituted-phenyl, R
2for the C atomicity alkyl that is 1-5.Organic acid alkyl ester comprises ethyl formate, propyl formate, tetryl formate, pentyl formate, ethyl acetate, butylacetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, jasmal, phenylacetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, Ethylisovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, Phenylacetic acid ethylester, n-propyl phenylacetate, butyl phenylacetate, the esters solvents such as isopentyl phenylacetate, in ketone and alkane mixing solutions, the volume fraction of ketone is 5%-65%, described ketone is selected from acetone, butanone, pimelinketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, and described alkane is selected from the alkane solvents such as Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane and octane-iso.
Self stabilization precipitation polymerization is novel, the more special free radical precipitation polymerization process of a class, and macromolecule chemical industry technical professional can understand its process characteristic by Literature Consult.
The reason that adopts self stabilization precipitation polymerization technique to prepare copolymer particle is, compare with common precipitation polymerization system, self stabilization precipitation polymerization system do not need to add linking agent, without stirring, and product is pure, easily separation, can obtain size distribution is monodispersed polymer particle, polymerization rate is fast simultaneously, and productive rate is high, and the particle diameter of product can regulate easily by the adjustment of monomer concentration, solvent composition (particle size range 200-2000nm).
(2) preparation of functional nucleocapsid structure polymer microballoon
Core-Shell Polymer Particles precursor process is classical way prepared by hollow microsphere, the present invention proposes using the prepared monodisperse polymer particle of self stabilization precipitation polymerization as template core, in reaction system, directly add shell to form required monomer, initiator and solvent, one kettle way preparation has the Multifunctional Aids for Paper--Core-shell Structure Polymer Particles of crosslinked shell structure.Concrete steps are as follows:
First, the monodisperse polymer micro-sphere suspension system that above-mentioned self stabilization precipitation polymerization is prepared is cooled to 20-60 ℃, preferred 20-45 ℃, and stirring makes monodisperse polymer micro-sphere dispersed in suspension system;
Next forms required functional monomer by appropriate alkane solvents, shell under agitation condition and linking agent joins in above-mentioned reaction system, and dissolving is uniformly dispersed.Wherein, adding of alkane solvents is in order to promote the formation of crosslinked shell and to prevent that secondary nucleation phenomenon from occurring, described alkane solvents can be comprised of one or several of Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane or octane-iso, preferably normal heptane; In the alkane solvents of adding and above-mentioned self stabilization precipitation polymerization reaction system, the volume ratio of solvent for use is between 1:5～1:1.5, preferably 1:3.5～1:2.Shell form functional monomer by MAH, maleimide and derivative thereof, itaconic anhydride, ±-methylene radical-
3one or several of-butyrolactone form, and described functional monomer can be in micro polymer ball template preparation process, to be subject to the excessive part of electronics monomer, also can form required linking agent with shell and add to reaction system.Shell forms required linking agent and can be comprised of one or several of divinyl aromatic compound, difunctionality or polyfunctionality (methyl) acrylate, (methyl) vinylformic acid allyl ester, conjugated diene, described divinyl aromatic compound be between position, contraposition divinyl benzol mixture (DVB), wherein DVB can be that Vinylstyrene content is 55% DVB-55 or 80% DVB-80, described difunctionality or polyfunctionality (methyl) acrylate comprises for example two (methyl) vinylformic acid glycol ester, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, two terminal hydroxyls of the ethylene glycol such as Tetraglycol 99 two (methyl) propylene or its oligopolymer carry out the product of esterification with acrylic or methacrylic acid, two terminal hydroxyls of propylene glycol or its oligopolymer carry out the product of esterification with acrylic or methacrylic acid, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid hexylene glycol ester, the hydroxyl of 2 yuan of alcohol such as two (methyl) vinylformic acid butanediol ester carries out the product of esterification with acrylic or methacrylic acid, dihydroxyphenyl propane, the ethylene oxide of dihydroxyphenyl propane or epoxy chloropropane affixture, or two terminal hydroxyls of their halogen substituent carry out the product of esterification with acrylic or methacrylic acid, TriMethylolPropane(TMP), the acrylic or methacrylic acid esterification products of the polyvalent alcohols such as tetramethylolmethane, there is 2 and the hydroxyl of above hydroxyl or aminocompound or the adduct (epoxy ring-opening addition) of amido and glycidyl acrylate or glycidyl methacrylate, glycidyl acrylate or glycidyl methacrylate are by epoxy ring-opening addition and succsinic acid, hexanodioic acid, terephthalic acid, phthalic acid, the ethylene glycol adduct of above-mentioned binary acid or the reaction product of halogen substituent, described conjugated diene comprises Isosorbide-5-Nitrae divinyl, isoprene, C 5 fraction, dicyclopentadiene etc., wherein, preferably use DVB-55, DVB-80, Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and neopentyl glycol dimethacrylate.In order to guarantee the crosslinking degree of shell and to prevent from generating offspring in system, the vinyl mol ratio that shell forms required functional monomer and linking agent is between 1:0.8～1:1.5, preferably 1:1.0～1:1.2.
Finally, reaction system is warmed up to 60-90 ℃ gradually, keeps constant temperature polyase 13-6 hour, and can obtain shell is the core-shell polymer microballoon of cross-linked mesoporous structure, and in polymerization process, initiator is to remain initiator in monodisperse polymer micro-sphere template preparation process; In order to guarantee speed of response, can in system, add appropriate initiator, the initiator of adding is conventional oil dissolubility radical initiator, the consumption of initiator is 0.05～2.5wt% of functional monomer and linking agent total mass, preferably 0.8～1.5wt%.Described initiator can be comprised of one or several of azo or peroxide radical initiator, and azo-initiator comprises: azo-bis-isobutyl cyanide, azo two cyanogen in different heptan etc.; Described peroxide initiator comprises: dibenzoyl peroxide, dicumyl peroxide, peroxidation two (2,4 dichloro-benzoyl), di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of benzoyl peroxide formic acid, peroxy dicarbonate diisopropyl ester and di-cyclohexylperoxy dicarbonate etc.
The change that in the size of the 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 can consist of polymerization system is simply controlled.
(3) preparation of polymeric hollow microsphere
The take monodisperse copolymerization thing microballoon prepared for said process is core, shell is the Core-Shell Polymer Particles of crosslinking structure, wherein copolymer microsphere template core is served as reasons to list monomer and is subject to electronics monomer through the formed preparing linear alternating multipolymer of radical polymerization, there is not crosslinking structure, can remove by the mode of dissolution with solvents, the dissolving of preparing linear alternating multipolymer can adopt acetone, tetrahydrofuran (THF), butanone, the low boiling point solvents such as pimelinketone, and formed shell has meso-hole structure, aperture is about 2-100nm, can be at an easy rate after preparing linear alternating multipolymer dissolves from microballoon internal divergence to solution, meanwhile, the shell of Core-Shell Polymer Particles is formed by precipitation polymerization by functional monomer and linking agent, has the crosslinking structure of dimensional stabilizing and high rigidity, even also can not there is the variation of shape and size through solvent treatment, finally, by simple solvent treatment, can obtain having the polymeric hollow microsphere of crosslinked shell structure, 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 microballoon presoma, the difference that forms functional monomer according to shell, contains the functional groups such as acid anhydrides, imide or carboxylicesters in shell.
DVB-MAH functional hollow polymer microballoon of the present invention can be realized by the synthetic route shown in accompanying drawing 1.Particularly, PMS particle is that core, DVB-MAH are the core-shell polymer microballoon of crosslinked shell, and the synthetic route of corresponding polymeric hollow microsphere and reaction system formula following (take nucleocapsid mol ratio be example for 1:1).
1.PMS polymer particle template core:
Monomer: vinylbenzene 1.30g (12.5mmol), maleic anhydride 2.45g (25mmol);
Solvent: Isoamyl Acetate FCC 25mL;
Initiator: AIBN/BPO 0.040g (1.0wt% of monomer)
2.DVB-MAH shell:
Monomer: 1.225g (12.5mmol) (being MAH remaining in PMS polymer particle preparation process);
Linking agent: DVB-55 1.15g (contents of ethylene 13.0mmol)
Initiator: AIBN/BPO 0.010g (1.0wt%)
Solvent: normal heptane 12.5mL,
Operation steps 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 FCC to logical nitrogen deoxygenation in 20 minutes;
(2) above-mentioned reaction system is heated to 60-100 degree Celsius, preferably 65-80 ℃, reacts 1.5-3.0 hour, obtains PMS polymer microballoon suspension system;
(3) PMS polymer microballoon suspension system is cooled to 20-60 ℃, and stirring is uniformly dispersed PMS polymer microballoon in system;
(4) under agitation condition, 12.5mL alkane solvents (can be comprised of one or several of normal hexane, normal heptane, octane etc., preferably normal heptane), 1.15g DVB are joined in above-mentioned PMS dispersion liquid, 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 ℃ gradually, keep constant temperature polyase 13-4 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell;
(6) in above-mentioned Core-Shell Polymer Particles dispersion system, add 20mL acetone solvent, stir 30 minutes, centrifugation, obtains DVB-MAH polymeric hollow microsphere of the present invention;
(7) above-mentioned polymeric hollow microsphere is dispersed in water, 50 ℃ are reacted 1 hour, anhydride group can be converted into hydroxy-acid group, obtain carboxylic acid functional polymeric hollow microsphere, similarly, acid anhydrides and polyamines reaction polyamines such as () diethylenetriamine, triethylene tetramines can be converted into acid anhydrides amine groups, obtains functional amido polymeric hollow microsphere.
From the dispersion system of hollow polymerizing microballoons, sample, by scanning electron microscope (SEM), observe the pattern of microballoon, according to the SEM photo of gained sample, use at least 100 microspherulite diameters of software measurement, via formula calculating below, the median size (D for size of microballoon
n) represent, dispersion coefficient for size distribution (U) expression, formula is as follows:
U=D
w/D
n
D wherein
ibe the diameter of i microballoon, N is microballoon sum, D
wmathematic(al) mean particle diameter for definition.
The shell thickness of polymeric hollow microsphere is determined by transmission electron microscope (TEM), according to the TEM photo of gained sample, uses the shell thickness of at least 100 microballoons of software measurement, via formula calculating below, average shell thickness (d for the size of shell thickness
n) represent,
D wherein
ibe the diameter of i microballoon, N is microballoon sum.
The median size of the polymeric hollow microsphere that the present invention is prepared is 500-1000nm, and average shell thickness is 50-250nm, and the dispersion coefficient of size distribution is 1.004-1.1, for singly disperseing or approaching monodispersity.The change that in the size of polymeric hollow microsphere, shell thickness, shell-crosslinked degree and shell, functional groups content all can consist of polymerization system is simply controlled.
The method of the invention has the following advantages:
1. reaction conditions is gentle, and reaction process is one kettle way, and without template polymer particle is carried out to separation and purification, preparation process is fairly simple, is easy to scale operation;
2. adopt self stabilization precipitation polymerization, without any stablizer with live stablizer, preparation efficiency is higher, and resulting polymers particle is easily separated, and solvent is easy to reclaim and reuses, and solvent for use is organic acid alkyl ester, ketone and alkane, and toxicity is lower;
3. by the optimization of reaction conditions and the adjustment of reaction composition, can prepare single dispersion, controlled, the shell-crosslinked core-shell polymer microballoon of nuclear shell size, and stratum nucleare polymkeric substance can remove simply by the mode of dissolution with solvents, thereby obtain polymeric hollow microsphere;
4. prepared polymeric hollow microsphere shell is cross-linked mesoporous structure, wherein linking agent adds the formation that causes crosslinking structure, improved the intensity of hollow polymer shell, made 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 groups such as carboxyl, amido by simple chemical modification, in fields such as removing of the absorption of acid-basicity dyestuff, metal ion, is with a wide range of applications.
Compared with prior art, method of the present invention can reduce energy consumption and solvent is used, process simplification, improve the preparation efficiency of polymeric hollow microsphere, and prepared polymeric hollow microsphere has unique cross-linked mesoporous structure and excellent functional, be therefore more suitable for industrial application.
Accompanying drawing explanation:
Fig. 1 is: PMS micro polymer ball, PMS DVB-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 that Fig. 2 (a) Multistep feeding one kettle way is prepared.
The stereoscan photograph of the polymer microballoon of the prepared hollow structure of Fig. 2 (b) Multistep feeding one kettle way.Scale is 1 μ m.
20000 times of (b) 40000 times of transmission electron microscope picture (a) of the different enlargement ratios of polymeric hollow microsphere that Fig. 3 (a) Multistep feeding one kettle way is prepared.
Fig. 4 is: the saturation curve of the polymeric hollow microsphere of carboxylated modification to basic dyestuff methylene blue.
Fig. 5 is: the saturation curve of the polymeric hollow microsphere of aminated modification to matching stain Methylene blue.
Embodiment
By example, technical scheme of the present invention is described below, yet these examples do not limit the present invention.Following nucleocapsid ratio is refered in particular to the molar ratio of monomer M AH in nuclear shell.
Self stabilization precipitation polymerization is prepared monodisperse copolymerization thing microballoon
The concrete monomer ratio of embodiment 1(, solvent, formula of initiator are in Table 1)
Monomer vinyl acetate 2.15g, maleic anhydride 4.90g, AIBN0.070g initiator are joined in reaction flask, add butylacetate 25mL to dissolve, stir, mix rear logical nitrogen and remove dissolved oxygen in 30 minutes, reaction system is warming up to 75 ℃ of temperature of reaction gradually afterwards, and condensing tube condensation refluxes.React to setting-up time, stop heating, obtain after cooling the single PMV of dispersion copolymer microsphere 1#.For vinylbenzene, monomer styrene 1.30g, maleic anhydride 2.45g, AIBN0.040g initiator are joined in reaction flask, add Isoamyl Acetate FCC 25mL to dissolve, stir, mix rear logical nitrogen and within 30 minutes, remove dissolved oxygen, reaction system is warming up to 75 ℃ of temperature of reaction gradually afterwards, and condensing tube condensation refluxes.React to setting-up time, stop heating, obtain after cooling the single PMS of dispersion copolymer microsphere 5#.According to formula in table 1, prepare respectively the monodisperse polymer particle template core of different copolymer thing composition and different-grain diameter.
Table 1 self stabilization precipitation polymerization system formulation
The preparation of nucleocapsid and hollow polymer microspheres
Embodiment 2
Single suspended dispersed system of PMV microballoon 1# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMV polymer microballoon in system, under agitation condition by 12.5mL normal heptane, MAH 2.45g and DVB 2.3g join in above-mentioned PMV dispersion liquid, after being uniformly dispersed, dissolving adds BPO initiator 0.025g in above-mentioned reaction system, reaction system is warmed up to 85 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMV particle is core, DVB-MAH is the Core-Shell Polymer Particles of crosslinked shell, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain DVB-MAH polymeric hollow microsphere of the present invention, transformation efficiency is more than 99%, the nucleocapsid ratio of this polymeric hollow microsphere is the amount ratio that 1:1(refers in particular to functional monomer MAH in nuclear shell, as follows), particle diameter is 530nm, size distribution coefficient is 1.04, shell thickness is 60nm.
Embodiment 3
Single suspended dispersed system of PMV microballoon 2# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMV polymer microballoon in system, under agitation condition by 12.5mL normal hexane and and 1,4-divinyl 0.675g joins in PMV dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.0150g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMV particle is the Core-Shell Polymer Particles that core, divinyl-maleic anhydride are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain divinyl-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, size distribution coefficient is 1.05, and shell thickness is 60nm.
Single suspended dispersed system of PMV copolymer microsphere 3# of disperseing is cooled to 20 ℃, start to stir is uniformly dispersed PMV polymer microballoon in system, under agitation condition, 12.5mL normal heptane and C 5 fraction 3.66g are joined in above-mentioned PMV dispersion liquid, after being uniformly dispersed, dissolving adds AIBN initiator 0.025g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMV particle is the Core-Shell Polymer Particles that core, C 5 fraction-maleic anhydride are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.06, and shell thickness is 65nm.
Embodiment 5
Be cooled to 25 ℃ to the suspended dispersed system of methoxy styrene-copolymer-maleic anhydride microballoon 4# single dispersion, start to stir is uniformly dispersed polymer microballoon in system, under agitation condition, the octane of 10mL and isoprene 0.425g are joined in above-mentioned dispersion liquid, after being uniformly dispersed, dissolving adds AIBN initiator 0.010g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ 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 crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.03, and shell thickness is 85nm.
Embodiment 6
The suspended dispersed system of single dispersion ±-vinyl toluene-copolymer-maleic anhydride microballoon 5# is cooled to 40 ℃, start to stir is uniformly dispersed polymer microballoon in system, under agitation condition, the normal heptane of 10mL and ethylene glycol diacrylate 1.063g are joined in above-mentioned dispersion liquid, after being uniformly dispersed, dissolving adds AIBN initiator 0.010g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain ±-vinyl toluene-maleic anhydride particle is core, ethylene glycol diacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.05, and shell thickness is 75nm.
Embodiment 7
Single suspended dispersed system of PMS copolymer microsphere 6# of disperseing is cooled to 40 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 7.5mL normal heptane, MAH 1.225g and DVB 1.15g are joined in PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.010g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.15, and shell thickness is 60nm.
Embodiment 8
Single suspended dispersed system of PMS microballoon 7# of disperseing is cooled to 20 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 10.0mL normal heptane and DVB1.15g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.005g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.004, and shell thickness is 90nm.
Embodiment 9
Single suspended dispersed system of PMS microballoon 7# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 12.5mL normal heptane and Ethylene glycol dimethacrylate 1.238g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.008g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is core, Ethylene glycol dimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir centrifugation 30 minutes, dry, obtain polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, particle diameter is 790nm, and size distribution coefficient is 1.09, and shell thickness is 110nm.
Single suspended dispersed system of PMS microballoon 7# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 12.5mL normal heptane and trimethylolpropane trimethacrylate 1.408g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.010g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain take PMS particle as core, trimethylolpropane trimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir centrifugation 30 minutes, dry, obtain polymeric hollow microsphere of the present invention, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1, particle diameter is 800nm, and size distribution coefficient is 1.15, and shell thickness is 100nm.
Embodiment 11
Single suspended dispersed system of PMS copolymer microsphere 8# of disperseing is cooled to 20 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 12.5mL normal heptane and DVB 0.88g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.005g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain take PMS particle as core, DVB-MAH be the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.01, and shell thickness is 75nm.
Embodiment 12
Single suspended dispersed system of PMS copolymer microsphere 9# of disperseing is cooled to 35 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 12.5mL hexanaphthene and DVB 0.60g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.005g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.10, and shell thickness is 65nm.
Embodiment 13
Single suspended dispersed system of PMS copolymer microsphere 10# of disperseing is cooled to 45 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, 12.5mL normal heptane and neopentyl glycol dimethacrylate 1.875g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.005g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ 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 crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.12, and shell thickness is 105nm.
Embodiment 14
Single suspended dispersed system of PMS microballoon 11# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, the alkane solvents octane of 10.0mL and DVB 1.96g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.015g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.02, and shell thickness is 110nm.
Embodiment 15
Single suspended dispersed system of PMS microballoon 12# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed PMS polymer microballoon in system, under agitation condition, the alkane solvents octane-iso of 12.5mL and DVB 2.60g are joined in above-mentioned PMS dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.015g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain PMS particle is the Core-Shell Polymer Particles that core, DVB-MAH are crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.08, and shell thickness is 70nm.
Embodiment 16
Single suspended dispersed system of vinylbenzene-maleimide copolymer microballoon 13# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed polymer microballoon in system, under agitation condition, 12.5mL normal heptane and DVB-80 1.0g are joined in above-mentioned vinylbenzene-maleimide dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.015g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain vinylbenzene-maleimide particle is core, diethylene glycol dimethacrylate-maleic anhydride is the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.05, and shell thickness is 75nm.
Embodiment 17
Single suspended dispersed system of vinylbenzene-itaconic anhydride microballoon 14# of disperseing is cooled to 30 ℃, start to stir is uniformly dispersed polymer microballoon in system, under agitation condition, the alkane solvents normal heptane of 10mL and dimethyl allene acid propylene glycol ester 1.325g are joined in above-mentioned vinylbenzene-itaconic anhydride dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.005g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain vinylbenzene-itaconic anhydride particle is core, dimethyl allene acid propylene glycol ester-maleic anhydride is the Core-Shell Polymer Particles of crosslinked shell, monomer conversion is more than 99%, in above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain 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, size distribution coefficient is 1.09, and shell thickness is 80nm.
Embodiment 18
The single dispersion of general vinylbenzene-±-methylene radical-
3the suspended dispersed system of-butyrolactone microballoon 15# is cooled to 30 ℃, start to stir is uniformly dispersed polymer microballoon in system, under agitation condition, 12.5mL normal heptane and diethylene glycol dimethacrylate 1.513g are joined in above-mentioned dispersion liquid, after being uniformly dispersed, add AIBN initiator 0.015g in above-mentioned reaction system, reaction system is warmed up to 75 ℃ gradually, keep constant temperature polyase 13 hour, can obtain vinylbenzene-±-methylene radical-
3-butyrolactone particle be core, diethylene glycol dimethacrylate-±-methylene radical-
3-butyrolactone is the Core-Shell Polymer Particles of crosslinked shell, and monomer conversion is more than 99%; In above-mentioned Core-Shell Polymer Particles dispersion system, add solvent acetone 50mL, stir 30 minutes, centrifugation, dry, obtain diethylene glycol dimethacrylate of the present invention-±-methylene radical-
3-butyrolactone polymeric hollow microsphere, the nucleocapsid ratio of this polymeric hollow microsphere is 1:1.0, and particle diameter is 830nm, and size distribution coefficient is 1.12, and shell thickness is 95nm.
The modification of polymeric hollow microsphere
Embodiment 19
Get appropriate embodiment 11 prepared DVB-MAH hollow polymer microspheres powder (3.0g), add 50mL water, and ultrasonic making it be uniformly dispersed, 60 ℃ of reaction 3h; Or under room temperature condition, add NaOH (1.4g), react after 2 hours and add excessive dilute hydrochloric acid to be neutralized to pH=3, then by polymer particle suspension at 8000radmin
-1centrifugation under rotating speed.Remove after supernatant liquid, then wash with water, centrifugation, repeats 2 times, afterwards by the vacuum-drying of resulting polymers particle room temperature, can obtain the polymeric hollow microsphere of carboxylated modification.The polymeric hollow microsphere of the carboxylated modification of gained can be used for the selective adsorption of basic dyestuff, take methylene blue as example, its saturation curve 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 lower, can reach adsorption equilibrium in 5 minutes, when methylene blue concentration is higher, within 15 minutes, can reach adsorption equilibrium.What under two kinds of conditions, obtain is all the polymeric hollow microsphere of carboxylated modification, and the effect of water and (NaOH+HCl) is all the same.
Embodiment 20
Prepared nucleocapsid structure polymer microballoon powder (2.0g) takes a morsel, add 50mL tetrahydrofuran (THF) (THF), ultrasonic making it is uniformly dispersed, add excessive trivinyl tetramine (TETA 10.0g) after stirring at room 30min, room temperature reaction after 3 hours reaction system be warming up to 60 ℃ and continue reaction 3h.Reaction system is cooled to after room temperature, at 10000radmin
-1centrifugation under rotating speed.Remove after supernatant liquid, again add 25mL THF to soak, centrifugation, repeats 3 times, removes excessive TETA, and room temperature vacuum-drying can obtain the crosslinked polymeric hollow microsphere of amino modified.The polymeric hollow microsphere of this aminated modification can be used for the removing and the field such as carbonic acid gas absorption of selective adsorption, metallics of matching stain.Take matching stain Methylene blue as example, and 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 Methylene blue concentration is lower, can reach adsorption equilibrium in 5 minutes, when methylene blue concentration is lower, within 10 minutes, can reach adsorption equilibrium.
Claims (10)
1. a preparation method for functional hollow polymer microballoon, is characterized in that comprising three continuous steps: first by self stabilization precipitation polymerization, prepare monodisperse polymer micro-sphere template; Reaction system, without separation, directly adds shell to form desired function monomer, linking agent, solvent and initiator, further by precipitation polymerization, prepares the core-shell polymer microballoon that shell is cross-linked mesoporous structure; Finally, micro polymer ball is removed by the mode of dissolution with solvents, can be obtained functional hollow polymer microballoon.
2. method according to claim 1; it is characterized in that; described monodisperse polymer micro-sphere is prepared by self stabilization precipitation polymerization process; self stabilization precipitation polymerization system is comprised of monomer, solvent and initiator; under protection of inert gas, monomer is dissolved and is dispersed in solvent; adopt oil soluble radical initiator initiated polymerization; temperature of reaction 50-100 ℃; react and can obtain monodisperse polymer micro-sphere template particles in 1-6 hour, prepared polymer microballoon stable dispersion is in reaction system.
3. method according to claim 2, it is characterized in that, by self stabilization precipitation polymerization, prepare copolymer microsphere template, in reaction system, monomer being by giving electronics monomer and jointly formed by electronics monomer, consists of wherein to electronics monomer one or several of styrene monomer, vinyl acetate; Be subject to electronics monomer by MAH, maleimide and derivative thereof, itaconic anhydride, ±-methylene radical-
3one or several of-butyrolactone form jointly, by self stabilization precipitation polymerization, obtain the different copolymer microsphere templates that form.The monomer mass percentage concentration of reaction system is 5-60%; Give electronics monomer and be subject to the mol ratio of electronics monomer between 1:1～1:5.
4. method according to claim 2, is characterized in that, by self stabilization precipitation polymerization, prepares copolymer microsphere template, and in reaction system, solvent is the mixing solutions of organic acid alkyl ester or ketone and alkane.The general structure of wherein said organic acid alkyl ester is
R wherein
1for H, C atomicity be 1-8 alkyl, benzyl, phenyl or substituted-phenyl, R
2for the C atomicity alkyl that is 1-5.In ketone and alkane mixing solutions, the volume fraction of ketone is 5%-65%, described ketone is selected from acetone, butanone, pimelinketone, methyl iso-butyl ketone (MIBK) or methyl isopropyl Ketone, and described alkane is selected from Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane or octane-iso.
5. method according to claim 2, it is characterized in that, by self stabilization precipitation polymerization, prepare copolymer microsphere template, in reaction system, initiator is comprised of one or several of azo or peroxide radical initiator, 0.05～2.5wt% that in system, initiator content is monomer mass.
6. method according to claim 1, is characterized in that, the core-shell polymer microballoon that described shell is cross-linked mesoporous structure is prepared by precipitation polymerization.The monodisperse polymer micro-sphere of preparing of take is template core, under the existence of initiator and linking agent, there is precipitation polymerization reaction in functional monomer, and be aggregated thing microsphere template absorption, be deposited on gradually polymer microballoon template core surface and form the shell with cross-linked mesoporous structure, the concrete preparation process of nucleocapsid structure functional polymer microballoon is as follows:
First, above-mentioned self stabilization precipitation polymerization system is cooled to 20-60 ℃, and stirring is dispersed in reaction system prepared monodisperse polymer micro-sphere;
Secondly, under agitation condition, alkane solvents, functional monomer and linking agent are added in above-mentioned polymer microballoon dispersion liquid, dissolving dispersing and mixing is even;
Finally, reaction system is warmed up to 60-90 ℃ gradually, keeps constant temperature polyase 13-6 hour, and can obtain shell is the core-shell polymer microballoon of cross-linked mesoporous structure.
7. according to the method described in claim 1 or 6, it is characterized in that, in shell forming process, need to add alkane solvents in reaction system; In the alkane solvents of adding and above-mentioned self stabilization precipitation polymerization reaction system, the volume ratio of solvent for use is between 1:5～1:1.5; The described alkane solvents of adding can be comprised of one or several of Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane and octane-iso.
8. according to the method described in claim 1 or 6, it is characterized in that, described shell form required functional monomer by MAH, maleimide and derivative thereof, itaconic anhydride, ±-methylene radical-
3one or several of-butyrolactone form, and described functional monomer is in micro polymer ball template preparation process, to be subject to the excessive part of electronics monomer, or with shell, form required linking agent and add to reaction system.
9. according to the method described in claim 1 or 6, it is characterized in that, described shell forms required linking agent and is comprised of one or several of divinyl aromatic compound, difunctionality or polyfunctionality (methyl) acrylate, (methyl) vinylformic acid allyl ester, conjugated diene; Described functional its shell of core-shell polymer microballoon consists of functional monomer and the linking agent of different ratios, and the vinyl mol ratio of functional monomer and linking agent is between 1:0.8～1:1.5; The amount of described functional Core-Shell Polymer Particles preparation process center shell matter is than between 1:0.5-1:3, and nucleocapsid amount of substance is than the amount ratio that refers in particular to functional monomer in nuclear shell.
10. according to the method described in claim 1-9 any one, it is characterized in that, after prepared functional hollow micro polymer ball warp modification, the polymeric hollow microsphere of formed carboxyl or functional amido is applied to respectively the absorption of acid-basicity dyestuff or the field that removes of metal ion.
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