CN103467640A - Preparation method of anisotropic particles with variable morphology - Google Patents
Preparation method of anisotropic particles with variable morphology Download PDFInfo
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- CN103467640A CN103467640A CN 201310412857 CN201310412857A CN103467640A CN 103467640 A CN103467640 A CN 103467640A CN 201310412857 CN201310412857 CN 201310412857 CN 201310412857 A CN201310412857 A CN 201310412857A CN 103467640 A CN103467640 A CN 103467640A
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Abstract
The invention relates to a preparation method of anisotropic particles with variable morphology. The method comprises the following steps: firstly utilizing silanol hydrophilic groups produced by hydrolysis of a silane coupling agent to prepare a series of seeds with different hydrophilicities, then enabling the seeds to be swollen by monomers incompatible to the hydrophilic groups, and controlling the phase separation degree according to different phase separation degrees of polymers, which are induced by different interfacial tensions and incompatible to the hydrophilic groups so as to obtain the composite particles with the variable morphology. The composite particles contain organic-inorganic-organic phase non-spherical composite particles, which have an important significance for developing novel multi-component materials. The composite particles prepared by the preparation method disclosed by the invention are amphipathic, and can be used as compatibilizers, emulsifiers and the like for modifying mixtures of the incompatible polymers. The synthesis process is simple and easy to operate, clean, environment-friendly and easy to realize large-scale production; furthermore, the preparation method has universality and is suitable for other polymer systems which are mutually incompatible.
Description
Technical field
The invention belongs to the synthetic of the asymmetric composite particles of anisotropy, specifically the preparation method of the variable anisotropy composite particles of a kind of form.
Technical background
The anisotropy composite particles makes a general reference shape, chemical constitution and/or performance is asymmetric, the particle of uneven distribution, also claims Janus particle or asymmetric particle.This particle can be by inorganic-inorganic, inorganic-organic, organic-organic constituent is compound forms, its preparation method is also varied, and the main preparation methods that is common in the anisotropy composite particles of bibliographical information has: microfluid method, template self-assembly method, dispersion copolymerization method, emulsion polymerization etc.This particle has shown tempting application prospect at aspects such as optical biosensor, electronical display, functional probe, self-assembly, tensio-active agents, thereby more and more receives people's concern.
At present, the form of the anisotropy composite particles that bibliographical information is more more single, Chemical Composition usually is generally one to two kind, and the preparation of complicated form particle and many Chemical Composition particle is still limited.Its preparation method adopts the method for seeded emulsion polymerization usually, in this method, crosslinked polymer seeds is at first by inconsistent monomer swell, and adding of linking agent makes polymer seeds more flexible, elastic force is induced the formation of new polymer phase, is separated and occurs in polymerization subsequently.GeWang etc. adopt the crosslinked polystyrene seed of 4-vinylpridine monomer swell, by the concentration of control swelling solvent and the type of linking agent, have made the anisotropic particles of puffed rice shape, water molecules shape, amino molecule shape and mushroom-shaped.But this kind of synthesis technique complexity is loaded down with trivial details, is difficult to accomplish scale production.It is silicon layer that Yang etc. have prepared shell, and the amphipathic ghost particle that inner casing is polydivinylbenezene is though the method has been introduced inorganic silicon layer on organic basis, still limited for the development of new multi-component material.
For adopting crosslinked polymer seeds swelling to prepare the method for anisotropy composite particles, highly cross-linked due to composite particles, will cause be applied to that the mobility that the course of processing exists is bad in the future, the poor shortcoming of levelling property during film forming.
In addition, for separating composite particles and adopting various organic solvents as swelling solvent, the inconvenience of operation and the drawbacks such as pollution of environment will be brought.
Summary of the invention
The present invention be directed to the problem of the poor fluidity that the synthesis technique of complexity prepared by current each diversity composite particles, the highly cross-linked course of processing caused exist, a kind of simple, environmental protection, the easy preparation method of processing are provided." cross-linked polymer macromolecular chain elastic shrinkage is induced the formation mechanism of novel polymer phase " of formation mechanism most of bibliographical informations different from the past of the anisotropy composite particles that the present invention is prepared, but by systematically changing amount with the silane coupling agent monomer of seed monomer copolymerization, (silane coupling agent is hydrolyzed into the silanol hydrophilic radical, in the process of copolymerization, hydrophilic radical can be distributed in the surface of seed, by regulating the amount of silane coupling agent, can change the amount of seed-coat hydrophilic radical), at first prepare a series of hydrophilic polymer seeds of different surfaces that have, then by inconsistent monomer swell with it, different interfacial tensions is that induce different from the degree be separated its incompatible polymers, control the degree be separated, thereby obtain the variable composite particles of form.And due to the adding and introduced silicon layer of silane coupling agent, thereby the composite particles obtained has many chemical compositions.
Technical scheme of the present invention is:
The preparation method of the anisotropic particles that a kind of form is variable, its material forms and comprises that step is as follows:
According to above proportioning, a certain amount of silane coupling agent is dissolved in appropriate deionized water, and join in reactor, stir after 30 minutes, add the seed monomer, whole process passes into nitrogen, reflux condensation mode, after system arrives 40～80 ℃, adds initiator, polymerization 5～8 hours, make seed emulsion;
Add deionized water in the seed emulsion obtained in step (a), after ultrasonic dispersion, open and stir, add the second monomer, at room temperature swelling half an hour, after the system temperature of reaction is upgraded to 40～80 ℃, add initiator, whole process passes into nitrogen, and carry out reflux condensation mode, polymerase 10 .5～8 hour; Emulsion to constant weight, makes aspheric composite particles through decompression, cryodrying.
Described step (a) or (b) in initiator be Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or Diisopropyl azodicarboxylate.
Described seed monomer styrene, tert-butyl acrylate, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate, n-BMA or vinyl cyanide.
Described silane coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane, tetraethoxysilane or APTES.
Described the second monomer is vinylbenzene, tert-butyl acrylate, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate, n-BMA or vinyl cyanide.
Beneficial effect of the present invention is:
The present invention is by changing the amount of silane coupling agent monomer, at first the seed emulsion particle that synthesizes a series of different hydrophilics, this seed had both had the polymer phase of seed monomer polymerization, top layer has again the composition of silicon, and then, by controlling feeding quantity and the polymerization time of the second monomer, can effectively control microscopic pattern and the size of composite particles.
The controlledly synthesis of nanometer or submicron-scale anisotropy composite particles is conducive to give full play to anisotropy and the self-assembling function of composite particles, show the advantage separately of two-component polymer in composite particles, the composite particles prepared as the present invention has amphipathic, they can realize absorption and ordered arrangement on the two-phase interface of oil phase and aqueous phase solution blend, play emulsifying effect, can be used as the compatilizer of incompatible polymer blend modification and emulsifying agent etc.
With the synthetic amphipathic nature block polymer of Transfer Radical Polymerization (ATRP), because its technique is difficult to accomplish scale production, for it, apply widely and brought difficulty.The inventive method adopts emulsifier-free emulsion polymerization, usings water as reaction medium, and the highly cross-linked seed of employing different from the past, various organic solvent, as the method for disperse phase, can be prepared noncrosslinking composite particles, are conducive to separate and further processing.Prepared non-spherical composite particles has amphipathic, and contained composition is organic and inorganic-organic phase, is different from single polymer phase common in document, and this has great significance for the development of new multi-component material.This synthesis technique is simple and easy to do, clean environment firendly, is easy to large-scale production, and has versatility, is applicable to other polymeric systems incompatible with each other.
The accompanying drawing explanation
The SEM photo that Fig. 1 is the prepared anisotropy composite particles of case study on implementation 1;
Fig. 2, Fig. 3 are respectively the TEM photo of anisotropy composite particles prepared by case study on implementation 2-3.
Embodiment
Case study on implementation 1:
According to above proportioning, a certain amount of silane coupling agent 3-(methacryloxypropyl) propyl trimethoxy silicane is dissolved in the 160.0g deionized water, and join in reactor, stir after 30 minutes, add 20.0g seed monomer styrene, whole process passes into nitrogen, reflux condensation mode, after system arrives 70 ℃, adds the 0.12g initiator potassium persulfate, polymerase 17 hour, make seed emulsion;
Get the seed emulsion that 11.5g step (a) obtains, add the 80.0g deionized water, after ultrasonic dispersion, open to stir, add the second monomer vinyl cyanide, at room temperature swelling half an hour, after being upgraded to 75 ℃, the system temperature of reaction adds the 0.024g initiator potassium persulfate, whole process passes into nitrogen, and carries out reflux condensation mode, polymerization 5 hours; Emulsion to constant weight, makes aspheric composite particles through decompression, cryodrying, and its electron scanning micrograph is shown in accompanying drawing 1.
By Fig. 1 SEM photo, can be found out, prepared composite particles presents aspheric form, further analyzes and learns that the major part of composite particles and microcephaly are respectively seed polystyrene phase and polyacrylonitrile phase, illustrate that this composite particles has anisotropy.
Case study on implementation 2-5
In case study on implementation 2-5, the amount that changes respectively silane coupling agent is 1.0g, 3.0g, and 4.0g, all the other steps of 8.0g are with case study on implementation 1.The transmission electron microscope photo of the composite particles that case study on implementation 2-3 is prepared is Fig. 2-3.
Analysis chart 2-3 can find out that the consumption when silane coupling agent is 1.0g, and during 3.0g, the projection of composite particles is becoming large gradually.
Case study on implementation 6-7
In case study on implementation 6-7, changing respectively silane coupling agent is tetraethoxysilane, APTES, and all the other steps are with case study on implementation 1.
Case study on implementation 8-9
In case study on implementation 8-9, changing respectively the seed monomer is tert-butyl acrylate, alpha-methyl styrene, and all the other steps are with case study on implementation 1.
Case study on implementation 10-11
In case study on implementation 10-11, changing respectively the second monomer is methyl methacrylate, ethyl propenoate, and all the other steps are with case study on implementation 1.
Hydrolysis by silane coupling agent produces the silanol hydrophilic radical, in the process with the seed monomer copolymerization, hydrophilic radical can be distributed in the surface of seed, by regulating the amount of silane coupling agent, can change the amount of seed-coat hydrophilic radical, thereby control the wetting ability of seed, then by inconsistent monomer swell with it, different interfacial tensions is that induce different from the degree be separated its incompatible polymers, controls the degree be separated, thereby obtains the variable composite particles of form.
It is the nucleocapsid structure that polymer phase, top layer are silicon layer that formed seed has core, the polymer phase that seeded emulsion polymerization newly adds in addition, thereby prepared contained composition, it is the non-spherical composite particles of organic and inorganic-organic phase, be different from single polymer phase common in document, this has great significance for the development of new multi-component material.
Composite particles prepared by the present invention has amphipathic, and they can realize absorption and ordered arrangement on the two-phase interface of oil phase and aqueous phase solution blend, play emulsifying effect, can be used as the compatilizer of incompatible polymer blend modification and emulsifying agent etc.This synthesis technique is simple and easy to do, clean environment firendly, is easy to large-scale production, and has versatility, is applicable to other polymeric systems incompatible with each other.
Claims (5)
1. the preparation method of the variable anisotropic particles of a form is characterized in that material composition and proportioning and step are as follows:
According to above proportioning, a certain amount of silane coupling agent is dissolved in appropriate deionized water, and join in reactor, stir after 30 minutes, add the seed monomer, whole process passes into nitrogen, reflux condensation mode, after system arrives 40～80 ℃, adds initiator, polymerization 5～8 hours, make seed emulsion;
Add deionized water in the seed emulsion obtained in step (a), after ultrasonic dispersion, open and stir, add the second monomer, at room temperature swelling half an hour, after the system temperature of reaction is upgraded to 40～80 ℃, add initiator, whole process passes into nitrogen, and carry out reflux condensation mode, polymerase 10 .5～8 hour; Emulsion to constant weight, makes aspheric composite particles through decompression, cryodrying.
2. the preparation method of the variable anisotropic particles of a kind of form as claimed in claim 1, it is characterized by described step (a) or (b) in initiator be Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or Diisopropyl azodicarboxylate.
3. the preparation method of the variable anisotropic particles of a kind of form as claimed in claim 1, is characterized by described seed monomer styrene, tert-butyl acrylate, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate, n-BMA or vinyl cyanide.
4. the preparation method of the variable anisotropic particles of a kind of form as claimed in claim 1, it is characterized by described silane coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane, tetraethoxysilane or APTES.
5. the preparation method of the variable anisotropic particles of a kind of form as claimed in claim 1, it is characterized by described the second monomer is vinylbenzene, tert-butyl acrylate, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate, n-BMA or vinyl cyanide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693907A (en) * | 2016-01-27 | 2016-06-22 | 上海交通大学 | Preparation method of Janus particle containing silicon dioxide with controllable particle size and asymmetrical degree |
| CN106519099A (en) * | 2016-11-04 | 2017-03-22 | 辽宁大学 | Method for preparing through-hole-structure polymer porous material from snowman-shaped Janus composite particles |
| CN112851869A (en) * | 2021-02-09 | 2021-05-28 | 辽宁大学 | Method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on seed polymerization method |
-
2013
- 2013-09-11 CN CN 201310412857 patent/CN103467640A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693907A (en) * | 2016-01-27 | 2016-06-22 | 上海交通大学 | Preparation method of Janus particle containing silicon dioxide with controllable particle size and asymmetrical degree |
| CN105693907B (en) * | 2016-01-27 | 2018-06-29 | 上海交通大学 | The preparation method of the silica containing Janus particles of grain size and asymmetric degree controllably |
| CN106519099A (en) * | 2016-11-04 | 2017-03-22 | 辽宁大学 | Method for preparing through-hole-structure polymer porous material from snowman-shaped Janus composite particles |
| CN112851869A (en) * | 2021-02-09 | 2021-05-28 | 辽宁大学 | Method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on seed polymerization method |
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