CN103394305A - pH-responsive star-shaped polymer emulsifier and preparation method thereof - Google Patents
pH-responsive star-shaped polymer emulsifier and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a pH-responsive star-shaped polymer emulsifier and a preparation method thereof. The polymer emulsifier is prepared by forming a polymer linear arm with a degree of polymerization of 20-500 from monomers with certain water solubility through a reversible addition-fragmentation chain transfer polymerization (RAFT) method and then forming a core cross-linked star-shaped polymer from the polymer linear arm by cross-linking a heterogeneous polymerization cross-linking agent with spacing monomers, wherein a core is formed by cross-linking polymerization of the cross-linking agent and the spacing monomers, and the polymer linear arm is the arm. The preparation method of the core cross-linked star-shaped polymer, disclosed by the invention, is simple and easy to operate, the synthesis is mainly performed in an ethanol-water mixed solvent, the use of a toxic and organic solvent is avoided, the preparation method belongs to an environment-friendly preparation process, and the large-scale industrial production is easy to implement; and the core cross-linked star-shaped polymer emulsifier belongs to a high-efficient, non-toxic, low-irritant and intelligent novel emulsifier, a formed emulsion can be directly used as a terminal product, and more industrial application and greater application values can be further realized.
Description
Technical field
The present invention relates to a kind of macromolecule emulsifier and preparation method thereof, particularly star-like macromolecule emulsifier of a kind of pH response and preparation method thereof.
Background technology
Emulsifying agent (emulsifier) is to make two kinds of immiscible liquid form the material of stable emulsion.Emulsifying agent is to have amphiphatic surfactant in general, and hydrophilic radical is generally the group of polarity, as carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof, and also hydroxyl, amide groups, ethyoxyl etc.; And the hydrophobic group is generally long hydrocarbon chain.In addition, micron or the solid particle of Nano grade also can be used as emulsifying agent, and as clay particle etc., this type of emulsifying agent is called the Pickering emulsifying agent, and they must possess the suitable wetability of two-phase, and the emulsion of formation has higher stability usually.
Star-like macromolecule, referring to that the linear polymer chain (image be called " macromolecule arm ") more than three or three is connected to " starlike " polymer that forms on a common tie point by its high molecular end, is that branching is opened up in the benefit structure one of the simplest structure.The tie point that has in the star-like macromolecule of less macromolecule arm number is generally an organic compound, and the high molecular tie point of core couple stars type with crosslinked larger macromolecule arm number is undersized, a highly cross-linked polymer core.Wherein must be much smaller than the size of macromolecule arm as the size of the core of handing over, its macromolecule arm can be unfolded and come well in good solvent, make star-like macromolecule have good dissolubility.Star-like high molecular unique texture characteristics make they drug delivery, catalysis, coating, and the aspect such as rheology modifiers good application is arranged.And it is also rarely seen in report used as the emulsifying agent aspect.At present, the crosslinked star-like high molecular preparation of nearly all core prepares in homogeneous phase solution (particularly organic solution), has that preparation efficiency is low, the sample dispersion degree is high and the shortcoming such as environmental pollution.
Summary of the invention
One of purpose of the present invention is to provide the star-like macromolecule emulsifier of a kind of pH response.
Two of purpose of the present invention is to provide the preparation method of the star-like macromolecule emulsifier of this pH response.
The present invention considers the crosslinked star-like high molecular unique texture characteristics of core, be the flexibility of its macromolecule arm and conformation multiplicity, with and nano level size (10-50 nanometer), think that the crosslinked star-like macromolecule of core can come as emulsifying agent the interface of stabilize oil-water.On the interface of oil-water, the crosslinked star-like high molecular flexible arm of core can make it adopt preferred conformation and two kinds of liquid effects, and the size of its Nano grade can make it have higher energy of adsorption, strengthens its existence on interface.
The present invention adopts reversible addition-fracture chain transfer polymerization (RAFT) method, by two, goes on foot and prepares the crosslinked star-like macromolecule of core, and the first step is the preparation of macromolecule arm; Second step is the crosslinked star-like high molecular preparation of core.The macromolecule arm is, by the RAFT method, some are had certain water miscible monomer, as
N,N-DMAA (DMA), methoxypolyethylene glycol methacrylate (PPEGMA), 2-(dimethylamino) EMA (DMAEMA) etc. come polymerization to form the polyamino polymer arm; Can also be by the RAFT method to two or more monomer, carry out copolymerization as 2-methoxy acrylate and methoxypolyethylene glycol acrylate and form the macromolecule arm of copolymerization.After forming the macromolecule arm, then by the crosslinked crosslinked star-like macromolecule of core that forms of the heteropolymerization in water, in this step, the spacer monomers that can select is
N-N-isopropylacrylamide, n-butyl acrylate, n-BMA, styrene etc., available crosslinking agent is
N,
N'-methylene-bisacrylamide, glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, HDDMA, three (ethylene glycol) dimethylacrylate etc.
According to above reaction mechanism, following reaction scheme is adopted in this experiment:
The star-like macromolecule emulsifier of a kind of pH response, it is characterized in that this macromolecule emulsifier is to have certain water miscible monomer by reversible addition-fracture chain transfer polymerization RAFT method, form the degree of polymerization at 20～500 Linear Polymer arm, then this Linear Polymer arm is by heteropolymerization crosslinking agent and the crosslinked star-like macromolecule of the crosslinked core that forms of spacer monomers, wherein crosslinking agent and spacer monomers cross-linked polymeric form core, and the Linear Polymer arm is arm; Described certain water miscible monomer is: acrylic acid class monomer or acrylamide monomers; Described spacer monomers is:
N-N-isopropylacrylamide, n-butyl acrylate, n-BMA or styrene; Described crosslinking agent is:
N,
N'-methylene-bisacrylamide, glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, HDDMA or three (ethylene glycol) dimethylacrylate; Wherein the mol ratio of Linear Polymer arm, spacer monomers and crosslinking agent is 1:10:5.
the acrylic acid class monomer of the above is: the methyl-prop diluted acid, acrylic acid, 2-(dimethylamino) EMA, 2-(lignocaine) EMA, 2-(dipropyl is amino) EMA, 2-(diisopropylaminoethyl) EMA, 2-(dibutylamino) EMA, 2-(dimethylamino) ethyl acrylate, 2-(lignocaine) ethyl acrylate, 2-(dipropyl is amino) ethyl acrylate, 2-(diisopropylaminoethyl) ethyl acrylate, 2-(dibutylamino) ethyl acrylate, 2-(tert-butyl group is amino) EMA or 2-(tert-butyl group is amino) ethyl acrylate.
Above-mentioned acrylamide monomers is:
N-[(3-(dimethylamino) propyl group] Methacrylamide,
N-[(3-(lignocaine) propyl group] Methacrylamide,
N-[(2-(dimethylamino) ethyl] Methacrylamide,
N-[(2-(lignocaine) ethyl] Methacrylamide,
N-[(2-(dipropyl is amino) ethyl] Methacrylamide,
N-[(2-(diisopropylaminoethyl) ethyl] Methacrylamide,
N-[(2-(dibutylamino) ethyl] Methacrylamide,
N-[(3-(dimethylamino) propyl group] acrylamide,
N-[(3-(lignocaine) propyl group] acrylamide,
N-[(2-(dimethylamino) ethyl] acrylamide,
N-[(2-(lignocaine) ethyl] acrylamide,
N-[(2-(dipropyl is amino) ethyl] acrylamide,
N-[(2-(diisopropylaminoethyl) ethyl] acrylamide or
N-[(2-(dibutylamino) ethyl] acrylamide.
A kind of preparation method who prepares the above-mentioned star-like macromolecule emulsifier of pH response is characterized in that the concrete steps of the method are:
A. with chain-transferring agent 2-cyanopropyl ethyl three sulfo-s, have certain water miscible monomer monomer, the oil-soluble AIBN of initator according to 1:(20～500): the mol ratio of (0.01～1.0) joins in solvent, under inert atmosphere, 50 ℃～80 ℃ reactions 0.5～20 hour, after polymerization finishes, polymer is purified, obtain star-like Linear Polymer arm;
B. with the star-like Linear Polymer arm for preparing in steps A, crosslinking agent, the water miscible V50 of initator according to 1:(3～30): the molar ratio of (0.01～1.0) joins water and ethanol by (20～60): in the mixed liquor that the volume ratio of (80～40) is mixed with, and to control solid content be 1～50 wt%; Under inert atmosphere, heating is 3 hours under 70 ℃, can obtain preparing the crosslinked star-like macromolecule of core, and centrifugal purification, obtain the pure star-like macromolecule emulsifier of pH response.
The inventive method uses spacer monomers can reduce the stress that is produced by crosslinking agent, thereby generates more flexible core, makes arm more easily be assembled into star-like macromolecule; In addition, spacer monomers can also be used to the hydrophobicity of growth regulation chain, strengthens the driving force of synthetic star-like thing.
Experiment showed, that the crosslinked star-like macromolecule of pH response core of the present invention can (can hang down and reach 0.02 wt%) the stable emulsion of formation under very low emulsifier concentration.At 0.3 wt% when above, the oil phase volume fraction of emulsification can, up to more than 85%, be the very efficient emulsifying agent of a class when the crosslinked star-like high molecular concentration of core.Higher than 75% the time, emulsion is had mobility hardly when the oil phase volume fraction, becomes the state of gel, image be called HIPE.HIPE can be used for preparing porous material, and its application relates to building, the energy, medical treatment, Industrial Catalysis, environment various aspects.Consider high efficiency and the high-temperature stability of the crosslinked star-like macromolecule of this core as emulsifying agent, we, as masterplate, have synthesized the material of similar porous aquagel with the HIPE of its formation, and it has potential application at medical domain.Wherein, the crosslinked star-like macromolecule of the core in the present invention has response to pH, not only can form stable HIPE in very wide pH scope (2～12), and can, as required by regulating pH to strong basicity 12.77 left and right, realize simply and rapidly breakdown of emulsion.The sample of breakdown of emulsion can carry out again emulsification by recalling to pH, and this character has very important application at aspects such as oil, chemical industry, biologies.
Content is higher, high-quality star-like macromolecule as the heteropolymerization method of dispersion liquid efficiently prepares at the mixed liquor take water and ethanol for the inventive method, has not only improved preparation efficiency, has reduced cost, has also alleviated environmental pollution.Its conversion ratio can reach more than 90%, with ultracentrifugation pipe (MW=30000) the 6000 centrifugal purifications of rpm for several times, can obtain pure star-like macromolecule.This experimental procedure is simple, and is easy to operate, and those skilled in the art can well realize.
Description of drawings
Fig. 1 is the star-like high molecular structural representation of pH response.
Fig. 2 is the nuclear-magnetism figure of linear arms corresponding to the star-like macromolecule of pH response.
Fig. 3 is before and after the star-like macromolecule of pH response is purified and the GPC figure of corresponding linear arms.
Fig. 4 is that concentration is that the star-like macromolecule of pH response of 0.5 wt% is 25
oC, and DLS figure during pH=7.98.
Fig. 5, for when the star-like macromolecule PDMAEMA of pH response concentration, being 1.0 wt%, increases the emulsion photo of its formation with oil phase dodecane volume fraction.
Fig. 6 is for when the oil phase volume fraction, being 80%, when the star-like macromolecule PDMAEMA of pH response concentration is respectively 0.3 wt%(A), 0.5 wt%(B), 1.0 wt%(C) time the burnt microphoto of copolymerization, wherein the oil phase dodecane is dyeed by Nile red, scale is 50 μ m.
Fig. 7 is that the star-like macromolecule PDMAEMA of pH response concentration is 0.5 wt%, when the dodecane volume fraction is 80%, can form the pH scope of stablizing HIPE.
Fig. 8 is that the star-like macromolecule PDMAEMA of pH response concentration is 0.5 wt%, when the oil phase volume fraction is 80%, and 4.24 (A) when different pH value; 7.89 (B); 11.40 the burnt photo of the copolymerization in the time of (C).
Fig. 9 is that the star-like macromolecule PDMAEMA of pH response concentration is 0.5 wt% and pH=11.40, when the oil phase volume fraction is 80%, and its elastic modulus G ' and loss modulus G " with the variation of shear stress strain, fixed shear frequency f=1 HZ (E) wherein; Its elastic modulus G ' and loss modulus G " with the variation of shearing frequency f, fixed shear power strain=1% (F) wherein.
Figure 10 is that the star-like macromolecule PDMAEMA of pH response concentration is 0.5 wt%, when the oil phase volume fraction is 80%, makes the photo of its breakdown of emulsion by regulating pH.Wherein A adds 75 μ L deionized waters, and B has added 75 μ L 6 mol/L NaOH solution, and C has added 75 μ L 6 mol/L NaCl solution.
Figure 11 is the sample that has just prepared for the porous hydrophilic material of preparation, a figure, and b is the appearance after the sample vacuum drying.
The burnt microphoto of the copolymerization of the HIPE that the left figure of Figure 12 forms while being the porous mass for preparing, right figure is the stereoscan photograph of many skies property material.
The specific embodiment
Embodiment one:
One, synthetic high polymer linear arms PDMAEMA
75:
With little strand transfer agent CTA (203.7 mg, 0.99 mmol), monomer DMAEMA (15.60 g, 99.2 mmol), internal reference 1,3,5-trioxane (, by surveying nuclear-magnetism, being used for calculating monomer conversion) (893.7 mg, 9.9 mmol), be dissolved in 31.2 mL DMFs (DMF) room temperature N
2Put into 70 ℃ of oil bath pans after bubbling deoxygenation 40 min, to the AIBN (16.3 mg, 0.1 mmol) that adds after constant temperature after deoxygenation, quencher in frozen water after reaction 24 h.Product is precipitated centrifugation in ether.After centrifugation was complete, the removal supernatant, collected lower sediment, dissolves with THF, then use ether sedimentation, repeats THF-ether process three times,, with the vacuum drying of final gained precipitation, obtains finally 11.2 g yellow solids, and productive rate is 72%, and its structural formula is:
Through nuclear-magnetism (Bruker AV 500 MHz spectrometer) test, solvent is heavy water, and the conversion ratio that calculates monomer reaction is 75%.。With gel permeation chromatograph (Waters Alliance e2695 GPC system) test molecule amount and dispersiveness, wherein concrete detecting information is, Waters styragel HR3 molecular weight ranges 5.0 * 10
2-3.0 * 10
4, HR4 molecular weight ranges 5.0 * 10
3-6.0 * 10
5, HR5 molecular weight ranges 5.0 * 10
4-4.0 * 10
6DMF is mobile phase (LiBr that comprises 1mg/mL), and flow velocity is 0.8 mL/min, column temperature 65
oC, 2414 scattering measuring actuator temperatures are 45
oC, analysis software are Empower 2, and polymetylmethacrylate is standard specimen, molecular weight ranges 2.4 * 10
2-1.0 * 10
6The GPC result records Mn=12.9 KDa, Mw/Mn=1.24; Calculate Mn=12.0 KDa through nuclear-magnetism.
Two,Synthetic star-like macromolecule PDMAEMA
75-15
With linear arms (10.03 g, 840 mmol), crosslinking agent 1,6-EDIA HDDA (2.84 g, 12.53 mmol), volume ratio is that water and alcohol mixed solvent 100 mL of 1:1 join in reaction bulb, in ice-water bath, with nitrogen bubble deoxygenation 40 min.Initator is V50(2,2 '-azo (2-methyl-propyl amidine)), according to mol ratio linear arms: V50=1: 0.2 reaction, initator be deoxygenation 15 min under same condition simultaneously.Again reaction vessel is put into the preheated in advance oil bath stirring reaction of 70 ℃, after temperature stabilization, added (347 of deoxygenation
μL, 45.3 mg, 0.17 mmol) storing solution, after isothermal reaction 3 h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000 rpm rotating centrifugals are purified for several times, by surveying GPC until linear arms is removed fully.Structural formula is as follows:
GPC records Mn=96.6 kDa, Mw/Mn=1.10.
Embodiment two:
One, synthetic high polymer linear arms PDMAEMA
93:
With little strand transfer agent CTA (165.2 mg, 0.8 mmol), monomer DMAEMA (12.65 g, 80.4 mmol), internal reference 1,3,5-trioxane (, by surveying nuclear-magnetism, being used for calculating monomer conversion) (800.1 mg, 8.2 mmol), be dissolved in 25.62 mL DMFs (DMF) room temperature N
2Put into 70 ℃ of oil bath pans after bubbling deoxygenation 40 min, to the AIBN (13.2 mg, 0.08 mmol) that adds after constant temperature after deoxygenation, quencher in frozen water after reaction 30 h.Product is precipitated centrifugation in ether.After centrifugation was complete, the removal supernatant, collected lower sediment, dissolves with THF, then use ether sedimentation, repeats THF-ether process three times,, with the vacuum drying of final gained precipitation, obtains finally 10.2 g yellow solids, and productive rate is 80%, and its structural formula is:
Through nuclear-magnetism (Bruker AV 500 MHz spectrometer) test, solvent is heavy water, and the conversion ratio that calculates monomer reaction is 93%.。With gel permeation chromatograph (Waters Alliance e2695 GPC system) test molecule amount and dispersiveness, wherein concrete detecting information is, Waters styragel HR3 molecular weight ranges 5.0 * 10
2-3.0 * 10
4, HR4 molecular weight ranges 5.0 * 10
3-6.0 * 10
5, HR5 molecular weight ranges 5.0 * 10
4-4.0 * 10
6DMF is mobile phase (LiBr that comprises 1mg/mL), and flow velocity is 0.8 mL/min, column temperature 65
oC, 2414 scattering measuring actuator temperatures are 45
oC, analysis software are Empower 2, and polymetylmethacrylate is standard specimen, molecular weight ranges 2.4 * 10
2-1.0 * 10
6The GPC result records Mn=14.9 KDa, Mw/Mn=1.14; Calculate Mn=14.7 KDa through nuclear-magnetism.
Two,Synthetic star-like macromolecule PDMAEMA
93-15
With linear arms (405.0 mg, 0.03 mmol), crosslinking agent 1,6-EDIA HDDA (93 mg, 0.41 mmol), volume ratio is that water and alcohol mixed solvent 4 mL of 1:1 join in reaction bulb, in ice-water bath, with nitrogen bubble deoxygenation 40 min.Initator is V50(2,2 '-azo (2-methyl-propyl amidine)), according to mol ratio linear arms: V50=1: 0.2 reaction, initator be deoxygenation 15 min under same condition simultaneously.Again reaction vessel is put into the preheated in advance oil bath stirring reaction of 70 ℃, after temperature stabilization, added (50 of deoxygenation
μL, 1.5 mg, 0.005 mmol) storing solution, after isothermal reaction 3 h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000 rpm rotating centrifugals are purified for several times, by surveying GPC until linear arms is removed fully.Structural formula is as follows:
GPC records Mn=98.7 kDa, Mw/Mn=1.21.
Three, synthetic star-like macromolecule PDMAEMA
93-20
With linear arms (405 mg, 0.03 mmol), crosslinking agent 1,6-EDIA HDDA (124 mg, 0.55 mmol), volume ratio is that water and alcohol mixed solvent 100 mL of 1:1 join in reaction bulb, in ice-water bath, with nitrogen bubble deoxygenation 40 min.Initator is V50(2,2 '-azo (2-methyl-propyl amidine)), according to mol ratio linear arms: V50=1: 0.2 reaction, initator be deoxygenation 15 min under same condition simultaneously.Again reaction vessel is put into the preheated in advance oil bath stirring reaction of 70 ℃, after temperature stabilization, added (50 μ L, 1.5 mg, 0.0055 mmol) storing solution of deoxygenation, after isothermal reaction 3 h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000 rpm rotating centrifugals are purified for several times, by surveying GPC until linear arms is removed fully.Structural formula is as follows:
GPC records Mn=101.6 kDa, Mw/Mn=1.25.
Embodiment three:
One, synthetic high polymer linear arms PDMAEMA
60:
With little strand transfer agent CTA (236.1 mg, 0.99 mmol), monomer DMAEMA (8.454 g, 99.2 mmol), internal reference 1,3,5-trioxane (, by surveying nuclear-magnetism, being used for calculating monomer conversion) (392 mg, 9.9 mmol), be dissolved in 16.9 mL DMFs (DMF) room temperature N
2Put into 70 ℃ of oil bath pans after bubbling deoxygenation 40 min, to the AIBN (14.7 mg, 99.2 mmol) that adds after constant temperature after deoxygenation, quencher in frozen water after reaction 20 h.Product is precipitated centrifugation in ether.After centrifugation was complete, the removal supernatant, collected lower sediment, dissolves with THF, then use ether sedimentation, repeats THF-ether process three times,, with the vacuum drying of final gained precipitation, obtains finally 3.8 g yellow solids, and productive rate is 75%, and its structural formula is:
Through nuclear-magnetism (Bruker AV 500 MHz spectrometer) test, solvent is heavy water, and the conversion ratio that calculates monomer reaction is 75%.。With gel permeation chromatograph (Waters Alliance e2695 GPC system) test molecule amount and dispersiveness, wherein concrete detecting information is, Waters styragel HR3 molecular weight ranges 5.0 * 10
2-3.0 * 10
4, HR4 molecular weight ranges 5.0 * 10
3-6.0 * 10
5, HR5 molecular weight ranges 5.0 * 10
4-4.0 * 10
6DMF is mobile phase (LiBr that comprises 1mg/mL), and flow velocity is 0.8 mL/min, column temperature 65
oC, 2414 scattering measuring actuator temperatures are 45
oC, analysis software are Empower 2, and polymetylmethacrylate is standard specimen, molecular weight ranges 2.4 * 10
2-1.0 * 10
6The GPC result records Mn=95.2 KDa, Mw/Mn=1.11; Calculate Mn=94.0 KDa through nuclear-magnetism.
Two,Synthetic star-like macromolecule PDMAEMA
60-15
With linear arms (0.4 g, 0.04 mmol), crosslinking agent 1,6-EDIA HDDA (144.2 mg, 0.64 mmol), volume ratio is that water and alcohol mixed solvent 100 mL of 1:1 join in reaction bulb, in ice-water bath, with nitrogen bubble deoxygenation 40 min.Initator is V50(2,2 '-azo (2-methyl-propyl amidine)), according to mol ratio linear arms: V50=1: 0.2 reaction, initator be deoxygenation 15 min under same condition simultaneously.Again reaction vessel is put into the preheated in advance oil bath stirring reaction of 70 ℃, after temperature stabilization, added (50 of deoxygenation
μL, 2.3 mg, 0.0085 mmol) storing solution, after isothermal reaction 3 h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000 rpm rotating centrifugals are purified for several times, by surveying GPC until linear arms is removed fully.Structural formula such as figure below:
GPC records Mn=93.3 kDa, Mw/Mn=1.10.
Three,Synthetic star-like macromolecule PDMAEMA
60-20
With linear arms (0.4 g, 0.04 mmol), crosslinking agent 1,6-EDIA HDDA (192.3 mg, 0.85 mmol), volume ratio is that water and alcohol mixed solvent 100 mL of 1:1 join in reaction bulb, in ice-water bath, with nitrogen bubble deoxygenation 40 min.Initator is V50(2,2 '-azo (2-methyl-propyl amidine)), according to mol ratio linear arms: V50=1: 0.2 reaction, initator be deoxygenation 15 min under same condition simultaneously.Again reaction vessel is put into the preheated in advance oil bath stirring reaction of 70 ℃, after temperature stabilization, added (50 of deoxygenation
μL, 2.3 mg, 0.0085 mmol) storing solution, after isothermal reaction 3 h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000 rpm rotating centrifugals are purified for several times, by surveying GPC until linear arms is removed fully.Structural formula is as follows:
GPC records Mn=95.6 kDa, Mw/Mn=1.20.
The star-like high molecular intelligent discussion scheme of response: because the tertiary amine groups of this star-like macromolecule end, as Fig. 1, make it have the pH response, namely as pH〉9 the time, star-like macromolecule mainly is in the unionized state, and with pH, increases, hydrophobicity also strengthens, as pH〉12 the time, become water insoluble and separate out, so can make its complete breakdown of emulsion to strong basicity 12.77 left and right by regulating pH.
Research method:
1. the impact of pH on the 0.5 star-like high molecular particle diameter of wt% PDMAEMA and Zeta potential, as table 8.
2. when the oil phase volume fraction is 80%, can form the pH scope of stablizing HIPE, Fig. 7 shows, emulsifying agent PDMAEMA in very wide pH scope (2～12) but all the emulsification dodecane becomes HIPE, illustrate that it all has very efficient emulsification function in very wide pH scope.
3. breakdown of emulsion condition, Figure 10 explanation, the emulsion that this emulsifying agent forms can be passed through again to regulate pH to 12.77 left and right and complete breakdown of emulsion, the breakdown of emulsion process rapidly and efficiently, and when recalling to the water pH of complete breakdown of emulsion, star-like macromolecule dissolution, and emulsification again, the invertibity of this emulsification has very important practical application.、
The application of the HIPE of the star-like macromolecule emulsion of pH response:
Conceptual design: when the oil phase volume fraction surpassed 80%, the emulsion of formation did not have mobility, is gel, i.e. HIPE.Before emulsification, add monomer and the crosslinking agent of solubility in continuous phase water, then be emulsified into HIPE.At a certain temperature (70
oC), continuous aqueous phase polymerization reaction take place, form hydrophilic skeleton, after the oil phase of the inside is extracted, can form many hollow structures, namely have the hydroaropic substance of loose structure, as the porous hydrophilic material of Figure 11 for preparation, a figure is the sample that has just prepared, and b is the appearance after the sample vacuum drying.
Concrete grammar: get 0.5 mL 1 wt% PDMAEMA emulsifying agent in 10 mL centrifuge tubes, and add inwards successively monomer N, N-DMAA DMA (0.28 g, 2.8 mmol), crosslinking agent N, N methylene-bisacrylamide BIS (0.04g, 0.26 mmol), stir.Draw a certain amount of V50 (2.3 mg, 8.5 μ mol) and join in centrifuge tube ice-water bath bubbling 5 minutes.Draw 2.1 mL dodecanes and be placed in centrifuge tube,, with 25000 rpm emulsification 2 minutes, form and stablize HIPE, sealing orifice,, the above bubbling deoxygenation of emulsion face 3 minutes, then be placed in 70
oHeat in the C oil bath, react and stopped reaction in 2.5 hours.Then product is taken out, be placed in benzinum and soaked 2 days, to displace oil phase wherein, then vacuum drying, can obtain the hydrophilic blocks of solid of porous.
We characterize synthetic porous material: 1. with Nile red, dodecane is dyeed, after being emulsified into HIPE, with its emulsion droplets size of confocal microscopy, left figure as Figure 12, about 0.900～10.311 μ m, emulsion droplets distribution of sizes scope is narrower greatly, and is very tight.2. the HIPE that will synthesize carries out water imbibition and porosity test, and its water absorption rate just can reach 15% in the time of 15 minutes, and porosity is 89.8%.3. then freeze drying after the porous material after vacuum drying fully being absorbed water, with its hole shape looks of scanning electron microscopic observation, as the right figure of Figure 12, its hole dimension 1.35 μ m～8.743 μ m, average wall thickness 0.956 μ m.The size of its hole dimension and emulsion droplets is very close, has illustrated that the HIPE of this stabilizing polymer is experiencing 70
oAfter C high temperature 2.5 hours, emulsion droplets does not have coalescence clearly, there is no breakdown of emulsion.This has illustrated that also our macromolecule is a kind of very efficient emulsifying agent, and has high-temperature stability.
Claims (4)
1. star-like macromolecule emulsifier of pH response, it is characterized in that this macromolecule emulsifier is to have certain water miscible monomer by reversible addition-fracture chain transfer polymerization RAFT method, form the degree of polymerization at 20～500 Linear Polymer arm, then this Linear Polymer arm is by heteropolymerization crosslinking agent and the crosslinked star-like macromolecule of the crosslinked core that forms of spacer monomers, wherein crosslinking agent and spacer monomers cross-linked polymeric form core, and the Linear Polymer arm is arm; Described certain water miscible monomer is: acrylic acid class monomer or acrylamide monomers; Described spacer monomers is:
N-N-isopropylacrylamide, n-butyl acrylate, n-BMA or styrene; Described crosslinking agent is:
N,
N'-methylene-bisacrylamide, glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, HDDMA or three (ethylene glycol) dimethylacrylate; Wherein the mol ratio of Linear Polymer arm, spacer monomers and crosslinking agent is 1:10:5.
2. the star-like macromolecule emulsifier of pH response according to claim 1, it is characterized in that described acrylic acid class monomer is: the methyl-prop diluted acid, acrylic acid, 2-(dimethylamino) EMA, 2-(lignocaine) EMA, 2-(dipropyl is amino) EMA, 2-(diisopropylaminoethyl) EMA, 2-(dibutylamino) EMA, 2-(dimethylamino) ethyl acrylate, 2-(lignocaine) ethyl acrylate, 2-(dipropyl is amino) ethyl acrylate, 2-(diisopropylaminoethyl) ethyl acrylate, 2-(dibutylamino) ethyl acrylate, 2-(tert-butyl group is amino) EMA or 2-(tert-butyl group is amino) ethyl acrylate.
3. the star-like macromolecule emulsifier of pH response according to claim 1 is characterized in that described acrylamide monomers is:
N-[(3-(dimethylamino) propyl group] Methacrylamide,
N-[(3-(lignocaine) propyl group] Methacrylamide,
N-[(2-(dimethylamino) ethyl] Methacrylamide,
N-[(2-(lignocaine) ethyl] Methacrylamide,
N-[(2-(dipropyl is amino) ethyl] Methacrylamide,
N-[(2-(diisopropylaminoethyl) ethyl] Methacrylamide,
N-[(2-(dibutylamino) ethyl] Methacrylamide,
N-[(3-(dimethylamino) propyl group] acrylamide,
N-[(3-(lignocaine) propyl group] acrylamide,
N-[(2-(dimethylamino) ethyl] acrylamide,
N-[(2-(lignocaine) ethyl] acrylamide,
N-[(2-(dipropyl is amino) ethyl] acrylamide,
N-[(2-(diisopropylaminoethyl) ethyl] acrylamide or
N-[(2-(dibutylamino) ethyl] acrylamide.
4. preparation method who prepares the star-like macromolecule emulsifier of pH response according to claim 1 is characterized in that the concrete steps of the method are:
A. with chain-transferring agent 2-cyanopropyl ethyl three sulfo-s, have certain water miscible monomer monomer, the oil-soluble AIBN of initator according to 1:(20～500): the mol ratio of (0.01～1.0) joins in solvent, under inert atmosphere, 50 ℃～80 ℃ reactions 0.5～20 hour, after polymerization finishes, polymer is purified, obtain star-like Linear Polymer arm;
B. with the star-like Linear Polymer arm for preparing in steps A, crosslinking agent, the water miscible V50 of initator according to 1:(3～30): the molar ratio of (0.01～1.0) joins water and ethanol by (20～60): in the mixed liquor that the volume ratio of (80～40) is mixed with, and to control solid content be 1～50 wt%; Under inert atmosphere, heating is 3 hours under 70 ℃, can obtain preparing the crosslinked star-like macromolecule of core, and centrifugal purification, obtain the pure star-like macromolecule emulsifier of pH response.
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