CN104628942A - Acrylamide copolymer, as well as preparation method and application thereof - Google Patents
Acrylamide copolymer, as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104628942A CN104628942A CN201310573775.3A CN201310573775A CN104628942A CN 104628942 A CN104628942 A CN 104628942A CN 201310573775 A CN201310573775 A CN 201310573775A CN 104628942 A CN104628942 A CN 104628942A
- Authority
- CN
- China
- Prior art keywords
- formula
- mole
- monomer
- content
- structural unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *C(*)(*NC(C(*)=C)=O)c1ccc(*)cc1 Chemical compound *C(*)(*NC(C(*)=C)=O)c1ccc(*)cc1 0.000 description 2
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an acrylamide copolymer, as well as a preparation method and an application thereof. The acrylamide copolymer comprises a structural unit as shown in a formula (1) and a structural unit as shown in a formula (2), wherein R1 and R2 are respectively hydrogen or alkyl of C1-C4 independently, R3 is alkyl of C1-C8, and M1 and M2 are respectively at least one of hydrogen, potassium and sodium independently; based on the total mole number of the structural units in the acrylamide copolymer, the content of the structural unit as shown in the formula (1) is 30-99 molar percent, the content of the structural unit as shown in the formula (2) is 1-70 molar percent; and the viscosity-average molecular weight of the acrylamide copolymer is 31-37 millions. A temperature-resistance salt-resistance product prepared from 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 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.
With acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization copolymer in heat-resistant salt-resistant performance comparatively HPAM really increase, as being entitled as " the low temperature synthesis of AMPS/AM multipolymer and performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) described in article.But, be entitled as " pyrohydrolysis of water-soluble AM/AA/AMPS multipolymer " (Zhu Linyong, applied chemistry, 2000,17,2) research finds, under the hot conditions of 90 DEG C, by the Molecular modelling effect closing on vinylformic acid (AA) unit, also there is hydrolysis reaction in AMPS unit, although along with hydrolysis reaction, in multipolymer, acrylic acid structure unit ratio increases, improve its Thermo-sensitive and salt sensitivity energy, but be at high temperature easily hydrolyzed, because which limit the application under the high temperature and high salt condition of this kind of polymkeric substance more than hydrolysis temperature due to AMPS.
Therefore, the temperature resistant antisalt performance how improving acrylamide copolymer is further still the problem needing solution badly.
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 the structural unit shown in the structural unit shown in formula (1) and formula (2), and with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 30-99 % by mole, the content of the structural unit shown in formula (2) is 1-70 % by mole, preferably, the content of the structural unit shown in formula (1) is 50-97.5 % by mole, and the content of the structural unit shown in formula (2) is 2.5-50 % by mole; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1and R
2be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3for the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
Present invention also offers a kind of preparation method of acrylamide copolymer, the method comprises: under solution polymerization condition, under initiator exists, make monomer mixture carry out polyreaction; Wherein, described monomer mixture contains the monomer of structure shown in formula (5) and the monomer of the shown structure of formula (6); With the total mole number of monomer in described monomer mixture for benchmark, shown in formula (5), the content of the monomer of structure is 30-99 % by mole, and shown in formula (6), the content of the monomer of structure is 1-70 % by mole; Preferably, shown in formula (5), the content of the monomer of structure is 50-97.5 % by mole, and shown in formula (6), the content of the monomer of structure is 2.5-50 % by mole; After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1' and R
2' be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3' be the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1' and M
2' be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
The invention provides the acrylamide copolymer obtained by above method.
Present invention also offers the application of aforesaid propylene amide copolymer as oil-displacing agent.
Acrylamide copolymer provided by the invention is not only high temperature resistant, and has good Efficient Adhesive Promotion under the degree of high ore deposit, can be widely used in petrochemical industry, particularly as the application of Flooding Agent for EOR.Trace it to its cause may for the alkyl around amide group in acrylamide copolymer of the present invention and the hydrophobic interaction of phenyl and the space steric effect of disulfonic acid base significantly limit hot conditions under carboxyl the Molecular modelling of amide group is hydrolyzed, therefore improve the anti-hydrolytic performance of this acrylamide copolymer; In addition, two sulfonic groups in this multipolymer are insensitive to divalent salts ion, therefore improve the anti-salt property of this acrylamide copolymer; Again because the structure of acrylamide copolymer has larger volume, copolymer chain is not easily occurred curling, thus make this acrylamide copolymer reach the effect with thickening.
The temperature resistant antisalt product of acrylamide copolymer of the present invention has 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.As can be seen here, 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 the structural unit shown in the structural unit shown in formula (1) and formula (2), and with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 30-99 % by mole, the content of the structural unit shown in formula (2) is 1-70 % by mole, preferably, the content of the structural unit shown in formula (1) is 50-97.5 % by mole, and the content of the structural unit shown in formula (2) is 2.5-50 % by mole; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1and R
2be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3for the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
According to the present invention, described acrylamide copolymer is also containing formula (3) and/or the structural unit shown in formula (4):
Wherein, R
4, R
5and R
6be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
7for the alkylidene group of C1-C8, be preferably the alkylidene group of C1-C4; M
3for at least one in hydrogen, potassium and sodium, be preferably potassium or sodium; M
4for potassium or sodium.
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-C8 can be straight chain, also can be side chain.The example of the alkyl of described C1-C8 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, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-thmethylpropyl, 1, 2, 2-thmethylpropyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-Ethyl-2-Methyl propyl group, n-heptyl and n-octyl.
In the present invention, the alkylidene group of described C1-C8 can be straight or branched, and the example of the alkylidene group of described C1-C8 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 and sub-n-octyl.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)-.
The content of the present invention to the structural unit shown in formula (3) and/or formula (4) does not specially require, such as, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 30-90 % by mole, structural unit content shown in formula (2) is 1-40 % by mole, and formula (3) and/or the structural unit content shown in formula (4) are 3-60 % by mole; Preferably, the content of the structural unit shown in formula (1) is 50-87.5 % by mole, and the structural unit content shown in formula (2) is 2.5-20 % by mole, and formula (3) and/or the structural unit content shown in formula (4) are 6-35 % by mole.
Present invention also offers a kind of preparation method of acrylamide copolymer, the method comprises: under solution polymerization condition, under initiator exists, make monomer mixture carry out polyreaction; Wherein, described monomer mixture contains the monomer of structure shown in formula (5) and the monomer of the shown structure of formula (6); With the total mole number of monomer in described monomer mixture for benchmark, shown in formula (5), the content of the monomer of structure is 30-99 % by mole, and shown in formula (6), the content of the monomer of structure is 1-70 % by mole; Preferably, shown in formula (5), the content of the monomer of structure is 50-97.5 % by mole, and shown in formula (6), the content of the monomer of structure is 2.5-50 % by mole; After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1' and R
2' be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3' be the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1' and M
2' be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
In the present invention, in order to make the acrylamide copolymer of described polyreaction gained obtain higher transformation efficiency, further preferably, the monomer of structure shown in formula (6) is the monomer of structure shown in formula (9):
Wherein, M
1' and M
2' be potassium or sodium independently of one another.
A preferred embodiment of the invention, shown in formula (6), the preparation process of the monomer of structure is as follows:
(1) under whipped state, slowly joined in excessive vinyl cyanide by the vitriol oil of 98%, obtain the first solution, the temperature controlling mixed solution is-5 DEG C to 10 DEG C.In the first solution, slowly add alpha-methyl styrene sodium sulfonate or alpha-methyl styrene potassium sulfonate, control reacting liquid temperature and be no more than 10 DEG C in adition process, reaction 1-8 hour, obtains the second solution.
(2) in the second solution, add suitable quantity of water, under normal temperature condition, continue reaction 1-8 hour, the pH adding sodium hydroxide or potassium hydroxide regulation system is 5-10, static, has crystal to separate out.
(3) vinyl cyanide that elimination is excessive, obtains thick product, and with vinyl cyanide by thick product washing 2-3 time, vacuum-drying obtains target product.
Wherein, the alpha-methyl styrene sodium sulfonate in step (1), alpha-methyl styrene potassium sulfonate can be that 5-10 obtains by alpha-methyl styrene sulphur aqueous acid through sodium hydroxide, potassium hydroxide regulation system pH respectively.
According to the present invention, primary object of the present invention is that the monomer providing structure shown in formula (6) is temperature resistant antisalt monomer, the acrylamide polymer synthesized is made to have good Efficient Adhesive Promotion at higher temperature and salinity, and the method for the monomer of structure shown in synthesis type (6) can be the method for this area routine, shown in the formula (6) of the present invention's synthesis, the monomer of structure such as can pass through Infrared Characterization, in infrared spectrum, 1500cm
-1near be the charateristic avsorption band of phenyl ring, 1185cm
-1near be the charateristic avsorption band of sulfonic acid group, 1650cm
-1near be the absorption peak of alkene, 1740cm
-1near be the charateristic avsorption band of ester group, 3340cm
-1near be the charateristic avsorption band of amide group, and at 2250cm
-1near do not occur which illustrating the charateristic avsorption band of itrile group method of the present invention and synthesized target product.Therefore, in the examples below, no longer further the monomer of structure formula (6) Suo Shi is characterized.
In the present invention, under the prerequisite reaching object of the present invention, in order to reduce reaction cost further, under preferable case, the monomer of described monomer mixture also containing structure shown in formula (7),
Wherein, R
4', R
5' and R
6' be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
7' be the alkylidene group of C1-C8, be preferably the alkylidene group of C1-C4; M
3' be at least one in hydrogen, potassium and sodium, be preferably potassium or sodium.Further preferably, the monomer of structure shown in formula (7) is 2-acrylamide-2-methylpro panesulfonic acid (AMPS).
According to the present invention, the description of the alkylidene group of the alkyl of C1-C4, the alkyl of C1-C8 and C1-C8 is all same as described above.
The content of the present invention to the monomer of structure formula (7) Suo Shi does not specially require, such as, preferably, with the total mole number of monomer in described monomer mixture for benchmark, shown in formula (5), the content of the monomer of structure is 30-98 % by mole, shown in formula (6), the content of the monomer of structure is 1-40 % by mole, and shown in formula (7), the content of the monomer of structure is 0.1-35 % by mole; Further preferably, shown in formula (5), the content of the monomer of structure is 70-97.5 % by mole, and shown in formula (6), the content of the monomer of structure is 1-20 % by mole, and shown in formula (7), the content of the monomer of structure is 1-20 % by mole.
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 series initiators.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 0.003-0.15 % by weight; Described azo series initiators is water-soluble azo series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, described reductive agent can be inorganic reducing agent and/or organic reducing agent, and the weight ratio of described oxygenant and described reductive agent can be 0.1-1:1.
In the present invention, described water-soluble azo series initiators can be 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), be preferably 2,2'-azo diisobutyl amidine dihydrochloride.
In the present invention, described oxygenant can be selected from least one in ammonium persulphate, Sodium Persulfate and Potassium Persulphate, is 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 ammonium sulphite, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite and sodium bisulfite, is preferably at least one in ammonium sulphite, potassium sulfite and sodium bisulfite; Described organic reducing agent is preferably amine reductive agent, and described amine reductive agent can be N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, tetramethyl-urea, N, N-dimethyl urea element, N, N, N ', N ' at least one in-Tetramethyl Ethylene Diamine and N, N-dimethyl-ethylenediamine, 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 solution polymerization carries 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-7 DEG C to 15 DEG C; Time is 1-20 hour, is preferably 3-8 hour; PH value is 4-12, is preferably 5-10.
In the present invention, 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: under hydrolysising condition, contacted with inorganic alkaline compound by resulting polymers after polyreaction, the condition of described hydrolysis makes the unit of the shown structure of a unit hydrolysis accepted way of doing sth (8) of structure shown in the some acrylamide structural unit in polymkeric substance and formula (1):
Wherein, M
4' be potassium or sodium.
In the present invention, described inorganic alkaline compound can realize above-mentioned purpose inorganic alkaline compound for conventional various in this area, and preferably, described inorganic alkaline compound is selected from least one in sodium hydroxide, potassium hydroxide and sodium carbonate.
According to the present invention, the condition of described hydrolysis can be the condition of this area routine.Such as, the condition of described hydrolysis can comprise: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After the condition of described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers is 10-30%.
According to the present invention, degree of hydrolysis refers to that the mole number of the structural unit shown in formula (8) accounts for the per-cent of the total mole number of the structural unit of acrylamide copolymer of the present invention.In the present invention, degree of hydrolysis is determined by the consumption of inorganic alkaline compound.
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 the structural unit shown in formula (8).
In the present invention, in order to obtain dry acrylamide copolymer product further, under preferable case, described method also comprises carries out drying by aforesaid method gained acrylamide copolymer.
According to the present invention, the present invention is to the method for drying and condition without particular requirement, and such as, the method for described drying can adopt hot air seasoning, and described warm air drying temperature can be 40-110 DEG C, is preferably 70-90 DEG C; The time of described 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 copolymer comprises the steps:
(1) acrylamide monomer, temperature resistant antisalt 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 the monomer of structure shown in Chinese style of the present invention (6), and also can contain the monomer of structure shown in formula (7), described inorganic alkaline compound is for regulating the pH value of the comonomer aqueous 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.
4, polymers soln antioxygen thermal ageing test is according to the method specified in SY/T5862-2008, with the salt solution of salinity 32000mg/L, polymkeric substance is made into the solution of 1500mg/L, oxygen level in solution is removed to required value, by the polymers soln that obtains at 95 DEG C of temperature, after aging 3 months, by the apparent viscosity of Brookfield viscometer determining polymers soln at 95 DEG C, with following formulae discovery apparent viscosity retention rate:
Apparent viscosity retention rate %=aging post-consumer polymer solution apparent viscosity/aging prepolymer solution apparent viscosity × 100%.
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.In the examples below, in the monomer of structure shown in formula (6), R
2' be hydrogen, R
3' be methyl (that is, the monomer of structure shown in formula (9)).
Embodiment 1
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof.
(1) preparation of the monomer of structure shown in formula (6)
In temperature-controlled glass reactor, add 1060 kilograms of vinyl cyanide, under whipped state, drip the vitriol oil 200 kilograms that concentration is 98%, mixed solution is cooled to-5 DEG C, after stirring, drip alpha-methyl styrene sodium sulfonate 440 kilograms, maintain temperature of reaction system below 10 DEG C.Reacting after 1 hour, add suitable quantity of water, continue reaction after 4 hours under normal temperature condition, is after 7 by the pH value of sodium hydroxide regulation system further, and after filtration, washing, dry and obtain pure monomer, the yield of product is 93.9%.This monomer is monomer (wherein, the M of structure shown in formula (6)
1' and M
2' be sodium).
(2) preparation of acrylamide polymer
In batching kettle, add monomer and 8834.04 kilograms of deionized waters of structure shown in 927.09 kilograms of acrylamides, 1281.42 kilograms of formulas (6), under whipped state, control solution temperature-7 DEG C with chilled brine, add sodium hydroxide and regulate pH to 5.Monomer solution is pumped in polymeric kettle, add 2,2'-azo diisobutyl amidine dihydrochloride 22.08 grams and N, N, N ', N '-Tetramethyl Ethylene Diamine 22.08 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 22.08 grams and ammonium persulphate 22.08 grams, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, reaction times 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.3MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.Mediated with 130.43 kilogram sodium hydroxide grain alkali by the little micelle obtained and contact, at temperature 90 DEG C, be hydrolyzed 4h, after secondary granulation, by crushing and screening and be packaged to be 20-80 object acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 60 % by mole, and the structural unit content shown in formula (2) is 20 % by mole, and the structural unit content shown in formula (4) is 20 % by mole.
Comparative example 1
Same process condition is adopted with embodiment 1, unlike, the monomer of structure formula (6) Suo Shi is changed into the 2-acrylamide-2-methylpro panesulfonic acid of same molar, thus obtain acrylamide copolymer product, the performance of product is as shown in table 1.
Embodiment 2
(1) preparation of the monomer of structure shown in formula (6)
In temperature-controlled glass reactor, add 636 kilograms of vinyl cyanide, under whipped state, drip the vitriol oil 107.8 kilograms that concentration is 98%, mixed solution is cooled to 5 DEG C, after stirring, drip alpha-methyl styrene potassium sulfonate 236 kilograms, maintain temperature of reaction system below 10 DEG C.Reacting after 1 hour, add suitable quantity of water, continue reaction after 6 hours under normal temperature condition, is after 7 by the pH value of potassium hydroxide regulation system, and after filtration, washing, dry and obtain pure monomer, the yield of product is 95.5%.This monomer is monomer (wherein, the M of structure shown in formula (6)
1' and M
2' be potassium).
(2) preparation of acrylamide polymer
In batching kettle, add monomer and 2983.98 kilograms of deionized waters of structure shown in 1108.85 kilograms of acrylamides, 170 kilograms of formulas (6), under whipped state, control solution temperature 15 DEG C with chilled brine, add sodium hydroxide and regulate pH to 10.Monomer solution is pumped in polymeric kettle, add 2,2'-azo diisobutyl amidine dihydrochloride 639.42 grams and N, N, N ', N '-Tetramethyl Ethylene Diamine 639.42 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 639.42 grams and ammonium persulphate 639.42 grams, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, reaction times 3h.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.3MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.The little micelle obtained is mediated with 64 kilogram sodium hydroxide grain alkali and contacts, 1h is hydrolyzed under temperature 70 C, after secondary granulation, dry 2h under 70 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 87.5 % by mole, and the structural unit content shown in formula (2) is 2.5 % by mole, and the structural unit content shown in formula (4) is 10 % by mole.
Embodiment 3
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof.
(1) preparation of the monomer of structure shown in formula (6)
In temperature-controlled glass reactor, add 1060 kilograms of vinyl cyanide, under whipped state, drip the vitriol oil 117.6 kilograms that concentration is 98%, mixed solution is cooled to 5 DEG C, after stirring, drip alpha-methyl styrene potassium sulfonate 236 kilograms, maintain temperature of reaction system below 10 DEG C.Reacting after 1 hour, add suitable quantity of water, continue reaction after 8 hours under normal temperature condition, is after 7 by the pH value of sodium hydroxide regulation system, and after filtration, washing, dry and obtain pure monomer, the yield of product is 94.5%.This monomer is monomer (wherein, the M of structure shown in formula (6)
1' be sodium, M
2' be potassium).
(2) preparation of acrylamide polymer
In batching kettle, add monomer and 4222.8 kilograms of deionized waters of structure shown in 1080.4 kilograms of acrylamides, 327.2 kilograms of formulas (6), under whipped state, control solution temperature 0 DEG C with chilled brine, add sodium hydroxide and regulate pH to 10.Monomer solution is pumped in polymeric kettle, add 2,2'-azo diisobutyl amidine dihydrochloride 200 grams and N, N, N ', N '-Tetramethyl Ethylene Diamine 200 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 150 grams and ammonium persulphate 200 grams, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, reaction times 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.3MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.The little micelle obtained is mediated with 192 kilogram sodium hydroxide grain alkali and contacts, 1.5h is hydrolyzed at temperature 85 DEG C, after secondary granulation, dry 2h under 70 DEG C of hot blast conditions, by crushing and screening and be packaged to be 20-80 object acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 65 % by mole, and the structural unit content shown in formula (2) is 5 % by mole, and the structural unit content shown in formula (4) is 30 % by mole.
Embodiment 4
Adopt and adopt same process condition with embodiment 1, difference is, also containing 2-acrylamide-2-methylpro panesulfonic acid (AMPS) in monomer mixture, with the total mole number of monomer in monomer mixture for benchmark, the consumption of acrylamide is 80 % by mole, and shown in formula (6), the consumption of the monomer of structure is 10 % by mole, and the consumption of 2-acrylamide-2-methylpro panesulfonic acid is 10 % by mole, thus obtaining acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 60 % by mole, structural unit content shown in formula (2) is 10 % by mole, structural unit content shown in formula (3) is 10 % by mole, and the structural unit content shown in formula (4) is 20 % by mole.
Embodiment 5
Adopt and adopt same process condition with embodiment 1, unlike, without hydrolysis, namely do not carry out being mediated with 130.43 kilogram sodium hydroxide grain alkali by the little micelle obtained in embodiment 1 to contact, the step of 4h is hydrolyzed at temperature 90 DEG C, thus obtaining acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 80 % by mole, and the structural unit content shown in formula (2) is 20 % by mole.
Embodiment 6
Adopt the monomer with structure shown in embodiment 1 same process condition preparation formula (6).
In batching kettle, add monomer and 6847.04 kilograms of deionized waters of structure shown in 430.34 kilograms of acrylamides, 1281.42 kilograms of formulas (6), under whipped state, control solution temperature-7 DEG C with chilled brine, add sodium hydroxide and regulate pH to 5.Monomer solution is pumped in polymeric kettle, add 2,2'-azo diisobutyl amidine dihydrochloride 17.12 grams and N, N, N ', N '-Tetramethyl Ethylene Diamine 17.12 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 17.12 grams and ammonium persulphate 17.12 grams, continue logical nitrogen until thermopair starts to heat up in polymeric kettle, reaction times 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, with 0.3MPa pressurized air, the copolymer colloid obtained is extruded, become the little micelle of 4-6 millimeter by granulator granulation.Mediated with 74.51 kilogram sodium hydroxide grain alkali by the little micelle obtained and contact, at temperature 90 DEG C, be hydrolyzed 4h, after secondary granulation, by crushing and screening and be packaged to be 20-80 object acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to charging capacity and determine, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 45 % by mole, and the structural unit content shown in formula (2) is 35 % by mole, and the structural unit content shown in formula (4) is 20 % by mole.
Table 1
Associative list 1 data are known, the molecular weight of the acrylamide copolymer product that embodiment 1 obtains can reach 3,580 ten thousand, and comparative example 1 obtains acrylamide copolymer molecular weight product is only 2,950 ten thousand, the molecular weight of copolymer that embodiment 1 obtains compared with comparative example 1 improves nearly 6,300,000, and corresponding 95 DEG C of apparent viscosity improve 9.7mPas.Illustrate that acrylamide copolymer provided by the invention is more conducive to improving the apparent viscosity under the molecular weight of multipolymer and hot conditions than acrylamide to be polymerized gained acrylamide copolymer with 2-acrylamide-2-methylpro panesulfonic acid.
By embodiment 1 compared with embodiment 4, in embodiment 4 except the monomer of structure shown in acrylamide and formula (6), also add 2-acrylamide-2-methylpro panesulfonic acid.The molecular weight obtaining acrylamide copolymer product is 3,150 ten thousand, and corresponding 95 DEG C of corresponding meter observing viscosities are 18.7mPas, lower than the index result of embodiment 1, but also have higher molecular weight and apparent viscosity.
By embodiment 1 compared with embodiment 5, the molecular weight obtaining acrylamide copolymer product in embodiment 5 is 3,260 ten thousand, and 95 DEG C of corresponding meter observing viscosities are 20.2mPas, lower than the index result of embodiment 1.Apparent viscosity under suitably introducing acrylate structural unit has the molecular weight and hot conditions being more conducive to improving multipolymer is described in copolymer structure.
Good by the temperature resistant antisalt performance of the known acrylamide copolymer provided by the invention of data in table 1, can as high temperature and high salt oil deposit Flooding Agent for EOR.
Claims (15)
1. an acrylamide copolymer, it is characterized in that, this acrylamide copolymer contains the structural unit shown in the structural unit shown in formula (1) and formula (2), and with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 30-99 % by mole, the content of the structural unit shown in formula (2) is 1-70 % by mole, preferably, the content of the structural unit shown in formula (1) is 50-97.5 % by mole, and the content of the structural unit shown in formula (2) is 2.5-50 % by mole; The viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1and R
2be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3for the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
2. acrylamide copolymer according to claim 1, wherein, described acrylamide copolymer is also containing formula (3) and/or the structural unit shown in formula (4):
Wherein, R
4, R
5and R
6be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
7for the alkylidene group of C1-C8, be preferably the alkylidene group of C1-C4; M
3for at least one in hydrogen, potassium and sodium, be preferably potassium or sodium; M
4for potassium or sodium.
3. acrylamide copolymer according to claim 2, wherein, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of the structural unit shown in formula (1) is 30-90 % by mole, structural unit content shown in formula (2) is 1-40 % by mole, and formula (3) and/or the structural unit content shown in formula (4) are 3-60 % by mole; Preferably, the content of the structural unit shown in formula (1) is 50-87.5 % by mole, and the structural unit content shown in formula (2) is 2.5-20 % by mole, and the unit content of formula (3) and/or the shown structure of formula (4) is 6-35 % by mole.
4. a preparation method for acrylamide copolymer, the method comprises: under solution polymerization condition, under initiator exists, make monomer mixture carry out polyreaction; Wherein, described monomer mixture contains the monomer of structure shown in formula (5) and the monomer of the shown structure of formula (6); With the total mole number of monomer in described monomer mixture for benchmark, shown in formula (5), the content of the monomer of structure is 30-99 % by mole, and shown in formula (6), the content of the monomer of structure is 1-70 % by mole; Preferably, shown in formula (5), the content of the monomer of structure is 50-97.5 % by mole, and shown in formula (6), the content of the monomer of structure is 2.5-50 % by mole; After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of resulting polymers is 3,100 ten thousand-3,700 ten thousand, is preferably 3,200 ten thousand-3,600 ten thousand,
Wherein, R
1' and R
2' be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
3' be the alkyl of C1-C8, be preferably the alkyl of C1-C4; M
1' and M
2' be at least one in hydrogen, potassium and sodium independently of one another, be preferably potassium or sodium.
5. method according to claim 4, wherein, the monomer of described monomer mixture also containing structure shown in formula (7),
Wherein, R
4', R
5' and R
6' be the alkyl of hydrogen or C1-C4 independently of one another, be preferably hydrogen or methyl; R
7' be the alkylidene group of C1-C8, be preferably the alkylidene group of C1-C4; M
3' be at least one in hydrogen, potassium and sodium, be preferably potassium or sodium.
6. method according to claim 5, wherein, with the total mole number of monomer in described monomer mixture for benchmark, shown in formula (5), the content of the monomer of structure is 30-98 % by mole, shown in formula (6), the content of the monomer of structure is 1-40 % by mole, and shown in formula (7), the content of the monomer of structure is 0.1-35 % by mole; Preferably, shown in formula (5), the content of the monomer of structure is 70-97.5 % by mole, and shown in formula (6), the content of the monomer of structure is 1-20 % by mole, and shown in formula (7), the content of the monomer of structure is 1-20 % by mole.
7. method according to claim 4, wherein, described solution polymerization carries out in water, and 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 4, 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, 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 ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Described inorganic reducing agent is selected from least one in ammonium sulphite, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite and sodium bisulfite; Described organic reducing agent is selected from N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, tetramethyl-urea, N, N-dimethyl urea element, N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine and N, N-dimethyl-ethylenediamine.
10. method according to claim 4, wherein, described solution polymerization carries out in the presence of an inert gas, and described solution polymerization condition comprises: temperature is-10 DEG C to 20 DEG C, is preferably-7 DEG C to 15 DEG C; Time is 1-20 hour, is preferably 3-8 hour; PH value is 4-12, is preferably 5-10.
11. according to the method in claim 4-10 described in any one, wherein, described method also comprises: under hydrolysising condition, contacted with inorganic alkaline compound by resulting polymers after polyreaction, the condition of described hydrolysis makes the unit of the shown structure of an acrylamide structural unit partial hydrolysis accepted way of doing sth (8) in polymkeric substance:
Wherein, M
4' be potassium or sodium.
12. methods according to claim 11, wherein, described inorganic alkaline compound is selected from least one in sodium hydroxide, potassium hydroxide and sodium carbonate.
13. 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%.
The acrylamide copolymer that method in 14. claim 4-13 described in any one is obtained.
Acrylamide copolymer in 15. claim 1-3 and 14 described in any one is as the application of oil-displacing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310573775.3A CN104628942B (en) | 2013-11-15 | A kind of acrylamide copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310573775.3A CN104628942B (en) | 2013-11-15 | A kind of acrylamide copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104628942A true CN104628942A (en) | 2015-05-20 |
| CN104628942B CN104628942B (en) | 2016-11-30 |
Family
ID=
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317307A (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 |
| CN115703723A (en) * | 2021-08-09 | 2023-02-17 | 中国石油化工股份有限公司 | Acrylamide compound, heat-resistant salt-tolerant polyacrylamide for oil displacement, and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317307A (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 |
| CN115703723A (en) * | 2021-08-09 | 2023-02-17 | 中国石油化工股份有限公司 | Acrylamide compound, heat-resistant salt-tolerant polyacrylamide for oil displacement, and preparation method and application thereof |
| CN115703723B (en) * | 2021-08-09 | 2024-03-26 | 中国石油化工股份有限公司 | Acrylamide compound, heat-resistant salt-resistant polyacrylamide for oil displacement, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107033293B (en) | A kind of double tail hydrophobic associated polymers with surface-active and preparation method thereof | |
| CN104650301A (en) | Acrylamide copolymer and its preparation method and use | |
| CN102050917B (en) | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent | |
| CN104628944B (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN104628940B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN103788295B (en) | A kind of two-step method prepares the method for acrylamide based copolymer | |
| CN104448122A (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN102464797B (en) | Enether monomer, water-soluble thermothickening copolymer, preparation method, application thereof | |
| CN104628943B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104628942A (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN104448123B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104628611A (en) | Acrylamide monomer, as well as preparation method and application thereof | |
| CN104448120A (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN104628942B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN103787928B (en) | Acrylamide monomers and method for making thereof and acrylamide based copolymer and method for making thereof and application | |
| CN104649940B (en) | A kind of acrylamide monomers and its preparation method and application | |
| CN103787926B (en) | Acrylamide monomer and acrylamide copolymer, method of preparation, application and oil displacement agent | |
| CN114874112B (en) | Surface active monomer containing sodium sulfonate group, and preparation method and application thereof | |
| CN108424490B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN106317309B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104649941A (en) | Acrylamide monomer and its preparation method and use | |
| CN107964067A (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104628941B (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN102050916B (en) | Tertiary aliphatic amine group-contained macromolecule as well as preparation method and application thereof | |
| CN104628610B (en) | A kind of acrylamide monomers and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |