CN104628943A - 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 30-35 millions. A temperature-endurance salt-resistance product of the acrylamide copolymer has the characteristic of high molecular weight; and the acrylamide copolymer has an advantage of greatly thickening, 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 based 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.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) in article, with acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization copolymer; Disclose a kind of comb-type structure activity polymer and preparation technology thereof and application in CN101260171A, synthesize by monomer copolymerizations such as polyurethanes surface-active macromonomer and acrylamides the target product that there is tackifying He reduce interfacial tension.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), the use of polymkeric substance is restricted.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of acrylamide based copolymer and its preparation method and application is provided.
The invention provides a kind of acrylamide based copolymer, this acrylamide based 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, structural unit B and 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 based copolymer is 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4and R
5be the alkyl of hydrogen or C1-C4 independently of one another; R
8, R
9, R
12, R
13and R
14be the alkyl of C1-C4 independently of one another, and 3 R
12, 3 R
13with 3 R
14identical or different independently of one another, M
1for at least one in H, Na and K, m is arbitrary integer in 1-16.
Present invention also offers a kind of preparation method of acrylamide based 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, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (9), described monomer F is for having at least one in the monomer of structure shown in formula (10)-Shi (13), described monomer G is for having the monomer of structure shown in formula (14), 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 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4' and R
5' be the alkyl of hydrogen or C1-C4 independently of one another; R
8', R
9', R
12', R
13' and R
14' be the alkyl of C1-C4 independently of one another, and 3 R
12', 3 R
13' and 3 R
14' identical or different independently of one another, M
3for at least one in H, Na and K, n is arbitrary integer in 1-16.
The invention provides the acrylamide based copolymer obtained by above method.
Present invention also offers the application of aforesaid propylene acid amides based copolymer as oil-displacing agent.
Acrylamide copolymer 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 siliceous surface active function monomeric building blocks, and this structural unit has the effect of generation Interpolymer Association, increases the time of relaxation of molecular motion, improves the effect of solution visco-elasticity and reduction oil water interfacial tension.
The temperature resistant antisalt product of acrylamide based copolymer of the present invention is adopted to have water-soluble good, residual monomer content is low and molecular weight is high feature, particularly under salinity 32000mg/L, the hot conditions of 95 DEG C, the apparent viscosity of solution can reach more than 22mPa.s, and the apparent viscosity of commercially available high molecular weight polyacrylamide solution is only 8.9mPa.s, comparatively commercially available prod, acrylamide based 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
According to a first aspect of the invention, the invention provides a kind of acrylamide based copolymer, wherein, this acrylamide based 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 described structural unit A, the mass ratio of structural unit B and 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 based copolymer is 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4and R
5be the alkyl of hydrogen or C1-C4 independently of one another; R
8, R
9, R
12, R
13and R
14be the alkyl of C1-C4 independently of one another, and 3 R
12, 3 R
13with 3 R
14identical or different independently of one another, M
1for at least one in H, Na and K, m is arbitrary integer in 1-16.
In the present invention, 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 alkylidene group of described C1-C14 can be straight or branched, 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, be preferably methylene radical.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 based 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
2for sodium or potassium.
The content 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.When structural unit B is for having at least one in the unit of structure shown in formula (2) and formula (4), and R
2and R
7be hydrogen or methyl independently of one another; When described structural unit C is for having the unit of structure shown in formula (8), when the quadripolymer of composition is used for oil-displacing agent, good oil displacement efficiency can be obtained:
Wherein, 3 R
12, 3 R
13with 3 R
14it is identical independently of one another,
Further preferred, described structural unit C for having the unit of structure shown in formula (16),
Present invention also offers a kind of preparation method of acrylamide based 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 (9), described monomer F is for having at least one in the monomer of structure shown in formula (10)-Shi (13), described monomer G is for having the monomer of structure shown in formula (14), 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 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4' and R
5' be the alkyl of hydrogen or C1-C4 independently of one another; R
8', R
9', R
12', R
13' and R
14' be the alkyl of C1-C4 independently of one another, and 3 R
12', 3 R
13' and 3 R
14' identical or different independently of one another, M
3for at least one in H, Na and K, n is arbitrary integer in 1-16.
The description of the alkyl of described C1-C4 and the alkylidene group of C1-C14 is all same as described above.
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 F and monomer G to react, can improve the oil displacement efficiency of the polymkeric substance of gained further.Such as, preferably, described monomer F is for having at least one in the monomer of structure shown in formula (10) and formula (12), and R
2' and R
7' be hydrogen or methyl independently of one another; Described monomer G for having the monomer of structure shown in formula (15),
Wherein, 3 R
12', 3 R
13' and 3 R
14' identical independently of one another.
Further preferably, described monomer G for having the monomer of structure shown in formula (17),
In the present invention, described monomer G can be prepared with reference to the synthetic route of CN102382211A.It is higher that difference is to adopt activity, adopts the maleic anhydride poly glycol monomethyl ether monoesters in sterically hindered less vinylformic acid or acrylate chloride replacement CN102382211A, introduce double bond with aminopropyl three (trimethylsiloxane group) silane reaction.Such as, can take toluene as solvent, N, N-dicyclohexylcarbodiimide (DCC) and 4-dimethylamino pyridine (DMAP) be condensing agent, vinylformic acid and aminopropyl three (trimethylsiloxane group) silane are fed intake by the mol ratio of 1:0.8-1.25, at 20-30 DEG C, stirring reaction is after 24 hours.Revolve steaming to desolventize, product with diethyl ether precipitates, and after washing away DCC and DMAP, obtains the monomer G of structure shown in formula (17).
According to the present invention, 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, be selected from azo series initiators and/or redox system initiator, be preferably azo series initiators and redox system initiator.The consumption of described azo series initiators can be the 0.0001-0.1 % by weight of the gross weight of monomer mixture, is preferably 0.001-0.05 % by weight; The consumption of described redox series initiators can be the 0.0002-0.3 % by weight of the gross weight of 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, and described reductive agent can be 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 can be 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), be preferably 2,2 '-azo diisobutyl amidine dihydrochloride.
In the present invention, described oxygenant can be at 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 transition metal low-oxidation-state salt and/or nonmetal low-oxidation-state material, described transition metal low-oxidation-state salt is preferably at least one in molysite and mantoquita, at least one more preferably in ferrous sulfate, ferrous ammonium sulphate and cuprous chloride, is further preferably ferrous ammonium sulphate.Described nonmetal low-oxidation-state material is preferably at least one of potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite and sodium bisulfite, more preferably sodium bisulfite.Described organic reducing agent is preferably amine reductive agent, and described amine reductive agent can be N, N-dimethylethanolamine, N, N-lupetazin, tetramethyl-urea and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine, be 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, is preferably 5-15 DEG C; Time is 2-12 hour, is preferably 4-8 hour; PH value is 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 contact.By hydrolysis, some acrylamide structural unit and the structural unit shown in formula (1) are transformed into acrylate structural unit, i.e. the unit of structure shown in Chinese style of the present invention (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, more preferably 70-90 DEG C; Time is 0.5-6 hour, more 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 in acrylamide based copolymer, and the mole number of acrylate structural unit accounts for the per-cent of the structural unit total mole number 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, described 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 based copolymer to be as the criterion, preferred inorganic alkaline compound consumption makes the degree of hydrolysis of acrylamide based copolymer be 10-30%.
In the present invention, the mole number of described inorganic alkaline compound consumption 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; The time of warm air drying can be 0.2-4 hour, is preferably 0.5-2 hour.
One of the present invention preferred embodiment in, the preparation method of described acrylamide based copolymer comprises the steps:
(1) acrylamide monomer, temperature resistant antisalt monomer, siliceous surface active function monomer and water are mixed to form the comonomer aqueous solution, regulate pH to 5-10 with inorganic alkaline compound, controlling solution temperature is-10 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;
(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 granulation, hydrolysis, secondary granulation, drying, pulverizing and a screening and obtain temperature-tolerant anti-salt polyacrylamide.
According to the present invention, the temperature resistant antisalt monomer in step (1) is monomer F of the present invention, and siliceous surface active function monomer is monomer G of the present invention.Inorganic alkaline compound in step (1) is for regulating the pH value of acrylamide and temperature resistant antisalt monomer solution.Described inorganic alkaline compound is one or more in sodium hydroxide, potassium hydroxide and sodium carbonate, and preferably, described inorganic alkaline compound is sodium hydroxide.
According to the present invention, described in step (2), logical nitrogen is carried out to the comonomer aqueous solution and carry out deoxygenation, control oxygen level in solution and be less than 1mg/L, be preferably less than 0.2mg/L.
Present invention also offers the acrylamide based copolymer prepared by above-mentioned polymerization process.
Present invention also offers by the application as fracturing fluid thickener of acrylamide based copolymer provided by the invention and the acrylamide based copolymer for preparing according to method provided by the invention.
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, 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 siliceous surface active function monomer of structure shown in formula (17) is prepared with reference to the method for embodiment 1 in CN102382211A: replace maleic anhydride poly glycol monomethyl ether monoesters and aminopropyl three (trimethylsiloxane group) silane reaction with the vinylformic acid of equimolar amount.
Embodiment 1
The present embodiment is for illustration of the preparation method of acrylamide based copolymer provided by the invention
The siliceous surface active function monomer of structure shown in 1000 grams of acrylamides, 10 grams of 2-acrylamide-2-methylpro panesulfonic acids and 10 grams of formulas (17) is added in beaker, 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 obtained is listed in table 1.Calculate according to charging capacity and determine, 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
Same process condition is adopted with embodiment 1, unlike, do not add the siliceous surface active function monomer of formula (17) structure, the performance of the acrylamide copolymer obtained is listed in table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of acrylamide based copolymer provided by the invention
The siliceous surface active function monomer of structure shown in 1000 grams of acrylamides, 1000 grams of 2-acrylamide-2-methylpro panesulfonic acids and 100 grams of formulas (17) is added in beaker, 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 obtained is listed in table 1.Calculate according to charging capacity and determine, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:1.374:0.137:0.495.
Embodiment 3
The present embodiment is for illustration of the preparation method of acrylamide based copolymer provided by the invention
The siliceous surface active function monomer of structure shown in 1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids and 50 grams of formulas (17) is added in beaker, 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 obtained is listed in table 1.Calculate according to charging capacity and determine, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.349.
Embodiment 4
1000 grams of acrylamides, 50 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of N are added in beaker, the siliceous surface active function monomer of structure shown in N-DMAA and 50 grams of formulas (17), 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 obtained is listed in table 1.Calculate according to charging capacity and determine, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.127:0.063:0.357.
Embodiment 5
The siliceous surface active function monomer of structure shown in 1000 grams of acrylamides, 50 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of vinyl pyrrolidones and 50 grams of formulas (17) is added in beaker, 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 obtained is listed in table 1.Calculate according to charging capacity and determine, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.127:0.063:0.355.
Embodiment 6
Adopt and embodiment 2 same process condition, 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, the performance obtaining acrylamide copolymer is as shown in table 1.Calculate according to charging capacity and determine, the mass ratio of structural unit A, structural unit B and structural unit C is 1:1:0.1.
Embodiment 7
Same process condition is adopted with embodiment 2, unlike, without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 and contact, at 80 DEG C, be hydrolyzed the step of 2 hours, the performance of the acrylamide copolymer obtained is listed in table 1.Calculate according to charging capacity and determine, 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 acrylamide copolymer molecular weight that embodiment 1 obtains can reach 3,420 ten thousand, and comparative example 1 obtains acrylamide copolymer product viscosity-average molecular weight is only 2,900 ten thousand, the molecular weight of copolymer that embodiment 1 obtains compared with comparative example 1 improves nearly 5,200,000, and corresponding 95 DEG C of apparent viscosity improve 9.2mPas.Illustrate that the introducing of siliceous 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 7, the molecular weight obtaining acrylamide copolymer in embodiment 7 is 3,000 ten thousand, 95 DEG C of corresponding meter observing viscosity 16.5mPas, lower than the index result 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.
Claims (15)
1. an acrylamide based copolymer, it is characterized in that, this acrylamide based 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, structural unit B and 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 based copolymer is 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4and R
5be the alkyl of hydrogen or C1-C4 independently of one another; R
8, R
9, R
12, R
13and R
14be the alkyl of C1-C4 independently of one another, and 3 R
12, 3 R
13with 3 R
14identical or different independently of one another, M
1for at least one in H, Na and K, m is arbitrary integer in 1-16.
2. acrylamide based copolymer according to claim 1, wherein, 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
2for potassium or sodium.
3. acrylamide based 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 based 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; Described structural unit C for having the unit of structure shown in formula (8),
Wherein, 3 R
12, 3 R
13with 3 R
14identical independently of one another.
5. the preparation method of an acrylamide based 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 (9), described monomer F is for having at least one in the monomer of structure shown in formula (10)-Shi (13), described monomer G is for having the monomer of structure shown in formula (14), 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 3,000 ten thousand-3,500 ten thousand, is preferably 3,200 ten thousand-3,400 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4' and R
5' be the alkyl of hydrogen or C1-C4 independently of one another; R
8', R
9', R
12', R
13' and R
14' be the alkyl of C1-C4 independently of one another, and 3 R
12', 3 R
13' and 3 R
14' identical or different independently of one another, M
3for at least one in H, Na and K, n is arbitrary integer in 1-16.
6. method according to claim 5, wherein, described monomer F is for having at least one in the monomer of structure shown in formula (10) and formula (12), and R
2' and R
7' be hydrogen or methyl independently of one another; Described monomer G for having the monomer of structure shown in formula (15),
Wherein, 3 R
12', 3 R
13' and 3 R
14' identical independently of one another.
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 mixture, and the consumption of described redox series initiators is the 0.0002-0.3 % by weight of the gross weight of monomer mixture; Described azo series initiators is water-soluble azo series initiators; 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, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 4, at least one in 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 and N, N, N ', N ' at least one in-Tetramethyl Ethylene Diamine.
10. method according to claim 5, wherein, described solution polymerization carries out in the presence of an inert gas, and the condition of described polyreaction comprises: temperature is-10 DEG C to 20 DEG C, is preferably 5-15 DEG C; Time is 2-12 hour, is preferably 4-8 hour; PH value is 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 by resulting polymers after polyreaction and dry.
12. methods according to claim 11, wherein, 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 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 based copolymer obtained by method described in 14. claim 5-13 any one.
15. claim 1-4 or acrylamide based copolymer according to claim 14 are as the application of oil-displacing agent.
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| 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 |
| 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 |
| CN106317312A (en) * | 2015-06-26 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer |
| CN110540618A (en) * | 2019-08-29 | 2019-12-06 | 中国石油化工股份有限公司 | Preparation method of temperature-resistant salt-resistant copolymer |
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| EP2705808B1 (en) * | 2010-07-30 | 2024-05-01 | Alcon Inc. | Silicone hydrogel lenses with water-rich surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106317312A (en) * | 2015-06-26 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer |
| 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 |
| CN110540618A (en) * | 2019-08-29 | 2019-12-06 | 中国石油化工股份有限公司 | Preparation method of temperature-resistant salt-resistant copolymer |
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