CN104592435B - A kind of preparation method of asymmetric polymer nanosphere - Google Patents
A kind of preparation method of asymmetric polymer nanosphere Download PDFInfo
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- CN104592435B CN104592435B CN201510078955.3A CN201510078955A CN104592435B CN 104592435 B CN104592435 B CN 104592435B CN 201510078955 A CN201510078955 A CN 201510078955A CN 104592435 B CN104592435 B CN 104592435B
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Abstract
A kind of preparation method of asymmetric polymer nanosphere, is related to polymer nanocomposite ball.Hydrophilic monomer, hydrophobic monomer, saturated hydrocarbons are added in solvent, leads to nitrogen, carries out polymerisation after heating, add initiator solution, continues logical nitrogen reaction, obtains monodispersed asymmetric polymer nanosphere.Prepared using soap-free emulsion one-step synthesis, there is the advantages of operation is simple, products therefrom abnormity microspherulite diameter size is homogeneous controllable.Due to not adding any emulsifying agent and stabilizer, products therefrom is pure, and subsequently preparing polymer photon crystal, to be not required to any processing i.e. usable.Resulting product, which has, post-processes the advantages of simple, pioneering strong.There is certain application prospect in field of medicaments such as insoluble drug release, pharmaceutical carriers.
Description
Technical field
The present invention relates to polymer nanocomposite ball, more particularly, to a kind of preparation method of asymmetric polymer nanosphere.
Background technology
In recent years, polymer asymmetry nanosphere is in dimension Anisotropy Photonic Crystals, biology sensor and drug release carrier
Etc. application prospect cause the extensive concerns of scientific circles.At present, the preparation method of polymer asymmetry nanosphere is main
There are three kinds, be respectively：Extension, template and the emulsion polymerization of regular bead.Wherein, the extension of regular bead can only obtain accordingly
Oval bead, application has certain limitation；Template preparation technology complicated and time consumption, nor preparing asymmetric nanometer
The effective ways of ball；Emulsion polymerization not only can be controlled accurately as one of effective ways for preparing polymer asymmetry nanosphere
Its particle diameter is made, and can effectively control the chemical and physical features of polymer asymmetry nanosphere, meanwhile, technique is relatively easy
Understand, there is certain application prospect.
At present, emulsion polymerization, which prepares the irregular nanosphere of polymer, certain development, such as Ian
(Langmuir 2007,23,8810-8814) such as D.Hosein and Chekesha M.Liddell is prepared by suspension polymerisation
Go out mushroom single dispersing PS polymer microballoons；Jin-Gyu Park (JACS 2010,132,5960-5961) etc. pass through two steps
Method seeded emulsion polymerization produces (PS-co-TMSPA) polymer of dumbbell shaped.
In document (Macromolecules 2011,44,2404-2409), Yu Huang et al. pass through emulsion polymerization system
It is standby gone out asymmetric polymer nanocomposite ball, but this method is by introducing crosslinked agent, using crosslinking agent to hydrophobic and hydrophilic list
The involving of body acts on polymer microballoon surface and forms different size, the projection of shape and depression, ultimately forms irregular
Polymer nanocomposite ball.This method is by the method for traditional introducing crosslinked agent, although obtained pattern is more traditional all the time
Regular bead is more novel, but product is insoluble not to be melted, and not only post processing is inconvenient, while also limit the application in its later stage.
The content of the invention
It is an object of the invention to provide a kind of preparation method of asymmetric polymer nanosphere.
The present invention's comprises the following steps that：
Hydrophilic monomer, hydrophobic monomer, saturated hydrocarbons are added in solvent, leads to nitrogen, carries out polymerisation after heating, add
Initiator solution, continue logical nitrogen reaction, obtain monodispersed asymmetric polymer nanosphere.
The solvent can use water；The temperature of the heating can be 65~85 DEG C, can be stirred during the polymerisation,
Mixing speed can be 200~600rpm；The time for continuing logical nitrogen reaction can be 24h.
The content of the hydrophilic monomer, hydrophobic monomer, saturated hydrocarbons, solvent and initiator solution by mass percentage is：Parent
Aqueous monomer and hydrophobic monomer are 1%~20%, and saturated hydrocarbons is 0.5%~10%, and initiator solution is hydrophilic monomer and hydrophobic list
The 0.1%~5% of body gross mass, remaining is solvent；The volume ratio of the hydrophilic monomer and hydrophobic monomer can be 1: (3~20)；
The hydrophilic monomer may be selected from GMA, hydroxyethyl methacrylate, acrylic acid, polypropylene
At least one of acid amides etc.；
The hydrophobic monomer can use styrene etc.；
The saturated hydrocarbons can use normal octane etc.；
The initiator solution can use potassium peroxydisulfate etc., and the mass percent concentration of initiator solution can be 0.2%~
2%.
Heretofore described monodispersed profiled polymer nanosphere is prepared using soap-free emulsion one-step synthesis, is had
The advantages of operation is simple, products therefrom abnormity microspherulite diameter size is homogeneous controllable.Due to do not add any emulsifying agent and
Stabilizer, products therefrom is pure, and subsequently preparing polymer photon crystal, to be not required to any processing i.e. usable.The soap-free emulsion of use
One-step polymerization method, raw material are hydrophilic and the two kinds of monomers and saturated hydrocarbons of oleophylic, and in the course of the polymerization process, hydrophilic segment is intended to water-soluble
Agent System forming shell, and lipophilic ingredient then forms the kernel of polymer microballoon to polymer spheres internal migration, while anti-
Should initial stage saturated hydrocarbons dissolved each other strongly with hydrophobic monomer and after the reaction both phases be separated from each other, along with mechanical agitation power, formed
Monodispersed profiled polymer nanosphere.Its particle size can change the concentration of hydrophilic and oleophilic amount of monomer as needed, and change is drawn
Hair agent is with measuring and change polymeric reaction temperature and mixing speed controls.
Saturated hydrocarbons is introduced in the course of the polymerization process, in initial reaction stage with hydrophobic monomer fusion reaction later stage and disconnected, companion
With mechanical agitation power, the controllable profiled polymer nanosphere of monodispersed particle size is formed.Product tool obtained by this method
There is the advantages of post processing simple (show as readily soluble easily melt), pioneering strong.Have one in field of medicaments such as insoluble drug release, pharmaceutical carriers
Fixed application prospect.
The present invention is different with preparing irregular nanosphere with crosslinking agent in the past, not only operates more simply, and gained
Product is linear nanosphere.Compared with the method for the build nanosphere obtained by adding crosslinking agent, the product obtained by this method
With post processing simple (show as readily soluble easily melt), it is pioneering strong the advantages of.Have in field of medicaments such as insoluble drug release, pharmaceutical carriers
Certain application prospect.The especially addition of saturated hydrocarbons so that monomer initial reaction stage dissolve each other strongly therewith and the later stage with
Be separated from each other.At the same time, reaction condition is maintained at certain temperature, saturated hydrocarbons is constantly volatilized during the course of the reaction, from
And prepare the irregular nanosphere different from conventional shape and structure.Crosslinking agent is not introduced into, is located after avoiding cross-linking type nanosphere
The difficulty of reason, make its application more wide.It polymerize to obtain the polymer of special-shaped core shell structure using soap-free emulsion one-step method
Microballoon, its operating process is simple and easy, and resulting polymer microballoon is pure without such as surfactant, buffer impurity, product
Only, particle size is controllable.Because prepared profiled polymer nanosphere is pure, its pharmaceutical carrier is extended with discharging field
Using.
Brief description of the drawings
Fig. 1 schemes for the SEM of the polymer nanocomposite ball obtained by embodiment 1.
Fig. 2 schemes for the SEM of the polymer nanocomposite ball obtained by embodiment 4.
Fig. 3 schemes for the SEM of the polymer nanocomposite ball obtained by embodiment 5.
Fig. 4 is the polymer asymmetry nanosphere obtained by embodiment 6.
Fig. 5 is the polymer asymmetry nanosphere obtained by embodiment 7.
Fig. 6 is the polymer asymmetry nanosphere obtained by embodiment 8.
Embodiment
Embodiment 1：
Hydrophilic monomer GMA 0.2mL, hydrophobic monomer styrene 2mL and saturated hydrocarbons 0.4mL are added
Enter to lead to 30~60min of nitrogen gas stirring in the three-necked bottle containing 30mL deionized waters and continuously lead to nitrogen, be warming up to 75 DEG C, then add
Dissolved with the aqueous solution of 0.04g potassium peroxydisulfate initiators.24h is reacted, obtains monodispersed styrene-divinylbenzene-methyl-prop
Olefin(e) acid ethylene oxidic ester (PS-PGMA) profiled polymer nanosphere emulsion.The SEM figures of profiled polymer nanosphere are as shown in Figure 1.
Embodiment 2~5：With the process conditions of embodiment 1, change saturated hydrocarbons addition respectively, synthesize the list of different-shape
Scattered styrene-t ethylene oxidic ester (PS-PGMA) profiled polymer nanosphere emulsion, the results are shown in Table 1.
Table 1
The SEM figures of polymer nanocomposite ball obtained by embodiment 4 are shown in Fig. 2, the polymer nanocomposite ball obtained by embodiment 5
SEM figures are shown in Fig. 3.
Embodiment 6~8：With the process conditions of embodiment 1, change monomeric species, synthesize the monodispersed benzene of different-shape
Ethylene-methyl methacrylate ethylene oxidic ester (PS-PGMA) profiled polymer nanosphere emulsion, the results are shown in Table 2.
Table 2
Polymer asymmetry nanosphere obtained by embodiment 6 is shown in Fig. 4, and the polymer asymmetry obtained by embodiment 7 is received
Rice ball is shown in Fig. 5, and the polymer asymmetry nanosphere obtained by embodiment 8 is shown in Fig. 6.
Emulsifier-free emulsion polymerization of the present invention adds saturated hydrocarbons compound, and it is strong with monomer in initial reaction stage
Dissolve each other and be separated from each other therewith in the later stage, ultimately form anisotropic structure.Due to no introducing crosslinked agent, product is not
Only maintain the adjustable advantage of stable homogeneous, while the solvable application melted the difficulty for solving post processing, expand product.
Claims (6)
1. a kind of preparation method of asymmetric polymer nanosphere, it is characterised in that it is comprised the following steps that：
Hydrophilic monomer, hydrophobic monomer, saturated hydrocarbons are added in solvent, leads to nitrogen, carries out polymerisation after heating, add initiation
Agent solution, continue logical nitrogen reaction, obtain monodispersed asymmetric polymer nanosphere；
The content of the hydrophilic monomer, hydrophobic monomer, saturated hydrocarbons, solvent and initiator solution by mass percentage is：Hydrophilic list
Body and hydrophobic monomer are 1%~20%, and saturated hydrocarbons is 0.5%~10%, and initiator solution is that hydrophilic monomer and hydrophobic monomer are total
The 0.1%~5% of quality, remaining is solvent；The volume ratio of the hydrophilic monomer and hydrophobic monomer is 1: (3~20)；
The mass percent concentration of the initiator solution is 0.2%~2%；
The temperature of the heating is 65~85 DEG C；
It is stirred during the polymerisation, mixing speed is 200~600rpm；It is described continue logical nitrogen reaction time be
24h。
2. a kind of preparation method of asymmetric polymer nanosphere as claimed in claim 1, it is characterised in that the solvent uses
Water.
A kind of 3. preparation method of asymmetric polymer nanosphere as claimed in claim 1, it is characterised in that the hydrophilic monomer
Selected from least one of GMA, hydroxyethyl methacrylate, acrylic acid, polyacrylamide.
A kind of 4. preparation method of asymmetric polymer nanosphere as claimed in claim 1, it is characterised in that the hydrophobic monomer
Using styrene.
5. a kind of preparation method of asymmetric polymer nanosphere as claimed in claim 1, it is characterised in that the saturated hydrocarbons is adopted
Use normal octane.
6. a kind of preparation method of asymmetric polymer nanosphere as claimed in claim 1, it is characterised in that the initiator is molten
Liquid uses potassium peroxydisulfate.
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