CN105131164A - Method for preparing monodisperse polymeric microspheres adopting snowman-shaped, dumbbell-shaped, raspberry-shaped or core-shell structure through one-step dispersion polymerization - Google Patents
Method for preparing monodisperse polymeric microspheres adopting snowman-shaped, dumbbell-shaped, raspberry-shaped or core-shell structure through one-step dispersion polymerization Download PDFInfo
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Abstract
The invention discloses a method for preparing monodisperse polymeric microspheres adopting a snowman-shaped, dumbbell-shaped, raspberry-shaped or core-shell structure through one-step dispersion polymerization, and belongs to a dispersion polymerization technology. According to the method, all reaction reagents (including monomers, a cross-linking agent, initiator, functional monomers and the like) are added in one step, and the polymeric microspheres adopting the snowman-shaped, dumbbell-shaped, raspberry-shaped or core-shell structure are prepared through dispersion polymerization. The method is simple and effective.
Description
Technical field
The present invention relates to a kind of method that the single dispersing functional polymer microsphere of snowman's shape, dumb-bell shape, raspberry shape and nucleocapsid structure is directly prepared in a step dispersion polymerization, particularly relate to and utilize an initial step to add all reaction reagents (comprising monomer, linking agent, initiator etc.) to carry out dispersion polymerization and prepare the polymer microballoon of snowman's shape, dumb-bell shape, raspberry shape and nucleocapsid structure, belonging to dispersion polymerization technology.
Background technology
Dispersion polymerization originates in a homogeneous system, and when namely starting, the reagent such as monomer, stablizer and initiator is all dissolved in reaction medium; Along with the carrying out of polyreaction, the polymer chain of generation reach critical chain length and separate out from reaction medium, precipitation, nucleation-this one-phase is the nucleation period; Afterwards, monomer also reacts to particle phase internal diffusion and makes particle growth, and monomer also can react in interface and external phase between particle and medium simultaneously, and this one-phase is the particle growth phase, and response class is like seeding polymerization.
Dispersion polymerization is initial adds functional reagent, can be easy to obtain the polymer microballoon containing specific function group.But, polymerization starts just to add the functional reagent such as linking agent, hydrophilic co-monomer (as vinylformic acid-AA) and their the comparatively large (1wt.% of content, relative main monomer weight percent, wt.%) time, system stability and microballoon monodispersity destructible, the easily inter-adhesive and size distribution of microballoon broadens.As: linking agent rapid reaction forms crosslinking structure makes growth particle tighten, and is unfavorable for that external phase monomer spreads mutually to particle, makes monomer be polymerized increase in external phase, cause secondary nucleation (SongJ.S., WinnikM.A., et.al., J.Am.Chem.Soc., 2004,126,6562-6563; Macromolecules, 2005,38,8300-8307; Macromolecules, 2006,39,8318-8325); Hydrophilic monomer copolymerization makes oligopolymer dissolving power in external phase increase, and causes the nucleation period elongated, size distribution broadens (ZhangH.T, Yuan, X.Y., HuangJ.X., Reactive & FunctionalPolymers, 2004,59,23-31).
For solving the problem, etc. WinnikM.A. add the function monomers such as linking agent after adopting the nucleation period, namely two steps are fed in raw material dispersion polymerization processes (2-Dis.P.), obtain the crosslinked (nucleocapsid structure of monodispersed homogeneous cross-link, only shell, PengB., WeeE., ImhofA., BlaaderenA., Langmuir, 2012,28,6776-6785; WangS.L., YueK., LiuL.Y., YangW.T., J.ColloidInterfaceSci., 2013,389,126-133; WangS.L., YangX.F., LiuL.Y., YangW.T., ChineseJ.Polym.Sci., 2012,30,865-872) or subregion highly cross-linked (dimple-shaped, CongH.L., WangJ.L, YuB., TangJ.G., CuiW., J.ColloidInterfaceSci., 2013,411,41-46) polymer microballoon.In addition, ZengZ.H etc. adopt the functional polymer microsphere (TanJ.B. that a step is reinforced, single dispersing simply, has directly been prepared in light-initiated RAFT dispersion polymerization (light trigger and RAFT reagent all add initial), height is crosslinked, RaoX., YangJ.W., ZengZ.H., Macromolecules, 2012,45,8790-8795; Macromolecules, 2013,46,8441-8448; Macromolecules, 2014,47 (19), 6856-6866; RSCAdv., 2015,5,18922-18931).ShimS.E. wait in a step feeds in raw material dispersion polymerization, use comparatively long-chain linking agent reduction cross-linking density to also obtain monodisperse cross-linked polymer microspheres (ShimS.E., JungH., LeeK., LeeJ.M., ChoeS.J.ColloidInterf.Sci., 2004,279,464-470; KimJ.W., SuhK.D., ColloidPolym.Sci., 1999,277,210-216).Can above-mentioned research be mainly paid close attention to and be obtained monodispersed spherical functional polymer microsphere, seldom relates to aspherical (as snowman's shape, dumb-bell shape) polymer microballoon; One step is fed in raw material, and the general thus obtained microsphere of dispersion polymerization mostly is spherical, the polymer microballoon of smooth surface, homogeneous cross-link (polymerization starts namely to be cross-linked), be difficult to obtain the polymer microballoon of surface irregularity (raspberry shape) and/or uneven crosslinked (nucleocapsid structure, only shell is cross-linked).
Compared with spherical polymer microballoon, aspherical microballoon has asymmetric or ununiformity in shape, structure, composition etc., and this makes it in the application such as emulsion-stabilizing, photoelectric display, bio-sensing and catalysis, show unique, excellent properties.Developed many methods preparing aspherical polymer microballoon at present, wherein, seed divides phase polymerisation process (MockE.B., DeBruynH., HawkettB.S., GilbertR.G., ZukoskiC.F., Langmuir2006,22 (9), 4037-4043; KimJ.W., LarsenR.J., WeitzD.A., J.Am.Chem.Soc.2006,128,14374-14377; ZhangC.L., QuX.Z., LiJ.L., QiuD., YangZ.Z., Macromolecules, 2012,45 (12), 5176-5184; PengB., VutukuriH.R., BlaaderenA., ImhofA., J.Mater.Chem., 2012,22,21893-21900; ThomasS.S., ChenY.H., BonS.A.F., Langmuir, 2014,30,13525-13532), namely preparing the method for snowman's shape or dumb-bell shape microballoon with spherical microballoons of gained such as dispersion, letex polymerizations through monomer swell, intensification, phase-splitting, polymerization for seed, is a kind of method being commonly recognized, can preparing aspherical microballoon in enormous quantities.But this method still has some limitations: as related to, step many (comprising Spawn preparation, crosslinked and surface modification etc.), swell cross seed are consuming time, aspherical microballoon each several part pattern, size and surfaceness can not regulate and control effectively continuously.For these problems, YangW.T. proposition is waited to utilize dispersion polymerization feature, adopt dispersion polymerization two-step approach, namely linking agent is added one pot of dispersion polymerization particle growth phase, initiator and function monomer etc., regulation and control growth particle is uneven to be cross-linked or to form closely knit crosslinked shell, make by monomer, oligopolymer or the swelling propagation crosslink particle of low-molecular weight polymer are separated in reaction process, prepare snowman's shape, dumb-bell shape or many parts functional polymer microsphere (LiuY.N., YangQ., ZhuJ.M., LiuL.Y., YangW.Y.ColloidPolym.Sci., 2015, 293, 523-532, LiuY.N., MaY.H., LiuL.Y., YangW.Y., JColloidInterf.Sci., 2015,445,268-276, LiuY.N., LiuW., MaY.H., LiuL.Y., YangW.Y., Langmuir, 2015,31 (3), 925-936, Liu Lianying, Yang Qing, Yang Wantai, Ma Yuhong, Liu Yanan, Liu Wang, the method for aspherical, raspberry shape and hollow polymer microsphere is prepared in one pot of dispersion polymerization, Chinese invention patent, application number: CN201310717922).But the method still needs two steps to feed in raw material, can not as preparing conventional ball particle by an initial step reinforced preparation aspherical polymer microballoon.
Compared with ganoid spherical polymer microballoon, raspberry shape microsphere surface has many small-particles or projection, and roughness is large, and specific surface area is large, gives prominence to constructing super hydrophilic/hydrophobic surface and prepare performance in photoelectricity, catalytic device etc.Usually, raspberry shape microballoon is formed by three kinds of modes: (1) large nuclear particle and small-particle are by interaction compounds such as hydrogen bond, electrostatic or soda acids; (2) small-particle or projection is formed by seeded emulsion polymerization at macronucleus seed particles surface in situ; (3) small-particle is adopted to carry out pik woods (Pickering) letex polymerization as tensio-active agent.Obviously, these method stepss are comparatively complicated.At present, existing report (SunY.Y., the YinY.Y. preparing single dispersing raspberry shaped polymer microballoon simply by a step emulsifier-free emulsion polymerization, ChenM., ZhouS.X., WuL.M., Polym.Chem., 2013,4,3020-3027), but the method relates to prehydrolysis and the surface aggregation of 3-(Trimethoxy silane) propyl acrylate-MPS, be not suitable for other systems, limit its application.The research of the people such as Liu Lianying shows to adopt one pot of dispersion polymerization two step charging process to prepare raspberry shaped polymer microballoon (Liu Lianying, Yang Qing, Yang Wantai, Ma Yuhong, Liu Yanan, Liu Wang, the method of aspherical, raspberry shape and hollow polymer microsphere is prepared in one pot of dispersion polymerization, Chinese invention patent, application number: CN201310717922), but do not relate to the dispersion polymerization of feeding in raw material of more simple, an initial step and prepare raspberry shaped polymer microballoon.
Summary of the invention
The object of the invention is to provide a kind of simple one pot, a step dispersion polymerization prepares the method for the monodisperse polymer micro-sphere of snowman's shape, dumb-bell shape, raspberry shape or nucleocapsid structure.That is: time initial, the reaction reagents such as monomer, linking agent, initiator are all dissolved in dispersion medium, then heat up and be polymerized, without the need to adding other reagent such as monomer in polymerization process, reaction terminates the method obtaining the monodisperse polymer micro-sphere of snowman's shape or dumb-bell shape or raspberry shape or nucleocapsid structure.
The technical solution used in the present invention is for achieving the above object:
Monomer styrene-St, Sodium styrene sulfonate-NaSS, initiator Diisopropyl azodicarboxylate-AIBN and linking agent are stirred, are dissolved in forming reactions liquid in the mixed solution of organic solvent and water; Reacting liquid temperature is risen to 75 DEG C to start to react certain hour, obtain the monodisperse polymer micro-sphere of snowman's shape or dumb-bell shape or raspberry shape or nucleocapsid structure.
The crosslinkers monomers D of crosslinkers monomers A or three end group of described linking agent to be two end groups be double bond to be a crosslinkers monomers B or end group double bond of double bond and connection agent monomer C or two end group of an end group triple bond be triple bond.
Also add function monomer in above-mentioned reaction solution, the consumption of functional group monomer is the 1-6wt.% of St consumption.
Concrete steps are as follows:
The reactor being furnished with agitator and reflux condensate device is placed in water bath with thermostatic control, add the mixed solution of organic solvent and water, then add monomer St, NaSS, initiator A IBN and linking agent, stir forming reactions liquid (rotating speed is preferably 200r/min); Reacting liquid temperature is risen to 75 DEG C, reaction 8h; By final dispersion liquid centrifugation, topple over removing supernatant liquor, then add methanol wash, centrifugation, repeatable operation like this at least 3 times, obtains powdered sample, is dried to constant weight.
Above-mentionedly further while adding monomer St, NaSS, initiator A IBN and linking agent, also add function monomer, described functional monomer is preferably selected from following monomer: containing epoxy based monomers, carboxyl group-containing monomer, amide containing class monomer, containing pyridyl monomer, containing alkynyl monomers, preferably end group is above-mentioned group further.
In the mixed solution of organic solvent used and water, organic solvent is selected from one or more in ethylene glycol, ethanol, methyl alcohol, and organic solvent accounts for the 60-80% of the mixed solution cumulative volume of organic solvent and water.
The concentration of monomer St used is the consumption of 8 ~ 15wt.% (in reaction solution weight percentage wt.%), NaSS is the 1 ~ 4wt.% of St; The consumption of initiator used is the 1-3wt.% of St.
Linking agent A used can be-containing the monomer of two double bonds, and its chemical structure is as follows:
Wherein: R
1, R
2can be H or CH
3; R
3can for containing benzophenone unit, fluorescein unit
or oxyethyl group-CH
2-CH
2the structure of-O-unit.
As, the above-mentioned two double bond linking agents that contain can be: 4,4'-dimethacryloxy benzophenone-DMABP:
Or 4,4'-dimethacryloxy fluorescein-DMA-Fluo:
Or polyethyleneglycol diacrylate-PEGDA:
preferably its molecular weight Mn=575 (PEGDA575), 700 (PEGDA700);
Linking agent used also can for B-be containing the monomer of three double bonds, as acrylic ester monomer, and Viscoat 295-TMPTA:
Linking agent used also can for C-be containing the monomer of a double bond and a triple bond, as: propargylacrylate-PGA:
or methacrylic acid alkynes propyl ester-PMA:
Linking agent used also can for D-be containing the monomer of two triple bonds, as: the pungent diine of 1,7--OTD:
Can be used alone a kind of linking agent, also can two kinds of linking agents used in combination, the consumption of linking agent used is the 1 ~ 20wt.% of St.
In addition, the monomer containing specific function group can in reaction system, be added, the monomer as containing epoxy group(ing): glycidyl methacrylate-GMA; Carboxyl group-containing monomer: vinylformic acid-AA, methacrylic acid-MAA; Amide containing monomer: NIPA-NIPAM; Containing pyridyl monomer: 4-vinylpridine (4-VP); Containing alkynyl monomers: propargyl acetate-PAT
propargyl bromide-PBR
bromo acid propynyl ester-PGBB
or 1-hexin (HE, HC ≡ C (CH
2)
3cH
3).The above-mentioned consumption containing specific function group monomer is 1-6wt.% (wt.% of relative St).
In the present invention, use different types of linking agent or/and function monomer, polymerization rate is different, in reaction process form crosslinked, the degree of swelling that increases particle and surface hydrophilicity different, cause the phase-splitting degree of propagation crosslink particle different, thus obtain pattern (snowman's shape, dumb-bell shape and raspberry shape), structure (crosslinked or be not cross-linked, nucleocapsid structure), surfaceness (smooth and coarse) and surface functional group and to distribute different polymer microballoons.Resulting polymers microballoon is a part of smooth surface or coarse or occur obviously protruding, internal crosslinking, and another part smooth surface, inside are not crosslinked or partial cross-linked or snowman's shape of (sparse crosslinked or be not cross-linked)-shell (closely knit be cross-linked) structure or dumb-bell shape polymer microballoon in core; Resulting polymers microballoon is surface irregularity or in flower-shaped, inner homogeneous or gradient crosslinked raspberry shaped polymer microballoon.Resulting polymers microballoon is the polymer microballoon of smooth surface or coarse, core (sparse crosslinked or be not cross-linked)-shell (closely knit crosslinked) structure.
As: be used alone the A linking agent containing benzophenone or fluorescein modular construction, in polymerization process propagation crosslink particle can by monomer and oligopolymer institute swelling, make to produce elastic stress in this particle; For discharging this elastic stress, particle is separated, finally obtain a part of surface irregularity, internal crosslinking (containing benzophenone or fluorescein modular construction), and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see embodiment 1-2, accompanying drawing 1a); Or it is all smooth to obtain two portions surface, a part crosslinked (containing benzophenone or fluorescein modular construction), and snowman's shaped polymer microballoon that another part is not cross-linked (see embodiment 3-4 and accompanying drawing 1b); Or obtain rough, the internal crosslinking in part surface, and another part smooth surface, internal portion are crosslinked, neck has multiple pimple, benzophenone or fluorescein modular construction snowman's shaped polymer pockety microballoon (see embodiment 5 and accompanying drawing 1c); Or obtain part surface rough (occurring multiple obvious pimple), internal crosslinking, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see embodiment 6-7 accompanying drawing 1d); Or obtain sparse and outside crosslinked closely knit, the ganoid nuclear-structure polymer shell microballoon (see embodiment 8 and accompanying drawing 4a) of internal crosslinking.
During by A linking agent and the C linking agent containing benzophenone or fluorescein modular construction as used together with PGA or PMA, because in C linking agent, double bond is different with the reactive behavior of triple bond, double bond can preferential reaction, and triple bond after reaction, obtain surface irregularity thus, the class snowman shaped polymer microballoon (see embodiment 9 and accompanying drawing 1e) that internal portion is crosslinked, part is core-shell structure copolymer (being cross-linked) structure; Or obtain a part of surface irregularity and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see embodiment 10-11 and accompanying drawing 2a) of core-shell structure copolymer (being cross-linked) structure; Or obtain part surface in raspberry shape (occur obviously a lot of pimple) and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see embodiment 12-13 and accompanying drawing 2b) of core-shell structure copolymer (being cross-linked) structure; Or obtain smooth surface, the polymer microballoon (see embodiment 14 and accompanying drawing 4b) of there is core (not being cross-linked)-shell (closely knit crosslinked) structure.
During by A linking agent and the D linking agent containing benzophenone or fluorescein modular construction as used together with OTD, obtain part surface rough (occurring multiple obvious pimple), internal crosslinking, and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see embodiment 15 and accompanying drawing 1d).
When being used together with difference in functionality monomer by the A linking agent containing benzophenone or fluorescein modular construction, increase the surface properties of particle in polymerization process, degree of swelling is different, the structure of resulting polymers microballoon, pattern and functional group present position are different.With containing epoxy based monomers as used together with GMA time, a part of surface irregularity (occurring point projection, containing epoxide group) can be obtained and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon (see embodiment 16 and accompanying drawing 2c).With carboxyl group-containing monomer as AA, when MAA uses together, obtain a part of surface irregularity (occurring multiple obvious projection, containing carboxyl) and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon (see embodiment 17-18 and Fig. 2 d).Add in system with amide containing class monomer together with NIPAM, obtain a part of surface irregularity (containing N-sec.-propyl), be cross-linked, and another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see embodiment 19 and accompanying drawing 1a).Add together with 4-VP with containing pyridyl monomer, obtain part surface and roughly (occur multiple obvious pimple, containing pyridyl), crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see embodiment 20 and accompanying drawing 1d).
With containing alkynyl monomers as PAT, PBR, PGBB, when HE etc. use together, because this type of monomer not easily reacts, can solvent action be played, increase when particle is separated and be easily expressed into the new jut formed, finally obtain that a part of surface is slightly coarse, internal crosslinking, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see embodiment 21-24 and accompanying drawing 1f).
In addition, when being used alone A linking agent containing oxyethyl group as PEGDA575 or PEGDA700, surface is obtained in flower-shaped, inner raspberry shaped polymer microballoon (see embodiment 25-26 and accompanying drawing 3a) crosslinked in gradient through a step dispersion polymerization; Or obtain the polymer microballoon (see embodiment 27 and accompanying drawing 4c) that surface is more coarse, have core (sparse crosslinked)-shell (closely knit crosslinked) structure; Or obtain surface irregularity, the polymer microballoon (see embodiment 28 and accompanying drawing 4d) of there is core (not being cross-linked)-shell (closely knit crosslinked) structure.
When being used alone B linking agent as TMPTA, obtain the polymer microballoon (see embodiment 29 and accompanying drawing 3b) that particle surface is coarse, crosslinked.
When being used alone C linking agent as PGA or PMA, because double bond in linking agent is different with the reactive behavior of triple bond, obtain ganoid core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon (see embodiment 30-31 and accompanying drawing 4b); Or obtain shaggy core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon (see embodiment 32 and accompanying drawing 4d).
After reaction terminates, gained dispersion liquid is known finishing sequence process according to those skilled in the art: namely centrifugal, be separated, washing and dry, obtain powdered samples.
For observing pattern and the structure of gained crosslinked microsphere, determine crosslinking sites and crosslinking degree, microballoon can be soaked in THF and stir 48 hours, every 6 hours of period changed fresh THF, no cross-linked polymer in removing particle.
Sample ultrasonic is disperseed, is suspended in methyl alcohol, and drop to sample preparation on clean sheet glass or copper mesh, adopt scanning electronic microscope (SEM, HitachiS-4700, acceleration voltage 20kV)) and transmission electron microscope (TEM, JEOLJEM-2100, acceleration voltage 200kV) observe resulting polymers particle morphology and structure.
Effect of the present invention:
1, in a step dispersion polymerization, directly monomer, linking agent, initiator and solvent etc. are just all added reaction is initial, do not need again to add, simplify reaction process.Achieve dispersion polymerization single stage method and prepare snowman's shape, dumbbell shaped, raspberry shape and core-shell polymer microsphere.The invention provides a kind of method that single dispersing aspherical/spherical polymer microballoon is directly prepared in simple, an effective step dispersion polymerization.
2, in a step dispersion polymerization, by changing surface topography and the structure of type of crosslinking agent and dosage of crosslinking agent controllable polymer microballoon, obtain a part of smooth surface or coarse or occur obviously protruding, internal crosslinking, and another part smooth surface, inside are not crosslinked or partial cross-linked or snowman's shape of (sparse crosslinked or be not cross-linked)-shell (closely knit be cross-linked) structure or dumb-bell shape polymer microballoon in core; Or obtain surface irregularity or in flower-shaped, inner homogeneous or gradient crosslinked raspberry shaped polymer microballoon; Or obtain the polymer microballoon of smooth surface or coarse, core (sparse crosslinked or be not cross-linked)-shell (closely knit crosslinked) structure.
3, use linking agent and function monomer in a step dispersion polymerization simultaneously, utilize and contain the polymerization of difference in functionality group monomer and the after reaction of triple bond, obtain start-up portion surface contains functional group snowman's shape or dumb-bell shape polymer microballoon containing difference in functionality group or new forming section surface.
Accompanying drawing explanation
SEM, TEM photo of Fig. 1 different-shape, structure and surfaceness snowman shaped polymer microballoon
A. a part of surface irregularity, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon;
B. two portions surface is all smooth, snowman's shaped polymer microballoon that a part is crosslinked, another part is not cross-linked;
C. part surface is rough, crosslinked, another part smooth surface, partial cross-linked, and neck has snowman's shaped polymer microballoon of multiple pimple;
D. part surface rough (occurring multiple obvious pimple), crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon;
E. surface irregularity, partial cross-linked, the class snowman shaped polymer microballoon of part in core-shell structure copolymer (being cross-linked) structure;
F. a part of surface is slightly coarse, crosslinked, a part of smooth surface, not crosslinked snowman's shaped polymer microballoon.
SEM, TEM photo of Fig. 2 different-shape, structure and surfaceness dumb-bell shape polymer microballoon
A. a part of surface irregularity and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon of core-shell structure copolymer (being cross-linked) structure;
B. part surface is in raspberry shape (occur obviously a lot of pimple) and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon of core-shell structure copolymer (being cross-linked) structure;
C. a part of surface irregularity (occurring point projection) and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon;
D. a part of surface irregularity (occurring multiple obvious projection) and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon.
SEM, TEM photo of Fig. 3 different surface roughness and internal structure raspberry shaped polymer microballoon
A. the raspberry shaped polymer microballoon that inner homogeneous is crosslinked;
B. surface is in flower-shaped, that inner gradient is crosslinked raspberry shaped polymer microballoon.
SEM, TEM photo of Fig. 4 different surface roughness nuclear-structure polymer shell microballoon
A. ganoid core (sparse crosslinked)-shell (closely knit crosslinked) polymer microballoon;
B. ganoid core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon;
C. core (sparse crosslinked)-shell (closely knit crosslinked) polymer microballoon that surface is more coarse;
D. shaggy core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon.
Embodiment
By the following examples implementation method of the present invention is described further, but the present invention is not limited to these embodiments, also comprises: do not departing under scope of the invention condition, the apparent various change of those skilled in the art is carried out to disclosed method.
Embodiment 1
The 100ml tri-mouthfuls of round bottom reaction flasks being furnished with mechanical stirring and reflux condensing tube by one are placed in water bath with thermostatic control, add methyl alcohol 15ml and deionized water 10ml (methanol/water=6/4, vol.), add monomer styrene St2.5ml (in reaction solution concentration 10wt.%), linking agent DMABP0.0906g (4wt.%, relative St weight), Sodium styrene sulfonate NaSS0.0453g (2wt.%, relative St weight), initiator Diisopropyl azodicarboxylate AIBN0.0453g (2wt.%, relative St weight); Open and stir, rotating speed is 200r/min; Thermostat water bath is heated to 75 DEG C, start reaction, reaction total time is 8h simultaneously.Gained stablized the centrifugation of micelle dispersion liquid, topple over removing supernatant liquor, then add methanol wash, centrifugation, repeatable operation like this at least 3 times, obtains powdered sample, is dried to constant weight.SEM, tem observation thus obtained microsphere are a part of surface irregularity, internal crosslinking (containing benzophenone modular construction), and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1a).
Embodiment 2
Other are as embodiment 1, replace with and add ethanol 17.5ml and deionized water 7.5ml (ethanol/water=7/3 to reaction system, vol.), add monomer styrene St2.24ml (in reaction solution concentration 8wt.%), add linking agent DMA-Fluo0.1133g (5wt.%, relatively initial St weight).SEM, tem observation thus obtained microsphere are a part of surface irregularity, internal crosslinking (containing fluorescein modular construction), and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1a).
Embodiment 3
Other are as embodiment 1, replace with and add linking agent DMA-Fluo0.0906g (4wt.%, relatively initial St weight) to reaction system.SEM, tem observation thus obtained microsphere are that two portions surface is all smooth, a part crosslinked (containing fluorescein modular construction), and snowman's shaped polymer microballoon (see accompanying drawing 1b) that another part is not cross-linked.
Embodiment 4
Other are as embodiment 1, replace with and add ethylene glycol 20ml and deionized water 5ml (glycol/water=8/2, vol.) to reaction system, add monomer styrene St3.75ml (in reaction solution concentration 15wt.%).SEM, tem observation thus obtained microsphere are that two portions surface is all smooth, a part crosslinked (containing benzophenone or fluorescein modular construction), and snowman's shaped polymer microballoon (see accompanying drawing 1b) that another part is not cross-linked.
Embodiment 5
Other are as embodiment 1, and replacing with the amount adding DMABP to reaction system is 0.1133g (5wt.%, relatively initial St weight).SEM, tem observation thus obtained microsphere are rough, the internal crosslinking in part surface, and another part smooth surface, internal portion are crosslinked, neck has multiple pimple, benzophenone or fluorescein modular construction snowman's shaped polymer pockety microballoon (see accompanying drawing 1c).
Embodiment 6
Other are as embodiment 1, replace with and add linking agent DMA-Fluo0.2265g (10wt.%, relatively initial St weight) to reaction system.SEM, tem observation thus obtained microsphere are part surface rough (occurring multiple obvious pimple), internal crosslinking, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1d).
Embodiment 7
Other are as embodiment 1, replace with and add ethylene glycol 20ml and deionized water 5ml (glycol/water=8/2 to reaction system, vol.), add linking agent DMA-Fluo0.2265g (10wt.%, relatively initial St weight), Sodium styrene sulfonate NaSS0.0906g (4wt.%, relative St weight), initiator Diisopropyl azodicarboxylate AIBN0.0680g (3wt.%, relative St weight).SEM, tem observation thus obtained microsphere are part surface rough (occurring multiple obvious pimple), internal crosslinking, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1d).
Embodiment 8
Other are as embodiment 1, and the amount adding DMABP to reaction system is 0.0227g (1wt.%, relatively initial St weight).SEM, tem observation thus obtained microsphere are sparse and outside crosslinked closely knit, the ganoid nuclear-structure polymer shell microballoon (see accompanying drawing 4a) of internal crosslinking.
Embodiment 9
Other are as embodiment 1, add two kinds of linking agent: DMABP0.1359g (6wt.%, relatively initial St weight) and PMA0.15ml (6vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are surface irregularity, and internal portion is crosslinked, the class snowman shaped polymer microballoon (see accompanying drawing 1e) of part in core-shell structure copolymer (being cross-linked) structure.
Embodiment 10
Other are as embodiment 1, add two kinds of linking agent: DMABP0.0906g (4wt.%, relatively initial St weight) and PMA0.1ml (4vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are for a part of surface irregularity and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see accompanying drawing 2a) of core-shell structure copolymer (being cross-linked) structure.
Embodiment 11
Other are as embodiment 1, add two kinds of linking agent: DMABP0.068g (3wt.%, relatively initial St weight) and PGA0.075ml (3vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are for a part of surface irregularity and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see accompanying drawing 2a) of core-shell structure copolymer (being cross-linked) structure.
Embodiment 12
Other are as embodiment 1, add two kinds of linking agent: DMABP0.1133g (5wt.%, relatively initial St weight) and PMA0.125ml (5vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are for part surface is in raspberry shape (occur obviously a lot of pimple) and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see accompanying drawing 2b) of core-shell structure copolymer (being cross-linked) structure.
Embodiment 13
Other are as embodiment 1, add two kinds of linking agent: DMABP0.0906g (4wt.%, relatively initial St weight) and PGA0.1ml (4vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are for part surface is in raspberry shape (occur obviously a lot of pimple) and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon (see accompanying drawing 2b) of core-shell structure copolymer (being cross-linked) structure.
Embodiment 14
Other are as embodiment 1, add two kinds of linking agent: DMABP0.0227g (1wt.%, relatively initial St weight) and PMA0.025ml (1vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are smooth surface, have the polymer microballoon (see accompanying drawing 4b) of core (not being cross-linked)-shell (closely knit crosslinked) structure.
Embodiment 15
Other are as embodiment 1, add two kinds of linking agents: DMABP0.0906g (4wt.% to reaction system simultaneously, relatively initial St weight) and OTD0.01ml (4vol.%, relatively initial St volume), obtain part surface rough (occurring multiple obvious pimple), internal crosslinking, and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1d).
Embodiment 16
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and function monomer GMA0.15ml (6vol.%, relatively initial St volume) to reaction system simultaneously.SEM, tem observation thus obtained microsphere are a part of surface irregularity (occurring point projection, containing epoxide group) and the dumb-bell shape polymer microballoon (see accompanying drawing 2c) that is not cross-linked of internal crosslinking and another part smooth surface and inside.
Embodiment 17
Other are as embodiment 1, add linking agent DMA-Fluo0.1812g (8wt.%, relatively initial St weight) and function monomer vinylformic acid 0.025ml (AA, 1%, relatively initial St volume) in reaction system simultaneously.SEM, tem observation thus obtained microsphere are a part of surface irregularity (occurring multiple obvious projection, containing carboxyl) and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon (see accompanying drawing 2d).
Embodiment 18
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and function monomer methacrylic acid (MAA, 2%, relatively initial St volume) in reaction system simultaneously.SEM, tem observation thus obtained microsphere are a part of surface irregularity (occurring multiple obvious projection, containing carboxyl) and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon (see accompanying drawing 2d).
Embodiment 19
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and function monomer NIPAM (4%, relatively initial St volume) in reaction system simultaneously.SEM, tem observation thus obtained microsphere are a part of surface irregularity (containing N-sec.-propyl), internal crosslinking, and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1a).
Embodiment 20
Other are as embodiment 1, replace with add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and function monomer 4-VP (4%, relatively initial St volume) simultaneously in reaction system.SEM, tem observation thus obtained microsphere are part surface rough (occurring multiple obvious pimple, containing pyridyl), are cross-linked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1d).
Embodiment 21
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and monomer PGA (4%, relatively initial St volume) in reaction system.SEM, tem observation thus obtained microsphere are that a part of surface is slightly coarse, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1f).
Embodiment 22
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and monomer propargyl bromide (PBR, 4vol.%, relatively initial St volume) in reaction system simultaneously.SEM, tem observation thus obtained microsphere are that a part of surface is slightly coarse, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1f).
Embodiment 23
Other are as embodiment 1, add linking agent DMABP0.0906g (4wt.%, relatively initial St weight) and monomer bromo acid alkynes propyl ester (PGBB, 3%, relatively initial St volume) in reaction system simultaneously.SEM, tem observation thus obtained microsphere are that a part of surface is slightly coarse, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1f).
Embodiment 24
Other are as embodiment 1, replace with and add linking agent DMABP0.0906g (4wt.% to reaction system, relatively initial St weight) and monomer PGA (4%, relatively initial St volume), Sodium styrene sulfonate NaSS0.0227g (1wt.%, relative St weight), initiator Diisopropyl azodicarboxylate AIBN0.0227g (1wt.%, relative St weight).SEM, tem observation thus obtained microsphere are that a part of surface is slightly coarse, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon (see accompanying drawing 1f).
Embodiment 25
Other are as embodiment 1, just change linking agent DMABP into PEGDA575, and consumption is 0.25ml (10vol.%).SEM, tem observation thus obtained microsphere are that surface is in flower-shaped, inner raspberry shaped polymer microballoon (see accompanying drawing 3a) crosslinked in gradient.
Embodiment 26
Other are as embodiment 1, just change linking agent DMABP into PEGDA700, and consumption is 0.25ml (10vol.%).SEM, tem observation thus obtained microsphere are that surface is in flower-shaped, inner raspberry shaped polymer microballoon (see accompanying drawing 3a) crosslinked in gradient.
Embodiment 27
Other are as embodiment 1, just change linking agent DMABP into PEGDA575, and consumption is 0.1ml (4vol.%).SEM, tem observation thus obtained microsphere are the polymer microballoon (see accompanying drawing 4c) that surface is more coarse, have core (sparse crosslinked)-shell (closely knit crosslinked) structure.
Embodiment 28
Other are as embodiment 1, just change linking agent DMABP into PEGDA700, and consumption is 0.1ml (4vol.%).SEM, tem observation thus obtained microsphere are surface irregularity, have the polymer microballoon (see accompanying drawing 4d) of core (not being cross-linked)-shell (closely knit crosslinked) structure.
Embodiment 29
Other are as embodiment 1, just linking agent DMABP are changed into the linking agent TMPTA containing three double bonds.SEM, tem observation thus obtained microsphere are surface irregularity, crosslinked polymer microballoon (see accompanying drawing 3b).
Embodiment 30
Other are as embodiment 1, and just change linking agent DMABP into PMA, the consumption of PMA can be 1%.SEM, tem observation thus obtained microsphere are ganoid core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon (see accompanying drawing 4b).
Embodiment 31
Other are as embodiment 1, and just change linking agent DMABP into PMA, the consumption of PMA can be 20%.SEM, tem observation thus obtained microsphere are ganoid core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon (see accompanying drawing 4b).
Embodiment 32
Other are as embodiment 1, and just change linking agent DMABP into PGA, PGA consumption is 4%.SEM, tem observation thus obtained microsphere are shaggy core (not being cross-linked)-shell (closely knit crosslinked) polymer microballoon (see accompanying drawing 4d).
Claims (9)
1. the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure is prepared in a step dispersion polymerization, it is characterized in that, monomer styrene-St, Sodium styrene sulfonate-NaSS, initiator Diisopropyl azodicarboxylate-AIBN and linking agent are stirred, are dissolved in forming reactions liquid in the mixed solution of organic solvent and water; Reacting liquid temperature is risen to 75 DEG C to start to react certain hour, obtain the monodisperse polymer micro-sphere of snowman's shape or dumb-bell shape or raspberry shape or nucleocapsid structure; Crosslinkers monomers A or three end group of described linking agent to be two end groups be double bond to be a crosslinkers monomers B or end group double bond of double bond and connection agent monomer C or two end group of an end group triple bond be in the crosslinkers monomers D of triple bond one or more.
2. the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure is prepared according to a step dispersion polymerization of claim 1, it is characterized in that, also add function monomer in above-mentioned reaction solution, the consumption of functional group monomer is the 1-6wt.% of St consumption.
3. the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure is prepared according to a step dispersion polymerization of claim 1, it is characterized in that, the reactor being furnished with agitator and reflux condensate device is placed in water bath with thermostatic control, add the mixed solution of organic solvent and water, then add monomer St, NaSS, initiator A IBN and linking agent, stir forming reactions liquid; Reacting liquid temperature is risen to 75 DEG C, reaction 8h; By final dispersion liquid centrifugation, topple over removing supernatant liquor, then add methanol wash, centrifugation, repeatable operation like this at least 3 times, obtains powdered sample, is dried to constant weight.
4. the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure is prepared according to a step dispersion polymerization of claim 3, it is characterized in that, while adding monomer St, NaSS, initiator A IBN and linking agent, also add function monomer, described functional monomer is preferably selected from following monomer: containing epoxy based monomers, carboxyl group-containing monomer, amide containing class monomer, containing pyridyl monomer.
5. the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure is prepared according to a step dispersion polymerization of claim 1, it is characterized in that, in the mixed solution of organic solvent used and water, organic solvent is selected from one or more in ethylene glycol, ethanol, methyl alcohol, and organic solvent accounts for the 60-80% of the mixed solution cumulative volume of organic solvent and water.
6. prepare the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure according to a step dispersion polymerization of claim 1, it is characterized in that, the concentration of monomer St used is the consumption of 8 ~ 15wt.%, NaSS is the 1 ~ 4wt.% of St; The consumption of initiator used is the 1-3wt.% of St.
7. prepare the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure according to a step dispersion polymerization of claim 1, it is characterized in that, linking agent A is the monomer containing two double bonds, and its chemical structure is as follows:
Wherein: R
1, R
2for H or CH
3; R
3for containing benzophenone unit
fluorescein unit
or oxyethyl group-CH
2-CH
2the structure of-O-unit;
Or linking agent A is: 4,4'-dimethacryloxy benzophenone-DMABP:
Or 4,4'-dimethacryloxy fluorescein-DMA-Fluo:
Or polyethyleneglycol diacrylate-PEGDA:
Crosslinking agent B is acrylic ester monomer Viscoat 295-TMPTA:
Linking agent C is propargylacrylate-PGA:
or methacrylic acid alkynes propyl ester-PMA:
Linking agent D is the pungent diine of 1,7--OTD:
8. prepare the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure according to a step dispersion polymerization of claim 1, it is characterized in that, the consumption of linking agent is the 1 ~ 20wt.% of St.
9. prepare the method for monodisperse polymer micro-sphere of snowman, dumbbell, raspberry shape or nucleocapsid structure according to a step dispersion polymerization of claim 2 or 7, it is characterized in that,
Be used alone the A linking agent containing benzophenone or fluorescein modular construction, obtain a part of surface irregularity, internal crosslinking, and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon; Or it is all smooth to obtain two portions surface, a part is crosslinked, and snowman's shaped polymer microballoon that another part is not cross-linked; Or obtain rough, the internal crosslinking in part surface, and another part smooth surface, internal portion are crosslinked, neck has multiple pimple, benzophenone or fluorescein modular construction snowman's shaped polymer pockety microballoon; Or obtain rough, the internal crosslinking in part surface, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon; Or obtain sparse and outside crosslinked closely knit, the ganoid nuclear-structure polymer shell microballoon of internal crosslinking;
When being used together with C linking agent PGA or PMA by the A linking agent containing benzophenone or fluorescein modular construction, obtain surface irregularity, internal portion be cross-linked, be partly the class snowman shaped polymer microballoon of nucleocapsid structure; Or obtain a part of surface irregularity and homogeneous cross-link and another part surface is more smooth and have the dumb-bell shape polymer microballoon of nucleocapsid structure; Or obtain part surface in raspberry shape and homogeneous cross-link another part surface more smooth and there is the dumb-bell shape polymer microballoon of nucleocapsid structure; Or obtain smooth surface, there is the polymer microballoon of nucleocapsid structure;
When being used together with D linking agent OTD by the A linking agent containing benzophenone or fluorescein modular construction, obtain rough, the internal crosslinking in part surface, and another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon;
When being used together with difference in functionality monomer by the A linking agent containing benzophenone or fluorescein modular construction, increase the surface properties of particle in polymerization process, degree of swelling is different, the structure of resulting polymers microballoon, pattern and functional group present position are different; With containing when using together with epoxy based monomers, obtain a part of surface irregularity and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon; When using together with carboxyl group-containing monomer, obtain a part of surface irregularity and crosslinked and another part smooth surface and crosslinked dumb-bell shape polymer microballoon; Add in system together with amide containing class monomer, obtain a part of surface irregularity, be cross-linked, and another part smooth surface, not crosslinked snowman's shaped polymer microballoon; With containing adding together with pyridyl monomer, obtain part surface rough, crosslinked, another part smooth surface, not crosslinked snowman's shaped polymer microballoon; In time using together with alkynyl monomers, because this type of monomer not easily reacts, play solvent action, increase when particle is separated and be easily expressed into the new jut formed, finally obtain that a part of surface is slightly coarse, internal crosslinking, another part smooth surface, inner not crosslinked snowman's shaped polymer microballoon;
When being used alone the A linking agent containing oxyethyl group, obtain surface in flower-shaped, inner raspberry shaped polymer microballoon crosslinked in gradient through a step dispersion polymerization; Or obtain the polymer microballoon that surface is more coarse, have nucleocapsid structure; Or obtain surface irregularity, there is the polymer microballoon of nucleocapsid structure;
When being used alone B linking agent as TMPTA, obtain the polymer microballoon that particle surface is coarse, crosslinked;
When being used alone C linking agent, because double bond in linking agent is different with the reactive behavior of triple bond, obtain ganoid core-shell polymer microsphere; Or obtain shaggy core-shell polymer microsphere.
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| CN109265615B (en) * | 2018-08-28 | 2021-09-24 | 中科广化（重庆）新材料研究院有限公司 | Raspberry-shaped porous micro-nano polymer particles and preparation method and application thereof |
| CN111961206A (en) * | 2020-08-20 | 2020-11-20 | 四川大学 | Raspberry-shaped functionalized microspheres containing cage-like silsesquioxane and preparation method thereof |
| TWI775423B (en) * | 2021-05-06 | 2022-08-21 | 財團法人工業技術研究院 | Copolymer and composite material |
| CN114621485A (en) * | 2022-04-12 | 2022-06-14 | 滨州学院 | Preparation method of raspberry-shaped porous polyamide microspheres and prepared polyamide material |
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