CN102746441B - Acrylamide terpolymer and polymer and preparation method and application thereof - Google Patents
Acrylamide terpolymer and polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an acrylamide terpolymer, characterized in that the acrylamide 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 a structural unit of formula (5) or (6), and the viscosity-average molecular weight of the acrylamide terpolymer is 18,000,000-25,000,000. 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
Technical field
The present invention relates to the preparation method of a kind of acrylamide terpolymer, a kind of polymkeric substance and the polymkeric substance prepared by the method, and described acrylamide terpolymer and described polymkeric substance are as the application of polymer oil-displacing agent.
Background technology
Oil field generally enters today of high water-cut development period at home, the polymer flooding that the high molecular partially hydrolyzed polyacrylamide (HPAM) of take is main representative improves the oil recovery factor technology and becomes effective day, and is used widely in one, two class oil reservoirs of low temperature, less salt.But the formation condition characteristics for 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, with divalent-metal ion complexings such as calcium, magnesium, easily generate the problems such as precipitation, and its actual oil displacement efficiency in three class oil reservoirs is significantly descended.
At present for the oil reservoir resource (formation temperature 70-95 ℃, 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 stratum condition has become the major fields of industry member, academia's research and development.
At present, adopt the 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 the acrylamide copolymerization, but still can't meet the requirement of three class oil reservoirs fully, have 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 the high temperature and high salt formation condition is not high; 2. differ larger due to above-mentioned functions monomer and acrylamide activity, in multipolymer, the content of functional monomer is not high, and its heat-resistant stability and salt tolerance remain further to be improved; 3. when 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: in reaction vessel, add acrylamide and sulfonated monomers, fully stir monomer is dissolved fully, add redox initiation system, polymerization temperature is controlled at 15-30 ℃, 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 than 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 the polyphosphazene polymer polysaccharide, are to integrate thickening, suspension, emulsification, stabilization, the xanthan gum that performance is comparatively superior.With HPAM, compare, Sclerotium gum and xanthan gum are because of the polysaccharide structures unit of its uniqueness had, and make it as oil-displacing agent, use and may have the following advantages: its solution still has high k value 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 the 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, will be with the polymerisable monomer of 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, can improve the apparent viscosity under the warm high salt geology condition of height when keeping the excellent viscoelasticity of linear macromolecule, 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 Copolymer Films with Pendant Monosaccharides, J Appl Polym Sci, 1995, 56:1615) reported the preparation method of a kind 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, under 70 ℃, reaction is 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, can't use as Flooding Agent for EOR.
Summary of the invention
The objective of the invention is to overcome the defect of above-mentioned prior art, provide a kind of molecular weight superelevation, apparent viscosity is high, heat-resisting and good salt tolerance, anti-high-shear performance are good, polymkeric substance that good water solubility and dissolution time are short and its preparation method and application.
The invention provides a kind of acrylamide terpolymer, it is characterized in that, this acrylamide terpolymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit of described structural unit A for thering is 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), the structural unit of described structural unit C for thering is structure shown in formula (5) and/or formula (6), and the total mole number of structural unit in described acrylamide terpolymer of take is 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 acrylamide terpolymer is 1,800 ten thousand-2,500 ten thousand,
Wherein, R
1alkylidene group for C1-C4; R
2, R
3, R
4and R
5be the alkyl of C1-C4 independently of one another; R
6-R
16be independently of one another-NHCOR
17or OH, R
17for the alkyl of C1-C4, and R
6-R
8in at least two be OH, R
9and R
10in at least one is OH, R
11-R
13in at least two be OH, R
14-R
16in at least two be OH; M
1for at least one in H, Na and K; M and 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 carry out polyreaction in water, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, the monomer of described monomer D for thering is structure shown in formula (12), described monomer E is for having at least one in the monomer of structure shown in formula (13)-Shi (15), the monomer of described monomer F for thering is structure shown in formula (16) and/or formula (17), and the total mole number of monomer in described monomer mixture of take is 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-2,500 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction,
Wherein, R
18alkylidene group for C1-C4; R
19-R
22be the alkyl of C1-C4 independently of one another; R
23-R
33be independently of one another-NHCOR
34or OH, R
34for the alkyl of C1-C4, and R
23-R
25in at least two be OH, R
26and R
27in at least one is OH, R
28-R
30in at least two be OH, R
31-R
33in at least two be OH; M
2for at least one in H, Na and K; O and p are the integer of 1-5 independently of one another.
In addition, the present invention also provides the polymkeric substance prepared by aforesaid method.And described acrylamide terpolymer and described polymkeric substance are as the application of polymer oil-displacing agent.
The polymkeric substance that contains the glycosyl structural unit of the present invention has high viscosity-average molecular weight, and the viscosity-average molecular weight of the polymkeric substance made in embodiment 1-3 all can reach more than 1,800 ten thousand; The solution of the 1500mg/L that the salt solution that is 33000mg/L by salinity is mixed with it is 7.34s in shearing rate
-1, under the condition that temperature is 25 ℃, the k value up to 60.4mPas is arranged, under the condition that is 85 ℃ in temperature, also still have the k value of 18-21mPas, illustrate that polymkeric substance of the present invention still has high apparent viscosity under high salt high temperature and shear conditions; The product P 1-P3 obtained in embodiment 1-3 is carried out to oil-displacing agent performance study and lab simulation oil displacement experiment, all show good solubility and injection, and the increase along with the oil-displacing agent solution viscosity, with the recovery ratio improvement value of water ratio, increase, and all kept recovery ratio preferably in the different injection phase, with the copolymer that does not contain the glycosyl structural unit, compare, its viscosity, anti-high speed shear and recovery ratio improvement value all are 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 acrylamide terpolymer, it is characterized in that, this acrylamide terpolymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit of described structural unit A for thering is 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), the structural unit of described structural unit C for thering is structure shown in formula (5) and/or formula (6), and the total mole number of structural unit in described acrylamide terpolymer of take is 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 acrylamide terpolymer is 1,800 ten thousand-2,500 ten thousand, is preferably 1,800 ten thousand-2,000 ten thousand,
Wherein, R
1alkylidene group for C1-C4, be preferably methylene radical; R
2, R
3, R
4and R
5be the alkyl of C1-C4 independently of one another, be preferably methyl; R
6-R
16be independently of one another-NHCOR
17or OH, R
17alkyl for C1-C4, be preferably methyl, and R
6-R
8in at least two be OH, R
9and R
10in at least one is OH, R
11-R
13in at least two be OH, preferably be OH; R
14-R
16in at least two be OH, preferably be OH; M
1for at least one in H, Na and K, be preferably H; M and n are the integer of 1-5 independently of one another, and preferably, m is that 1, n is 3.
In the present invention, in structural formula
for well known in the art, mean that the substituting group on the 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 meaning that O can be both that a key is connected with the mode of connection of two sugar rings, can be also that the e key connects.
The present inventor finds under study for action, the polymer oil-displacing agent that the ter-polymers be comprised 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 the synthetic core of setting up irreducible water, the calculating of recovery ratio etc.) can be 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, the structural unit of described structural unit B for thering is structure shown in formula (2), the structural unit that more preferably there is structure shown in formula (7), under most preferred case, R
1for methylene radical; Simultaneously, the structural unit of described structural unit C for thering is structure shown in formula (5), the structural unit that more preferably there is structure shown in formula (8);
Perhaps, preferably, the structural unit of described structural unit B for thering is structure shown in formula (3); The structural unit of described structural unit C for thering is structure shown in formula (6), the structural unit that more preferably there is structure shown in formula (9);
Again or, preferably, described structural unit B is structural unit with structure shown in formula (4), the structural unit that more preferably has structure shown in formula (10); The structural unit of described structural unit C for thering is structure shown in formula (6), the structural unit that more preferably there is structure shown in formula (11);
formula (10),
The present invention also 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 carry out polyreaction in water, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, the monomer of described monomer D for thering is structure shown in formula (12), described monomer E is for having at least one in the monomer of structure shown in formula (13)-Shi (15), the monomer of described monomer F for thering is structure shown in formula (16) and/or formula (17), and the total mole number of monomer in described monomer mixture of take is 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-2,500 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction, is preferably 1,800 ten thousand-2,000 ten thousand,
Wherein, R
18alkylidene group for C1-C4, be preferably methylene radical; R
19-R
22be the alkyl of C1-C4 independently of one another, be preferably methyl; R
23-R
33be independently of one another-NHCOR
34or OH, R
34alkyl for C1-C4, be preferably methyl, and R
23-R
25in at least two be OH, R
26and R
27in at least one is OH, R
28-R
30in at least two be OH, preferably be OH; R
31-R
33in at least two be OH, preferably be OH; M
2for at least one in H, Na and K, be preferably H; O and p are the integer of 1-5 independently of one another, and preferably, o is that 1, p is 3.
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 0.15-0.4 more preferably: 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 0.0001-10 % by mole that the consumption of described initiator is the total mole number of monomer in monomer mixture.
In 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], more 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; The total mole number of monomer in described monomer mixture of take is benchmark, the consumption of described sequestrant can be 0-2 % by mole, be preferably 0.0001-1 % by mole, 0.001-0.05 % by mole more preferably, the consumption of described other auxiliary agents can be 0-2 % by mole, be preferably 0.0001-1 % by mole, 0.001-0.2 % by mole more preferably, preferably, the consumption of described sequestrant and other auxiliary agents makes: the total mole number of monomer in described monomer mixture of take is benchmark, and 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 is such as thinking 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 access 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 ℃-80 ℃, is preferably 4-60 ℃; Time is 1-32 hour, is preferably 11-28 hour; The pH value is 5-13, and described pH value is by adding acid to be regulated, 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.While in comonomer, AMPS being arranged, need add alkali regulation system pH value, described alkali can be mineral alkali or organic amine compound, as be 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 access the polymkeric substance of ultra-high molecular weight:, preferably, described polyreaction comprises the three phases carried out successively, the reaction conditions of first stage comprises: temperature is 0-10 ℃, be preferably 4-10 ℃, the time is 1-10 hour, more preferably 3-8 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 ℃, and the time is 1-8 hour, more preferably 3-6 hour; The reaction conditions of phase III comprises: temperature is 35-60 ℃, and the time is 2-14 hour, more preferably 7-12 hour.
In addition, the present inventor finds under study for action, when selecting specific monomer E to be reacted with monomer F, the polymkeric substance of gained can be obtained fabulous oil displacement efficiency, for example, and preferably, the monomer of described monomer E for thering is structure shown in formula (13), the monomer that more preferably there is structure shown in formula (18), most preferably, R
1for methylene radical; The monomer of described monomer F for thering is structure shown in formula (16), the monomer that more preferably there is structure shown in formula (19);
formula (18),
Perhaps, preferably, the monomer of described monomer E for thering is structure shown in formula (14); The monomer of described monomer F for thering is structure shown in formula (17), the monomer that more preferably there is structure shown in formula (20);
Again or, preferably, described monomer E is monomer with structure shown in formula (15), the monomer that more preferably has structure shown in formula (21); The monomer of described monomer F for thering is structure shown in formula (17), the monomer that more preferably there is structure shown in formula (22);
The present invention also provides the polymkeric substance made according to aforesaid method.
In addition, described acrylamide 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 GB 12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M=([η]/K)
1 α, K=4.5 * 10 wherein
-3, α=0.80 is calculated; Solid content carries out according to GB12005.2-89 determination of solid content method; Apparent viscosity is measured with the Brookfield viscosmeter specify measuring at temperature, during measurement shearing rate constant be 7.34s
-1; Dissolution time is measured by GB12500.8-89, and the dissolution time of the product made in following examples all is 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 displacement effect (as the synthetic core of setting up irreducible water, the calculating of recovery ratio etc.) 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 formula (19) of the AMPS of the acrylamide of 50.0g (AM), 50.0g and 63.43g (according to document Macromolecules 1997, Vol.30, No.7, the method of 2016-2020 makes) join in reaction flask, add deionized water 287.0g, stir monomer is dissolved fully, then slowly add the NaOH aqueous solution that 38.6g concentration is 25 % by weight, and stir.Respectively to the EDTA aqueous solution 5.5g that adds 1 % by weight in flask, 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.1g, chainextender N ', N-dimethyl-ethylenediamine 0.066g, urea 0.11g, fully stir it is mixed, with the sodium hydroxide solution regulation system pH to 7.5 of 1 % by weight.Hierarchy of control initial temperature to 4 ℃, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight ammonium persulfate aqueous solution 1.1g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, remain on 4 ℃, after reacting 5 hours, after temperature is risen to 25 ℃, reaction is 4 hours, then temperature is risen to 50 ℃ of reactions 10 hours, the gluey product obtained is taken out, can receive the polymeric articles P1 of the sugary based structures unit of ultra-high molecular weight through granulation, drying, pulverizing.
P1 is carried out to various mensuration, quantitatively
13occur the characteristic peak of C1～C6 in formula (19) sugar ring in the C spectrum at 61.02～102.77ppm place, occurred the characteristic peak of the propanesulfonic acid carbon of AMPS at 50.01～59.20ppm, on the while main chain-CH-CH
2-and the C characteristic peak of C=O stack, can determine that the copolymer molecule obtained has the structure shown in formula (23), and it is 1: 0.33: 0.16 that the integral area by characteristic peak can calculate x1: y1: z1.Recording its viscosity-average molecular weight Mv by viscosity method is 1,820 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (23) and x1, y1 and z1 only express type and the number of structural unit, and do not mean the mode of connection of structural unit,
Comparative Examples 1
Method according to embodiment 1 prepares the acrylamide based copolymer, 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 1,600 ten thousand.
Embodiment 2
AM by 45.0g, 34.2g NVP NVP and the formula (20) of 103.2g shown in the monomer of structure (according to document Biomacromolecules, 2009, Vol.10, No.7, the method of 1846-1853 makes) join in polymerization bottle, add the 495.2g deionized water, stirring is dissolved monomer fully, add the sodium citrate aqueous solution 5.65g that concentration is 0.1 % by weight respectively in flask, 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 ℃, 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 ℃, after reacting 8 hours, be warming up to 18 ℃, after reacting 6 hours, be warming up to 40 ℃ of reactions 12 hours, the gluey product obtained is taken out, can receive the polymeric articles P2 of the sugary based structures unit of ultra-high molecular weight through granulation, drying, pulverizing.
P2 is measured, quantitatively
13occur the characteristic peak of C1～C6 in formula (20) sugar ring in the C spectrum 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 of C=O stack, can determine that the multipolymer obtained has the structure shown in formula (24), and it is 1: 0.49: 0.27 that the integral area by characteristic peak can calculate x2: y2: z2.Recording its viscosity-average molecular weight Mv by viscosity method is 1,843 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (24) and x2, y2 and z2 only express type and the number of structural unit, and do not mean the mode of connection of structural unit,
Embodiment 3
Under room temperature, AM by 50.0g, 28.9g DMAM and 78.8g formula (22) shown in the monomer of structure (according to document Biomacromolecules, 2009, Vol.10, No.7, the method of 1846-1853 makes) join in polymerization bottle, add the 298.0g deionized water, stirring is dissolved monomer fully, add the EDTA aqueous solution 5.65g that concentration is 0.5 % by weight respectively in flask, adding concentration is the two methylvaleric acid salt brine solution 1.5g 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 ℃, logical nitrogen deoxygenation is after 30 minutes, and to add concentration be 1 % by weight sodium persulfate aqueous solution 15g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 8 ℃, after reacting 3 hours, be warming up to 30 ℃, after reacting 3 hours, be warming up to 60 ℃ of reactions 8 hours, the gluey product obtained is taken out, can receive the polymeric articles P3 of the sugary based structures unit of ultra-high molecular weight through granulation, drying, pulverizing.
P3 is carried out to various mensuration, quantitatively
13occur the characteristic peak of C1～C6 in formula (22) sugar ring in the C spectrum 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 of C=O stack, can determine that the multipolymer obtained has the structure shown in formula (25), and it is 1: 0.41: 0.19 that the integral area by characteristic peak can calculate x3: y3: z3.Recording its viscosity-average molecular weight Mv by viscosity method is 1,902 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (25) and x3, y3 and z3 only express type and the number of structural unit, and do not mean the mode of connection of structural unit.
Test case 1
P1-P3 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-L3 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), at 25 ℃ and 85 ℃ of lower test soln apparent viscosities, data are as shown in table 1.
Table 1
| Embodiment | L1 | L2 | L3 | DP1 |
| Apparent viscosity under 25 ℃ (mPas) | 60.4 | 52.1 | 53.8 | 48.6 |
| Apparent viscosity under 85 ℃ (mPas) | 20.1 | 19.9 | 18.2 | 14.3 |
Table 1 has shown the apparent viscosity of the solution that 25 ℃ and 85 ℃ of lower P1-P3 and DP1 are mixed with.In the salt solution of high salinity, the apparent viscosity of L1-L3 is very high, illustrates that the solution of polymer formulation of the present invention, under high temperature and high salt and shear conditions, still possesses higher apparent viscosity, especially with the polymkeric substance DL1 that does not contain the glycosyl structure, compare, advantage is remarkable.
Test case 2
P1-P3 and DP1 are carried out to oil-displacing agent performance study and lab simulation oil displacement experiment, and condition and step are as described below.
Synthetic core porosity used is about 30%, rate of permeation is about 2.0 μ m
2, containing 90 % by weight SiO
2with 10% weight Na
2o.The 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, it forms 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-P3 records after 105 ℃ of dry 90min is respectively 95.4 % by weight, 90.4 % by weight and 89.9 % by weight.
Take separately the 1g in above-mentioned dried P1-P3, be dissolved in 1000ml distilled water under 400r/min stirs in, place and spend the night after continuously stirring 90min, membrane filtration with aperture 5 μ m, filter cake is measured after dry 90min under 105 ℃ together with filter membrane, and the content (with respect to the dried product of the 1g taken) that records water-insoluble on filter membrane (being filter cake) is respectively 0.02 % by weight, 0.01 % by weight and 0.03 % by weight.Explanation polymer dissolution according to the present invention is functional, the solution homogeneous made.
(2) test result of injectability
Above-mentioned synthetic core is found time and use the stratum water saturation, the solution with the P1-P3 preparation that is 1000mg/L at 80 ℃ of lower implantation concentrations, injection pressure increases with the increase of injection speed is linear substantially, does not find the pressure jump phenomenon in injection process.The screen factor that experiment records the solution of P1-P3 preparation is respectively 18.2,19.4,17.3, and filterable agent is respectively 1.02,1.10,1.02, and this solution that shows the P1-P3 preparation has good injectability as oil-displacing agent.
Test case 3
This test case is for the viscosity of the oil-displacing agent solution testing polymer formulation of the present invention and become and the relation of recovery ratio.
Flow with 0.2ml/min pumps into injected water the synthetic core of built vertical irreducible water under 80 ℃, to moisture 98 % by weight of rock core effluent liquid, calculates waterflood recovery efficiency factor Rw.The reinject oil-displacing agent solution of the different viscositys of 0.3PV (injection pore volume) (being different concns), be driven to moisture 98 % by weight of effluent liquid with injected water, calculates 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
| Sequence number | Strength of solution (mg/L) | Solution viscosity (mPas) | Rw(％) | Rp(％) | ΔR(％) |
| P1-1 | 500 | 21.2 | 55.86 | 60.34 | 4.48 |
| P1-2 | 1000 | 40.3 | 68.63 | 82.88 | 14.25 |
| P1-3 | 1500 | 60.4 | 61.44 | 81.60 | 20.16 |
| P2-1 | 500 | 20.3 | 55.86 | 58.43 | 2.57 |
| P2-2 | 1000 | 38.4 | 68.63 | 80.64 | 12.01 |
| P2-3 | 1500 | 52.1 | 61.44 | 80.10 | 18.66 |
| P3-1 | 500 | 19.4 | 55.86 | 57.62 | 1.76 |
| P3-2 | 1000 | 39.2 | 68.63 | 80.17 | 11.54 |
| P3-3 | 1500 | 53.8 | 61.44 | 80.05 | 18.61 |
| DP1 | 1500 | 48.6 | 61.44 | 77.54 | 16.1 |
Table 3 has shown viscosity, recovery ratio and the recovery ratio improvement value that P1-P3 and DP1 is mixed with to the solution of different concns.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 used for testing the oil displacement efficiency of the oil-displacing agent solution of polymer formulation one-tenth of the present invention in the different injection phase.
For the particular case of Shengli Oil Field, investigated the displacement effect of the oil-displacing agent solution that the different injection phase utilizes polymer formulation of the present invention to become under 80 ℃.The synthetic glass long tube rock core of the quartz sand filling of long 30cm, internal diameter 2.3cm is found time, use the stratum water saturation, and use the injected water displacement after setting up irreducible water by simulated oil, after reaching 4 indicating values of following table, calculates the effluent liquid water ratio corresponding waterflood recovery efficiency factor Rw, the oil-displacing agent solution that the P1-P3 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 that annotates 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(％) | 20.91 | 18.67 | 17.82 | 15.63 |
| P2 | ΔR(％) | 19.54 | 17.61 | 15.98 | 14.10 |
| P3 | ΔR(％) | 18.66 | 16.82 | 14.25 | 12.87 |
| DP1 | ΔR(％) | 15.42 | 14.13 | 11.84 | 10.32 |
As can be seen from Table 4, even the oil-displacing agent solution that the effluent liquid water ratio adds P1-P3 to make in 98.60 % by weight still has obvious recovery ratio improvement value, all than DP1, increase significantly.
Above-mentioned test result illustrates 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, increase along with the oil-displacing agent solution viscosity, with the recovery ratio improvement value of water ratio, increase, and all kept recovery ratio preferably in the different injection phase, with the copolymer that does not contain the glycosyl structural unit, compare, 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. an acrylamide terpolymer, it is characterized in that, this acrylamide terpolymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit of described structural unit A for thering is 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), the structural unit of described structural unit C for thering is structure shown in formula (5) and/or formula (6), and the total mole number of structural unit in described acrylamide terpolymer of take is 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 acrylamide terpolymer is 1,800 ten thousand-2,500 ten thousand,
Wherein, R
1alkylidene group for C1-C4; R
2, R
3, R
4and R
5be the alkyl of C1-C4 independently of one another; R
6-R
16be independently of one another-NHCOR
17or OH, R
17for the alkyl of C1-C4, and R
6-R
8in at least two be OH, R
9and R
10in at least one is OH, R
11-R
13in at least two be OH, R
14-R
16in at least two be OH; M
1for at least one in H, Na and K; M and n are the integer of 1-5 independently of one another.
2. acrylamide terpolymer according to claim 1, wherein, the total mole number of structural unit in described acrylamide terpolymer of take is 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 acrylamide terpolymer is 1,800 ten thousand-2,000 ten thousand.
3. acrylamide terpolymer according to claim 1, wherein, the structural unit of described structural unit B for thering is structure shown in formula (2), the structural unit of described structural unit C for thering is structure shown in formula (5).
4. acrylamide terpolymer according to claim 3, wherein, the structural unit of described structural unit B for thering is structure shown in formula (7), the structural unit of described structural unit C for thering is structure shown in formula (8);
5. acrylamide terpolymer according to claim 1, wherein, the structural unit of described structural unit B for thering is structure shown in formula (3), the structural unit of described structural unit C for thering is structure shown in formula (6).
6. acrylamide terpolymer according to claim 5, wherein, the structural unit of described structural unit C for thering is structure shown in formula (9),
7. acrylamide terpolymer according to claim 1, wherein, the structural unit of described structural unit B for thering is structure shown in formula (4), the structural unit of described structural unit C for thering is structure shown in formula (6).
8. acrylamide terpolymer according to claim 7, wherein, the structural unit of described structural unit B for thering is structure shown in formula (10), the structural unit of described structural unit C for thering is structure shown in formula (11);
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 carry out polyreaction in water, it is characterized in that, described monomer mixture contains monomer D, monomer E and monomer F, the monomer of described monomer D for thering is structure shown in formula (12), described monomer E is for having at least one in the monomer of structure shown in formula (13)-Shi (15), the monomer of described monomer F for thering is structure shown in formula (16) and/or formula (17), and the total mole number of monomer in described monomer mixture of take is 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-2,500 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction,
Wherein, R
18alkylidene group for C1-C4; R
19-R
22be the alkyl of C1-C4 independently of one another; R
23-R
33be independently of one another-NHCOR
34or OH, R
34for the alkyl of C1-C4, and R
23-R
25in at least two be OH, R
26and R
27in at least one is OH, R
28-R
30in at least two be OH, R
31-R
33in at least two be OH; M
2for at least one in H, Na and K; O and p are the integer of 1-5 independently of one another.
10. method according to claim 9, wherein, the total mole number of monomer in described monomer mixture of take is benchmark, and 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-2,000 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction.
11. method 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. method 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 0.15-0.4:1.
13. according to the described method of any one in claim 9-12, wherein, described initiator is selected from azo series initiators and redox series initiators, the 0-10 % by mole that the consumption of described azo series initiators is the total mole number of monomer in monomer mixture, the 0-10 % by mole that the consumption of described redox series initiators is the total mole number of monomer in monomer mixture, and the consumption of the described initiator 0.0001-10 % by mole that is 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. method 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; The total mole number of monomer in described monomer mixture of take is benchmark, and 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; Described other auxiliary agents are selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite.
15. method according to claim 14, wherein, the total mole number of monomer in described monomer mixture of take is benchmark, and the consumption of described sequestrant is 0.0001-1 % by mole, and 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 ℃-80 ℃, and the time is 1-32 hour, and the pH value is 5-13.
17. method according to claim 16, wherein, described polyreaction comprises the three phases carried out successively, and the reaction conditions of first stage comprises: temperature is 0-10 ℃, and the time is 1-10 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 ℃, and the time is 1-8 hour; The reaction conditions of phase III comprises: temperature is 35-60 ℃, and the time is 2-14 hour.
18. method according to claim 9, wherein, the monomer of described monomer E for thering is structure shown in formula (13), the monomer of described monomer F for thering is structure shown in formula (16).
19. method according to claim 18, wherein, the monomer of described monomer E for thering is structure shown in formula (18), the monomer of described monomer F for thering is structure shown in formula (19);
20. method according to claim 9, wherein, the monomer of described monomer E for thering is structure shown in formula (14), the monomer of described monomer F for thering is structure shown in formula (17).
21. method according to claim 20, wherein, the monomer of described monomer F for thering is structure shown in formula (20),
formula (20).
22. method according to claim 9, wherein, the monomer of described monomer E for thering is structure shown in formula (15), the monomer of described monomer F for thering is structure shown in formula (17).
23. method according to claim 22, wherein, the monomer of described monomer E for thering is structure shown in formula (21), the monomer of described monomer F for thering is structure shown in formula (22);
24. according to the polymkeric substance that in claim 9-23, the described method of any one makes.
25. in claim 1-8, the described acrylamide terpolymer of any one or the described polymkeric substance of claim 24 are as the application of polymer oil-displacing agent.
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