CN102746456B - Terpolymer and polymer and preparation method and application thereof - Google Patents

Terpolymer and polymer and preparation method and application thereof Download PDF

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CN102746456B
CN102746456B CN201110104197.XA CN201110104197A CN102746456B CN 102746456 B CN102746456 B CN 102746456B CN 201110104197 A CN201110104197 A CN 201110104197A CN 102746456 B CN102746456 B CN 102746456B
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CN102746456A (en
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杜凯
刘晓光
魏小林
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a terpolymer, characterized in that the terpolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit of formula (1), the structural unit B is at least one of the structural units of formula (2)-(4), the structural unit C is at least one of the structural units of formula (5)-(9), and the viscosity-average molecular weight of the terpolymer is 18,000,000-28,000,000. The invention further provides a polymer and its preparation method and application. According to the invention, the polymer of the invention has the advantages of high viscosity, good dissolvability, good high-speed shearing resistance, good injection and good advancing value of recovery efficiency.

Description

A kind of terpolymer and a kind of polymkeric substance and preparation method thereof and application
Technical field
The present invention relates to a kind of terpolymer, a kind of preparation method of polymkeric substance and the polymkeric substance being prepared by the method, and described terpolymer and polymkeric substance are as the application of described polymer oil-displacing agent.
Background technology
Oil field generally enters today of high water-cut development period at home, polymer flooding taking high molecular partially hydrolyzed polyacrylamide (HPAM) as main representative improves oil recovery factor technology and becomes effective day, and is used widely in one, two class oil reservoirs of low temperature, less salt.But for the formation condition feature of high temperature, high salt in three class oil reservoirs, high molecular partially hydrolyzed polyacrylamide (HPAM) exists that salt tolerance is poor, facile hydrolysis, easily degraded, easily generate the problems such as precipitation with the divalent-metal ion complexing such as calcium, magnesium, and its actual oil displacement efficiency in three class oil reservoirs is significantly declined.
At present for the oil reservoir resource (formation temperature 70-95 DEG C, stratum salinity 10000-30000mg/L) of three class formation conditions, in worldwide, still do not have ripe, industrialization, commercial polymer oil-displacing agent product to come out.In order to address the above problem, improve three class oil recoveries, the oil-displacing agent of research and development adaptation high temperature, high salt formation condition has become the major fields of industry member, academia's research and development.
At present, adopt temperature resistant antisalt monomer, as 2-acrylamide-2-methylpro panesulfonic acid (AMPS), NVP (NVP) or N, N-DMAA (DMAM) has improved polyacrylamide temperature resistant antisalt performance to a certain extent with acrylamide copolymerization, but still cannot meet the requirement of three class oil reservoirs completely, there is following shortcoming mainly due to aforesaid propylene amides copolymer: 1., owing to being difficult to prepare the copolymer that relative molecular mass is higher, the apparent viscosity of its solution under high temperature and high salt formation condition is not high; 2. because above-mentioned functions monomer and acrylamide activity differ larger, in multipolymer, the content of functional monomer is not high, and its heat-resistant stability and salt tolerance need further to be improved; 3. in the time injecting well head, anti-high speed shear performance is needed raising badly; 4. dissolution time needs to shorten.
As CN1240797A discloses the preparation method of a kind of sulfonated monomers and acrylamide copolymer: add acrylamide and sulfonated monomers in reaction vessel, fully stir monomer is dissolved completely, add redox initiation system, polymerization temperature is controlled at 15-30 DEG C, obtain sulfonated monomers and acrylamide copolymer, molecular weight is 1 × 10 6-1 × 10 7product has good use properties, and its temperature resistant antisalt has had improvement to a certain degree compared with polyacrylamide, but relative molecular mass and apparent viscosity still need further raising, its anti-high speed shear performance, anti-absorption property are needed raising badly, and its dissolution time needs a step to shorten.
Sclerotium gum (Scleroglucan), xanthan gum (Xanthan gum, XG) are all polyphosphazene polymer polysaccharide, are to integrate thickening, suspension, emulsification, stabilization, the xanthan gum that performance is comparatively superior.Compared with HPAM, Sclerotium gum and xanthan gum, because of its unique polysaccharide structures unit having, make it use and have the following advantages as oil-displacing agent: its solution still has high viscosity number under high temperature, high salinity condition; Anti-mechanical shearing ability is strong; Short and the solution of dissolution time is difficult for by reservoir rock absorption etc.But how polysaccharide structures unit is introduced and is still a still open question.
Use for reference the constructional feature of the poly-polysaccharide such as Sclerotium gum and xanthan gum, by the polymerisable monomer with glycosyl units by the method for terpolymer, be incorporated on the macromolecular chain of monomer (AMPS/NVP/DMAM) of acrylamide, above-mentioned temperature resistant antisalt performance, in keeping the excellent viscoelasticity of linear macromolecule, can improve the apparent viscosity under the warm high salt geologic condition of height, improve anti-shear performance and the anti-rock absorption property of its solution, can further improve the recovery ratio of three class oil reservoirs.
Document (Properties of Biomedical Pressure-Sensitive Adhesive CopolymerFilms with Pendant Monosaccharides, J Appl Polym Sci, 1995, 56:1615) report a kind of preparation method of butyl acrylate-methacrylic acid glucosyloxy ethyl ester multipolymer: in glass test tube, add a certain amount of dimethyl sulfoxide (DMSO), butyl acrylate, methacrylic acid glucosyloxy ethyl ester, Diisopropyl azodicarboxylate, logical nitrogen deoxygenation, at 70 DEG C, react 12 hours, by product water/acetone precipitation, obtain butyl acrylate-methacrylic acid glucosyloxy ethyl ester multipolymer, but butyl acrylate-methacrylic acid glucosyloxy ethyl ester multipolymer is water-soluble very poor, cannot use as Flooding Agent for EOR.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, provide high, the heat-resisting and good salt tolerance of a kind of molecular weight superelevation, apparent viscosity, anti-high-shear performance good, polymkeric substance that good water solubility and dissolution time are short and its preparation method and application.
The invention provides a kind of terpolymer, it is characterized in that, this terpolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A has the structure shown in formula (1), described structural unit B is for having at least one in the structural unit of structure shown in formula (2)-Shi (4), described structural unit C is for having at least one in the structural unit of structure shown in formula (5)-Shi (9), and taking the total mole number of structural unit in described terpolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, the viscosity-average molecular weight of described terpolymer is 1,800 ten thousand-2,800 ten thousand,
formula (1),
formula (2), formula (3), formula (4),
formula (5),
formula (6),
formula (7),
formula (8),
formula (9),
Wherein, R 1for the alkylidene group of C1-C4; R 2, R 3, R 4and R 5be the alkyl of C1-C4 independently of one another; R 6-R 8, R 10-R 18, R 20-R 24, R 26-R 30, R 32-R 36respectively do for oneself-NHCOR 38or OH, R 38for the alkyl of C1-C4, and R 6-R 8in at least two be OH, R 10-R 12in at least two be OH, R 13-R 15in at least two be OH, R 16-R 18in at least two be OH, R 20-R 22in at least two be OH, R 23and R 24in at least one is OH, R 26-R 28in at least two be OH, R 29and R 30in at least one is OH, R 32-R 34in at least two be OH, R 35and R 36in at least one is OH, R 9for the alkylidene group of C1-C5, R 19for the alkylidene group of C3-C8, R 25, R 31and R 37be the alkylidene group of C2-C5 independently of one another; M 1for at least one in H, K and Na, m, n are the integer of 1-5 independently of one another.
The invention provides a kind of preparation method of polymkeric substance, it is characterized in that, this preparation method comprises the following steps, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, described monomer D has the structure shown in formula (17), described monomer E is for having at least one in the monomer of structure shown in formula (18)-Shi (20), described monomer F is for having at least one in the monomer of structure shown in formula (21)-Shi (25), and taking the total mole number of monomer in monomer mixture as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, it is 1,800 ten thousand-2,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of gained multipolymer after polyreaction,
formula (17),
formula (18), formula (19), formula (20),
formula (21),
formula (22),
formula (23),
formula (24),
formula (25);
Wherein, R 39for the alkylidene group of C1-C4; R 40-R 42be the alkyl of C1-C4 independently of one another; R 44-R 46, R 48-R 56, R 58-R 62, R 64-R 68, R 70-R 74respectively do for oneself-NHCOR 76or OH, R 76for the alkyl of C1-C4, and R 44-R 46in at least two be OH, R 48-R 50in at least two be OH, R 51-R 53in at least two be OH, R 54-R 56in at least two be OH, R 58-R 60in at least two be OH, R 61and R 62in at least one is OH, R 64-R 66in at least two be OH, R 67and R 68in at least one is OH, R 70-R 72in at least two be OH, R 73and R 74in at least one is OH, R 47for the alkylidene group of C1-C5, R 57for the alkylidene group of C3-C8, R 63, R 69and R 75be the alkylidene group of C2-C5 independently of one another; M 2for at least one in H, K and Na, o and p are the integer of 1-5 independently of one another.
In addition, the present invention also provides the polymkeric substance preparing by aforesaid method.And described terpolymer and described polymkeric substance are as the application of polymer oil-displacing agent.
The polymkeric substance that contains glycosyl structural unit of the present invention has high viscosity-average molecular weight, and the apparent viscosity of the solution being made by it is high: the viscosity-average molecular weight of the polymkeric substance making in embodiment 1-5 all can reach more than 1,800 ten thousand; The solution of the 1500mg/L being mixed with the salt solution that salinity is 33000mg/L is 7.34s in shearing rate -1, temperature is, under the condition of 25 DEG C, to have the k value up to 68mPas, is under the condition of 85 DEG C in temperature, also still has the k value of 18-26mPas, illustrates that polymkeric substance of the present invention still has high apparent viscosity under high salt high temperature and shear conditions; The product P 1-P5 obtaining in embodiment 1-5 is carried out to oil-displacing agent performance study and lab simulation oil displacement experiment, all there is good solubility and injection, and along with the increase of oil-displacing agent solution viscosity, increase with the recovery ratio improvement value of water ratio, and all keep good recovery ratio in the different injection phase, compared with not containing the copolymer of glycosyl structural unit, its viscosity, anti-high speed shear and recovery ratio improvement value are all improved largely.In addition, the preparation method of polymkeric substance provided by the invention has advantages of easy and monomer conversion is high.
Embodiment
The invention provides a kind of terpolymer, it is characterized in that, this terpolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A has the structure shown in formula (1), described structural unit B is for having at least one in the structural unit of structure shown in formula (2)-Shi (4), described structural unit C is for having at least one in the structural unit of structure shown in formula (5)-Shi (9), and taking the total mole number of structural unit in described terpolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, preferably, the content of described structural unit A is 10-70 % by mole, and the content of described structural unit B is 20-50 % by mole, and the content of described structural unit C is 10-40 % by mole, more preferably, the content of described structural unit A is 50-70 % by mole, and the content of described structural unit B is 20-30 % by mole, and the content of described structural unit C is 10-20 % by mole, the viscosity-average molecular weight of described terpolymer is 1,800 ten thousand-2,800 ten thousand, is preferably 1,800 ten thousand-2,500 ten thousand,
formula (1),
formula (2), formula (3), formula (4),
formula (5),
formula (6),
formula (7),
formula (8),
formula (9),
Wherein, R 1for the alkylidene group of C1-C4, be preferably methylene radical; R 2-R 5be the alkyl of C1-C4 independently of one another, be preferably methyl; R 6-R 8, R 10-R 18, R 20-R 24, R 26-R 30, R 32-R 36respectively do for oneself-NHCOR 38or OH, R 38for the alkyl of C1-C4, be preferably methyl; And R 6-R 8in at least two be OH, be preferably OH; R 10-R 12in at least two be OH, R 13-R 15in at least two be OH, be preferably OH; R 16-R 18in at least two be OH, R 20-R 22in at least two be OH, be preferably OH; R 23and R 24in at least one is OH, R 26-R 28in at least two be OH, be preferably OH; R 29and R 30in at least one is OH, R 32-R 34in at least two be OH, be preferably OH; R 35and R 36in at least one is OH, R 9for the alkylidene group of C1-C5, be preferably ethylidene; R 19for the alkylidene group of C3-C8, be preferably pentylidene; R 25, R 31and R 37be the alkylidene group of C2-C5 independently of one another, be all preferably propylidene; M 1for at least one in H, K and Na, be preferably H; M, n are the integer of 1-5 independently of one another, and m is preferably 3, n and is preferably 1.
In the present invention, in structural formula for well known in the art, represent that the substituting group on sugar ring both can be upper at straight key (a key), also can be upper at flat key (e key), similarly, in structural formula with also representing that O can be both that a key is connected with the mode of connection of two sugar rings, can be also that e key connects.
The present inventor finds under study for action, the polymer oil-displacing agent that the ter-polymers being made up of specific structural unit B and structural unit C is made can be obtained fabulous oil displacement efficiency, in the present invention, the foundation of polymer oil-displacing agent displacement system and the mensuration of oil displacement efficiency (as set up synthetic core, the calculating of recovery ratio etc. of irreducible water) can be for the method for this area routine, as carried out according to enterprise's method: Q/HNYJ316-2007 (Henan Oil Field experimental center instruction).
For example, preferably, described structural unit B, for having the structural unit of structure shown in formula (2), more preferably has the structural unit of structure shown in formula (10), under most preferred case, and R 1for methylene radical; Described structural unit C is for having the structural unit of structure shown in formula (5), more preferably there is the structural unit of structure shown in formula (11), or described structural unit C, for having the structural unit of structure shown in formula (8), more preferably has the structural unit of structure shown in formula (12);
formula (10), formula (11),
formula (12).
Or preferably, described structural unit B is for having the structural unit of structure shown in formula (3); Described structural unit C, for having the structural unit of structure shown in formula (6), more preferably has the structural unit of structure shown in formula (13);
formula (13).
Again or, preferably, described structural unit B, for having the structural unit of structure shown in formula (4), more preferably has the structural unit of structure shown in formula (14); Described structural unit C is for having the structural unit of structure shown in formula (7), more preferably there is the structural unit of structure shown in formula (15), or described structural unit C, for having the structural unit of structure shown in formula (9), more preferably has the structural unit of structure shown in formula (16).
formula (14),
formula (15),
formula (16).
The invention provides a kind of preparation method of polymkeric substance, it is characterized in that, this preparation method comprises the following steps, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, described monomer D has the structure shown in formula (17), described monomer E is for having at least one in the monomer of structure shown in formula (18)-Shi (20), described monomer F is for having at least one in the monomer of structure shown in formula (21)-Shi (25), and taking the total mole number of monomer in monomer mixture as benchmark, the content of described monomer D is 5-95 % by mole, the content of described monomer E is 2.5-90 % by mole, the content of described monomer F is 0.5-90 % by mole, preferably, the content of described monomer D is 10-70 % by mole, and the content of described monomer E is 20-50 % by mole, and the content of described monomer F is 10-40 % by mole, more preferably, the content of described monomer D is 50-70 % by mole, and the content of described monomer E is 20-30 % by mole, and the content of described monomer F is 10-20 % by mole, it is 1,800 ten thousand-2,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of gained multipolymer after polyreaction, is preferably 1,800 ten thousand-2,500 ten thousand,
formula (17),
formula (18), formula (19), formula (20),
formula (21),
formula (22),
formula (23),
formula (24),
formula (25);
Wherein, R 39for the alkylidene group of C1-C4, be preferably methylene radical; R 40-R 42be the alkyl of C1-C4 independently of one another, be preferably methyl; R 44-R 46, R 48-R 56, R 58-R 62, R 64-R 68, R 70-R 74respectively do for oneself-NHCOR 76or OH, R 76for the alkyl of C1-C4, be preferably methyl, and R 44-R 46in at least two be OH, be preferably OH; R 48-R 50in at least two be OH, R 51-R 53in at least two be OH, be preferably OH; R 54-R 56in at least two be OH, R 58-R 60in at least two be OH, be preferably OH; R 61and R 62in at least one is OH, R 64-R 66in at least two be OH, be preferably OH; R 67and R 68in at least one is OH, R 70-R 72in at least two be OH, be preferably OH; R 73and R 74in at least one is OH, R 47for the alkylidene group of C1-C5, be preferably ethylidene; R 57for the alkylidene group of C3-C8, be preferably pentylidene; R 63, R 69and R 75be the alkylidene group of C2-C5 independently of one another, be all preferably propylidene; M 2for at least one in H, K and Na, be preferably H; O and p are the integer of 1-5 independently of one another, and o is preferably 3, p and is preferably 1.
According to the present invention, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is preferably 0.05-0.5: 1, and more preferably 0.15-0.4: 1, most preferably be 0.2-0.4: 1.
According to the present invention, described initiator can be the various initiators in this area, as be selected from azo series initiators and redox series initiators, the consumption of described azo series initiators can be the 0-10 % by mole of the total mole number of monomer in monomer mixture, the consumption of described redox series initiators can be the 0-10 % by mole of the total mole number of monomer in monomer mixture, and the total amount of described azo series initiators and redox series initiators preferably meets: the consumption of described initiator is the 0.0001-10 % by mole of the total mole number of monomer in monomer mixture.
According to the present invention, preferably, described azo series initiators is selected from Diisopropyl azodicarboxylate, the two methylpent hydrochlorates, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride], be preferably 2,2 '-azo diisobutyl amidine hydrochloride, 2,2 '-azo two [at least one in the two methylpent hydrochlorates of 2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride and azo.
Described redox series initiators comprises Oxidizing and Reducing Agents, preferably, the mol ratio of described oxygenant and described reductive agent is 0.1-10: 1, meet under the condition of aforementioned proportion, the consumption of described oxygenant is preferably the 0.0001-1 % by mole of the total mole number of monomer in monomer mixture, more preferably 0.001-0.1 % by mole; Preferably, described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide, more preferably at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate; The consumption of described reductive agent is preferably the 0.0001-0.1 % by mole of the total mole number of monomer in monomer mixture, is preferably the 0.001-0.01 % by mole of the total mole number of monomer in monomer mixture; Described reductive agent can be inorganic reducing agent and/or organic reducing agent (chainextender), preferably, described inorganic reducing agent is selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate and vat powder, more preferably sodium bisulfite and/or S-WAT; Described organic reducing agent is preferably and is selected from N, N '-dimethyl-ethylenediamine, N, N '-dimethylated propyl diethylenetriamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, at least one in N-dimethyl amine, 3-methylamino-propylamine, Dimethylaminoethyl Methacrylate, N-(3-dimethylamino-propyl) Methacrylamide, most preferably be N, N '-dimethyl-ethylenediamine, N, N '-dimethylated propyl diethylenetriamine and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine.
According to the present invention, described polyreaction can also be carried out under various auxiliary agents exist; Described auxiliary agent can be selected from sequestrant and/or other auxiliary agents; Taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described sequestrant can be 0-2 % by mole, be preferably 0.0001-1 % by mole, more preferably 0.001-0.05 % by mole, the consumption of described other auxiliary agents can be 0-2 % by mole, be preferably 0.0001-1 % by mole, more preferably 0.001-0.2 % by mole, preferably, the consumption of described sequestrant and other auxiliary agents makes: taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described auxiliary agent is 0.0001-4 % by mole; Described sequestrant is preferably at least one in disodium ethylene diamine tetraacetate (EDTA), Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic, more preferably EDTA and/or Citrate trianion, described Citrate trianion can be for example Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate etc.; Described other auxiliary agents are preferably at least one being selected from urea, sodium formiate, Virahol and sodium hypophosphite, are preferably at least one in urea, sodium formiate.
The present inventor finds, exists at the same time under the condition of above-mentioned various initiator and auxiliary agent, can obtain the polymkeric substance that viscosity-average molecular weight is very high.
According to the present invention, the condition of described polyreaction can be the condition of this area routine, under existing at rare gas element, carries out, and the condition of described polyreaction can comprise: temperature is 0 DEG C-80 DEG C, is preferably 4-60 DEG C; Time is 1-32 hour, is preferably 11-28 hour; PH value is 5-13, and described pH value is by adding acid to regulate, and described acid is preferably mineral acid, and described mineral acid is preferably at least one in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid.In the time having AMPS in comonomer, need add alkali regulation system pH value, described alkali can be mineral alkali or organic amine compound, as being selected from least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, thanomin and trolamine, is preferably sodium hydroxide.
The present inventor finds under study for action, take following condition can obtain the polymkeric substance of ultra-high molecular weight:, preferably, described polyreaction comprises the three phases carrying out successively, the reaction conditions of first stage comprises: temperature is 0-10 DEG C, be preferably 4-10 DEG C, the time is 1-10 hour, more preferably 3-8 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 DEG C, and the time is 1-8 hour, more preferably 3-6 hour; The reaction conditions of phase III comprises: temperature is 35-60 DEG C, and the time is 2-14 hour, more preferably 7-12 hour.
The present inventor finds under study for action, in the time selecting specific monomer E to react with monomer F, the polymkeric substance of gained can be obtained fabulous oil displacement efficiency, for example preferably, described monomer E is for having the monomer of structure shown in formula (18), more preferably there is the monomer of structure shown in formula (26), under most preferred case, R 1for methylene radical; Described monomer F is for having the monomer of structure shown in formula (21), more preferably there is the monomer of structure shown in formula (27), or described monomer F, for having the monomer of structure shown in formula (24), more preferably has the monomer of structure shown in formula (28);
formula (26), formula (27),
formula (28).
Or preferably, described monomer E is for having the monomer of structure shown in formula (19); Described monomer F, for having the monomer of structure shown in formula (22), more preferably has the monomer of structure shown in formula (29);
formula (29).
Again or, preferably, described monomer E, for having the monomer of structure shown in formula (20), more preferably has the monomer of structure shown in formula (30); Described monomer F is for having the monomer of structure shown in formula (23), more preferably there is the monomer of structure shown in formula (31), or described monomer F, for having the monomer of structure shown in formula (25), more preferably has the monomer of structure shown in formula (32);
formula (30),
formula (31),
formula (32).
The present invention also provides the polymkeric substance making according to aforesaid method.
In addition, described terpolymer provided by the invention and described polymkeric substance can be as the polymer oil-displacing agents of three class oil reservoirs.
Below, by following examples, the present invention will be described in more detail.
Described intrinsic viscosity is measured according to GB12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M=([η]/K) 1 α, wherein K=4.5 × 10 -3, calculate α=0.80; Solid content carries out according to GB12005.2-89 determination of solid content method; Apparent viscosity is measured with Brookfield viscosmeter specifying to measure at temperature, when measurement shearing rate constant be 7.34s -1; Dissolution time is measured by GB12500.8-89, and the dissolution time of the product making in following examples is all less than 2 hours; The composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration.The mensuration of screen factor and filterable agent is carried out according to the method for SY/T 5862-93; The foundation of polymer oil-displacing agent displacement system and the mensuration of oil displacement efficiency (as set up synthetic core, the calculating of recovery ratio etc. of irreducible water) are according to enterprise's method: Q/HNYJ 316-2007 (Henan Oil Field experimental center instruction) carries out.
Embodiment 1
Under room temperature, by the monomer of structure shown in the acrylamide of 50.0g (AM), the AMPS of 50.0g and the formula of 35.3g (27) (according to document Journal of applied polymer science.1995, Vol.56, the method of 1615-1623 makes) join in reaction flask, add deionized water 287.0g, stirring is dissolved monomer completely, and the concentration that then slowly adds 38.6g is the NaOH aqueous solution of 25 % by weight, and stirs.Be the EDTA aqueous solution 5.5g of 1 % by weight to adding concentration in flask respectively, concentration is 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.1g, chainextender N, and N '-dimethyl-ethylenediamine 0.066g, urea 0.11g, fully stirs it is mixed.With concentration be 1 % by weight sodium hydroxide solution regulation system pH to 7.5.Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation is after 30 minutes, and adding concentration is 1 % by weight ammonium persulfate aqueous solution 1.1g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, reactor is airtight, remain on 4 DEG C, react after 5 hours, after being risen to 25 DEG C, temperature reacts 4 hours, then temperature is risen to 50 DEG C of reactions 10 hours, the gluey product obtaining is taken out, through granulation, dry, the polymeric articles P1 that pulverizes the sugary based structures unit that can receive ultra-high molecular weight.
P1 is carried out to various mensuration, quantitatively 13in C spectrum, there is the characteristic peak of C1~C6 in formula (27) sugar ring at 61.02~102.77ppm place, occurred the characteristic peak of the propanesulfonic acid carbon of AMPS at 50.01~59.20ppm, on while main chain-CH-CH 2-and the C characteristic peak stack of C=O, can determine that the copolymer molecule obtaining has the structure shown in formula (33), can calculate x1: y1: z1 by the integral area of characteristic peak is 1: 0.33: 0.17.Recording its viscosity-average molecular weight Mv by viscosity method is 2,065 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (33) and x1, y1 and z1 only express the number of types of structural unit, and do not represent the mode of connection of structural unit,
formula (33).
Comparative example 1
Method according to embodiment 1 is prepared multipolymer, different, does not add the monomer of structure shown in formula (19), thereby obtains the copolymer DP1 of AM and AMPS, and recording its viscosity-average molecular weight is 16,000,000.
Embodiment 2
By the AM of 45.0g, shown in the formula (29) of the NVP NVP of 34.2g and 49.1g, the monomer of structure is (according to document J.Chem.Soc., Perkin Trans.1, 2000, the method of 2091-2103 makes) join in polymerization bottle, add 495g deionized water, stirring is dissolved monomer completely, be the sodium citrate aqueous solution 5.65g of 0.1 % by weight to adding concentration in flask respectively, adding concentration is 2 of 0.1 % by weight, 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride aqueous solution 1.13g, add chainextender N, N '-dimethylated propyl diethylenetriamine 0.01g, adding concentration is 0.1 % by weight sodium sulfite solution 1.13g, add sodium formiate 0.01g, fully stir it is mixed.Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation is after 30 minutes, and to add concentration be 1 % by weight persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 2 DEG C, react after 8 hours, be warming up to 18 DEG C, react after 6 hours, be warming up to 40 DEG C of reactions 12 hours, the gluey product obtaining is taken out, through granulation, dry, the polymeric articles P2 that pulverizes the sugary based structures unit that can receive ultra-high molecular weight.
P2 is measured, quantitatively 13in C spectrum, there is the characteristic peak of C1~C6 in formula (29) sugar ring at 61.02~102.77ppm place, occurred the charateristic avsorption band of NVP simultaneously, and on main chain-CH-CH 2-and the C characteristic peak stack of C=O, can determine that the multipolymer obtaining has the structure shown in (34), can calculate x2: y2: z2 by the integral area of characteristic peak is 1: 0.49: 0.27.Recording its viscosity-average molecular weight Mv by viscosity method is 2,130 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (34) and x2, y2 and z2 only express type and the number of structural unit, and do not represent the mode of connection of structural unit,
formula (34).
Embodiment 3
Under room temperature, by the AM of 50.0g, shown in the DMAM of 28.9g and 39.4 formulas (31), the monomer of structure is (according to document Biomacromolecules, 2009, Vol.10, No.7, the method of 1846-1853 makes) join in polymerization bottle, add 298.0g deionized water, stirring is dissolved monomer completely, be the EDTA aqueous solution 5.65g of 0.5 % by weight to adding concentration in flask respectively, adding concentration is the two methylvaleric acid salt brine solution 1.13g of 1 % by weight azo, add chainextender N, N, N ', N '-Tetramethyl Ethylene Diamine 0.11g, adding concentration is 1 % by weight sodium sulfite solution 1.13g, add urea 0.05g, fully stir it is mixed.Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation is after 30 minutes, and to add concentration be 1 % by weight sodium persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 8 DEG C, react after 3 hours, be warming up to 30 DEG C, react after 3 hours, be warming up to 60 DEG C of reactions 8 hours, the gluey product obtaining is taken out, through granulation, dry, the polymeric articles P3 that pulverizes the sugary based structures unit that can receive ultra-high molecular weight.
P3 is carried out to various mensuration, quantitatively in 13C spectrum, occurred the characteristic peak of C1~C6 in formula (31) sugar ring at 61.02~102.77ppm place, occur the charateristic avsorption band of DMAM simultaneously, and on main chain-CH-CH 2-and the C characteristic peak stack of C=O, can determine that the multipolymer obtaining has the structure shown in formula (35), can calculate x3: y3: z3 by the integral area of characteristic peak is 1: 0.41: 0.19.Recording its viscosity-average molecular weight Mv by viscosity method is 2,489 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (35) and x3, y3 and z3 only express the number of types of structural unit, and do not represent the mode of connection of structural unit,
formula (35).
Embodiment 4
Under room temperature, by the monomer of structure shown in the acrylamide of 50.0g (AM), the AMPS of 50.0g and the formula of 59.8g (28) (according to document Carbohydrate Research.1998,305, the method of 443-461 makes) join in reaction flask, add deionized water 350g, stirring is dissolved monomer completely, and the concentration that then slowly adds 38.6g is the NaOH aqueous solution of 25 % by weight, and stirs.Be the EDTA aqueous solution 5.3g of 1 % by weight to adding concentration in flask respectively, concentration is 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.08g, chainextender N, and N '-dimethyl-ethylenediamine 0.06g, urea 0.1g, fully stirs it is mixed.With concentration be 1 % by weight sodium hydroxide solution regulation system pH to 7.5.Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation is after 30 minutes, and adding concentration is 1 % by weight ammonium persulfate aqueous solution 1.1g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, remain on 3 DEG C, react after 5 hours, after being risen to 20 DEG C, temperature reacts after 4 hours, temperature is risen to 50 DEG C of reactions 10 hours, the gluey product obtaining is taken out, through granulation, dry, the polymeric articles P4 that pulverizes the sugary based structures unit that can receive ultra-high molecular weight.
P4 is carried out to various mensuration, quantitatively 13in C spectrum, there is the characteristic peak of C1~C6 in formula (28) sugar ring at 61.02~102.77ppm place, occurred the characteristic peak of the propanesulfonic acid carbon of AMPS at 50.01~59.20ppm, on while main chain-CH-CH 2-and the C characteristic peak stack of C=O, can determine that the copolymer molecule obtaining has the structure shown in formula (36), can calculate x4: y4: z4 by the integral area of characteristic peak is 1: 0.34: 0.18.Recording its viscosity-average molecular weight Mv by viscosity method is 1,920 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (36) and x4, y4 and z4 only express type and the number of structural unit, and do not represent the mode of connection of structural unit,
formula (36).
Embodiment 5
Under room temperature, by the AM of 50.0g, shown in the DMAM of 23.9g and 163.6 formulas (32), the monomer of structure is (according to document J.Chem.Soc., Perkin Trans.1, 2000, the method of 3000-3005 makes) join in polymerization bottle, add 602g deionized water, stirring is dissolved monomer completely, be the EDTA aqueous solution 5.65g of 1 % by weight to adding concentration in flask respectively, adding concentration is 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.13g, add chainextender N ', N-dimethyl-ethylenediamine 0.01g, adding concentration is 0.1 % by weight sodium sulfite solution 1.13g, add urea 0.11g, fully stir it is mixed.Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation is after 30 minutes, and to add concentration be 1 % by weight ammonium persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 5 DEG C, react after 6 hours, be warming up to 25 DEG C, react after 4 hours, be warming up to 45 DEG C of reactions 12 hours, the gluey product obtaining is taken out, through granulation, dry, the polymeric articles P5 that pulverizes the sugary based structures unit that can receive ultra-high molecular weight.
P5 is carried out to various mensuration, quantitatively 13in C spectrum, there is the characteristic peak of C1~C6 in formula (32) sugar ring at 61.02~102.77ppm place, occurred the charateristic avsorption band of DMAM simultaneously, and on main chain-CH-CH 2-and the C characteristic peak stack of C=O, can determine that the multipolymer obtaining has the structure shown in formula (37), can calculate x5: y5: z5 by the integral area of characteristic peak is 1: 0.34: 0.17.Recording its viscosity-average molecular weight Mv by viscosity method is 2,556 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (37) and x5, y5 and z5 only express type and the number of structural unit, and do not represent the mode of connection of structural unit,
formula (37).
Test case 1
P1-P5 and DP1 are dissolved in the salt solution that salinity is 33000mg/L, be made into respectively concentration and be the as clear as crystal thick liquid L1-L5 of 1500mg/L and DL1 (in the present invention, for the water of polymer dissolution is to the salt solution that above-mentioned salinity is 33000mg/L), test soln apparent viscosity at 25 DEG C and 85 DEG C, data are as shown in table 1.
Table 1
Embodiment L1 L2 L3 L4 L5 DL1
Apparent viscosity (mPas) at 25 DEG C 63.4 55.9 52.8 64.3 68.0 48.6
Apparent viscosity (mPas) at 85 DEG C 20.5 19.4 18.8 21.8 26.0 14.3
Table 1 shown 25 DEG C and 85 DEG C at the apparent viscosity of the solution that is mixed with of P1-P5 and DP1.In the salt solution of high salinity, the apparent viscosity of L1-L5 is very high, illustrates that polymkeric substance of the present invention, under high temperature and high salt and shear conditions, still possesses higher apparent viscosity, and especially, compared with not containing the polymkeric substance DL1 of glycosyl structure, advantage is remarkable.
Test case 2
P1-P5 and DP1 are carried out to oil-displacing agent performance study and lab simulation oil displacement experiment.
Synthetic core porosity used is about 30%, rate of permeation is about 2.0 μ m 2, containing 90 % by weight SiO 2, 10 % by weight Na 2o.Simulation oil sample is mixing oil, and it consists of oil from Shengli oil field and neutral kerosene, and wherein the ratio of oil from Shengli oil field and neutral kerosene is 1: 0.9.Experimental water, as local water and injected water are respectively Shengli Oil Field local water and injected water, its composition is in table 2.
Table 2
Water sample Ca 2+ Mg 2+ Na +And K + Cl - SO 4 2- HCO 3 -
Local water 612 302 13732 16373 64 1398
Injected water 220 30 4537 3885 119 783
Table 2 has shown the moiety of Shengli Oil Field local water and injected water.
(1) test result of solubility property
The solid content that P1-P5 and DP1 record after 105 DEG C of dry 90min is respectively 95.2 % by weight, 90.6 % by weight, 89.7 % by weight, 91.5 % by weight and 93.2 % by weight.
Take separately the 1g in above-mentioned dried P1-P5, under stirring, 400r/min is dissolved in 1000ml distilled water, after continuously stirring 90min, place and spend the night, with the membrane filtration of aperture 5 μ m, filter cake is measured after dry 90min at 105 DEG C together with filter membrane, and the content (with respect to the dried product of the 1g taking) that records water-insoluble on filter membrane (being filter cake) is respectively 0.05 % by weight, 0.03 % by weight, 0.01 % by weight, 0.03 % by weight and 0.02 % by weight.Illustrate that polymer dissolution according to the present invention is functional, the solution homogeneous making.
(2) test result of injectability
Above-mentioned synthetic core is found time and use stratum water saturation, the solution with P1-P5 and DP1 preparation that implantation concentration is 1000mg/L at 80 DEG C, injection pressure increases with the increase linearity of injection speed substantially, in injection process, do not find pressure jump phenomenon, the screen factor of the solution of the P1-P5 that experiment records and DP1 preparation is respectively 18.1,19.2,17.5,17.6 and 18.7, filterable agent is respectively 1.04,1.02,1.07,1.05 and 1.03, and this solution that shows P1-P5 preparation has good injectability as oil-displacing agent.
Test case 3
The viscosity of oil-displacing agent solution and the relation of recovery ratio that this test case becomes for testing polymer formulation of the present invention.
With the flow of 0.2ml/min, injected water is pumped into the synthetic core of built vertical irreducible water at 80 DEG C, to moisture 98 % by weight of rock core effluent liquid, calculate waterflood recovery efficiency factor Rw.The oil-displacing agent solution of the different viscositys of 0.3PV (injection pore volume) (being different concns) reinjects, be driven to moisture 98 % by weight of effluent liquid with injected water, calculate recovery ratio Rp and the recovery ratio improvement value Δ R=(Rp-Rw) of oil-displacing agent solution.Result is as shown in table 3.
Table 3
Table 3 has shown the viscosity, recovery ratio and the recovery ratio improvement value that P1-P5 are mixed with to the solution of different concns, and wherein, P1-1, P1-2 and P1-3 represent that respectively all the other roughly the same with the solution of the different concns of P1 preparation.Result by table 3 can find out, along with the increase of oil-displacing agent solution viscosity, recovery ratio improvement value Δ R increases.
Test case 4
This test case is for testing the oil-displacing agent solution of polymer formulation one-tenth of the present invention at the oil displacement efficiency of different injection phase.
For the particular case of Shengli Oil Field, at 80 DEG C, investigate the different injection phase and utilized the displacement effect of the oil-displacing agent solution of polymer of the present invention.The synthetic glass long tube rock core of the quartz sand filling of long 30cm, internal diameter 2.3cm is found time, use stratum water saturation, and use injected water displacement after setting up irreducible water by simulated oil, after reaching 4 indicating values of following table, effluent liquid water ratio calculates corresponding waterflood recovery efficiency factor Rw, the oil-displacing agent solution that the P1-P5 of metaideophone 0.3PV concentration 1500mg/l and DP1 make, be driven to moisture 98 % by weight of effluent liquid with oil-displacing agent solution, calculate the recovery ratio improvement value Δ R of note oil-displacing agent solution.
Result is as shown in table 4.
Table 4
Water ratio (% by weight) 90.91 93.23 96.00 98.60
P1 ΔR(%) 22.96 19.37 18.62 16.33
P2 ΔR(%) 19.59 17.68 16.05 14.19
P3 ΔR(%) 19.71 17.92 16.35 14.97
P4 ΔR(%) 24.79 21.18 21.10 19.41
P5 ΔR(%) 24.96 21.47 21.32 19.66
DP1 ΔR(%) 18.67 16.85 14.28 12.89
As can be seen from Table 4, even if the oil-displacing agent solution that effluent liquid water ratio adds P1-P5 to make in 98.60 % by weight still has obvious recovery ratio improvement value.
Above-mentioned test result can illustrate that the solution that polymkeric substance of the present invention is made still has high apparent viscosity under high salt high temperature and shear conditions; And all show good solubility and injection, along with the increase of oil-displacing agent solution viscosity, increase with the recovery ratio improvement value of water ratio, and all keep good recovery ratio in the different injection phase, compared with not containing the copolymer of glycosyl structural unit, its viscosity, anti-high speed shear and recovery ratio improvement value all improve a lot.In addition, the preparation method of polymkeric substance provided by the invention has advantages of easy and monomer conversion is high.

Claims (25)

1. a terpolymer, it is characterized in that, this terpolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A has the structure shown in formula (1), described structural unit B is for having at least one in the structural unit of structure shown in formula (2)-Shi (4), described structural unit C is for having at least one in the structural unit of structure shown in formula (5)-Shi (9), and taking the total mole number of structural unit in described terpolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, the viscosity-average molecular weight of described terpolymer is 1,800 ten thousand-2,800 ten thousand,
Wherein, R 1for the alkylidene group of C1-C4; R 2-R 5be the alkyl of C1-C4 independently of one another; R 6-R 8, R 10-R 18, R 20-R 24, R 26-R 30, R 32-R 36respectively do for oneself-NHCOR 38or-OH, R 38for the alkyl of C1-C4, and R 6-R 8in at least two be-OH, R 10-R 12in at least two be-OH, R 13-R 15in at least two be-OH, R 16-R 18in at least two be-OH, R 20-R 22in at least two be-OH, R 23and R 24in at least one is-OH, R 26-R 28in at least two be-OH, R 29and R 30in at least one is-OH, R 32-R 34in at least two be-OH, R 35and R 36in at least one is-OH, R 9for the alkylidene group of C1-C5, R 19for the alkylidene group of C3-C8, R 25, R 31and R 37be the alkylidene group of C2-C5 independently of one another; M 1for at least one in H, K and Na, m, n are the integer of 1-5 independently of one another.
2. terpolymer according to claim 1, wherein, taking the total mole number of structural unit in described terpolymer as benchmark, the content of described structural unit A is 10-70 % by mole, the content of described structural unit B is 20-50 % by mole, and the content of described structural unit C is 10-40 % by mole; The viscosity-average molecular weight of described terpolymer is 1,800 ten thousand-2,500 ten thousand.
3. terpolymer according to claim 1, wherein, described structural unit B is for having the structural unit of structure shown in formula (2); Described structural unit C is for having the structural unit of structure shown in the structural unit of structure shown in formula (5) or formula (8).
4. terpolymer according to claim 3, wherein, described structural unit B is for having the structural unit of structure shown in formula (10); Described structural unit C is for having the structural unit of structure shown in the structural unit of structure shown in formula (11) or formula (12);
5. terpolymer according to claim 1, wherein, described structural unit B is for having the structural unit of structure shown in formula (3); Described structural unit C is for having the structural unit of structure shown in formula (6).
6. terpolymer according to claim 5, wherein, described structural unit C is for having the structural unit of structure shown in formula (13);
7. terpolymer according to claim 1, wherein, described structural unit B is for having the structural unit of structure shown in formula (4); Described structural unit C is for having the structural unit of structure shown in the structural unit of structure shown in formula (7) or formula (9).
8. terpolymer according to claim 7, wherein, described structural unit B is for having the structural unit of structure shown in formula (14); Described structural unit C is for having the structural unit of structure shown in the structural unit of structure shown in formula (15) or formula (16);
9. the preparation method of a polymkeric substance, it is characterized in that, this preparation method comprises the following steps, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, described monomer D has the structure shown in formula (17), described monomer E is for having at least one in the monomer of structure shown in formula (18)-Shi (20), described monomer F is for having at least one in the monomer of structure shown in formula (21)-Shi (25), and taking the total mole number of monomer in monomer mixture as benchmark, the content of described monomer D is 5-95 % by mole, the content of described monomer E is 2.5-90 % by mole, the content of described monomer F is 0.5-90 % by mole, it is 1,800 ten thousand-2,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of gained multipolymer after polyreaction,
Wherein, R 39for the alkylidene group of C1-C4; R 40-R 42be the alkyl of C1-C4 independently of one another; R 44-R 46, R 48-R 56, R 58-R 62, R 64-R 68, R 70-R 74respectively do for oneself-NHCOR 76or-OH, R 76for the alkyl of C1-C4, and R 44-R 46in at least two be-OH, R 48-R 50in at least two be-OH, R 51-R 53in at least two be-OH, R 54-R 56in at least two be-OH, R 58-R 60in at least two be-OH, R 61and R 62in at least one is-OH, R 64-R 66in at least two be-OH, R 67and R 68in at least one is-OH, R 70-R 72in at least two be-OH, R 73and R 74in at least one is-OH, R 47for the alkylidene group of C1-C5, R 57for the alkylidene group of C3-C8, R 63, R 69and R 75be the alkylidene group of C2-C5 independently of one another; M 2for at least one in H, K and Na, o and p are the integer of 1-5 independently of one another.
10. method according to claim 9, wherein, taking the total mole number of monomer in monomer mixture as benchmark, the content of described monomer D is 10-70 % by mole, and the content of described monomer E is 20-50 % by mole, and the content of described monomer F is 10-40 % by mole; It is 1,800 ten thousand-2,500 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of gained multipolymer after polyreaction.
11. methods according to claim 9, wherein, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.05-0.5:1.
12. methods according to claim 11, wherein, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.15-4:1.
13. according to the method described in any one in claim 9-12, wherein, described initiator is selected from azo series initiators and redox series initiators, the consumption of described azo series initiators is the 0-10 % by mole of the total mole number of monomer in monomer mixture, the consumption of described redox series initiators is the 0-10 % by mole of the total mole number of monomer in monomer mixture, and the consumption of described initiator is the 0.0001-10 % by mole of the total mole number of monomer in monomer mixture; Described azo series initiators is selected from Diisopropyl azodicarboxylate, the two methylpent hydrochlorates, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, described redox series initiators comprises Oxidizing and Reducing Agents, the mol ratio of described oxygenant and described reductive agent is 0.1-10:1, and described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide; Described reductive agent is inorganic reducing agent and/or organic reducing agent, described inorganic reducing agent is selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate and vat powder, described organic reducing agent is selected from N, N '-dimethyl-ethylenediamine, N, N '-dimethylated propyl diethylenetriamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, at least one in N-dimethyl amine, 3-methylamino-propylamine, dimethylaminoethyl methacrylate, N-(3-dimethylamino-propyl) Methacrylamide.
14. methods according to claim 9, wherein, described polyreaction is carried out under auxiliary agent exists, and described auxiliary agent is selected from sequestrant and/or other auxiliary agents; Taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described sequestrant is 0-2 % by mole, and the consumption of described other auxiliary agents is 0-2 % by mole, and the consumption of described auxiliary agent is 0.0001-4 % by mole; Described sequestrant is selected from least one in disodium ethylene diamine tetraacetate, citric acid, Citrate trianion and poly-hydroxyl acrylic; Other auxiliary agents are selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite.
15. methods according to claim 14, wherein, taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described sequestrant is 0.0001-1 % by mole, the consumption of described other auxiliary agents is 0.0001-1 % by mole.
16. method according to claim 9, wherein, described polyreaction is carried out under rare gas element exists, and the condition of described polyreaction comprises: temperature is 0 DEG C-80 DEG C, and the time is 1-32 hour, and pH value is 5-13.
17. methods according to claim 16, wherein, described polyreaction comprises the three phases carrying out successively, and the reaction conditions of first stage comprises: temperature is 0-10 DEG C, and the time is 1-10 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 DEG C, and the time is 1-8 hour; The reaction conditions of phase III comprises: temperature is 35-60 DEG C, and the time is 2-14 hour.
18. methods according to claim 9, wherein, described monomer E is for having the monomer of structure shown in formula (18); Described monomer F is for having the monomer of structure shown in the monomer of structure shown in formula (21) or formula (24).
19. methods according to claim 18, wherein, described monomer E is for having the monomer of structure shown in formula (26); Described monomer F is for having the monomer of structure shown in the monomer of structure shown in formula (27) or formula (28);
20. methods according to claim 9, wherein, described monomer E is for having the monomer of structure shown in formula (19); Described monomer F is for having the monomer of structure shown in formula (22).
21. methods according to claim 20, wherein, described monomer F is for having the monomer of structure shown in formula (29);
22. methods according to claim 9, wherein, described monomer E is for having the monomer of structure shown in formula (20); Described monomer F is for having the monomer of structure shown in the monomer of structure shown in formula (23) or formula (25).
23. methods according to claim 22, wherein, described monomer E is for having the monomer of structure shown in formula (30); Described monomer F is for having the monomer of structure shown in the monomer of structure shown in formula (31) or formula (32);
24. polymkeric substance that make according to the method described in any one in claim 9-23.
Polymkeric substance described in acrylamide terpolymer or claim 24 in 25. claim 1-8 described in any one is as the application of polymer oil-displacing agent.
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