CN104628944A - Acrylamide copolymer, as well as preparation method and application thereof - Google Patents
Acrylamide copolymer, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an acrylamide copolymer, as well as a preparation method and an application thereof. The copolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a unit having a structure as shown in a formula (1), the structural unit B is at least one unit having a structure as shown in formulae from (2) to (5), and the structural unit C is a unit having a structure as shown in a formula (6); the mass ratio of the structural unit A to structural unit B to structural unit C is 1:(0.001-3):(0.001-0.5); and the viscosity-average molecular weight of the acrylamide copolymer is 31-39 millions. A temperature-resistance salt-resistance product prepared from the acrylamide copolymer has the characteristics of good water solubility, low content of residual monomer, high molecular weight and high apparent viscosity, and can be used as an oil-displacing agent for tertiary recovery of a high temperature and high salinity reservoir.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and its preparation method and application.
Background technology
Polymer flooding mainly by injecting the polymers soln of certain scale, increases displacing fluid viscosity, reduces oil-reservoir water phase permeability and reduces mobility ratio, adjustment intake profile, to reach the object improving sweeping phase volume, and then improve recovery ratio.As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (HPAM), in conventional oil reservoir tertiary oil recovery (EOB) technology, has obtained large-scale promotion and application, for oilfield stable production and volume increase have played vital role.Along with the minimizing of conventional reservoir reserve, high temperature and high salt oil deposit makes the application of HPAM be faced with many difficult problems, the compound action that in high temperature, high salt and solution when being mainly reflected in exploitation high temperature and high salt oil deposit, dissolved oxygen produces makes HPAM soltion viscosity significantly reduce, and causes HPAM oil displacement efficiency not remarkable.Research shows, when temperature is higher than 70 DEG C, the amido hydrolysis reaction of HPAM generates carboxyl significantly to be aggravated, and when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution
2+, Mg
2+ion generates precipitation, and soltion viscosity is lost.In addition, at high temperature, when there is dissolved oxygen in oxygen and solution in air, main polymer chain also can be caused to rupture soltion viscosity is significantly declined.
In order to improve the temperature resistant antisalt performance of polyacrylamide, carry out a large amount of tackling key problem research both at home and abroad, the main chain yardstick around polymkeric substance, chain size distribution, construction unit composition, micro-sequential structure carry out a large amount of correlative study work, as temperature resistant antisalt monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb shaped polymer, template polymer and surface-active polymer etc.As being entitled as " the low temperature synthesis of AMPS/AM multipolymer and performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) with acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization copolymer; CN200810015349.7 discloses a kind of comb-type structure activity polymer and preparation technology thereof and application, by monomers such as polyurethanes surface-active macromonomer and acrylamides altogether
Aggregate into and there is tackifying and reduce interfacial tension target product.Its feature of each tool of polymkeric substance that above-mentioned two kinds of methods obtain, in some performance as more traditional polyacrylamide in temperature tolerance, salt resistance, shear resistant and surfactivity index increases really, but obtain molecular weight of product little (being no more than 2,000 ten thousand), cause the use of polymkeric substance to be restricted.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of acrylamide copolymer and its preparation method and application is provided.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10, R
11and R
12be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8, R
9and R
13be the alkyl of C1-C4 independently of one another, R
14for the alkyl of C1-C18, M
1and M
2be at least one in H, Na and K independently of one another, n is arbitrary integer in 1-20, and m is arbitrary integer in 1-20.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, wherein, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10', R
11' and R
12' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8', R
9' and R
13' be the alkyl of C1-C4 independently of one another, R
14' be the alkyl of C1-C18, M
1' and M
2' be at least one in H, Na and K independently of one another, n ' is integer arbitrary in 1-20, and m ' is integer arbitrary in 1-20.
The main chain of acrylamide copolymer molecular chain of the present invention is formed primarily of acrylamide and temperature resistant antisalt monomeric building blocks, at guarantee polymeric water-soluble simultaneously, can improve temperature resistant antisalt and the anti-shear performance of polymer molecule.Multipolymer side chain is made up of surface active function monomer, has and produces Interpolymer Association effect, increases the time of relaxation of molecular motion, improves solution visco-elasticity and reduces oil water interfacial tension effect.
The temperature resistant antisalt product of acrylamide copolymer of the present invention is adopted to have water-soluble good, residual monomer content is low and molecular weight is high feature.Acrylamide copolymer molecular weight of the present invention can reach more than 3,300 ten thousand, particularly under salinity 32000mg/L, the hot conditions of 95 DEG C, the apparent viscosity of solution can reach more than 20mPa.s, and the molecular weight of commercially available high molecular weight polyacrylamide is only about 2,000 ten thousand, the apparent viscosity of solution is only 8.9mPa.s, comparatively commercially available prod, acrylamide copolymer of the present invention has significantly thickening advantage, can as high temperature and high salt oil deposit Flooding Agent for EOR.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10, R
11and R
12be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8, R
9and R
13be the alkyl of C1-C4 independently of one another, R
14for the alkyl of C1-C18, M
1and M
2be at least one in H, Na and K independently of one another, n is arbitrary integer in 1-20, and m is arbitrary integer in 1-20.
In the present invention, the alkyl of described C1-C4 can be straight chain, also can be side chain.The example of the alkyl of described C1-C4 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.
In the present invention, the alkyl of described C1-C18 can be straight chain, also can be side chain.The example of the alkyl of described C1-C18 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive undecyl, positive dodecyl, positive tridecyl, positive tetradecyl, positive pentadecyl, positive hexadecyl, positive heptadecyl and positive octadecyl.
In the present invention, the alkylidene group of described C1-C14 can be straight or branched, and the example of the alkylidene group of described C1-C14 can include but not limited to: methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tertiary butyl, sub-n-pentyl, isopentylidene, sub-tert-pentyl, sub-neo-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, sub-n-nonyl, sub-positive decyl, sub-positive undecyl, sub-positive dodecyl, sub-positive tridecyl and the positive tetradecyl in Asia.Described alkylidene group refer to alkane lose two hydrogen atoms after residue, described two hydrogen atoms can be two hydrogen atoms on same carbon atom, also can two hydrogen atoms on different carbon atom, it can be straight chain, also can be side chain, such as, described ethylidene can be-CH
2cH
2-or-CH (CH
3)-.
In the present invention, although can realize object of the present invention as long as contain structural unit A, structural unit B and structural unit C and meet aforementioned proportion relation, under preferable case, the amount of structural unit A accounts for the 30-99 % by weight of described acrylamide copolymer.
According to the present invention, described acrylamide based copolymer also contains structural unit D, described structural unit D for having the unit of structure shown in formula (7):
Wherein, M
3for potassium or sodium, be preferably sodium.
The quality of the present invention to structural unit D does not specially require, such as, preferably, the mass ratio of described structural unit A, described structural unit B, described structural unit C and described structural unit D is 1:0.001-3:0.001-0.5:0.1-1, more preferably 1:0.01-1.5:0.01-0.2:0.1-1.
The present inventor finds under study for action, can obtain good oil displacement efficiency good specific structural unit A, structural unit B, structural unit C and structural unit D when the quadripolymer be made up of is used for oil-displacing agent.Such as, preferably, described structural unit B is for having at least one in the unit of structure shown in formula (2) and (4), and R
2and R
7be hydrogen or methyl independently of one another, R
3for the alkylidene group of C1-C4, M
1for sodium; In described structural unit C, R
13for methyl, R
14for the alkyl of C5-C18, M
2for sodium, n is the arbitrary integer in 8-12, when m is the arbitrary integer in 2-8, can obtain good oil displacement efficiency when the quadripolymer of composition is used for oil-displacing agent.Still more preferably, described structural unit C for having the unit of structure shown in formula (14),
Wherein, R
14for the straight chained alkyl of C8-C16.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, wherein, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10', R
11' and R
12' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8', R
9' and R
13' be the alkyl of C1-C4 independently of one another, R
14' be the alkyl of C1-C18, M
1' and M
2' be at least one in H, Na and K independently of one another, n ' is integer arbitrary in 1-20, and m ' is integer arbitrary in 1-20.
The alkyl of described C1-C4, the alkylidene group of C1-C14 are all identical with foregoing description with the alkyl of C1-C18.
In the present invention, monomer E is preferably the 40-99 % by weight of monomer mixture total mass.
The present inventor finds under study for action, when selecting specific monomer E, monomer F and monomer G to react, can improve the oil displacement efficiency of the polymkeric substance of gained further.Such as, preferably, when described monomer F is for having at least one in the monomer of structure shown in formula (9) and formula (11), and R
2' and R
7' be hydrogen or methyl independently of one another, R
3' be the alkylidene group of C1-C4, M
1' be sodium; In described monomer G, R
13' be methyl, R
14' be the alkyl of C5-C18, M
2' be sodium, n ' is the arbitrary integer in 8-12, and when m ' is for arbitrary integer in 2-8, the polymkeric substance of synthesis has higher oil displacement efficiency, and still more preferably, described monomer G is for having the monomer of structure shown in formula (15):
Wherein, R
14' be the straight chained alkyl of C8-C16.
In the present invention, described monomer G can the method according to CN101327413A obtain: such as, 1) first maleic anhydride is reacted from the fat alcohol polyethylene ether of different ethoxymer distribution, feed intake by equimolar ratio, heated and stirred melts to maleic anhydride, at 70-100 DEG C of reaction 2-5 hour, after reaction terminates, obtain toxilic acid list polyoxyethylene ether-ester; 2) toxilic acid list polyoxyethylene ether-ester is heated to 40-80 DEG C, drip acyl chlorides reagent phosphorus trichloride, both mol ratios are 1:0.5-3, carry out acyl chloride reaction at 40-80 DEG C, obtain fatty alcohol-polyoxyethylene ether monoesters fumaryl chloride; 3) be 8-10 by concentrated hydrochloric acid adjust ph by the aqueous solution of N methyl taurine sodium under 50-80 DEG C of condition; fatty alcohol-polyoxyethylene ether monoesters fumaryl chloride is slowly added drop-wise in the aqueous solution of N methyl taurine sodium; reaction 1-3 hour, namely obtains monomer G of the present invention.
According to the present invention, described solution polymerization carries out in water, when described solution polymerization starts, there is no particular limitation for the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture, can change in wider scope, under preferable case, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.15-0.4:1, more preferably 0.2-0.3:1.
In the present invention, described initiator can be the various initiator in this area.Such as, described initiator can be selected from azo series initiators and/or redox body class initiator, is preferably azo series initiators and redox body class initiator.The consumption of described azo series initiators is the 0.0001-0.1 % by weight of the gross weight of monomer in monomer mixture, is preferably 0.001-0.05 % by weight; The consumption of described redox series initiators is the 0.0002-0.3 % by weight of the gross weight of monomer in monomer mixture, is preferably 0.002-0.15 % by weight.Described azo series initiators is preferably water-soluble azo series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, described reductive agent is inorganic reducing agent and/or organic reducing agent, and the weight ratio of described oxygenant and described reductive agent is 0.1-1:1.
In the present invention, described water-soluble azo series initiators is preferably 2,2'-azo diisobutyl amidine dihydrochloride, 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 4, at least one in 4'-azo two (4-cyanopentanoic acid), more preferably 2,2'-azo diisobutyl amidine dihydrochlorides.
In the present invention, described oxygenant can be selected from least one in acyl peroxide, hydroperoxide and persulphate, be preferably benzoyl peroxide, hydrogen peroxide, tertbutyl peroxide, 2,5-dimethyl-2, at least one in 5 pairs of (hydrogen peroxide) hexanes, ammonium persulphate, Sodium Persulfate and Potassium Persulphates, more preferably ammonium persulphate and/or Potassium Persulphate.
In the present invention, described reductive agent can be inorganic reducing agent and/or organic reducing agent, is preferably inorganic reducing agent and organic reducing agent.Described inorganic reducing agent can be selected from least one in ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite and sodium bisulfite, is preferably sodium bisulfite; Described organic reducing agent is preferably amine reductive agent, and described amine reductive agent is preferably N, N-dimethylethanolamine, N, N-lupetazin, tetramethyl-urea and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine, more preferably N, N, N ', N '-Tetramethyl Ethylene Diamine.
According to the present invention, the condition of described solution polymerization can be the condition of this area routine.Such as, described polyreaction is carried out in the presence of an inert gas, and described polymeric reaction condition can comprise: temperature is-10 DEG C to 20 DEG C, preferably 5 DEG C to 15 DEG C; Time is 2-12 hour, preferred 4-8 hour; PH value is 4-12, is preferably 5-10.
Described rare gas element is the gas do not reacted with raw material and product, such as, can be at least one in the nitrogen of this area routine or the periodic table of elements in neutral element gas, be preferably nitrogen.
According to the present invention, described method also comprises and to be hydrolyzed by resulting polymers after polyreaction and dry.Those skilled in the art can know, and the process of hydrolysis comprises hydrolytic reagent and polymer reaction.By hydrolysis, some acrylamide structural unit and the structural unit shown in formula (1) are transformed into acrylate structural unit, that is, the unit of structure shown in formula (7).
In the present invention, the condition of described hydrolysis is not particularly limited, and under preferable case, the condition of described hydrolysis comprises: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers can be 10-30%.
In the present invention, described degree of hydrolysis refers to that the mole number of acrylate structural unit accounts for the per-cent of the total mole number of the structural unit of acrylamide copolymer of the present invention.Described degree of hydrolysis is determined by the consumption of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds that can realize above-mentioned purpose that this area is commonly used, and can be selected from one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of described hydrolytic reagent can carry out appropriate selection according to the degree of hydrolysis of acrylamide copolymer, meet service requirements to make the degree of hydrolysis of acrylamide copolymer to be as the criterion, the consumption of preferred inorganic alkaline compound makes the degree of hydrolysis of acrylamide copolymer be 10-30%.
Those skilled in the art can know, and by regulating the consumption of inorganic alkaline compound, can obtain the acrylamide copolymer of different degree of hydrolysis.
In the present invention, the mole number of described inorganic alkaline compound equals the mole number of acrylate structural unit.
According to the present invention, the present invention is to drying conditions without particular requirement, and described drying means can adopt hot air seasoning, and described warm air drying temperature can be 40-120 DEG C, is preferably 70-90 DEG C; Time is 0.2-4 hour, is preferably 0.5-2 hour.
One of the present invention preferred embodiment in, the preparation method of described acrylamide copolymer comprises the steps:
(1) acrylamide monomer, temperature resistant antisalt monomer, surface active function monomer and water are mixed to form the comonomer aqueous solution, regulate pH to 5-10 with inorganic alkaline compound, control solution temperature-10 DEG C to 20 DEG C;
(2) in the comonomer aqueous solution, logical nitrogen carries out deoxygenation, controls oxygen level in solution and is less than 1mg/L, be preferably less than 0.2mg/L;
(3) under logical condition of nitrogen gas, add composite initiation system to monomer solution, carry out adiabatic polymerisation, obtain copolymer gel;
(4) copolymer gel is carried out the acrylamide copolymer product that granulation, hydrolysis, secondary granulation, drying, pulverizing and a screening obtain temperature resistant antisalt.
According to the present invention, in step (1), described temperature resistant antisalt monomer is monomer F of the present invention, and described surface active function monomer is monomer G of the present invention, and described inorganic alkaline compound is for regulating the pH value of acrylamide and temperature resistant antisalt monomer solution.Described inorganic alkaline compound can be at least one in sodium hydroxide, potassium hydroxide and sodium carbonate, is preferably sodium hydroxide.
Present invention also offers the acrylamide copolymer obtained according to aforesaid method.
In addition, present invention also offers the application of described acrylamide copolymer in oil-displacing agent.
Below, by following examples, the present invention will be described in more detail
In following examples, the performance test of product adopts following methods to carry out:
1, the solid content of polymkeric substance, dissolution time, filtration ratio, AM residual monomer content and intrinsic viscosity is measured according to the method specified in People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008.
2, polymkeric substance viscosity-average molecular weight is according to the method specified in SY/T5862-2008, adopts formula M=([η]/0.000373)
1.515calculate, wherein, M is viscosity-average molecular weight, and [η] is intrinsic viscosity.
3, the apparent viscosity of polymers soln is the solution with the salt solution of salinity 32000mg/L, polymkeric substance being made into 1500mg/L, with Brookfield viscometer at 95 DEG C, and 7.34s
-1measure under condition.
In following examples, acrylamide is purchased from Bao Mo biochemical industry limited-liability company, and 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., 2,2'-azo diisobutyl amidine dihydrochloride business available from Aldrich Co.The surface active function monomer of structure shown in formula (15) obtains according to the method described in CN101327413A.
Embodiment 1
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
Add in beaker 1000 grams of acrylamides, 10 grams of 2-acrylamide-2-methylpro panesulfonic acids, 10 grams of surface active function monomers such as formula (15) described structure (n ' be 10, m ' be 2, R
14' be dodecyl) and 4080 grams of deionized waters, under whipped state, control solution temperature 5 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 10.2 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 10.2 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 10.2 milligrams of sodium bisulfites and 10.2 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 8 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 90 DEG C, be hydrolyzed 0.5 hour, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.013:0.013:0.333.
Comparative example 1
Adopt same process condition with embodiment 1, difference is, do not add structure as the formula (15) surface active function monomer (n ' be 10, m ' be 2, R
14' be dodecyl), thus obtaining the product of acrylamide copolymer, its performance is listed in table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
Add in beaker 1000 grams of acrylamides, 1000 grams of 2-acrylamide-2-methylpro panesulfonic acids, 100 grams as the formula (15) structure surface active function monomer (n ' be 10, m ' be 2, R
14' be dodecyl) and 4900 grams of deionized waters, under whipped state, control solution temperature 15 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 1.05 gram 2,2'-azo diisobutyl amidine dihydrochloride and 1.05 grams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 1.05 grams of sodium bisulfites and 1.05 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 4 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, under temperature 70 C, be hydrolyzed 4 hours, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:1.370:0.137:0.489.
Embodiment 3
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
Add in beaker 1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams such as formula (15) body structure surface active function monomer (n ' be 10, m ' be 2, R
14' be dodecyl) and 3450 grams of deionized waters, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.347.
Embodiment 4
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
Add in beaker 1000 grams of acrylamides (AM), 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams as the formula (15) structure surface active function monomer (n ' be 10, m ' be 2, R
14' be hexadecyl) and 3450 grams of deionized waters, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.347.
Embodiment 5
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
Add in beaker 1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams such as formula (15) body structure surface active function monomer (n ' be 10, m ' be 2, R
14' be octadecyl) and 3450 grams of deionized waters, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.347.
Embodiment 6
Add in beaker 1000 grams of acrylamides (AM), 50 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of N,N-DMAAs, 50 grams as the formula (15) structure surface active function monomer (n ' be 10, m ' be 2, R
14' be dodecyl) and 3450 grams of deionized waters, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, obtaining 20-80 object product by crushing and screening.The performance of the acrylamide copolymer product obtained is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.063:0.063:0.355.
Embodiment 7
Adopt the processing condition identical with embodiment 6, difference is, replace N,N-DMAA with the vinyl pyrrolidone of equal mass, thus obtain acrylamide copolymer product, its performance is as shown in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.063:0.063:0.355.
Embodiment 8
Adopt the same process condition with embodiment 2, difference is, 2-acrylamide-2-methylpro panesulfonic acid is replaced with the vinylformic acid of equal mass, and without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 to contact, at 80 DEG C, be hydrolyzed the step of 2 hours, thus obtain acrylamide copolymer product, its performance is as shown in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B and structural unit C is 1:1:0.1.
Embodiment 9
Adopt and embodiment 2 same process condition, difference is, without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 to contact, the step of 2 hours is hydrolyzed at 80 DEG C, thus obtaining the product of acrylamide copolymer, its performance is listed in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B and structural unit C is 1:1:0.1.
Table 1
The data of associative list 1 are known, the molecular weight of the acrylamide copolymer product that embodiment 1 obtains can reach 3,760 ten thousand, and the molecular weight that comparative example 1 obtains acrylamide copolymer product is only 2,610 ten thousand, the molecular weight of copolymer that embodiment 1 obtains compared with comparative example 1 improves nearly 1,150 ten thousand, and corresponding 95 DEG C of apparent viscosity improve 14.9mPas.Illustrate that the introducing of surface active function monomer in the present invention is more conducive to improving the apparent viscosity of copolymer solution under the molecular weight of multipolymer and hot conditions.
By embodiment 2 compared with embodiment 9, the molecular weight obtaining acrylamide copolymer product in embodiment 9 is 3,300 ten thousand, 95 DEG C of corresponding meter observing viscosity 18.2mPas, and both are all lower than the result of the products obtained therefrom of embodiment 2.The apparent viscosity suitably introduced sodium acrylate structural unit and be more conducive to improving the copolymer solution under the molecular weight of multipolymer and hot conditions is described in copolymer structure.
For embodiment 1, the temperature resistant antisalt acrylamide copolymer that the present invention obtains is in high salinity
32000mg/L, under high temperature 95 DEG C of conditions, solution sees viscosity can reach 28.0mPas, and commercially available high molecular weight polyacrylamide solution apparent viscosity is only 9.0mPas, comparatively contrasts commercially available prod, and acrylamide copolymer of the present invention has significantly thickening advantage.Accordingly, known acrylamide copolymer provided by the invention has good temperature resistant antisalt performance.
Claims (15)
1. an acrylamide copolymer, it is characterized in that, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10, R
11and R
12be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8, R
9and R
13be the alkyl of C1-C4 independently of one another, R
14for the alkyl of C1-C18, M
1and M
2be at least one in H, Na and K independently of one another, n is arbitrary integer in 1-20, and m is arbitrary integer in 1-20.
2. acrylamide copolymer according to claim 1, wherein, described acrylamide copolymer also contains structural unit D, described structural unit D for having the unit of structure shown in formula (7):
Wherein, M
3for potassium or sodium.
3. acrylamide copolymer according to claim 2, wherein, the mass ratio of described structural unit A, described structural unit B, described structural unit C and described structural unit D is 1:0.001-3:0.001-0.5:0.1-1, is preferably 1:0.01-1.5:0.01-0.2:0.1-1.
4. according to the acrylamide copolymer in claim 1-3 described in any one, wherein, described structural unit B is for having at least one in the unit of structure shown in formula (2) and (4), and R
2and R
7be hydrogen or methyl independently of one another, R
3for the alkylidene group of C1-C4, M
1for sodium; In described structural unit C, R
13for methyl, R
14for the alkyl of C5-C18, M
2for sodium, n is the arbitrary integer in 8-12, and m is the arbitrary integer in 2-8.
5. the preparation method of an acrylamide copolymer, this preparation method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, it is characterized in that, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,900 ten thousand, is preferably 3,400 ten thousand-3,800 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10', R
11' and R
12' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8', R
9' and R
13' be the alkyl of C1-C4 independently of one another, R
14' be the alkyl of C1-C18, M
1' and M
2' be at least one in H, Na and K independently of one another, n ' is integer arbitrary in 1-20, and m ' is integer arbitrary in 1-20.
6. method according to claim 5, wherein, described monomer F is for having at least one in the monomer of structure shown in formula (9) and formula (11), and R
2' and R
7' be hydrogen or methyl independently of one another, R
3' be the alkylidene group of C1-C4, M
1' be sodium; In described monomer G, R
13' be methyl, R
14' be the alkyl of C5-C18, M
2' be sodium, n ' is the arbitrary integer in 8-12, and m ' is the arbitrary integer in 2-8.
7. method according to claim 5, wherein, when described solution polymerization 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, is preferably 0.2-0.3:1.
8. method according to claim 5, wherein, described initiator is selected from azo series initiators and redox series initiators, the consumption of described azo series initiators is the 0.0001-0.1 % by weight of the gross weight of monomer in monomer mixture, and the consumption of described redox series initiators is the 0.0002-0.3 % by weight of the gross weight of monomer in monomer mixture; Described azo series initiators is water-soluble azo series initiators, and described redox series initiators comprises Oxidizing and Reducing Agents, and described reductive agent is inorganic reducing agent and/or organic reducing agent, and the weight ratio of described oxygenant and described reductive agent is 0.1-1:1.
9. method according to claim 8, wherein, described water-soluble azo series initiators is selected from 2,2'-azo diisobutyl amidine dihydrochloride, 2, at least one in 2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 4,4'-azo two (4-cyanopentanoic acid); Described oxygenant is selected from least one in benzoyl peroxide, hydrogen peroxide, tertbutyl peroxide, 2,5-dimethyl-2,5 pairs of (hydrogen peroxide) hexanes, ammonium persulphate, Sodium Persulfate and Potassium Persulphates; Described inorganic reducing agent is selected from least one in ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite and sodium bisulfite; Described organic reducing agent is selected from N, N-dimethylethanolamine, N, N-lupetazin, tetramethyl-urea, N, N – dimethyl-ethylenediamine and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine.
10. method according to claim 5, wherein, described solution polymerization carries out in the presence of an inert gas, and described polymeric reaction condition comprises: temperature is-10 DEG C to 20 DEG C, is preferably 5 DEG C to 15 DEG C; Time is 2-12 hour, preferred 4-8 hour; PH value is 4-12, is preferably 5-10.
11. according to the method in claim 5-10 described in any one, and wherein, described method also comprises and to be hydrolyzed to resulting polymers after polyreaction and dry.
12. methods according to claim 11, wherein, described hydrolysising condition comprises: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers is 10-30%.
13. methods according to claim 11, wherein, the condition of described drying comprises: temperature is 40-120 DEG C, is preferably 70-90 DEG C; Time is 0.2-4 hour, is preferably 0.5-2 hour.
The acrylamide copolymer that method in 14. claim 5-13 described in any one is obtained.
Acrylamide copolymer in 15. claim 1-4 and 14 described in any one is as the application of oil-displacing agent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279525A (en) * | 2016-08-08 | 2017-01-04 | 东营华力石油技术股份有限公司 | Tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof |
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327413A (en) * | 2008-07-24 | 2008-12-24 | 大连理工大学 | Boletic acid type polymerisable emulsifier containing negative ion and non-ionic group and preparation method thereof |
| CA2789831A1 (en) * | 2010-03-15 | 2011-09-22 | S.P.C.M. Sa | Enhanced oil recovery process using water soluble polymers having improved shear resistance |
| CN103319649A (en) * | 2012-03-22 | 2013-09-25 | 中国石油化工股份有限公司 | Polynary copolymer and preparation method thereof, and applications of modified ternary copolymer |
-
2013
- 2013-11-15 CN CN201310574499.2A patent/CN104628944B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327413A (en) * | 2008-07-24 | 2008-12-24 | 大连理工大学 | Boletic acid type polymerisable emulsifier containing negative ion and non-ionic group and preparation method thereof |
| CA2789831A1 (en) * | 2010-03-15 | 2011-09-22 | S.P.C.M. Sa | Enhanced oil recovery process using water soluble polymers having improved shear resistance |
| CN103319649A (en) * | 2012-03-22 | 2013-09-25 | 中国石油化工股份有限公司 | Polynary copolymer and preparation method thereof, and applications of modified ternary copolymer |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN106317299B (en) * | 2015-06-18 | 2018-08-17 | 中国石油化工股份有限公司 | Acrylamide copolymer and its preparation method and application |
| CN106317339A (en) * | 2015-06-26 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN106317339B (en) * | 2015-06-26 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN106279525A (en) * | 2016-08-08 | 2017-01-04 | 东营华力石油技术股份有限公司 | Tertiary oil recovery surface-active polymer oil displacement agent and preparation method thereof |
| CN107814873A (en) * | 2016-09-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of polymer for having surface active function and its preparation method and application |
| CN107814873B (en) * | 2016-09-12 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of polymer and its preparation method and application having surface active function |
| CN110938026A (en) * | 2018-09-21 | 2020-03-31 | 中国石油化工股份有限公司 | Monomer compound and preparation method thereof, copolymer and preparation method and application thereof |
| CN112708019A (en) * | 2019-10-25 | 2021-04-27 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
| CN112708019B (en) * | 2019-10-25 | 2024-04-30 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
| CN111349192A (en) * | 2020-04-03 | 2020-06-30 | 中国石油大学(华东) | Fluorescent gel dispersion, fluorescent gel, fluorescent modified polyacrylamide composite material, and preparation method and application thereof |
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