CN102040707A - Zwitterionic polymer and preparation method thereof - Google Patents
Zwitterionic polymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to salt-resistant emulsion type zwitterionic polymer and a preparation method thereof. The invention is characterized in that: a reverse emulsion polymerization method is adopted and betaine type zwitterionic monomer and two or more types of nonionic monomers are copolymerized to form high polymer with nonionic copolymer characteristics. While oil is taken as a disperse phase preferably, the hydrophile-lipophile balance (HLB) value of an emulsifying agent is 4.7-6.0, and the molecular weight of the polymer and the stability of polymer emulsion are improved. The polymer emulsion is easy to disperse and dissolve in fresh water and salinity brine, has good salt resistance and can be applied to improving recovery ratio in offshore oil fields and drilling wells.
Description
Technical field
The present invention relates generally to a kind of amphoteric ion polymer and inverse emulsion polymerization method thereof, be specifically related to utilize a kind of zwitterionic monomer and two kinds and above nonionic monomers copolymerization, obtain that general performance goes out the characteristic of non-ionic copolymer in water, the insensitive emulsion polymer of aqueous solution salinity.
Technical background
In recent years, the needs of tertiary oil recovery make the development of heat-resistant salt-resistant polymkeric substance become the focus of domestic and international water-soluble polymers development.The measure that improves the polymkeric substance anti-salt temperature-resistant has: the amphiphilic polymers, the introducing hydrophobic grouping that improve the polymkeric substance relative molecular mass, introduce functional monomer, preparation have anti-polyelectrolyte effect make intermolecular association etc., these methods all are in order to have increased the ydrodynamics volume of polymer molecule under high temperature and high salinity condition, in the hope of obtaining higher soltion viscosity.
Wherein, amphiphilic polymers is meant the polymkeric substance that has the both positive and negative electric charge on the polymer chain simultaneously, in amphiphilic polymers solution, when contained positive and negative charge group number equates, when net charge is zero on the macromolecular chain, be amphoteric ion polymer when being in iso-electric point (isoeloztric point), the electrostatic force between group shows as and attracts each other, and molecular chain shrinks.At this moment, if add small molecule salt, because the repulsive interaction between the electric charge, the segment expansion can appear in polymkeric substance, and the ydrodynamics size increases, and this is anti-polyelectrolyte effect (anfipolyelerolyte effect).Amphoteric ion polymer can be divided into two kinds: the one, form by zwitterionic monomer homopolymerization or zwitterionic monomer and nonionic monomers copolymerization, and the 2nd, form by cationic monomer, anionic monomer copolymerization or cationic monomer, anionic monomer and nonionic monomers copolymerization.From whole polymer molecule electrically, positive and negative electric charge equates in the former polymer molecular chain, and intramolecularly or intermolecular positive and negative electric charge attract each other, neutralize in the aqueous solution, and general performance goes out the characteristic of non-ionic copolymer in water.And the positively charged ion chain link of positively charged and electronegative negatively charged ion chain link number can equate in the latter's the polymer molecule, also can be unequal, because the difference of different monomers polymerization, expect that the polymer molecule difficulty that positive and negative charge number equates is very big, this just causes polymer molecule positive and negative electric charge in the aqueous solution and can not neutralize fully and show positive polarity or electronegativity.
The amphoteric ion polymer of using always in oilfield exploitation mostly is the amphoteric ion polymer of cation chain link and negatively charged ion chain link at present, such amphoteric ion polymer viscosity is subjected to the influence of salinity bigger, and viscosity-depression agent XY27 that uses as drilling fluid in oilfield exploitation and coating agent FA-367, profile control are with FT-213 etc.But pure amphoteric ion polymer is few.
U.S. Pat 3497482 discloses N the earliest, N-dimethyl-N-(2-methacryloyloxyethyl)-N-(3-sulphopropyl ammonium inner salt) (SPE), be N, the polyreaction of N`-dimethyl-N-(2-methylacryoyloxyethyl)-N-(3-propyl sulfonic acid ammonium inner salt) and Jia Jibingxisuanyizhi and acrylamide, obtain amphoteric ion polymer, the polymerization methods that is adopted is an aqueous solution polymerization.
Zimehl etc. are at Colloid Polym.Sci. (1990) 268, described among the 924-933 with N-(3-sulphopropyl)-N-methacrylomidyl propyl (N, N-dimethylammonium betaine) (SPP), be N-(3-sulfonic acid propyl group)-N-methacryloxypropyl-N, the emulsion polymerization of N`-dimethyl betaine obtains amphoteric ion polymer.
Han Yugui etc. are in document " reversed emulsion polymerization prepares a kind of novel amphoteric ion polymer " (" petrochemical complex " 2006 (3)), introduced with ampholytic monomer methylacryoyloxyethyl-N, N`-dimethyl-N-propanesulfonic acid amine salt (DMPS) makes the amphiphilic polymers poly (AM-co-DMPS) with anti-polyelectrolyte character with acrylamide (AM) copolymerization.But the prepared amphoteric ion polymer molecular weight of the document is not high, and its intrinsic viscosity has only 6.5dL/g, and viscosity is on the low side, can be used as the drilling fluid coating agent of anti-salt, can not be used for offshore oilfield as salt-resistant polymer oil displacement agents and improve recovery ratio.
Because zwitterionic monomer belongs to acid, alkali type inner salt, easily dissolving in water, suitable method and other non-ionic monomer copolymerization of adopting inverse emulsion polymerization obtains the whole electrical interior amine ester type amphoteric ion polymer that do not show.And the high molecular polymer of emulsion polymerization way preparation has, and solid content height, dissolving are fast, relative molecular mass distributes relatively advantage of uniform.But, when prepared amphoteric ion polymer molecular weight is big, dissolution rate in the aqueous solution is slack-off, because the N that contains in the used zwitterionic monomer, the N`-dimethyl is sterically hindered less, and the negative ions group is easy to generate intramolecularly or intermolecular sat linkage in the polymer of feasible preparation, forms cross-linked structure, have the portion water gelling properties, dissolve slower.Add the non-ionic monomer that contains aerobic ethylene chain joint when polymerization, the polymer molecule integral body that obtains does not still show electrically, but the non-ionic monomer chain link of the type hinders the formation of intramolecularly or intermolecular sat linkage, and the dissolution rate of polymkeric substance is improved greatly.
Summary of the invention
The inventor finds by great deal of experimental, when in the inverse emulsion polymerization system, except that adding acrylamide, adding the non-ionic monomer that contains aerobic ethylene chain joint again, not only can improve the stability to hydrolysis of polymkeric substance, and help to improve the dissolution rate of polymkeric substance, prepared polymer emulsion still has higher viscosity when preparing with seawater, can be used as anti-salt oil-displacing agent and drilling fluid flow pattern conditioning agent that offshore oilfield improves recovery ratio.
Purpose of the present invention just provides a kind of betaine type amphoteric ionic polymer emulsion with non-ionic copolymer characteristic, this polymer emulsion is stable and soluble in water more, and have fabulous anti-salt property, be particularly suited for the polymer oil-displacing agent of the used for tertiary oil recovery of chain-wales preparation at sea.
A kind of amphoteric ion polymer of the present invention, this polymkeric substance is the multipolymer that adopts the inverse emulsion polymerization method to obtain by non-ionic monomer a, non-ionic monomer b and zwitterionic monomer, wherein said non-ionic monomer a is acrylamide, N hydroxymethyl acrylamide, N, N-DMAA, N-ethyl acrylamide, N, one or more in N-diethyl acrylamide and the N-propyl group acrylamide; Described non-ionic monomer b is the polymerisable monomer that contains aerobic ethylene chain joint; Described zwitterionic monomer is the sulphonic acid betaine type, shown in general formula (I):
In the formula, R is CH
2=CH-COOCH
2CH
2-or
N=2～4
In the present invention, be preferably non-ionic monomer a: non-ionic monomer b: zwitterionic monomer (weight ratio)=40～80: 1～8: 3～15.
In the present invention, described non-ionic monomer b is preferably alkylphenol polyoxyethylene acrylate, alkyl polyoxyethylene ether acrylate, alkylphenol polyoxyethylene-propylene-1 or alkyl polyoxyethylene ether-propylene-1, more preferably octyl phenol polyoxy ethene (7) ether acrylate, dodecyl polyoxyethylene (9) ether acrylate or 3-octyl phenol polyoxy ethene (7) ether-propylene-1,3-dodecyl polyoxyethylene (9) ether-propylene-1.
In the inverse emulsion polymerization method that is adopted, the emulsifying agent that uses is preferably with Span-80 (sorbitan monooleate) or Span-60 (sorbitan monostearate) and is selected from a kind of among sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Tween-80 (polyoxyethylene 20 sorbitan monooleate), Tween-60 (polyoxyethylene 20 sorbitan monostearate) and the OP-10 (octyl phenol polyoxy ethene (10) ether) and carries out composite compound emulsifying agent, the HLB value of this compound emulsifying agent is between 4.4～7.0, and preferred HLB value is between 4.7～6.0.
The present invention further provides the preparation method of above-mentioned amphoteric ion polymer.
One of preparation method of amphoteric ion polymer of the present invention is characterized in that may further comprise the steps:
(1) preparation water: described zwitterionic monomer and non-ionic monomer a, non-ionic monomer b are dissolved in the deionized water, add complexing agent;
(2) preparation oil phase: emulsifying agent is dissolved in white oil, forms uniform oil phase;
(3) emulsification: the water that step (1) is obtained slowly splashes in the oil phase that step (2) obtains, and stirs fast, and logical nitrogen deoxygenation 20～40 minutes obtains the emulsified monomer emulsion;
(4) reaction: step (3) is obtained the emulsified monomer emulsion be divided into two parts of A, B, wherein A part is 1/4～1 of a total amount, B part is 0～3/4 of a total amount, in A part emulsified monomer emulsion, successively drip the aqueous solution of reductive agent and oxygenant, be warming up to 20～60 ℃, reacted 20～60 minutes, drip B part emulsified monomer emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.
The preparation method's of amphoteric ion polymer of the present invention two is characterized in that may further comprise the steps:
(1) preparation water: described zwitterionic monomer and non-ionic monomer a are dissolved in the deionized water, add complexing agent, logical nitrogen deoxygenation 20～40 minutes;
(2) preparation oil phase: emulsifying agent, non-ionic monomer b are dissolved in white oil, form uniform oil phase;
(3) emulsification: the water that step (1) is obtained slowly splashes in the oil phase that step (2) obtains, and stirs fast, and logical nitrogen deoxygenation 20～40 minutes obtains the emulsified monomer emulsion;
(4) reaction: step (3) is obtained the emulsified monomer emulsion be divided into two parts of A, B, wherein A part is 1/4～1/2 of a total amount, B part is 1/2～3/4 of a total amount, in A part emulsified monomer emulsion, successively drip the aqueous solution of reductive agent and oxygenant, be warming up to 20～60 ℃, reacted 20～60 minutes, drip B part emulsified monomer emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.
Be 100 weight parts in deionized water among described preparation method one and the preparation method two, described zwitterionic monomer is that 3～15 weight parts and non-ionic monomer a are that 40～80 weight parts, non-ionic monomer b are 1～8 weight part, emulsifying agent is 4～8 weight parts, white oil is 40～60 weight parts, the consumption of reductive agent is 0.05%～0.5% of a total polymerization monomer weight, and the consumption of oxygenant is 0.05%～0.5% of a total polymerization monomer weight.
Wherein said complexing agent is a disodium edta.
Wherein said emulsifying agent be Span-80 (sorbitan monooleate) or Span-60 (sorbitan monostearate) with sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Tween-80 (polyoxyethylene 20 sorbitan monooleate), Tween-60 (polyoxyethylene 20 sorbitan monostearate) OP-10 (octyl phenol polyoxy ethene (10) ether) in a kind of carry out composite, the HLB value of the composite emulsifying agent that goes out is between 4.4～7.0, and the preferred HLB value of emulsifying agent is between 4.7～6.0.
Wherein said oxygenant is Potassium Persulphate, ammonium persulphate or hydrogen peroxide, and described reductive agent is sodium bisulfite or Tetramethyl Ethylene Diamine.
Amphoteric ion polymer emulsion stability in storage with non-ionic copolymer characteristic of the present invention is good, easily disperses, dissolves in fresh water and high-salinity brine, uses very convenient.It is little that this amphoteric ion polymer viscosity in aqueous solution is influenced by salinity, the apparent viscosity in seawater and in fresh water apparent viscosity almost equal; Its preparation method adopts the method for inverse emulsion polymerization, and technology is simple, and the solid content of polymer emulsion is between 20～40%, and the intrinsic viscosity of amphoteric ion polymer can reach 15dL/g.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment.
Measuring method
Intrinsic viscosity: according to GB 12005.1-89
Embodiment 1
(1) water: take by weighing acrylamide 28g, octyl phenol polyoxy ethene (7) ether acrylate 1.5g, zwitterionic monomer methylacryoyloxyethyl-N, N-dimethyl propylene sulfonate (DMPS) 3g, be dissolved in the 40g deionized water, add the aqueous solution 5g of complexing agent disodium edta (EDTA).
(2) oil phase: taking by weighing by the composite HLB value that goes out of Span-80 (sorbitan monooleate) and Tween-80 (polyoxyethylene 20 sorbitan monooleate) is 5.2 emulsifying agent 4.5g, mixes with the 30g white oil.
(3) emulsification: under the high-speed stirring, lentamente water is added drop-wise in the oil phase, fully stirs, form uniform W/O emulsion, logical nitrogen deoxygenation 30min.
(4) reaction: gradation successively drips the aqueous solution (the 0.03g Tetramethyl Ethylene Diamine is in 2mL water) of reductive agent and the aqueous solution (the 0.04g ammonium persulphate is in 2mL water) of oxygenant in 1/2 above-mentioned emulsion, be warming up to 30 ℃, reacted 20～60 minutes, drip remaining 1/2 above-mentioned emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.The amphiphilic polymers pulvis that obtains after ethanol sedimentation, drying, intrinsic viscosity are 12.8dL/g.
Embodiment 2
(1) water: take by weighing acrylamide 28g, zwitterionic monomer (DMPS) 4g, be dissolved in the 40g deionized water, add the aqueous solution 5g of complexing agent EDTA, logical nitrogen 20min.
(2) oil phase: take by weighing the HLB value and be 4.7 composite emulsifier 3g, octyl phenol polyoxy ethene (7) ether acrylate 2g, mix with the 27g white oil.
(3) emulsification: under the high-speed stirring, lentamente water is added drop-wise in the oil phase, fully stirs, form uniform W/O emulsion, logical nitrogen deoxygenation 20min.
(4) reaction: gradation successively drips the aqueous solution (the 0.02g Tetramethyl Ethylene Diamine is in 2mL water) of reductive agent and the aqueous solution (the 0.04g ammonium persulphate is in 2mL water) of oxygenant in 1/2 above-mentioned emulsion, be warming up to 30 ℃, reacted 20～60 minutes, drip remaining 1/2 above-mentioned emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.The amphiphilic polymers pulvis that obtains after ethanol sedimentation, drying, intrinsic viscosity are 13.4dL/g.
Embodiment 3
(1) water: take by weighing acrylamide 30g, 3-dodecyl polyoxyethylene (9) ether-propylene-11.5g, zwitterionic monomer DMPS 4g, be dissolved in the 42g deionized water, add the aqueous solution 3g of complexing agent EDTA.
(2) oil phase: take by weighing the HLB value and be 4.7 composite emulsifier 3g, mix with the 27g white oil.
(3) emulsification: under the high-speed stirring, lentamente water is added drop-wise in the oil phase, fully stirs, form uniform W/O emulsion, logical nitrogen deoxygenation 40min.
(4) reaction: gradation successively drips the aqueous solution (the 0.02g Tetramethyl Ethylene Diamine is in 2mL water) of reductive agent and the aqueous solution (the 0.03g ammonium persulphate is in 2mL water) of oxygenant in 1/2 above-mentioned emulsion, be warming up to 35 ℃, reacted 20～60 minutes, drip remaining 1/2 above-mentioned emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.The amphiphilic polymers pulvis that obtains after ethanol sedimentation, drying, intrinsic viscosity are 15.0dL/g.
Comparative example 1:
(1) water: take by weighing acrylamide 30g, zwitterionic monomer DMPS 4g, be dissolved in the 42g deionized water, add the aqueous solution 3g of complexing agent EDTA, logical nitrogen 20min.
(2) oil phase: take by weighing the HLB value and be 4.7 composite emulsifier 3g, mix with the 27g white oil.
(3) emulsification: under the high-speed stirring, lentamente water is added drop-wise in the oil phase, fully stirs, form uniform W/O emulsion, logical nitrogen deoxygenation 20min.
(4) reaction: gradation successively drips the aqueous solution (the 0.02g Tetramethyl Ethylene Diamine is in 2mL water) of reductive agent and the aqueous solution (the 0.03g ammonium persulphate is in 2mL water) of oxygenant in 1/2 above-mentioned emulsion, be warming up to 35 ℃, reacted 20～60 minutes, drip remaining 1/2 above-mentioned emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.The amphiphilic polymers pulvis that obtains after ethanol sedimentation, drying, intrinsic viscosity are 15.1dL/g.
The solvability comparison test: take by weighing prepared polymer emulsion, be dissolved under the mechanical stirring in the seawater that contains 0.05%OP-10, be configured to the sea water solution of 0.2g/dL, comparing result sees Table 1.
Table 1
From table 1 data contrasts as can be seen, do not add the comparative example 1 of non-ionic monomer 3-dodecyl polyoxyethylene (9) ether-propylene-1, the multipolymer of preparation dissolves slower in seawater, and is scattered in following 20 minutes of the room temperature, but dissolves bad.And adding non-ionic monomer 3-dodecyl polyoxyethylene (9) ether-propylene-1 o'clock, the polymer dissolution of preparation is good, all dissolvings in following 20 minutes of the room temperature.
The apparent viscosity comparison test:
Under 25 ℃, surveying concentration on Brookfield DV-III ULTRA rheometer is the apparent viscosity (6 rev/mins) of the aqueous solutions of polymers of 0.2g/dL, data such as table 2
Table 2
From the contrast of table 2 data as can be seen, contain the terpolymer of non-ionic monomer 3-dodecyl polyoxyethylene (9) ether-propylene-1 and the copolymer that does not contain, their apparent viscosity in seawater is suitable substantially with apparent viscosity in distilled water, is subjected to the influence of salinity very little.
Embodiment 4
(1) water: take by weighing N,N-DMAA 25.3g, zwitterionic monomer (DMPS) 8.7g, be dissolved in the 42g deionized water, add the aqueous solution 5g of complexing agent EDTA, logical nitrogen 20min.
(2) oil phase: take by weighing the HLB value and be 5.0 emulsifying agent 4.5g, 3-dodecyl polyoxyethylene (9) ether-propylene-11.5g, mix with the 30g white oil.
(3) emulsification: under the high-speed stirring, lentamente water is added drop-wise in the oil phase, fully stirs, form uniform W/O emulsion.Logical nitrogen deoxygenation 30min.
(4) reaction: gradation successively drips the aqueous solution (the 0.02g Tetramethyl Ethylene Diamine is in 2mL water) of reductive agent and the aqueous solution (the 0.04g ammonium persulphate is in 2mL water) of oxygenant in 1/2 above-mentioned emulsion, be warming up to 30 ℃, reacted 20～60 minutes, drip remaining 1/2 above-mentioned emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.The amphiphilic polymers pulvis that obtains after ethanol sedimentation, drying, intrinsic viscosity are 12.1dL/g.
Claims (9)
1. amphoteric ion polymer, this polymkeric substance is the multipolymer that adopts the inverse emulsion polymerization method to obtain by non-ionic monomer a, non-ionic monomer b and zwitterionic monomer, wherein said non-ionic monomer a is acrylamide, N hydroxymethyl acrylamide, N, N-DMAA, N-ethyl acrylamide, N, one or more in N-diethyl acrylamide and the N-propyl group acrylamide; Described non-ionic monomer b is the polymerisable monomer that contains aerobic ethylene chain joint; Described zwitterionic monomer is the sulphonic acid betaine type, shown in general formula (I):
In the general formula (I), R is CH
2=CH-COOCH
2CH
2-or
N=2～4.
2. amphoteric ion polymer according to claim 1 is characterized in that non-ionic monomer a: non-ionic monomer b: zwitterionic monomer (weight ratio)=40～80: 1～8: 3～15.
3. amphoteric ion polymer according to claim 1, it is characterized in that in the inverse emulsion polymerization method that is adopted, the emulsifying agent that uses is as sorbitan monooleate or sorbitan monostearate and be selected from a kind of in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan monostearate and octyl phenol polyoxy ethene (10) ether and carry out composite compound emulsifying agent, and the HLB value of this compound emulsifying agent is between 4.4～7.0.
4. amphoteric ion polymer according to claim 3, the HLB value that it is characterized in that described compound emulsifying agent is 4.7～6.0.
5. amphoteric ion polymer according to claim 1 is characterized in that described non-ionic monomer b is alkylphenol polyoxyethylene acrylate, alkyl polyoxyethylene ether acrylate, alkylphenol polyoxyethylene-propylene-1 or alkyl polyoxyethylene ether-propylene-1.
6. amphoteric ion polymer according to claim 5 is characterized in that described non-ionic monomer b is octyl phenol polyoxy ethene (7) ether acrylate, dodecyl polyoxyethylene (9) ether acrylate, 3-octyl phenol polyoxy ethene (7) ether-propylene-1,3-dodecyl polyoxyethylene (9) ether-propylene-1.
7. the preparation method of amphoteric ion polymer as claimed in claim 1 is characterized in that may further comprise the steps:
(1) preparation water: described zwitterionic monomer and non-ionic monomer a, non-ionic monomer b are dissolved in the deionized water, add complexing agent;
(2) preparation oil phase: emulsifying agent is dissolved in white oil, forms uniform oil phase;
(3) emulsification: the water that step (1) is obtained splashes in the oil phase that step (2) obtains, and stirs fast, and logical nitrogen deoxygenation 20～40 minutes obtains the emulsified monomer emulsion;
(4) reaction: step (3) is obtained the emulsified monomer emulsion be divided into two parts of A, B, wherein A part is 1/4～1 of a total amount, B part is 0～3/4 of a total amount, in A part emulsified monomer emulsion, successively drip the aqueous solution of reductive agent and oxygenant, be warming up to 20～60 ℃, reacted 20～60 minutes, drip B part emulsified monomer emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.
8. the preparation method of amphoteric ion polymer as claimed in claim 1 is characterized in that may further comprise the steps:
(1) preparation water: described zwitterionic monomer and non-ionic monomer a are dissolved in the deionized water, add complexing agent, logical nitrogen deoxygenation 20～40 minutes;
(2) preparation oil phase: emulsifying agent, non-ionic monomer b are dissolved in white oil, form uniform oil phase;
(3) emulsification: the water that step (1) is obtained splashes in the oil phase that step (2) obtains, and stirs fast, and logical nitrogen deoxygenation 20～40 minutes obtains the emulsified monomer emulsion;
(4) reaction: step (3) is obtained the emulsified monomer emulsion be divided into two parts of A, B, wherein A part is 1/4～1 of a total amount, B part is 0～3/4 of a total amount, in A part emulsified monomer emulsion, successively drip the aqueous solution of reductive agent and oxygenant, be warming up to 20～60 ℃, reacted 20～60 minutes, drip B part emulsified monomer emulsion again, continue reaction 1～4 hour, obtain oyster white homogeneous heavy-gravity amphiphilic polymers emulsion.
9. according to the preparation method of claim 7,8 described amphoteric ion polymers, wherein said complexing agent is a disodium edta, the HLB value of described emulsifying agent is 4.4～7.0, described oxygenant is Potassium Persulphate, ammonium persulphate or hydrogen peroxide, and described reductive agent is sodium bisulfite or Tetramethyl Ethylene Diamine.
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