CN104525067B - A kind of functional composite microsphere with Punica granatum L. shape structure and preparation method thereof - Google Patents
A kind of functional composite microsphere with Punica granatum L. shape structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to functional composite microsphere of a kind of Punica granatum L. shape structure and preparation method thereof.The present invention is with polymer monomer as raw material, under emulsifying agent, initiator and buffer solution existence condition, after being coated to multiple organic/inorganic core-shell nanos form Punica granatum L. type composite construction microsphere inside organic polymer, wrap up inorganic shell again on its surface, after functionalization, obtain the functional composite microsphere with the Punica granatum L. shape structure of superelevation water retention property.Except functionalization, it is also possible to remove the Punica granatum L. shape hollow composite structure microsphere that organic polymer compositions obtains having high-water performance.This preparation method is flexible, and equipment is simple, and applicable system is extensive, it is simple to introduce functional group, and functionalization degree is controlled.Especially in the application of the PEM water conservation and proton conductivity that improve fuel cell advantageously, medicine carrying, cosmetics, catalyst carrier, biomarker carrier and cement-based material damage location microcapsule intellectuality perception and in real time in terms of self-healing system multistage slow-release, also have potential using value.
Description
Technical field
The invention belongs to polymer composite and function micro-nano material field, particularly to a kind of Punica granatum L. shape structure
Functional composite microsphere and preparation method thereof.
Background technology
The nucleocapsid structure complex microsphere set two or more material advantage of nucleocapsid structure, and the function of material can be realized
Change.Nucleocapsid structure composite nanoparticle has the feature that surface area is big, size is controlled, is increasingly becoming in medicine, biochemistry, painting
The field widely used specific function materials such as material and electronic information material.Additionally, in conventional document report, nucleocapsid is tied
Structure nanoparticle is commonly used for preparing the precursor of polymeric hollow microsphere.Hollow-core construction microsphere has low bulk density, high-ratio surface
Amass and there is the cavity structure characteristic that can accommodate a large amount of guest molecule or large scale object, can be used for low-density composite system
The field such as the migrating and discharge of standby, sustained-release drug carrier, biomacromolecule, catalyst carrier, microreactor is current chemistry with
One of study hotspot of material science.
Wang Sheng etc. the Chinese invention patent of CN1O2604122A (published application number be) be prepared for a kind of referred to as " Punica granatum L. "
The composite nanoparticle of shape, the method with polyvinyl alcohol (PVA) as core, Nano particles of silicon dioxide (SiO2) at polyvinyl alcohol ball
Surface self-organization forms the regular nucleocapsid double-decker of arrangement, due to be little distribution of particles at bulky grain outer surface, this structure is real
More like " Fructus Rubi " shape on border, and non-real " Punica granatum L. " shape, the composite nanoparticle preparing similar structures such as favorable to the people in force
(Macromolecules 2005,38,6411-6417), name is called Fructus Rubi shape or Fructus Rubi shape structure.Qi Dongming etc.
Many solid inorganic nano-particles are wrapped in polymer breast by the Chinese invention patent of CN1O3467678A (published application number be)
Make the Punica granatum L. shape complex microsphere of submicron order in micelle, then inorganic template etching is removed, obtain the polymerization of many cavity structures
Thing emulsion particle, this structure is actually the polymer including multiple through hole cavitys, wherein polymer drops a size of about 200nm,
Including through hole cavity mean inside diameter is 50nm, Punica granatum L. structure the most truly, and the cavity volume that can use is less, and
Simple polymer microballoon mechanical performance is poor, easily caves in.
The functional composite microsphere of the Punica granatum L. structure prepared by the present invention, is by the nanometer of polymer microballoon coated core-shell structure
Particle obtains, and this microsphere outer layer is also coated with one layer of inorganic shell.The particle diameter of microsphere and the size tunable including nucleocapsid structure particle,
The part of polymer can have two kinds of processing modes: one is further functionalization, and grafting hydrophilic group strengthens its hydrophilic, water-retaining property
Energy；Two is to wash away the cavity structure obtaining large specific surface area with volume, utilizes the hydrophilic of cage structure and inorganic particulate to obtain
To high-water performance, inorganic shell plays two main effects: one is as backing material, makes Punica granatum L. structure microspheres more steady
Fixed, there are certain intensity and rigidity；Two is that the frame structure of multilamellar can hinder interior aqueous release, plays the effect of slow release,
Thus improve the water retention property of this structure.Concrete structural representation is shown in description of drawings 8 and Fig. 9.At present, also there is not the present invention
Report prepared by the functional composite microsphere of this Punica granatum L. structure.
Summary of the invention
It is an object of the invention to provide functional composite microsphere of a kind of Punica granatum L. shape structure and preparation method thereof.
The present invention has the functional composite microsphere of Punica granatum L. shape structure, and described functional composite microsphere is the knot that Punica granatum L. shape has multilamellar
Structure, has four-layer structure: first prepare polymer nano-particle with emulsifier-free emulsion polymerization or emulsion polymerization and make on the whole
For kernel；It is then passed through coated inorganic shell after silane coupler is modified, obtains organic/inorganic core-shell nano；Then
Using this core-shell structure nanometer particle as template, after being carried out surface modification so that it is be stable in reaction system, and surface band
There is polymerizable groups, recycle the organic/inorganic nucleocapsid structure particle after surface modification and polymer monomer generation polyreaction,
Thus multiple organic/inorganic core-shell nano Surface coating are entered polymer layers of balls, obtain comprising multiple nuclear shell structure nano
The polymer microballoon of particle；After finally being modified with silane coupler by this microsphere, utilize the hydrolysis-condensation reaction between silicone hydroxyl, shape
One-tenth is coated with the functional composite microsphere of inorganic shell, controlled Punica granatum L. shape structure, and this Punica granatum L. shape complex microsphere has multilamellar knot
Structure, and can carry out function modified by sulfonation；The diameter of this novel Punica granatum L. shape hollow core-shell microsphere at 400-1000nm, and this
The microsphere dynamic light scattering breadth coefficient PDI value of kind of composite construction < 0.7, it is distributed in appropriateness dispersibility；Described polymer is by being polymerized
Thing monomer polymerization reactions prepares, and described inorganic matter is that tetraalkyl orthosilicate hydrolysis-condensation reaction prepares, and its raw material composition includes:
Polymer monomer 1 ~ 30 part, in terms of mass number,
Initiator 0.1 ~ 9 part, in terms of mass number,
Stabilizer 0.5 ~ 15 part, in terms of mass number,
Silane coupler 0.025 ~ 2 part, in terms of mass number,
Tetraalkyl orthosilicate 0.5 ~ 40 part, in terms of mass number.
In the present invention, described polymer monomer is arbitrary in double bond containing acrylic compounds, styrene or styrene derivative
Kind.
In the present invention, using the initiator used in emulsifier-free emulsion polymerization or emulsion polymerization is 2,2'-azo two isobutyl
In amidine hydrochlorate, azodiisobutyronitrile or persulfate any one.
In the present invention, described tetraalkyl orthosilicate is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester or positive silicic acid fourth
In ester any one.
In the present invention, described silane coupler is any one in alkenes silane coupler or amino silicane coupling agent, institute
Stating stabilizer is polyvinylpyrrolidone.
The preparation method of the Punica granatum L. shape structure function complex microsphere that the present invention proposes, specifically comprises the following steps that
(1) in preparing ground floor, nuclear particle P1:1-10wt% polymer monomer adds the ethanol of 5.5wt% with 0.5-5wt%'s
In the mixture of stabilizer, ultrasonic 5-15min to uniformly, is added into the water-soluble of 94.5wt% dissolved with 0.3-3wt% initiator
In liquid, temperature controls at 60-80 DEG C, mechanical agitation under the conditions of 400r-600rpm, when conversion ratio reaches 70%-80%, to solution
The silane coupler of middle addition 0.1-10%, after response time 12-24h, with ethanol centrifuge washing 3-5 time, obtaining mean diameter is
The high molecular nanometer particles P1 of 50-200nm；
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer grain 1-10wt% step (1) prepared is prepared
Sub-P1 is dispersed in 100wt% alcoholic solution, drips 0.3-0.5mol/L ammonia, regulates pH to 8 ~ 11, at 40-60 DEG C and 250rpm
Stir speed (S.S.) under be slowly added dropwise tetraalkyl orthosilicate, drop rate 0.5-2mL/h, react 8-16h, obtaining mean diameter is
The hud typed organic-inorganic nano particle P2 of 100-240nm, by being put in the 4mol/L sulphuric acid of its 4 ~ 10 times of mass parts,
Grafting sulfonic groups group obtains the organic-inorganic nano particle P ' 2 of functionalization；
(3) Punica granatum L. type complex microsphere is prepared: the organic-inorganic nano particle P ' 2 of 0.5-3wt% step (2) is modified it
After the silane coupler of quality 0.5-20%, it is dispersed in the mixed solution of 94.5g alcohol and 5.5g water, adds the PVP of 1-3g, super
Sound dispersion 5-15min to homogeneous reaction system, nitrogen purging 1-3h, by the polymer monomer of the 5-10 times amount of P2 mass with
0.25-9wt%AIBA mixing ultrasonic disperse 5-15min is to uniformly, and with after nitrogen purging 1-3h, pours rapidly above-mentioned reactant into
System, 50-70 DEG C of reaction 10-16h, when conversion ratio reaches 70-80%, adds the silane coupler of 0. 5-20wt% under nitrogen protection,
Reaction terminates rear centrifuge washing 3-5 time, obtains the organo-mineral complexing microsphere P3 with unique Punica granatum L. shape structure；
(4) outer shell of functionalization Punica granatum L. shape structure composite microsphere is prepared: take the organo-mineral complexing that step (3) obtains micro-
Ball P3 1.00 ~ 3.00g is dispersed in 100g alcoholic solution, the ammonia of dropping 0.3-0.5mol/L, regulates pH to 8 ~ 11, with 0.5-
Speed dropping 1.50 ~ 12.00g tetraalkyl orthosilicate of 2mL/h, reaction temperature 40-60 DEG C, with the stir speed (S.S.) of 150-250rpm
After reaction 8-12h, centrifuge washing obtains the organo-mineral complexing microsphere P4 of novel Punica granatum L. shape structure；
(5) by during in step (4), 1.00 ~ 5.00g complex microsphere P4 puts into the 4mol/L sulphuric acid of its 4 ~ 10 times of mass parts,
30-60 DEG C of oil bath stirring 0-12h, by sulfonation Punica granatum L. shape organo-mineral complexing microsphere in various degree, through ethanol centrifuge washing 3-5
Secondary, obtain Punica granatum L. shape functional composite microsphere P ' 4.
In the present invention, in the polymer nanocomposite prepared by step (1), reaction rotating speed during nuclear particle is at 250-500rpm, grain
Footpath controls at 50-200nm, its even particle size distribution, and breadth coefficient PDI value < 0.05, for monodisperse system.
In the present invention, the nanoparticle mean diameter of the nucleocapsid structure prepared in step (2) is 60-240nm, DLS
Sign even particle size distribution, and breadth coefficient PDI value < 0.08, it is distributed in nearly monodispersity.
In the present invention, put into described Punica granatum L. shape functional composite microsphere P4 the organic solvent of its 2-10 times of quality dissolves and gather
Polymer component or the method by sintering, i.e. can get Punica granatum L. shape hollow structure microsphere P5.
In the present invention, organic solvent used by Punica granatum L. shape hollow composite structure microsphere and method be following any one:
Method one: 1, stirs in the mixed solution of 2-dichloroethanes and concentrated sulphuric acid 1:1 ratio, is incubated 30-40 DEG C, reaction
4h, the product centrifuge washing obtained 3-5 time.
Method two: be dissolved under normal temperature condition in N ' dinethylformamide (DMF) solution of 2-10 times of microspheres quality, 8h
Rear centrifuge washing changes DMF solution, is repeated 2 times.
Method three: after Punica granatum L. shape composite construction microsphere lyophilization, with Muffle furnace burning-off polymer moieties, obtain hollow
Punica granatum L. shape composite construction microsphere, with the ramp of 2-5 DEG C/min to 450 DEG C, be incubated 2h.
In the present invention, when megalosphere layer ruptures in Punica granatum L. structure multilayer hollow microsphere, it is coated on multiple little empty ball therein
Form is complete.
In above-mentioned Punica granatum L. structure function complex microsphere, it is preferred that a diameter of 80-of nuclear particle in described macromolecule
100nm.In above-mentioned Punica granatum L. structure function complex microsphere, it is preferred that microsphere diameter is at 500-800nm.
The beneficial effects of the present invention is: by the organic/inorganic core-shell structure nanometer particle of functionalization is embedded into poly-
After compound micelle, then coated inorganic shell obtains the Punica granatum L. structure composite microsphere of grafting functional group.This microsphere combine organic,
The advantage of inorganic material, core-shell nano good dispersion；Utilize inorganic shell to keep stablizing of structure, and intensity be higher,
The polymer of middle stratum nucleare also can functionalization, obtain the complex microsphere with functionalization layer.Simultaneously can also be by polymer moieties
Remove, obtain Punica granatum L. structure hollow structure microspheres.The feature of the microsphere uniqueness of both structures is to have the water-retaining property that superelevation is strong
Can, due to the multiple structure that it is special, can hinder or slow down again the release of the contents such as water.Its mechanism See Figure (exemplary plot 8 He
Fig. 9).This microsphere also has that specific surface area is big, size is controlled stable, and has the cavity structure of larger capacity, can be as low
The material of main part of density, prepares composite, classification slow release thing carrier, catalyst carrier, medicine carrying, coating, self-healing system etc.,
Particularly in the PEM of fuel cell, improve the water retention property of PEM.Utilize them special many
Level structure, the multistage slow-release of self repairing agent in realizing coating and novel concrete, in the intelligence of concrete cracking damage location
Before allelopathic is known and in the most real-time self-healing system, dispersed and classification release reparation material application also has optimism
Scape.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the Punica granatum L. structure hollow complex microsphere of embodiment 1,2 preparation.Wherein: (a) is to implement
The transmission electron microscope photo of the Punica granatum L. structure hollow complex microsphere of example 1 preparation, (b) is that the Punica granatum L. structure hollow of embodiment 2 preparation is multiple
Close the transmission electron microscope photo of microsphere.
Fig. 2 is two grades of slow release effect figures of transmission electron microscope of the hollow complex microsphere of the Punica granatum L. structure of embodiment 1 preparation.
Fig. 3 is core-shell structure nanometer particle and the particle diameter of Punica granatum L. type composite construction microsphere after functionalization prepared by embodiment 3
Distribution.
Fig. 4 be example 3,4 preparation functionalization after the transmission electron microscope photo of Semen Granati core-shell structure nanometer particle.Wherein:
A () is the TEM figure of core-shell structure nanometer particle sulfonation 4h in embodiment 3, (b) is core-shell structure nanometer particle sulphur in embodiment 4
Change the TEM figure of 8h.
Fig. 5 is embodiment 2,3,4 functionalization Punica granatum L. structure composite microsphere infared spectrum, and there is more apparent change at water suction peak.
Fig. 6 is core-shell structure nanometer particle and the particle diameter of Punica granatum L. type composite construction microsphere after functionalization prepared by embodiment 5
Distribution.
Fig. 7 is the stereoscan photograph of the Punica granatum L. type hollow composite structure microsphere section of embodiment 6 preparation.
Fig. 8 is the functional composite microsphere structural representation of Punica granatum L. structure prepared by the present invention, the function and service of Punica granatum L. structure
Microsphere, sulfonic acid group and the inorganic shell of functionalization layer all have hydrophilic, embody high-water performance.
Fig. 9 is the structural representation of Punica granatum L. structure hollow complex microsphere prepared by the present invention, Punica granatum L. structure hollow microsphere, in
Empty inorganic microsphere is cage shape, can comprise free water, and silica shell the most adsorbable the most hydrophilic Free water also embodies height
Water retention property.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
The characterizing method explanation related in embodiment 1-6:
Organic-inorganic nucleocapsid structure breast is measured by dynamic light scattering DLS (Malvern company of Britain produces Nano-ZS90 type)
The microspherulite diameter distribution of liquid and Punica granatum L. shape composite construction, and obtain its mean diameter and particle diameter profile exponent PDI value.Pass through transmission
Electronic Speculum (Hitachi company of Japan produces H-600 type) observes the morphosis of Punica granatum L. type organo-mineral complexing structure microspheres.By field
Hollow Punica granatum L. prepared by transmitting scanning electron microscope (Quanta200 FEG) observation Punica granatum L. shape composite construction microsphere and sintering process
The pattern of shape composite construction microsphere, characterizes functionalization by Fourier transformation infrared spectrometer Nicolet Magna-550 micro-
The characteristic group of ball and water suction peak.
Embodiment 1
(1) ground floor kernel P1 is prepared: added by 3g styrene monomer in the ethanol of 5.5g and the stabilizer of 1.5g PVP,
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.39g AIBA by ultrasonic 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 500rpm, when conversion ratio reaches 80%, adds the silane coupler γ-metering system of 0.3g in solution
Acryloxypropylethoxysilane trimethoxy silane (γ-MPS), uses ethanol centrifuge washing 3 times after total reaction time 24h, obtains mean diameter
High molecular nanometer particles core P1 for 80nm.
(2) organic-inorganic core-shell structure nanometer particle P2 is prepared: take the high molecular nanometer particles core P1 that 1g step (1) prepares
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise tetraethyl orthosilicate (TEOS) 1.5g, drop rate 1mL/h, reacts 12h, obtain the nucleocapsid that mean diameter is 90nm
Type organic/inorganic nano particle P2.
(3) Punica granatum L. shape complex microsphere is prepared: 3wt% γ-MPS is added the ethanol solution of organic/inorganic nano-particle P2
In, centrifuge washing 3 times after 72h, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with addition
10g styrene monomer, to homogeneous reaction system, nitrogen purging 2h, is mixed by 3g PVP, ultrasonic disperse 10min with 1g initiator A IBA
Close ultrasonic disperse 10min to uniformly, and pour rapidly above-mentioned reaction system, under nitrogen protection, 70 DEG C into after nitrogen purging 2h
Under the conditions of, response time 12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3 times,
Obtain comprising the polymer microballoon P3 of multiple nucleocapsid organo-mineral complexing nanoparticle.
(4) the Punica granatum L. shape composite construction inorganic shell of microsphere outermost layer is prepared: take the polymer microballoon that 1.5g step (3) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 2.25 with the speed of 1mL/h
TEOS, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel Punica granatum L. shape organic/
Inorganic compounding structure microspheres P4.
(5) the organic/inorganic composite construction microsphere P4 sample 1g that will obtain in step (4), is dispersed in its 4 times of quality
In DMF, 40 DEG C are at the uniform velocity stirred, and every 8h centrifuge washing and change fresh DMF solvent, are repeated 3 times, obtain in novel Punica granatum L. shape
Hollow structure complex microsphere P5.
Embodiment 2
(1) ground floor kernel P1 is prepared: added by 3g styrene monomer in the ethanol of 5.5g and the stabilizer of 1.5g PVP,
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.39g AIBA by ultrasonic 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 450rpm, when conversion ratio reaches 80%, adds the γ-MPS of 0.3g, after total reaction time 24h in solution
With ethanol centrifuge washing 3 times, obtain the high molecular nanometer particles core P1 that mean diameter is 100nm.
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer particles core P1 1g step (1) prepared is prepared
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise TEOS 3g, drop rate 1mL/h, reacts 12h, obtain the hud typed organic/inorganic that mean diameter is 130nm and receive
Rice corpuscles P2.
(3) Punica granatum L. shape complex microsphere P3 is prepared: added by 3wt% γ-MPS in the ethanol solution of P2, centrifuge washing 3 after 72h
Secondary, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with adding 3g PVP, ultrasonic disperse
10min is to homogeneous reaction system, and nitrogen purging 2h, by 10g styrene monomer and 1g initiator A IBA mixing ultrasonic disperse 10min
To uniformly, and pour rapidly above-mentioned reaction system into after nitrogen purging 2h, under nitrogen protection, under the conditions of 70 DEG C, the response time
12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3 times, obtains comprising multiple nucleocapsid
The polymer microballoon P3 of organo-mineral complexing nanoparticle, mean diameter is 514nm.
(4) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (3) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 4.5g's with the speed of 1mL/h
TEOS, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel Punica granatum L. shape organic
Inorganic compounding structure microspheres S0。
(5) taking the P4 sample 1g obtained in step (4), be dispersed in the DMF of its 4 times of quality, 40 DEG C are at the uniform velocity stirred, every
8h centrifuge washing also changes fresh DMF solvent, is repeated 3 times, and obtains the hollow structure complex microsphere P5 of novel Punica granatum L. shape.
Embodiment 3
(1) ground floor kernel P1 is prepared: added by 3g styrene monomer in the ethanol of 5.5g and the stabilizer of 1.5g PVP,
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.39g AIBA by ultrasonic 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 500rpm, when conversion ratio reaches 80%, adds the γ-MPS of 0.3g, after total reaction time 24h in solution
With ethanol centrifuge washing 3 times, obtain the high molecular nanometer particles core P1 that mean diameter is 100nm.
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer particles core P1 1g step (1) prepared is prepared
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise TEOS 1.5g, drop rate 1mL/h, reacts 12h, obtain the hud typed organic/inorganic that mean diameter is 130nm
Nanoparticle P2.
(3) prepare functionalized organic inorganic core-shell structure nanometer particle P ' 2: organic/inorganic nano particle P2 is put into its 4
In the 4mol/L concentrated sulphuric acid of times quality, 40 DEG C of constant temperature stirring at low speed 4h, obtain sulfonation nucleocapsid structure for 3 times with ethanol centrifuge washing and receive
Rice corpuscles P ' 2.
(4) Punica granatum L. shape complex microsphere P3 is prepared: added by 3wt% γ-MPS in the ethanol solution of P2, centrifuge washing after 72h
3 times, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with adding 3g PVP, ultrasonic disperse
10min is to homogeneous reaction system, and nitrogen purging 2h, by 10g styrene monomer and 1g initiator A IBA mixing ultrasonic disperse 10min
To uniformly, and pour rapidly above-mentioned reaction system into after nitrogen purging 2h, under nitrogen protection, under the conditions of 70 DEG C, the response time
12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3 times, obtains comprising multiple nucleocapsid
The polymer microballoon P3 of organo-mineral complexing nanoparticle.
(5) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (4) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 1.5 times with the speed of 1mL/h
The TEOS of microspheres quality, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel
Punica granatum L. shape organo-mineral complexing structure microspheres P4.
(6) the dense sulfur that the machine inorganic compounding structure microspheres P4 obtained in step (5) puts into the 4mol/L of its 4 times of mass numbers is taken
Acid stirs 4h 40 DEG C of oil baths, washs 3 times through ethanol centrifugation, obtains the sulfonation complex microsphere S of Punica granatum L. structure4, its polyphenyl
Ethylene moiety is all with the sulfonation layer of grafting sulfonic groups group.
Embodiment 4
(1) ground floor kernel P1 is prepared: added by 3g styrene monomer in the ethanol of 5.5g and the stabilizer of 1.5g PVP,
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.39g AIBA by ultrasonic 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 500rpm, when conversion ratio reaches 80%, adds the γ-MPS of 0.3g, after total reaction time 24h in solution
With ethanol centrifuge washing 3 times, obtain the high molecular nanometer particles core P1 that mean diameter is 80nm.
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer particles core P1 1g step (1) prepared is prepared
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise TEOS 1.5g, drop rate 1mL/h, reacts 12h, obtain the hud typed organic/inorganic that mean diameter is 100nm
Nanoparticle P2.
(3) prepare functionalized organic inorganic core-shell structure nanometer particle P ' 2: organic/inorganic nano particle P2 is put into its 4
In the 4mol/L concentrated sulphuric acid of times quality, 40 DEG C of constant temperature stirring at low speed 8h, obtain sulfonation nucleocapsid structure for 3 times with ethanol centrifuge washing and receive
Rice corpuscles P ' 2.
(4) Punica granatum L. shape complex microsphere P3 is prepared: by molten for the ethanol of the 3wt% γ-MPS organic/inorganic nano-particle P2 of addition
In liquid, centrifuge washing 3 times after 72h, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with adding
Enter 3g PVP, ultrasonic disperse 10min and purge 2h to homogeneous reaction system, nitrogen, by 10g styrene monomer and 1g initiator A IBA
Ultrasonic disperse 10min is to uniformly in mixing, and pours rapidly above-mentioned reaction system, under nitrogen protection, 70 into after nitrogen purging 2h
Under the conditions of DEG C, response time 12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3
Secondary, obtain comprising the polymer microballoon P3 of multiple nucleocapsid organo-mineral complexing nanoparticle.
(5) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (4) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 1.5 times with the speed of 1mL/h
The TEOS of microspheres quality, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel
Punica granatum L. shape organo-mineral complexing structure microspheres P4.
(6) take the complex microsphere P4 obtained in step (5) and put into the concentrated sulphuric acid of 4mol/L of its 4 times of mass numbers at 40 DEG C of oil
Bath stirring 8h, washs 3 times through ethanol centrifugation, obtains the sulfonation complex microsphere S of Punica granatum L. structure8, its polystyrene moieties is equal
Sulfonation layer with grafting sulfonic groups group.
Embodiment 5
(1) ground floor kernel P1 is prepared: added by 5g styrene monomer in the ethanol of 5.5g and the stabilizer of 2g PVP, super
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.78g AIBA by sound 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 400rpm, when conversion ratio reaches 80%, adds the γ-MPS of 0.5g, after total reaction time 24h in solution
With ethanol centrifuge washing 3 times, obtain the high molecular nanometer particles core P1 that mean diameter is 180nm.
(2) organic-inorganic core-shell structure nanometer particle P2 is prepared: the P1 that 1g step (1) prepares is dispersed in 100g alcoholic solution
In, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, be slowly added dropwise TEOS 3g under the conditions of stir speed (S.S.) 250rpm,
Drop rate 1mL/h, reacts 12h, obtains the hud typed organic/inorganic nano particle P2 that mean diameter is 193nm.
(3) Punica granatum L. shape complex microsphere P3 is prepared: added by 3wt% γ-MPS in the ethanol solution of P2, centrifuge washing after 72h
3 times, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with adding 3g PVP, ultrasonic disperse
10min is to homogeneous reaction system, and nitrogen purging 2h, by 10g styrene monomer and 1g initiator A IBA mixing ultrasonic disperse 10min
To uniformly, and pour rapidly above-mentioned reaction system into after nitrogen purging 2h, under nitrogen protection, under the conditions of 70 DEG C, the response time
12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3 times, obtains comprising multiple nucleocapsid
The polymer microballoon P3 of organo-mineral complexing nanoparticle, mean diameter is 957nm.
(4) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (3) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 4.5g's with the speed of 1mL/h
TEOS, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel Punica granatum L. shape organic
Inorganic compounding structure microspheres P4.
Embodiment 6
(1) ground floor kernel P1 is prepared: added by 3g styrene monomer in the ethanol of 5.5g and the stabilizer of 1.5g PVP,
This mixed solution, to uniformly, is added in the aqueous solution dissolved with the 94.5g of 0.39g AIBA by ultrasonic 10min, and temperature controls 70 DEG C,
Mechanical agitation under the conditions of 500rpm, when conversion ratio reaches 80%, adds the silane coupler γ-metering system of 0.3g in solution
Acryloxypropylethoxysilane trimethoxy silane (γ-MPS), uses ethanol centrifuge washing 3 times after total reaction time 24h, obtains mean diameter
High molecular nanometer particles core P1 for 80nm.
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer particles core P1 1g step (1) prepared is prepared
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise tetraethyl orthosilicate (TEOS) 1.5g, drop rate 1mL/h, reacts 12h, obtain the nucleocapsid that mean diameter is 90nm
Type organic/inorganic nano particle P2.
(3) Punica granatum L. shape complex microsphere is prepared: 3wt% γ-MPS is added the ethanol solution of organic/inorganic nano-particle P2
In, centrifuge washing 3 times after 72h, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with addition
10g styrene monomer, to homogeneous reaction system, nitrogen purging 2h, is mixed by 3g PVP, ultrasonic disperse 10min with 1g initiator A IBA
Close ultrasonic disperse 10min to uniformly, and pour rapidly above-mentioned reaction system, under nitrogen protection, 70 DEG C into after nitrogen purging 2h
Under the conditions of, response time 12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3 times,
Obtain comprising the polymer microballoon P3 of multiple nucleocapsid organo-mineral complexing nanoparticle.
(4) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (3) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 2.25 with the speed of 1mL/h
TEOS, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel Punica granatum L. shape organic
Inorganic compounding structure microspheres P4.
(5) take the organo-mineral complexing structure microspheres P4 sample 1g obtained in step (4), utilize solution substitution method by ethanol
Solvent replaces to deionized water, then carries out lyophilization and obtain sample, and the method using sintering prepares the hollow of novel Punica granatum L. shape
Structure composite microsphere P5, sintering warming machine is made as: 5 DEG C/min, to 450 DEG C, is incubated 2h, and Temperature fall obtains product P5.
Embodiment 7
(1) emulsion method prepares ground floor kernel P1: add 10g styrene monomer containing 0.2g sodium lauryl sulphate (breast
Agent), in the 100g aqueous solution of 0.2g buffer solution (being prepared by sodium dihydrogen phosphate and disodium hydrogen phosphate, be adjusted to pH=7), ultrasonic
10min, to uniformly, adds 0.1g initiator A IBN, and temperature controls 70 DEG C, and mechanical agitation under the conditions of 500rpm, conversion ratio reaches
When 80%, in solution, add the γ-MPS of 0.3g, use ethanol centrifuge washing 3 times after total reaction time 24h, obtain mean diameter
High molecular nanometer particles core P1 for 80nm.
(2) organic-inorganic core-shell structure nanometer particle P2: high molecular nanometer particles core P1 1g step (1) prepared is prepared
Be dispersed in 100g alcoholic solution, drip 0.4mol/L ammonia, regulate pH to 8 ~ 11,50 DEG C, under the conditions of stir speed (S.S.) 250rpm
It is slowly added dropwise TEOS 1.5g, drop rate 1mL/h, reacts 12h, obtain the hud typed organic/inorganic that mean diameter is 100nm
Nanoparticle P2.
(3) prepare functionalized organic inorganic core-shell structure nanometer particle P ' 2: organic/inorganic nano particle P2 is put into its 4
In the 4mol/L concentrated sulphuric acid of times quality, 40 DEG C of constant temperature stirring at low speed 4h, obtain sulfonation nucleocapsid structure for 3 times with ethanol centrifuge washing and receive
Rice corpuscles P ' 2.
(4) Punica granatum L. shape complex microsphere P3 is prepared: by molten for the ethanol of the 3wt% γ-MPS organic/inorganic nano-particle P2 of addition
In liquid, centrifuge washing 3 times after 72h, the MPS-P2 obtained takes in the mixed solution that 1g is dispersed in 94.5g alcohol and 5.5g water, with adding
Enter 3g PVP, ultrasonic disperse 10min and purge 2h to homogeneous reaction system, nitrogen, by 10g styrene monomer and 1g initiator A IBA
Ultrasonic disperse 10min is to uniformly in mixing, and pours rapidly above-mentioned reaction system, under nitrogen protection, 70 into after nitrogen purging 2h
Under the conditions of DEG C, response time 12h, wherein conversion ratio reaches the γ-MPS of dropping 10wt% when 80%, and reaction terminates centrifuge washing 3
Secondary, obtain comprising the polymer microballoon P3 of multiple nucleocapsid organo-mineral complexing nanoparticle.
(5) Punica granatum L. shape composite construction microsphere outermost layer inorganic shell is prepared: take the polymer microballoon that 1.5g step (4) obtains
P3, is dispersed in 100g alcoholic solution, the ammonia of dropping 0.4mol/L, regulates pH to 8 ~ 11, drips 1.5 times with the speed of 1mL/h
The TEOS of microspheres quality, reaction temperature 50 DEG C, after reacting 12h with the stir speed (S.S.) of 250rpm, centrifuge washing 3 times, obtain novel
Punica granatum L. shape organo-mineral complexing structure microspheres P4.
(6) take the complex microsphere P4 obtained in step (5) and put into the concentrated sulphuric acid of 4mol/L of its 4 times of mass numbers at 40 DEG C of oil
Bath stirring 4h, washs 3 times through ethanol centrifugation, obtains the sulfonation complex microsphere P ' 4 of Punica granatum L. structure, and its polystyrene moieties is equal
Sulfonation layer with grafting sulfonic groups group.
In above-described embodiment, each component raw material and consumption and the parameter of preparation process, for better embodiment of the present invention
Representative, but embodiments of the present invention being not restricted to the described embodiments, other any spirit without departing from the present invention
The change made under essence and principle, modify, substitute, combine, simplify, all should be the substitute mode of equivalence, be included in this
Within bright protection domain, all can obtain the complex microsphere of similar structures.
Claims (10)
1. a functional composite microsphere with Punica granatum L. shape structure, it is characterised in that described functional composite microsphere is that Punica granatum L. shape has four
The structure of layer, first prepares polymer nano with emulsion polymerization under initiator and stabilizer polyvinylpyrrolidone effect
Rice corpuscles P1 is as kernel；It is then passed through coated inorganic shell after silane coupler is modified, obtains organic/inorganic core-shell nano
Particle P2；Organic/inorganic core-shell nano P2 obtains organic/inorganic core-shell nano P ' 2 after concentrated acid sulfonation, so
After using this organic/inorganic core-shell nano P ' 2 as template, after being carried out surface modification so that it is be stable at reaction system
In, and surface is with polymerizable groups, recycles the organic/inorganic nucleocapsid structure particle after surface modification and sends out with polymer monomer
Raw polyreaction, thus multiple organic/inorganic core-shell nano Surface coating are entered polymer layers of balls, obtain Punica granatum L. shape structure
The complex microsphere P3 comprising multiple nucleocapsid structure particle；After finally being modified with silane coupler by this microsphere, utilize silicone hydroxyl
Between hydrolysis-condensation reaction, formed and be coated with inorganic shell, the Punica granatum L. shape functional composite microsphere P4 of controlled Punica granatum L. shape structure,
Punica granatum L. shape functional composite microsphere P4 obtains functional composite microsphere P ' 4 through sulfonation, and described polymer is anti-by polymer monomer polymerization
Should prepare, described inorganic matter is that tetraalkyl orthosilicate hydrolysis-condensation reaction prepares, and its raw material composition includes:
Polymer monomer 1 ~ 30 part, in terms of mass number,
Initiator 0.1 ~ 9 part, in terms of mass number,
Polyvinylpyrrolidone 0.5 ~ 15 part, in terms of mass number,
Silane coupler 0.025 ~ 2 part, in terms of mass number,
Tetraalkyl orthosilicate 0.5 ~ 40 part, in terms of mass number.
The functional composite microsphere with Punica granatum L. shape structure the most according to claim 1, it is characterised in that: described polymer list
Body is any one in double bond containing acrylic compounds, styrene or styrene derivative.
The functional composite microsphere with Punica granatum L. shape structure the most according to claim 1, it is characterised in that: use emulsion polymerization
The initiator added in method is any one in 2,2'-azo-bis-isobutyrate hydrochloride, azodiisobutyronitrile or persulfate.
The functional composite microsphere with Punica granatum L. shape structure the most according to claim 1, it is characterised in that: described positive silicic acid alkane
Base ester is any one in methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
The preparation method of the functional composite microsphere with Punica granatum L. shape structure the most according to claim 1, it is characterised in that: institute
The silane coupler stated is amino silicane coupling agent.
6. the preparation method of a functional composite microsphere as claimed in claim 1 with Punica granatum L. shape structure, it is characterised in that
Specifically comprise the following steps that
(1) in preparing ground floor, nuclear particle P1:1-10g polymer monomer adds the ethanol of 5.5g and the poly-second of stabilizer of 0.5-5g
In the mixture of alkene pyrrolidone, ultrasonic 5-15min to uniformly, is added into the water-soluble of 94.5g dissolved with 0.3-3g initiator
In liquid, temperature controls at 60-80 DEG C, mechanical agitation under the conditions of 400-600rpm, when conversion ratio reaches 70%-80%, to solution
The silane coupler of middle addition 0.1-10g, after response time 12-24h, with ethanol centrifuge washing 3-5 time, obtaining mean diameter is
The polymer nano-particle P1 of 50-200nm；
(2) organic/inorganic core-shell nano P ' 2: polymer nano-particle P1 dispersion 1-10g step (1) prepared is prepared
In 100g alcoholic solution, drip 0.3-0.5mol/L ammonia, regulate pH to 8 ~ 11, in the stir speed (S.S.) of 40-60 DEG C He 250rpm
Under be slowly added dropwise tetraalkyl orthosilicate, drop rate 0.5-2mL/h, react 8-16h, obtaining mean diameter is 100-240nm's
Hud typed organic/inorganic nano particle P2, by being put in the 4mol/L sulphuric acid of its 4 ~ 10 times of mass parts, grafting sulfonic groups
Group obtains the organic/inorganic core-shell nano P ' 2 of functionalization；
(3) the complex microsphere P3 comprising multiple nucleocapsid structure particle of Punica granatum L. shape structure is prepared: by having of 0.5-3g step (2)
After machine/inorganic core core/shell nanoparticles P ' 2 modifies the silane coupler of its quality 0.5-20% upper, it is dispersed in 94.5g alcohol and 5.5g water
Mixed solution in, add the PVP, ultrasonic disperse 5-15min of 1-3g to homogeneous reaction system, nitrogen purging 1-3h, by P ' 2 matter
The polymer monomer of 5-10 times amount and the AIBA mixing ultrasonic disperse 5-15min of 0.25-9g of amount is to uniformly, and purges with nitrogen
After 1-3h, pouring rapidly above-mentioned reaction system into, 50-70 DEG C of reaction 10-16h, when conversion ratio reaches 70-80%, adds under nitrogen protection
Entering the silane coupler of 0. 5-20g, reaction terminates rear centrifuge washing 3-5 time, obtains having comprising of unique Punica granatum L. shape structure many
The complex microsphere P3 of individual nucleocapsid structure particle；
(4) outer shell of functionalization Punica granatum L. shape structure composite microsphere is prepared: take comprising of the Punica granatum L. shape structure that step (3) obtains many
The complex microsphere P3 1.00 ~ 3.00g of individual nucleocapsid structure particle is dispersed in 100g alcoholic solution, the ammonia of dropping 0.3-0.5mol/L
Water, regulates pH to 8 ~ 11, drips 1.50 ~ 12.00g tetraalkyl orthosilicate with the speed of 0.5-2mL/h, reaction temperature 40-60 DEG C,
After reacting 8-12h with the stir speed (S.S.) of 150-250rpm, centrifuge washing obtains novel Punica granatum L. shape functional composite microsphere P4；
(5) 1.00 ~ 5.00g Punica granatum L. shape functional composite microsphere P4 in step (4) is put into the 4mol/L sulfur of its 4 ~ 10 times of mass parts
In acid, stir 0-12h 30-60 DEG C of oil bath, by sulfonation Punica granatum L. shape complex microsphere in various degree, through ethanol centrifuge washing 3-5
Secondary, obtain the functional composite microsphere P ' 4 of Punica granatum L. shape structure.
The preparation method of the functional composite microsphere of Punica granatum L. shape structure the most according to claim 6, it is characterised in that: step
(1) reaction rotating speed during polymer nano-particle P1 prepared by 250-500rpm, size controlling at 50-200nm, its particle diameter
It is evenly distributed, and breadth coefficient PDI value < 0.05, for monodisperse system.
The preparation method of the functional composite microsphere of Punica granatum L. shape structure the most according to claim 6, it is characterised in that: by described
Punica granatum L. shape functional composite microsphere P4 puts into and dissolves component of polymer or the side by sintering in the organic solvent of its 2-10 times of quality
Method, i.e. can get Punica granatum L. shape hollow structure microsphere P5.
The preparation method of the functional composite microsphere of Punica granatum L. shape structure the most according to claim 8, it is characterised in that: prepare stone
Method used by pomegranate shape hollow structure microsphere P5 be following any one:
Method one: be dissolved in the N ' dinethylformamide of 2-10 times of Punica granatum L. shape functional composite microsphere P4 mass under normal temperature condition
(DMF), in solution, after 8h, centrifuge washing changes fresh DMF solution, is repeated 2 times；
Method two: after Punica granatum L. shape functional composite microsphere P4 lyophilization, with Muffle furnace burning-off polymer moieties, obtain hollow
Punica granatum L. shape composite construction microsphere, with the ramp of 2-5 DEG C/min to 450 DEG C, is incubated 2h.
The preparation method of the functional composite microsphere of Punica granatum L. shape structure the most according to claim 1, it is characterised in that: Punica granatum L.
When megalosphere layer ruptures in structure multilayer hollow microsphere, it is coated on multiple spherical state of little sky therein complete.
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