CN102653580A - Preparation method of Janus-structure composite emulsion particle - Google Patents
Preparation method of Janus-structure composite emulsion particle Download PDFInfo
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Abstract
The invention relates to a preparation method of a Janus-structure composite emulsion particle. The method comprises the following steps: adding deionized water into a PVDF seed emulsion, performing ultrasonic dispersion for 1 hour, pouring the dispersed emulsion into a reactor equipped with a reflux condensing tube, a stirring device, and a nitrogen introducing port, starting stirring and continuously introducing nitrogen, after 15 min, heating the reaction system, adding monomers, introducing cooling water into the reflux condensing tube; when the system is heated to a reaction temperature, adding an initiator, performing a polymerization reaction at a reaction temperature of 20-80 DEG C for 1-8 hours; drying the emulsion at a reduced pressure and a low temperature to obtain a constant weight so as to obtain the Janus-structure composite particle. Through the selection of PVDF seeds with different particle sizes, the seed monomer mass ratio and the polymerization time, the invention can effectively control the form and the size of the composite particle. The invention is widely applicable to various fields in polymer blending modification, such as compatilizers, self-cleaned coatings, and the like.
Description
Technical field:
The invention belongs to the synthetic of anisotropic asymmetric non-spherical composite gel particle; Specifically a kind of preparation method of Janus structure composite emulsion particle; This method is a seed with pvdf (PVDF) emulsion; Carry out seeded emulsion polymerization with its incompatible polymers monomer, obtain the preparation method of Janus structure composite emulsion particle.
Technical background:
" Janus " this term be used for describing have different chemical composition with (or) object or the object of character.The Janus composite particles can through inorganic-inorganic, inorganic-organic and organic-organic constituent is compound to be constituted; Its preparation method is also varied, and the Janus structured particles preparation method who is common in bibliographical information has: template, microfluid method, segmented copolymer derivatization method, dispersion copolymerization method and emulsion polymerization etc.In recent years, people have more and more keen interest to the research of Janus colloidal particle, and this interest comes from its potential widespread use field.For example, be used as building block, function surface promoting agent, functional probe and the electronic console etc. of optical biosensor, complicated superstructure material.
At present, the Janus particle that bibliographical information is maximum is mainly the composite particles that mixes of inorganic particulate and polymkeric substance or metal and polymkeric substance composition, and its synthesis technique complicacy is loaded down with trivial details, is difficult to form large-scale production.Synthetic report for the Janus structure composite emulsion particle that is made up of polymkeric substance and polymkeric substance is few; The preparation overwhelming majority of the non-spherical asymmetric polymer emulsion particle of finding bibliographical information originates from the mechanisms of phase separation due to the elastic shrinkage of crosslinked polystyrene seed macromolecular chain, thereby obtains to have the polymorphic structure composite particles of micron-scale.EL-Aasser etc. adopt the unsymmetrical structure particle of crosslinked PS (PS) seed through the swollen-state polymerization formation partial interpenetrating of styrene monomer, and its size range is at the 5-10 micron, and its shape has snowman, balanate and dumb-bell shape.Because the chemical ingredients and the crosslinked PS composition of parent of this asymmetric irregular particle bossing are basic identical, and incomplete isolating PS linear polymer is contained in inside.So be not proper Janus structured particles.And aforesaid method prepares the asymmetric gel particles of nanometer and submicron-scale with failing.[M.S.EL-Aasser?et?al，J.Polym.Sci.，Part?A：Polym.Chem.1990，28，629-651，653-667；David?A.Weitz?et?al，J?Am.Chem.Soc.，2006，128，14374-14377]。
Exist bossing for the non-spherical Janus particle of anisotropy that adopts the preparation of crosslinked swelling method and can not strictly distinguish, and highly cross-linked composite particles is applied in the future that the course of processing exists that flowability is bad, the shortcoming of leveling characteristics difference during film forming with parent.
In addition, for the core-shell type composite particles that coats the stratum nucleare polymkeric substance fully, its constructional feature is partly covered and has been influenced giving full play to of stratum nucleare polymer property.
Summary of the invention:
The objective of the invention is to be directed against synthesis technique complicacy, newborn polymer projection that exists in the current techniques and the deficiency that parent can not better be distinguished, there is mobile difference in high crosslinked Janus particle in processed and applied, the preparation method of a kind of crystalline polymer and the compound formation Janus emulsion particle of its incompatible polymer is provided." the formation mechanism of cross-linked polymer macromolecular chain elastic shrinkage " of formation mechanism most of bibliographical informations different from the past of the Janus particle that the present invention is prepared; But the crystallinity PVDF seed of indissoluble with its incompatible polymer monomer generation polymerization process in; Because of the high-crystallinity of PVDF seed makes monomer be difficult to spread swelling wherein; The residual emulsifiers of seed-coat grappling makes the nascent polyketide compound in the seed-coat nucleation then; Be separated with PVDF, eccentric growth, result successfully synthesize has anisotropic Janus structure composite particles.
Technical scheme of the present invention is:
A kind of preparation method of Janus structure composite emulsion particle is characterized in that this composite particles is to be made up of with the PVDF incompatible polymers with another kind of the PVDF composition, and has nanometer or submicron-scale and anisotropic non-globosity characteristic.
Material is formed and proportioning is:
The constituent mass umber
PVDF seed emulsion 2.5～25.0
Deionized water 47.5～70.0
Monomer 2.0～8.0
Initiator 0.006～0.12
Reactions step is following:
According to above proportioning; In the PVDF seed emulsion, add deionized water; Ultra-sonic dispersion 1 hour is equipped with the emulsion impouring after disperseing in the reactor drum of reflux condensing tube, whipping appts and nitrogen inlet, opens and stirs and feed continuously nitrogen; After 15 minutes system is heated up, add monomer simultaneously and in reflux condensing tube, feed water coolant; When the system of treating is warming up to temperature of reaction, add initiator again, under 20～80 ℃ temperature of reaction polyreaction 1-8 hour then; Emulsion to constant weight, promptly makes the composite particles with Janus structure through decompression, cryodrying then;
Described initiator is Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium sulfite anhy 96 or Diisopropyl azodicarboxylate;
Said monomer is meant vinylbenzene, p-chloromethyl styrene, tert-butyl acrylate, SY-Monomer G, Bing Xisuandingzhi, alpha-methyl styrene or vinyl cyanide.
The solid content of described PVDF seed emulsion is 10～17%, and particle diameter is 50～200nm.
Beneficial effect of the present invention is:
PVDF and copolymer material thereof have noticeable dielectric, piezoelectricity and ferroelectric properties, remarkable physics and chemical property, and excellent anti-soil self-cleaning function and performance such as anti-aging, its broad application comprises: (1) paint and coating; (2) electrical equipment and electronics; (3) application specific IC is in fields such as micropore filtering film, piezoelectric transducer, chemical capacitor, engine fan page or leaf and fuel cells.
The PVDF seed of the present invention through selecting different-grain diameter, seed monomer mass be polymerization time when, can effectively control the form and the size of composite particles.The controlledly synthesis of nanometer or submicron-scale Janus emulsion particle helps giving full play to the anisotropy and the self-assembly function of composite particles; Show the advantage separately of two-component polymer in the composite particles, can be widely used in the numerous areas such as compatilizer, self-cleaning coating in the polymer blending modification.
Make compatilizer with Transfer Radical Polymerization (ATRP) synthetic segmented copolymer, because of its difficult technique to accomplish scale production, for its widespread use has brought difficulty.The present invention needs harsh anhydrous and oxygen-free operational condition unlike the ATRP that kind; The seeded emulsion polymerization technology that is adopted is simple and direct; Be easy to large-scale production; Two phase behaviours of the synthetic Janus of institute emulsion particle help its absorption fully and ordered arrangement at polymer blend interface, and the composite particles structure shown in Fig. 5 (embodiment 5) has anisotropic asymmetric configuration.The black bulb of this Janus particle one end is PVDF, and the white bulb of the other end is PS.Therefore, this particle has the double properties of PS and PVDF simultaneously, and they can realize absorption and ordered arrangement on the two-phase interface of PVDF and PS blend, play compatibilization, for polymer blending modification provides a kind of new thought.In addition, the preparation method of this structure composite particles is applicable to other bi-component polymeric system incompatible with each other.
Description of drawings:
Fig. 1-Figure 12 is respectively the transmission electron microscope photo of the prepared Janus structure PVDF/PS composite particles of case study on implementation 1-12 of the present invention;
Figure 13-Figure 17 is respectively the transmission electron microscope photo of the prepared Janus structure PVDF/PS composite particles of case study on implementation 18-22 of the present invention;
Figure 18-Figure 21 is respectively the transmission electron microscope photo of the prepared Janus structure PVDF/PS composite particles of case study on implementation 25-28 of the present invention;
Figure 22-Figure 24 is respectively the transmission electron microscope photo of the prepared Janus structure composite particles of case study on implementation 29-31 of the present invention;
Above-mentioned Fig. 2, Fig. 5-Figure 10, Figure 15-Figure 17, the TEM photo that Figure 22-Figure 24 showed is taken through the electron energy filter technology.Black part is divided into the PVDF composition in the photo, and white portion is then represented PS composition or other component of polymer;
Fig. 1, Fig. 3, Fig. 4, Figure 11-Figure 14, the TEM photo that Figure 18-Figure 21 showed are the common TEM photos of not taking through the electron energy filter technology.
Embodiment:
The preparation of case study on implementation 1 Janus structure PVDF/PS composite particles
Constituent mass
PVDF emulsion 10.5g
Deionized water 60.0g
Vinylbenzene 6.0g
Initiator 0.042g
In the beaker of a 250ml, add solid content and be 10.4% median size at the PVDF of 180nm seed emulsion (industrial goods) 10.5g, add the 60.0g deionized water subsequently, ultra-sonic dispersion 1 hour.Emulsion impouring behind the ultra-sonic dispersion is equipped with in the four-hole reaction flask of prolong, magnetic agitation, nitrogen ingress pipe, opens and stir and feeding nitrogen, stir speed (S.S.) is set at 400 rev/mins.Begin after 15 minutes reaction system is heated up, in reaction flask, add 6.0g vinylbenzene simultaneously, open the water coolant of reflux condensing tube.When the system of treating was warming up to 75 ℃, disposable adding contained the aqueous solution 5ml of 0.042g Potassium Persulphate, insulation reaction 2 hours.From reaction flask, directly extract samples of latex immediately, with the form of transmission electron microscope observing PVDF/PS composite emulsion particle, its TEM photo is seen accompanying drawing 1.All the other emulsions are dried to constant weight through decompression (the about 0.095MPa of vacuum tightness), low temperature (40 ℃), make Janus structure composite particles product 4.7g.
Transmission electron microscope (TEM) is analyzed: at first synthetic composite particles emulsion is diluted to translucently with deionized water, used ultrasonic oscillation then 10 minutes, latex particle is better disperseed.Then, drawing an emulsion droplets with clean dropper is supporting on the copper mesh.After treating that emulsion is dried, through the morphological structure of Zeiss Libra 200FE type transmission electron microscope observing composite particles.
Can find out that from Fig. 1 TEM photo composite polymer particle presents non-sphere asymmetric " snowman's type " form (Janus structure).Particle one end wherein, the dark part of smaller size smaller is the PVDF seed; The particle the other end, the light grey part of comparatively large vol is the PS phase.The average largest dimensions of composite polymer particle is 282nm, than PVDF seed median size 180nm, has increased 102nm.
Case study on implementation 2-4
The polymerization reaction time of case study on implementation 2-4 was respectively 1 hour, 3 hours, 4 hours, and all the other implementation processes are with case study on implementation 1, and the form TEM photo of case study on implementation 2-4 prepared composite particle is seen accompanying drawing 2-4 respectively.The TEM photo that Fig. 2 shows is through the electron energy filter technology, takes in the characteristic that the maximum loss peak appears in a certain specific electron energy according to fluorine cpd.From Fig. 2 photo, we can clearly tell PVDF and PS two mutually, and the morphological structure of composite particles and upgrowth situation.Wherein black part is divided into the PVDF seed, and white portion then is the PS polymer projection of new growth.So, Fig. 1 photo that contrast does not adopt electron energy filter technology to take, we therefrom then are difficult for picking out PVDF and PS two mutually.
We are not difficult to find out by Fig. 2, and composite particles has non-sphere and asymmetric morphological structure.One on its two bulbs (or claiming protruding) are PVDF, and one is PS, and they have different physics and chemical property, thereby present anisotropy.This .Janus composite emulsion particle is dispersed in the co-mixing system of PS and PVDF composition, this particle is because have PS and PVDF double properties simultaneously, and they possibly realize ordered arrangement on two-phase interface, thereby have the self-assembly characteristic.
Case study on implementation 5
In case study on implementation 5, polymerization temperature is 65 ℃, and the add-on of styrene monomer is 8.0g, and the initiator potassium persulfate add-on is 0.08g, and all the other operation stepss are with case study on implementation 1.The TEM photo of case study on implementation 5 prepared composite particle shapes is seen accompanying drawing 5.
Case study on implementation 6-10
The polymerization reaction time of case study on implementation 6-10 was respectively 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, and all the other experimental implementation are with case study on implementation 5.The TEM photo of case study on implementation 6-10 prepared composite particle shape is seen accompanying drawing 6-10.
Case study on implementation 11-12
Polymeric reaction temperature in case study on implementation 11 and the case study on implementation 12 is respectively 70 ℃, 80 ℃, and polymerization time was respectively 6.5 hours, 3.5 hours, and all the other operation stepss are identical with case study on implementation 5.The TEM photo of case study on implementation 11-12 prepared composite particle shape is seen accompanying drawing 11-12.
Case study on implementation 13-17
The add-on of PVDF seed emulsion is respectively 2.5g, 5.0g, 15.0g, 20.0g, 25.0g among the case study on implementation 13-17, and all the other operations are identical with case study on implementation 1.
Case study on implementation 18
The add-on that changes monomer styrene in the case study on implementation 18 is 3.0g, and the initiator potassium persulfate add-on is 0.010g, and all the other are operated with case study on implementation 1.The TEM photo of the composite particles form of case study on implementation 18 preparations is seen accompanying drawing 13.
Case study on implementation 19
Adopting median size in the case study on implementation 19 is 120nm, and solid content is that 13.1% PVDF emulsion is made seed, and all the other operation stepss are with case study on implementation 1.The TEM photo of the composite particles form of case study on implementation 19 preparations is seen accompanying drawing 14.
Case study on implementation 20-22
Polymerization reaction time among the case study on implementation 20-22 was respectively 1 hour, 3 hours, 4 hours, and all the other implementation processes are with case study on implementation 18, and the TEM photo of case study on implementation 20-22 prepared composite particle shape is seen accompanying drawing 15-17 respectively.
Case study on implementation 23-24
Replace the Potassium Persulphate initiator in the case study on implementation 1 with ammonium persulphate, Diisopropyl azodicarboxylate initiator respectively among the case study on implementation 23-24, all the other operations are identical with case study on implementation 1.
Case study on implementation 25
The add-on that changes monomer styrene in the case study on implementation 25 is 2.0g, and the initiator potassium persulfate add-on is 0.012g, and all the other are operated with case study on implementation 1.The TEM photo of case study on implementation 25 prepared composite particle shapes is seen accompanying drawing 18.
Case study on implementation 26-28
Polymerization reaction time among the case study on implementation 26-28 was respectively 1 hour, 1.5 hours, 3 hours, and all the other implementation processes are with case study on implementation 25, and the TEM photo of case study on implementation 26-28 prepared composite particle shape is seen accompanying drawing 19-21 respectively.
Case study on implementation 29-33
Replace the styrene monomer in the case study on implementation 5 with p-chloromethyl styrene, tert-butyl acrylate, SY-Monomer G, Bing Xisuandingzhi or vinyl cyanide respectively among the case study on implementation 29-33, all the other are operated with case study on implementation 5.The TEM photo of case study on implementation 29-31 prepared composite particle shape is seen accompanying drawing 22-24.
Janus composite particles hydrolysis under alkaline condition of PVDF and the ROHM tert-butyl ester or PVDF and polyacrylonitrile formation is formed amphipathic Janus particle, and useful as surfactants can be self-assembled into the particle micella.If use as coating; Because the amphipathic and anisotropy of its structure, composite particles is different with adhesivity to the affinity of base material, realizes spontaneous ordered arrangement and the accumulation of Janus particle; Utilize the self-cleaning property of PVDF polymkeric substance, thereby obtain functional self-cleaning coating.
Case study on implementation 34
Adopt alpha-methyl styrene to replace the styrene monomer in the case study on implementation 1 in the case study on implementation 34; Initiator adopts oxidation-reducting system initiator Potassium Persulphate-sodium sulfite anhy 96, and the initiator add-on is 0.09g, and polymerization temperature is 20 ℃; Polymerization time is 8h, and all the other are operated with case study on implementation 1.
Case study on implementation 35
Adopting median size in the case study on implementation 35 is that 50nm, solid content are that 16.7% PVDF emulsion is made seed, and all the other operation stepss are with case study on implementation 1.
Can find out that from the TEM photo of above-mentioned case study on implementation composite particles has aspheric unsymmetrical structure and anisotropy.In polymerization process, seldom see the nascent polyketide compound and break away from the independent nucleating growth of PVDF seed, forming the homopolymer particle is so-called offspring.
Relatively case study on implementation 1, example 18, example 25 corresponding Fig. 1, Figure 13, Figure 18 TEM photos can be found out; Increase along with seed/monomer mass ratio; The size of composite particles reduces gradually; The nascent polyketide compound increases at the nucleation number of each PVDF seed-coat, the homogeneity variation of composite particles Janus form.Fig. 5 from case study on implementation 5-10-10 photo can find out obviously that along with the increase of polymerization time, the size of the Janus composite polymer particle of formation increases gradually, and newborn polymer volume increases gradually, and visual PVDF volume reduces gradually.Therefore, the present invention can pass through control seed monomer ratio and polymerization time, thereby effectively controls the form and the size of composite particles.
This patent synthetic Janus particle is formed by two linear polymer copolymerization, and the processing fluidity of composite particles is better than the non-spherical asymmetric particle of high-crosslinking-degree.Simultaneously, being compounded with of second polymeric constituent benefits the processing characteristics of improving the PVDF homopolymer, realizes that two have complementary advantages mutually.
Claims (4)
1. the preparation method of a Janus structure composite emulsion particle is characterized in that material composition and proportioning and step are following:
The constituent mass umber
PVDF seed emulsion 2.5～25.0
Deionized water 47.5～70.0
Monomer 2.0～8.0
Initiator 0.006～0.12
According to above proportioning; In the PVDF seed emulsion, add deionized water; Ultra-sonic dispersion 1 hour is equipped with the emulsion impouring after disperseing in the reactor drum of reflux condensing tube, whipping appts and nitrogen inlet, opens and stirs and feed continuously nitrogen; After 15 minutes system is heated up, add monomer simultaneously and in reflux condensing tube, feed water coolant; When the system of treating is warming up to temperature of reaction, add initiator again, under 20～80 ℃ temperature of reaction polyreaction 1-8 hour then; Emulsion to constant weight, promptly makes the composite particles with Janus structure through decompression, cryodrying then.
2. the preparation method of Janus structure composite emulsion particle as claimed in claim 1 is characterized in that described initiator is Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium sulfite anhy 96 or Diisopropyl azodicarboxylate;
3. the preparation method of Janus structure composite emulsion particle as claimed in claim 1 is characterized in that said monomer is meant vinylbenzene, p-chloromethyl styrene, tert-butyl acrylate, SY-Monomer G, Bing Xisuandingzhi, alpha-methyl styrene or vinyl cyanide.
4. the preparation method of Janus structure composite emulsion particle as claimed in claim 1, the solid content that it is characterized in that described PVDF seed emulsion is 10～17%, particle diameter is 50～200nm.
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| CN102432764A (en) * | 2011-10-09 | 2012-05-02 | 河北工业大学 | Method for preparing polyvinylidene fluoride (PVDF)-constructed composite particles with nuclear shell interpenetrating network structure |
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