CN103819633A - Star polymer emulsifier corresponding to temperature and salt and preparation method thereof - Google Patents
Star polymer emulsifier corresponding to temperature and salt and preparation method thereof Download PDFInfo
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- CN103819633A CN103819633A CN201310267793.9A CN201310267793A CN103819633A CN 103819633 A CN103819633 A CN 103819633A CN 201310267793 A CN201310267793 A CN 201310267793A CN 103819633 A CN103819633 A CN 103819633A
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Abstract
The invention relates to a star polymer emulsifier corresponding to temperature and salt and a preparation method thereof. The preparation method of the emulsifier comprises the following steps: a monomer with a certain water-solubility forms a linear polymer arm with the degree of polymerization being 20-500 through an RAFT (Reversible Additive Fragment Transfer) polymerization method, and then the polymer arm as a control reagent and a space monomer form core-crosslinked star polymer through an out-phase polymerization crosslinking agent, wherein the crosslinking agent and the space monomer are subjected to cross-linking polymerization to form a core, and the linear polymer arm is arm. The star polymer has double responsiveness for the temperature and ions, formed stable emulsion can realize rapid and complete emulsion breaking by regulating the temperature or ion strength and can be recycled, the recycle times can be up to a dozen times, and the emulsification effect cannot be reduced. The double-responsiveness core-crosslinked star polymer emulsifier belongs to a high-efficiency, non-toxic, low-irritation and intelligent novel emulsifier, the formed emulsion can be directly used as a terminal product to use, and the star polymer emulsifier can bring more industrial applications and greater practical values.
Description
Technical field
The present invention relates to a kind of macromolecule emulsifier and preparation method thereof.Particularly a kind of to temperature and the corresponding star-like macromolecule emulsifier of salt 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 tensio-active agent 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 group, oxyethyl group etc.; And hydrophobic group is generally longer hydrocarbon chain.In addition, micron or the solid particulate of Nano grade also can be used as emulsifying agent, and as clay particle etc., this type of emulsifying agent is called Pickering emulsifying agent, and they must possess the wettability suitable to two-phase, and the emulsion of formation has higher stability conventionally.
Star-like polymer, referring to that the above linear polymer chain of three or three (image be called " polymer arm ") is connected to " starlike " polymkeric substance forming on a common tie point by its high molecular one end, is that branching is opened up in benefit structure one of the simplest structure.The tie point having in the star-like polymer of less polymer arm number is generally an organic compound, and the crosslinked star-like high molecular tie point of core with larger polymer arm number is undersized, a highly cross-linked polymer core.Wherein must be much smaller than the size of polymer arm as the size of crosslinked core, its polymer arm can be unfolded and come well in good solvent, makes star-like polymer have good solubility.Star-like high molecular unique texture feature makes them have good application at aspects such as drug conveying, catalysis, coating and rheology modifiers.And it is also rarely seen in report used as emulsifying agent aspect.At present, the crosslinked star-like high molecular preparation of nearly all core is prepared in homogeneous phase solution (particularly organic solution), has that preparation efficiency is low, sample dispersion degree is high and the shortcoming such as environmental pollution.
Summary of the invention
One of object of the present invention is to provide a kind of to temperature and the corresponding star-like macromolecule emulsifier of salt.
Two of object of the present invention is to provide a kind of preparation method of this emulsifying agent.
The present invention adopts reversible addition-fracture chain transfer polymerization (RAFT) method, prepares the crosslinked star-like polymer of core by two steps.The first step is the preparation of polymer arm; Second step is the crosslinked star-like high molecular preparation of core.Polymer arm is to the certain water miscible monomer of having of two or more by RAFT method, the polymer arm that carries out copolymerization and form copolymerization as N,N-DMAA (DMA), methoxypolyethylene glycol methacrylic ester (PPEGMA), 2-methoxy acrylate and methoxypolyethylene glycol acrylate.Forming after polymer arm, then be cross-linked to form the crosslinked star-like polymer of core by the heteropolymerization in water, in this step, the spacer monomers that can select is NIPA, n-butyl acrylate, n-BMA, vinylbenzene etc., available linking agent is N, N '-methylene-bisacrylamide, glycol diacrylate, 1, 3-butylene glycol diacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, three (ethylene glycol) dimethacrylate etc.Below the synthesis mechanism take 2-methoxy acrylate MEA and methoxypolyethylene glycol acrylate PEGA as monomer preparation temperature and the star-like macromolecule emulsifier of ion responsitivity:
Reaction 3
The present invention considers that core is cross-linked star-like high molecular unique texture feature, be the flexibility of its polymer arm and the multiplicity of conformation, with and nano level size (10-50 nanometer), think the interface that the crosslinked star-like polymer of core can be stablized oil-water as emulsifying agent.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 sorptive power, strengthens its existence on interface.
Experiment showed, the crosslinked star-like polymer of our double responsiveness core of the present invention can be under very low emulsifier concentration, (can the low 0.02wt% of reaching) forms stable emulsion.When the crosslinked star-like high molecular concentration of core is in the time that 0.3wt% is above, the oil phase volume fraction of emulsification can be up to more than 90%, is the very efficient emulsifying agent of a class.When oil phase volume fraction is higher than 75% time, emulsion is had mobility hardly, 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 all respects.And the crosslinked star-like high molecular structure of core and character have Modulatory character flexibly, can, by changing kind or the ratio of polymerization single polymerization monomer, prepare easily emulsifying agent and intelligent emulsifying agent that hydrophilic and oleophilic character is different, for different actual needs.Wherein, the emulsion that the crosslinked star-like polymer of core in the present invention forms has temperature and ionic strength responsiveness, can as required, carry out simple breakdown of emulsion efficiently, and the sample of breakdown of emulsion can also carry out emulsification again as required by external conditions.This character has very important application at aspects such as oil, chemical industry, biologies.
According to above reaction mechanism, this experiment adopts following reaction scheme:
A kind of star-like macromolecule emulsifier to temperature and salt response, it is characterized in that this emulsifying agent has certain water miscible monomer by reversible addition-fracture chain transfer polymerization RAFT method, form the polymerization degree at 20～500 Linear Polymer arm, then form the crosslinked star-like polymer of core take polymer arm as regulation and control reagent by heteropolymerization linking agent and spacer monomers, wherein linking agent and spacer monomers crosslinking polymerization form core, and Linear Polymer arm is arm; Described certain water miscible monomer is: methoxypolyethylene glycol methacrylic ester PPEGMA, methoxypolyethylene glycol acrylate PEGA, NIPA NIPAM, one in 2-methoxy acrylate MEA or two kind; Described spacer monomers is: NIPA, n-butyl acrylate, n-BMA or vinylbenzene; Described linking agent is: N, N '-methylene-bisacrylamide, glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, BDO dimethacrylate, HDDMA or three (ethylene glycol) dimethacrylate; Wherein the mol ratio of Linear Polymer arm, spacer monomers and linking agent is generally 1: 10: 5.
Prepare the above-mentioned method to temperature and the corresponding star-like macromolecule emulsifier of salt, it is characterized in that the concrete steps of the method are:
A. by chain-transfer agent benzyl ethyl trithio, there is certain water miscible monomer, the oil-soluble AIBN of initiator according to 1: (20～500): the mol ratio of (0.01～1.0) joins in solvent, under inert atmosphere, at 50 ℃～80 ℃, react 0.5～20 hour, after polymerization finishes, polymkeric substance is purified, obtain Linear Polymer arm;
B. by gained Linear Polymer arm, spacer monomers, linking agent, the water miscible V50 of initiator in steps A according to 1: (0～30): (3～30): the molar ratio of (0.01～1.0) joins in the mixed solution of water and ethanol, wherein ethanol volumn concentration is 0～60%; Under inert atmosphere, 30 ℃～80 ℃ reactions 10 minutes～2 hours, can obtain temperature and the corresponding star-like macromolecule emulsifier of salt.
The present invention uses spacer monomers can reduce the stress being produced by linking agent, thereby generate more flexible core, make arm more easily assemble nucleation, in addition, spacer monomers can also be used to the hydrophobic nature of growth regulation chain, affects its self-assembly in synthetic star-like thing process.In a word, it plays conjugation to linking agent, forms together the core of star-like thing.
The transformation efficiency of the inventive method can reach more than 90%, with the centrifugal purification several of ultracentrifugation pipe (MW=30000) 6000rpm, can obtain pure star-like polymer.This experimental procedure is simple, easy to operate, and those skilled in the art can well realize.
The crosslinked star-like polymer of double responsiveness core of the present invention is as efficient emulsifying agent, can under low emulsifier concentration, form stable emulsion, and can realize the complete breakdown of emulsion under mild conditions, the mixed solution after breakdown of emulsion can re-start emulsification, and the emulsion property of formation can not change.The consumption low (0.01%～2.0%) that it is characterized in that emulsifying agent, can carry out fast emulsion breaking (1～10 minute) to formed emulsion as required, the emulsion oleaginousness high (10～95%) forming, and the emulsion-stabilizing (1～6 month) forming.
Accompanying drawing explanation
Fig. 1 is the star-like high molecular structural representation of temperature and ion responsitivity.
Fig. 2 is the nuclear-magnetism figure of the temperature linear arms corresponding with the star-like polymer of ion responsitivity.
Fig. 3 is the star-like high molecular GPC figure of temperature and ion responsitivity.
Fig. 4 is that temperature and the star-like polymer of ion responsitivity are 0.5wt% in concentration, the DLS figure at 25 ℃.
Fig. 5 is the temperature variant figure of the star-like high molecular granularity of temperature and ion responsitivity.
When Fig. 6 is 1.0wt% for working as temperature and the star-like polymer S of ion responsitivity (19nm, 31 ℃) concentration, with the increase of oil phase dodecane volume fraction, the emulsion photo of formation.
Fig. 7 is for working as temperature and the star-like polymer S of ion responsitivity (43nm, 38 ℃) concentration is 0.5wt%, oil phase volume fraction is 30% (A), 50% (B), the burnt Photomicrograph of copolymerization when 80% (C), wherein oil phase dodecane is dyeed by Nile red, and scale is 50 μ m.
Fig. 8 is 80% for working as oil phase volume fraction, the star-like polymer S of temperature and ion responsitivity (43nm, 38 ℃) concentration is respectively 0.3wt% (A), 0.5wt% (B), the burnt Photomicrograph of copolymerization when 1.0wt% (C), wherein oil phase dodecane is dyeed by Nile red, and scale is 50 μ m.
Fig. 9 for when oil phase volume fraction be 80%, the star-like polymer S of temperature and ion responsitivity (43nm, 38 ℃) under different concns, its elastic modulus G ' with out-of-phase modulus G " with the variation of shear-stress strain, wherein fixed shear frequency f=1HZ.
Figure 10 for when oil phase volume fraction be 80%, the star-like polymer S of temperature and ion responsitivity (43nm, 38 ℃) under different concns, its elastic modulus G ' with out-of-phase modulus G " with the variation of shearing frequency f, wherein fixed shear power strain=1%.
Figure 11 is temperature and the star-like polymer S of ion responsitivity (43nm, 38 ℃) concentration is 0.5wt%, when oil phase volume fraction is 80%, at 50 ℃, heat 10 minutes (A), the breakdown of emulsion photo while heating 5 minutes (B) at 60 ℃.
Figure 12 is that the star-like polymer S of temperature and ion responsitivity (43nm, 31 ℃) concentration is 0.5wt%, when oil phase volume fraction is 80%, heats 11 minutes (A) at 30 ℃; At 40 ℃, heat 9.5 minutes (B); At 50 ℃, heat the breakdown of emulsion photo while heating 6 minutes (D) at 8min (C) and 60 ℃.
Figure 13 is that the star-like polymer S of temperature and ion responsitivity (43nm, 38 ℃) concentration is 0.5wt%, in different salt ionic concentrations, to the emulsification photo of dodecane.
Figure 14 is that the star-like polymer S of temperature and ion responsitivity (43nm, 31 ℃) concentration is 0.5wt%, at 0.1MNa
2sO
4in solution, to the breakdown of emulsion photo of dodecane.
Figure 15 is that the star-like polymer S of temperature and ion responsitivity (43nm, 31 ℃) concentration is 0.5wt%, in 0.5MNaSCN solution, to the breakdown of emulsion photo of dodecane.
Embodiment
Embodiment mono-:
One, synthetic Linear Polymer arm P (MEA
80-co-PEGA
20)
By small molecules chain-transfer agent CTA (0.044g, 0.19mmol), monomer M EA (2.0g, 15.37mmol), PEGA (1.844g, 3.8mmol), internal reference 1,3,5-trioxane (by surveying nuclear-magnetism, being used for calculating monomer conversion) (0.17g, 1.88mmol), be dissolved in 6.6mL DMF (DMF) room temperature N
2after bubbling deoxygenation 40min, put into 70 ℃ of oil bath pans, to constant temperature, add the AIBN (2,2 '-azo two (isopropyl cyanide)) (6.3mg, 0.09mmol) after deoxygenation, quencher in frozen water after reaction 2h.Product is precipitated in ether to centrifugation.After centrifugation is complete, remove supernatant liquor, collect lower sediment, with THF (tetrahydrofuran (THF)) dissolving, use again ether sedimentation, repeat THF-ether process three times, by the vacuum-drying of final gained precipitation, finally obtain 3.38g yellow liquid, productive rate is 89%, obtains product P (MEA
80-co-PEGA
20), the structural formula of this product is:
Through nuclear-magnetism (Bruker AV500MHz spectrometer) test, solvent is heavy water, and the transformation efficiency that calculates monomer reaction is 99%.By gel permeation chromatograph (Waters Alliance e2695GPC system) test molecule amount and dispersiveness, wherein concrete detecting information is, Waters styragel HR3 molecular weight ranges 5.0 × 10
2-3.0 × 10
5, HR4 molecular weight ranges 5.0 × 10
3-6.0 × 10
5, HR5 molecular weight ranges 5.0 × 10
4-4.0 × 10
6.DMF is moving phase (LiBr that comprises 1mg/mL), and flow velocity is 0.8mL/min, 65 ℃ of column temperatures, and 2414 scattering measuring actuator temperatures are 45 ℃, and analysis software is Empower2, and polymetylmethacrylate is standard specimen, molecular weight ranges 2.4 × 10
2-1.0 × 10
6.GPC result records Mn=12.9KDa, Mw/Mn=1.09; Calculate Mn=19.8KDa through nuclear-magnetism.
Two, synthetic star-like polymer S (16nm, 51 ℃)
By linear arms P (MEA
80-co-PEGA
20) (3.1g, 0.16mmol), spacer monomers n-butyl acrylate BA (0.201g, 1.57mmol), linking agent polyethylene glycol dimethacrylate PEGDA (201.9mg, 78.3mmol), water 30mL joins in reaction flask, in ice-water bath, with nitrogen bubble deoxygenation 40min.Initiator KPS and NaAs are respectively at N simultaneously
2lower deoxygenation 15min.Again reaction vessel is put into the oil bath stirring reaction of 35 ℃ heating in advance, after temperature-stable, added successively KPS and the NaAs initiator of deoxygenation, after isothermal reaction 6h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000rpm rotating centrifugal is purified for several times, by surveying GPC until linear arms is removed completely, obtains end product, and its structural formula is:
GPC result records Mn=127KDa, Mw/Mn=1.16.
Embodiment bis-:
One, synthesizing linear arm P (MEA
56-co-PEGA
9)
By CTA (204.1mg, 0.89mmol), monomer M EA (10g, 76.8mmol), PEGA (6.004g, 12.5mmol), internal reference 1,3,5-trioxane (804.1mg, 8.75mmol), is dissolved in 30.74mL DMF room temperature N
2after bubbling deoxygenation 40min, put into 70 ℃ of oil bath pans, to constant temperature, add the AIBN (29.2mg, 0.18mmol) after deoxygenation, quencher in frozen water after reaction 2h.Product is precipitated in ether to centrifugation.After centrifugation is complete, removal supernatant liquor, collects lower sediment, with THF dissolving, then uses ether sedimentation, repeats THF-ether process three times, by the vacuum-drying of final gained precipitation, finally obtains 7.2g yellow solid, and productive rate is 45%.Structural formula is:
Through nuclear-magnetism test, the transformation efficiency that calculates monomer reaction is 66%.GPC result records Mn=9.6KDa, Mw/Mn=1.10; Calculate Mn=12.0KDa through nuclear-magnetism.
Two, synthetic star-like polymer S (35nm, 40 ℃)
By linear arms P (MEA
74-co-PEGA
8) (3.00g, 0.25mmol), linking agent HDDA (0.563g, 2.49mmol), water and alcohol mixed solvent that 30 mL volume ratios are 1: 1 join in reaction flask, in ice-water bath, with nitrogen bubble deoxygenation 40min.The mol ratio of linear arms and initiator V50 is 1: 0.2, and V50 is simultaneously at N
2lower bubbling deoxygenation 15min.Again reaction vessel is put into the oil bath stirring reaction of 70 ℃ heating in advance, after temperature-stable, added V50 (60 μ L, the 0.025mmol) storing solution of deoxygenation, after isothermal reaction 3h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000rpm rotating centrifugal is purified for several times, by surveying GPC until linear arms is removed completely.Structural formula is:
GPC result records Mn=100.7KDa, Mw/Mn=1.19.
Three, synthetic star-like polymer S (43nm, 38 ℃)
By linear arms P (MEA
74-co-PEGA
8) (3.940g, 0.33mmol), linking agent HDDA (1.48g, 6.54mmol), the water that 39.4mL volume ratio is 1: 1 and alcohol mixed solvent join in reaction flask, in ice-water bath, with nitrogen bubble deoxygenation 40min.The mol ratio of linear arms and initiator V50 is 1: 0.2, and V50 is simultaneously at N
2lower bubbling deoxygenation 15min.Again reaction vessel is put into the oil bath stirring reaction of 70 ℃ heating in advance, after temperature-stable, added V50 (117 μ L, the 0.033mmol) storing solution of deoxygenation, after isothermal reaction 3h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000rpm rotating centrifugal is purified for several times, by surveying GPC until linear arms is removed completely.Structural formula is:
GPC result records Mn=110.6KDa, Mw/Mn=1.26.
Embodiment tri-:
One, synthesizing linear arm P (MEA
74-co-PEGA
8)
By CTA (135.7mg, 0.69mmol), monomer M EA (6.96g, 53.47mmol), PEGA (2.85g, 5.94mmol), internal reference 1,3,5-trioxane (535.2mg, 5.94mmol), is dissolved in 20.4mL DMF room temperature N
2after bubbling deoxygenation 40min, put into 70 ℃ of oil bath pans, to constant temperature, add the AIBN (19.5mg, 0.12mmol) after deoxygenation, quencher in frozen water after reaction 2h.Product is precipitated in ether to centrifugation.After centrifugation is complete, removal supernatant liquor, collects lower sediment, with THF dissolving, then uses ether sedimentation, repeats THF-ether process three times, by the vacuum-drying of final gained precipitation, finally obtains 7.5g yellow solid, and productive rate is 77%.Structural formula is:
Through nuclear-magnetism test, the transformation efficiency that calculates monomer reaction is 83%.GPC result records Mn=13.9KDa, Mw/Mn=1.11; Calculate Mn=10.6KDa through nuclear-magnetism.
Two, synthetic star-like polymer S (19nm, 31 ℃)
By linear arms P (MEA
74-co-PEGA
8) (3.02g, 0.22mmol), linking agent HDDA (0.49g, 2.17mmol), the water that 30.2mL volume ratio is 1: 1 and alcohol mixed solvent join in reaction flask, in ice-water bath, with nitrogen bubble deoxygenation 40min.The mol ratio of linear arms and initiator V50 is 1: 0.2, and V50 is simultaneously at N
2lower bubbling deoxygenation 15min.Again reaction vessel is put into the oil bath stirring reaction of 70 ℃ heating in advance, after temperature-stable, added V50 (60 μ L, 5.9mg, the 0.02mmol) storing solution of deoxygenation, after isothermal reaction 3h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000rpm rotating centrifugal is purified for several times, by surveying GPC until linear arms is removed completely.Structural formula is:
GPC result records Mn=94.1KDa, Mw/Mn=1.17.
Three, synthetic star-like polymer S (43nm, 31 ℃)
By linear arms P (MEA
74-co-PEGA
8) (3.183g, 0.23mmol), linking agent HDDA (1.034g, 4.56mmol), the water that 31.8mL volume ratio is 1: 1 and alcohol mixed solvent join in reaction flask, in ice-water bath, with nitrogen bubble deoxygenation 40min.The mol ratio of linear arms and initiator V50 is 1: 0.2, and V50 is simultaneously at N
2lower bubbling deoxygenation 15min.Again reaction vessel is put into the oil bath stirring reaction of 70 ℃ heating in advance, after temperature-stable, added V50 (82 μ L, the 6.19mmol) storing solution of deoxygenation, after isothermal reaction 3h, quencher reaction in frozen water.Then with ultracentrifugation pipe MW=30000, rotating speed 6000rpm rotating centrifugal is purified for several times, by surveying GPC until linear arms is removed completely.Structural formula is:
GPC result records Mn=128.6KDa, Mw/Mn=1.16.
The concrete data of the synthetic method of three kinds of different linear arms P are as table 1:
Preparation condition and the result of the star-like polymer tube of table 1 double responsiveness
Note: polymerizing condition: the concentration of chain-transfer agent CTA is 29mM, mol ratio CTA: [MEA+PEGA]: AIBN=1: 100: 0.2,70 ℃, solvent DMF.
In the present invention due to adopt linear arms and the ratio of linking agent be respectively 1: 10 and 1: 20, so obtained the end product S (16nm of five kinds of different performance parameters, 51 ℃) S (35nm, 40 ℃), S (43nm, 38 ℃), S (19nm, 31 ℃), S (43nm, 31 ℃), concrete data are as table 2.
The star-like high molecular preparation condition of table 2 double responsiveness and result
Note: 1. star-like high molecular productive rate is to obtain by gel permeation chromatography GPC, star-like polymer productive rate=A
star-like polymer/ (A
star-like polymer+ A
star-like polymer arm); 2. preparation condition mol ratio P (MEA
80-co-PEGA
20): PEGDA: BA: (NaAs/KPS)=1: 5: 10: (0.1/0.1), and 35 ℃, 6h, deionized water;
3. mol ratio P (MEA
56-co-PEGA
9) or P (MEA
74-co-PEGA
8): HDDA: V-50=1: 10or20: 0.1,70 ℃ of 3h, water/ethanol (1: 1).
Study star-like high molecular emulsifying property:
Emulsification condition: total emulsion volume is 1.5mL, emulsive rate is by high-speed stirring instrument (model Polytron PT1200E homogenizer, rotary head diameter 7mm) control, emulsifying manner is the 1/4 place emulsification of maximum speed of revolution 30 seconds, then adjust to gradually 25000 revs/min of maximum speed of revolution and locate, emulsification finishes for 30 seconds.
Emulsification scheme:
1. fix emulsifier concentration, increase gradually the volume fraction of oil phase dodecane, inquire into its emulsifying effectiveness, if Fig. 6 is for working as temperature and the star-like polymer S of ion responsitivity (19nm, 31 ℃) concentration is while being 1.0wt%, with the increase of oil phase dodecane volume fraction, the emulsion photo of formation.
2., when discussion energy oil in water emulsion phase volume fraction reaches 80%, the minimum concentration of required emulsifying agent, as table 3.
3. inquire under each emulsifier concentration, emulsible maximum oil phase volume fraction, as table 3.
4. inquire into type and emulsion droplets size and dispersiveness and the homogeneity of emulsion by observing Laser Scanning Confocal Microscope.As seen from Figure 7, in the time that emulsifier concentration is identical, with the increase of oil phase volume volume fraction, droplet size does not have a great difference, and median size is in 20 μ m left and right, and Fig. 8 shows, in the time that oil phase volume fraction is 80%, emulsion droplets size diminishes gradually with the increase of emulsifier concentration, and in the time that emulsifier concentration is 0.3wt%, 0.5wt% and 1.0wt%, corresponding emulsion droplets median size is respectively: 35 μ m, 20 μ m and 12 μ m.
5. observe and rheometer test by long-term placement, inquire into stability and the rheological of emulsion.Fig. 9 demonstration, when oil phase volume fraction is identical, when emulsifier concentration increases, Young's modulus also increases gradually.When fixed shear frequency, increase gradually shearing force, in the time that shearing force reaches certain value, Young's modulus can decline rapidly, and out-of-phase modulus can sharply increase, and then meets at a bit, this point claims yield-point, shows that emulsion transfers flowable state to by viscoelastic state, and yield-point can be used for characterizing the interfacial film intensity of emulsion.Figure 10 shows, when fixed shear power constant, with the increase of shearing frequency, Young's modulus and out-of-phase modulus all increase, but Young's modulus is all greater than out-of-phase modulus all the time, also show that the interfacial film intensity of emulsion is very high, interfacial film intensity is higher, can effectively prevent that this has also illustrated the stability of emulsion from the side because of the poly-breakdown of emulsion of emulsion droplets.
The star-like high molecular emulsification result of double responsiveness is as table 3.
The star-like high molecular emulsifying property of table 3 dual responsiveness
Star-like high molecular intelligent:
The star-like polymer intelligent type of double responsiveness is inquired into scheme:
1. star-like polymer is due to the polymerization ratio difference of two kinds of monomers, so there is different LCST (lowest critical solution temperature), exceed after LCST, star-like polymer becomes not hydrophilic and separates out, so can, by heating, make stable emulsion breaking.Figure 11 shows, as star-like polymer S (43nm, 38 ℃) concentration is 0.5wt%, when oil phase volume fraction is 80%, heat 5 minutes breakdowns of emulsion completely at 60 ℃, Figure 12 shows, emulsifying agent S (the 43nm that is 0.5wt% for concentration, 31 ℃), while forming the stable emulsion that oil phase volume fraction is 80%, can at 60 ℃, heat 6min and complete breakdown of emulsion.And this phenomenon has reversibility, so can realize recycling of emulsifying agent.The breakdown of emulsion condition of the HIPE that various emulsifying agents form is specifically in table 4.
2. salt ion can affect star-like high molecular LCST, the affect difference of different salt ions on LCST, for example Na
2sO
4can make LCST temperature reduce with NaCl, NaClO
4can make its LCST raise with NaSCN, but not affect the emulsifying property of emulsifying agent, so can add by change type and the concentration of salt ion, to realize the adjustability of breakdown of emulsion temperature, can as required, arbitrarily reduce or rising breakdown of emulsion temperature, practicality is stronger.Figure 14 and Figure 15 show, add Na
2sO
4salt ion can reduce breakdown of emulsion temperature effectively, 50 degree are lower gets final product complete breakdown of emulsion, and the breakdown of emulsion time needing at 60 ℃ is shorter, if add NaSCN ion can improve breakdown of emulsion temperature, or need time breakdown of emulsion completely more of a specified duration, thereby improve the temperature stability of emulsion.In a word, this emulsifying agent itself not only has very efficient emulsifying property, and can realize complete breakdown of emulsion by adjusting temperature, and emulsifying agent can recycle.In addition, again can be by adding different salt ions to regulate breakdown of emulsion temperature, and don't affect its emulsifying property, as Figure 13.
Research method: referring to table 5 and table 6,1. inquire into different ions and the impact of concentration on LCST; 2. inquire under different ions and concentration, can form the maximum oil phase volume fraction 3. breakdown of emulsion conditions of stablizing HIPE
The star-like high molecular breakdown of emulsion condition of table 4 double responsiveness
LCST to the star-like polymer S of 0.5wt% (43nm, 38 ℃) of table 5 different ions and concentration and the impact of emulsifying property
LCST to the star-like polymer S of 0.5wt% (43nm, 31 ℃) of table 6 different ions and concentration and the impact of emulsifying property
Fig. 1 is the structural representation of the star-like thing that synthesizes, and two kinds of monomer M EA and PEGA, in different ratio copolymerization, form long water miscible arm, and center is the core of the hydrophobic nature that forms of linking agent HDDA or spacer monomers BA and linking agent PEGDA.
Claims (2)
1. the star-like macromolecule emulsifier to temperature and salt response, it is characterized in that this emulsifying agent has certain water miscible monomer by reversible addition-fracture chain transfer polymerization RAFT method, form the polymerization degree at 20～500 Linear Polymer arm, then form the crosslinked star-like polymer of core take polymer arm as regulation and control reagent by heteropolymerization linking agent and spacer monomers, wherein linking agent and spacer monomers crosslinking polymerization form core, and Linear Polymer arm is arm; Described certain water miscible monomer is: methoxypolyethylene glycol methacrylic ester PPEGMA, methoxypolyethylene glycol acrylate PEGA, NIPA NIPAM, one in 2-methoxy acrylate MEA or two kind; Described spacer monomers is:
n-N-isopropylacrylamide, n-butyl acrylate, n-BMA or vinylbenzene; Described linking agent is:
n,
n'-methylene-bisacrylamide, glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediyl ester, three (ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, HDDMA or three (ethylene glycol) dimethacrylate; Wherein the mol ratio of Linear Polymer arm, spacer monomers and linking agent is generally 1:10:5.
2. prepare the method to temperature and the corresponding star-like macromolecule emulsifier of salt according to claim 1, it is characterized in that the concrete steps of the method are:
A. by chain-transfer agent benzyl ethyl trithio, there is certain water miscible monomer, the oil-soluble AIBN of initiator according to 1:(20～500): the mol ratio of (0.01～1.0) joins in solvent, under inert atmosphere, at 50 ℃～80 ℃, react 0.5～20 hour, after polymerization finishes, polymkeric substance is purified, obtain Linear Polymer arm;
B. by gained Linear Polymer arm, spacer monomers, linking agent, the water miscible V50 of initiator in steps A according to 1:(0～30): (3～30): the molar ratio of (0.01～1.0) joins in the mixed solution of water and ethanol, wherein ethanol volumn concentration is 0～60%; Under inert atmosphere, 30 ℃～80 ℃ reactions 10 minutes～2 hours, can obtain temperature and the corresponding star-like macromolecule emulsifier of salt.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368503A (en) * | 2018-04-13 | 2019-10-25 | 上海市第十人民医院 | PEG core is crosslinked star gear transmission nano-contrast agent and its preparation method and application |
| CN112679666A (en) * | 2020-11-11 | 2021-04-20 | 北京化工大学 | Method capable of quickly and efficiently separating stimulus-responsive star-shaped and linear polymers |
| CN115368518A (en) * | 2022-07-15 | 2022-11-22 | 西南石油大学 | Colloidal particle emulsifier and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070244018A1 (en) * | 2004-10-25 | 2007-10-18 | Visger Daniel C | Star Polymers and Compositions Thereof |
| US20100273949A1 (en) * | 2009-04-23 | 2010-10-28 | Wojciech Jakubowski | Star macromolecules for personal and home care |
| CN103172806A (en) * | 2013-03-16 | 2013-06-26 | 太原理工大学 | Core-crosslinked multi-responsiveness miktoarm star-like polymer and preparation method thereof |
-
2013
- 2013-06-28 CN CN201310267793.9A patent/CN103819633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070244018A1 (en) * | 2004-10-25 | 2007-10-18 | Visger Daniel C | Star Polymers and Compositions Thereof |
| US20100273949A1 (en) * | 2009-04-23 | 2010-10-28 | Wojciech Jakubowski | Star macromolecules for personal and home care |
| CN103172806A (en) * | 2013-03-16 | 2013-06-26 | 太原理工大学 | Core-crosslinked multi-responsiveness miktoarm star-like polymer and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| QIAN QIU等: "Efficient and versatile synthesis of star polymers in water and their use as emulsifiers", 《CHEM. COMMUN.》 * |
| QIJING CHEN等: "pH-responsive high internal phase emulsions stabilized by core cross-linked star (CCS) polymers", 《POLYMER CHEMISTRY》 * |
| 邱倩: "RAFT异相聚合制备不同构型的高分子", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368503A (en) * | 2018-04-13 | 2019-10-25 | 上海市第十人民医院 | PEG core is crosslinked star gear transmission nano-contrast agent and its preparation method and application |
| CN110368503B (en) * | 2018-04-13 | 2021-10-29 | 上海市第十人民医院 | PEG (polyethylene glycol) core cross-linked star-shaped high-molecular nano contrast agent as well as preparation method and application thereof |
| CN112679666A (en) * | 2020-11-11 | 2021-04-20 | 北京化工大学 | Method capable of quickly and efficiently separating stimulus-responsive star-shaped and linear polymers |
| CN112679666B (en) * | 2020-11-11 | 2022-07-12 | 北京化工大学 | Method capable of quickly and efficiently separating stimulus-responsive star-shaped and linear polymers |
| CN115368518A (en) * | 2022-07-15 | 2022-11-22 | 西南石油大学 | Colloidal particle emulsifier and preparation method and application thereof |
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