CN106317300B - Acrylamide based copolymer and its preparation method and application - Google Patents
Acrylamide based copolymer and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of acrylamide based copolymers and its preparation method and application.The acrylamide based copolymer contains the structural unit A of structure shown in formula (1), the structural unit C of structure shown in the structural unit B and formula (3) of structure shown in formula (2), and the content of structural unit A is 85-98.9 weight %, the content of structural unit B is 1-10 weight %, and the content of structural unit C is 0.1-5 weight %；The viscosity average molecular weigh of the acrylamide based copolymer is 23,000,000-3,000 ten thousand, wherein R1‑R3It is identical or different, it is each independently hydrogen or the alkyl of C1-C4, M is hydrogen, sodium or potassium, and p is the integer of 8-16, and m is the integer of 2-4, and n is the integer of 3-9.The acrylamide based copolymer molecular weight with higher, preferable temperature-resistant anti-salt performance and excellent surface-active.
Description
Technical field
The present invention relates to a kind of acrylamide based copolymer, the preparation method of the acrylamide based copolymer, and by this
The acrylamide based copolymer of method preparation, the application the invention further relates to the acrylamide based copolymer as oil displacement agent.
Background technique
Flooding polymers used in agent for improving oilfield recovery are mainly partially hydrolyzed polyacrylamide (PHPA) (HPAM) at present, tool
There is the features such as high molecular weight, good water solubility, is widely used to improve aqueous viscosity and reduce oil and water mobility ratio, is mentioned to reach
The purpose of high displacement efficiency.But HPAM is not suitable for high temperature and high salt oil deposit：The HPAM meeting when reservoir temperature is higher than 75 DEG C
Serious degradation occurs, leads to the reduction of viscosity, while the viscosity of HPAM solution declines rapidly with the increase of salinity.
For the above deficiency, domestic and foreign scholars are in order to improve the heat and salt resistance of polyacrylamide solution, to polymerization
Tackifying effect mechanism, thermal degradation and the salt tolerance of object oil displacement agent and the structure of polymer and heatproof, the relationship of salt resistant character are made
Numerous studies, to develop function admirable temperature-resistant and anti-salt type polymer oil-displacing agent.
Hydrophobic association polyacrylamide (HAPAM) and parents' polyacrylamide have been synthesized and have been applied to many fields, by
This also just inspires the copolymer of scholar and industrial research institutes synthesized high-performance to be applied to tertiary oil recovery field and HPAM.Parents
Polymer not only has surface-active but also the characteristic with macromolecular itself.Bistline once reported the conjunction of parents' polymer
At and its application.For HAPAM, stronger heat resistance and salt tolerance brings excellent temperature-resistant anti-salt performance.
However, current hydrophobic association is studied mainly using the monomer for the alkyl for containing long-chain as hydrophobic monomer.And due to
The cohesion energy density of hydrocarbon chain and surface can be higher, and the active force between hydrocarbon chain is weaker, therefore parents' sexual function obtained is poly-
The surface-active of object and the heat and salt resistance as oil displacement agent are closed still wait improve.
Summary of the invention
It is living as surface existing for oil displacement agent it is an object of the invention to solve acrylamide polymer in the prior art
Property low and heat and salt resistance difference technical problem, to provide a kind of acrylamide based copolymer and its preparation method and application.
The present inventor has found in the course of the research, by polymerisable monomer and fluorine-containing list with surface active function
The structural unit of body is introduced on the macromolecular chain of polyacrylamide, on the one hand which has water-soluble high score
The tackifying of sub- polymer；Another aspect and surface-active with higher, pass through emulsification increase-volume and reduce surface and interface tension etc.
Characteristic can increase the displacement efficiency of polymer.Tracing it to its cause may is that, introducing on strand has surface active function
Structural unit can make copolymer have certain surface-active, and there is fluorocarbon chain lower cohesion energy density and surface can make
Heat resistance and salt tolerance between fluorine carbon is better than hydrocarbon active force of identical carbochain.Based on the discovery, the present invention is completed.
According to the first aspect of the invention, the present invention provides a kind of acrylamide based copolymer, the acrylamides
It is the list with structure shown in formula (1) that copolymer, which contains structural unit A, structural unit B and structural unit C, the structural unit A,
Member, the structural unit B are the unit with structure shown in formula (2), and the structural unit C is with structure shown in formula (3)
Unit, and on the basis of the total weight of structural unit in the acrylamide based copolymer, the content of the structural unit A is
The content of 85-98.9 weight %, the structural unit B are 1-10 weight %, and the content of the structural unit C is 0.1-5 weight
Measure %；The viscosity average molecular weigh of the acrylamide based copolymer is 23,000,000-3,000 ten thousand, preferably 24,000,000-2,800 ten thousand,
Wherein, R1-R3It is identical or different, it is each independently hydrogen or the alkyl of C1-C4, M is hydrogen, sodium or potassium, p 8-16
Integer, m be 2-4 integer, n be 3-9 integer.
According to the second aspect of the invention, the present invention provides a kind of preparation methods of acrylamide based copolymer, should
Preparation method includes the following steps：Under the conditions of solution polymerization, in the presence of initiator, make monomer mixture in water into
Row polymerization reaction, it is with structure shown in formula (4) that the monomer mixture, which contains monomer D, monomer E and monomer F, the monomer D,
Monomer, the monomer E be the monomer with structure shown in formula (5), the monomer F be the monomer with structure shown in formula (6),
And on the basis of the total weight of the monomer mixture, the dosage of the monomer D is 85-98.9 weight %, the use of the monomer E
Amount is 1-10 weight %, and the dosage of the monomer F is 0.1-5 weight %；The solution polymerization condition makes polymerization reaction
The viscosity average molecular weigh of resulting polymers is 23,000,000-3,000 ten thousand, preferably 24,000,000-2,800 ten thousand afterwards；
Wherein, R1’-R3' identical or different, it is each independently hydrogen or the alkyl of C1-C4, M ' is hydrogen, sodium or potassium, and p ' is
The integer of 8-16, m ' are the integer of 2-4, and n ' is the integer of 3-9.
According to the third aspect of the present invention, the present invention provides the acrylamide based copolymers prepared by the above method.
According to the fourth aspect of the present invention, the present invention provides above-mentioned acrylamide based copolymer answering as oil displacement agent
With.
Acrylamide based copolymer molecular weight with higher of the invention, especially in salinity 25000mg/L, 80 DEG C
Hot conditions under, the apparent viscosity of solution is up to 48mPa.s or more, therefore heat and salt resistance with higher, in addition, this third
The structural unit of acrylamide based copolymer, which has, generates Interpolymer Association effect, increases the slack time of molecular motion, plays drop
The effect of low oil water interfacial tension makes the copolymer have excellent surface-active.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of acrylamide based copolymer, the acrylamides
It is the list with structure shown in formula (1) that copolymer, which contains structural unit A, structural unit B and structural unit C, the structural unit A,
Member, the structural unit B are the unit with structure shown in formula (2), and the structural unit C is with structure shown in formula (3)
Unit, and on the basis of the total weight of structural unit in the acrylamide based copolymer, the content of the structural unit A is
The content of 85-98.9 weight %, the structural unit B are 1-10 weight %, and the content of the structural unit C is 0.1-5 weight
Measure %；The viscosity average molecular weigh of the acrylamide based copolymer is 23,000,000-3,000 ten thousand, preferably 24,000,000-2,800 ten thousand,
Wherein, R1-R3It is identical or different, it is each independently hydrogen or the alkyl of C1-C4, M is hydrogen, sodium or potassium, p 8-16
Integer, m be 2-4 integer, n be 3-9 integer.
In the present invention, the example of the alkyl of the C1-C4 may include：Methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, sec-butyl, isobutyl group and tert-butyl.
In the present invention, the structural unit content of the acrylamide based copolymer can be according to preparing the acrylamide
The dosage of monomer corresponding to each structural unit determines when copolymer.
Preferably, in the unit of structure shown in formula (1)-formula (3), R1-R3It is each independently selected from hydrogen or methyl, M is hydrogen, p
For 10-14.It is highly preferred that in the unit of structure shown in formula (1)-formula (3), R1-R3It is hydrogen, M is hydrogen, and p is the integer of 11-14.
According to the second aspect of the invention, the present invention provides a kind of preparation methods of acrylamide based copolymer, should
Preparation method includes the following steps：Under the conditions of solution polymerization, in the presence of initiator, make monomer mixture in water into
Row polymerization reaction, it is with structure shown in formula (4) that the monomer mixture, which contains monomer D, monomer E and monomer F, the monomer D,
Monomer, the monomer E be the monomer with structure shown in formula (5), the monomer F be the monomer with structure shown in formula (6),
And on the basis of the total weight of the monomer mixture, the dosage of the monomer D is 85-98.9 weight %, the use of the monomer E
Amount is 1-10 weight %, and the dosage of the monomer F is 0.1-5 weight %；The solution polymerization condition makes polymerization reaction
The viscosity average molecular weigh of resulting polymers is 23,000,000-3,000 ten thousand, preferably 24,000,000-2,800 ten thousand afterwards；
Wherein, R1’-R3' identical or different, it is each independently hydrogen or the alkyl of C1-C4, M ' is hydrogen, sodium or potassium, and p ' is
The integer of 8-16, m ' are the integer of 2-4, and n ' is the integer of 3-9.
The description of the alkyl of the C1-C4 is same as described above.
The introduction of the acrylamide copolymer of higher molecular weight is easy to get and is easy to get from raw material, it is preferable that formula
(4) in the monomer of structure shown in-formula (6), R1’-R3' it is each independently selected from hydrogen or methyl, M ' is hydrogen, and p ' is 10-14.It is more excellent
Selection of land, in the monomer of structure shown in formula (4)-formula (6), R1’-R3' it is hydrogen, M ' is hydrogen, and p ' is the integer of 11-14.
In the present invention, the monomer E is surface active monomer, and specific example includes but is not limited to 2- acrylamido
Myristyl sulfonic acid, 2- acrylamido myristyl sodium sulfonate, 2- acrylamido myristyl potassium sulfonate, 2- acrylamide
Base dodecyl sodium sulfonate, 2- acrylamido dodecyl sodium sulfate, 2- acrylamido potassium dodecanesulfonate, 2- acryloyl
Amido cetyl sulfonic acid, 2- acrylamido sodium cetanesulfonate and 2- acrylamido cetyl potassium sulfonate etc..
According to the present invention, the monomer E can be made according to the method for this field routine, and the process of this method can wrap
It includes：Under stirring, oleum is added drop-wise to in the raw material of the 1- alkene containing acrylonitrile, C11-C19 (temperature is not first
More than 5 DEG C) in, 15-40min is then stirred, then be warming up to 20-35 DEG C of isothermal reaction 20 hours or more, is filtered, washed, is done
The processes such as dry are made.The detailed process for preparing the monomer E is referred in bright equal (the glad table of Yu Yaming, Gao Baojiao, Wang Rui in Asia
Research [J] the colloid and polymer of synthesis and its micellization behavior of face activated monomer 2- acrylamido tetradecane sodium sulfonate,
2005,23 (4):26-28) or Wang Xiangying etc. (synthesis of Wang Xiangying, Tong Ruili .2- acrylamido dodecane sulfonic acid sodium and its
Micellization behavioral study [J] Hunan University of Technology journal, 2007,21 (2):Method disclosed in 68-71) carries out.
In the present invention, the monomer F is a kind of fluorochemical monomer, and fluorocarbon chain existing for the monomer is more hydrocarbon than identical hydrocarbon chain
The heat resistance and salt tolerance of key is stronger, therefore acrylamide based copolymer obtained is made to have certain surface-active.
According to the present invention, when the solution polymerization starts, the weight of the monomer mixture is mixed with water and monomer
There is no particular limitation for the ratio of the total weight of object, can change in a wider scope, under preferable case, the monomer mixing
The ratio of the total weight of the weight and water and monomer mixture of object is 0.15-0.5：1, further preferably 0.2-0.4：1.
In the present invention, the initiator can be the various initiators in this field.For example, causing selected from water-soluble azo system
Agent and/or redox system initiator.
The water-soluble azo series initiators can be 2,2'- azo diisobutyl amidine dihydrochloride, 2,2'- azo [2-
(2- imidazoline -2- base) propane] at least one of dihydrochloride and 4,4 '-azos bis- (4- cyanopentanoic acids).The water solubility
The dosage of azo initiators can be the 0.001-0.05 weight % of the total weight of monomer mixture；
Preferably, the initiator is selected from redox system initiator.The redox series initiators include oxidation
Agent and reducing agent；The dosage of the oxidant can be the 0.01-0.1 weight % of the total weight of monomer mixture, the reduction
The dosage of agent can be the 0.005-0.05 weight % of the total weight of monomer mixture.
According to the present invention, the oxidant can be benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5-
At least one of bis- (hydrogen peroxide) hexanes of dimethyl -2,5, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate, further preferably
For ammonium persulfate and/or potassium peroxydisulfate.The reducing agent can be selected from ferrous sulfate, iron ammonium sulfate, stannous chloride, sulfurous acid
Potassium, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite, sodium hydrogensulfite, N,
N- dimethylethanolamine, N, N- lupetazin, tetramethylurea and N, N, N ', at least one of N '-tetramethylethylenediamine, into
One step is preferably sodium hydrogensulfite and/or potassium bisulfite.
According to the present invention, the condition of the solution polymerization can be the condition of this field routine.For example, the polymerization
Reaction carries out in the presence of an inert gas, and the solution polymerization condition may include：Temperature is 0-70 DEG C, time 10-
14 hours, pH 6-10.The pH by be added alkali be adjusted, the alkali can selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide,
At least one of methylamine, ethamine, ethanol amine and triethanolamine, preferably sodium hydroxide.
In the present invention, under preferable case, after monomer mixture is mixed with water and adjust after the pH value of reaction system again plus
Enter initiator initiated polymerization.
In the present invention, in order to further increase the molecular weight of polymer, under preferable case, the polymerization reaction include according to
Two stages of secondary progress：The reaction condition of first stage includes：Temperature is 0-10 DEG C, and the time is 6-8 hours；Second stage
Reaction condition includes：Temperature is 50-70 DEG C, and the time is 4-6 hours.
According to the present invention, simultaneously in order to avoid the influence of the impurity (for example originating from water, monomer and initiator) in reaction system
Improve monomer dissolubility in water, under preferable case, the polymerization reaction in the presence of complexing agent and/or other auxiliary agents into
Row；On the basis of the total weight of the monomer mixture, the dosage of the complexing agent is 0.01-0.1 weight %, and described other help
The dosage of agent is 0.01-0.1 weight %；The complexing agent is selected from disodium ethylene diamine tetraacetate (EDTA-2Na), citric acid, lemon
At least one of hydrochlorate and poly- hydroxy acrylic acid；Other described auxiliary agents are in urea, sodium formate, isopropanol and sodium hypophosphite
At least one.It is highly preferred that the complexing agent is disodium ethylene diamine tetraacetate, other described auxiliary agents are urea.
In the present invention, the complexing agent and other auxiliary agents can also be added in reaction system before initiator addition.
Normally, after the polymerization reaction, obtained polymer is blob of viscose.In order to obtain acrylamide copolymer product,
The method also includes：Polymer blob of viscose such as is cut, is granulated, is crushed and is sieved at the processes.Wherein, aforementioned process is specific
Condition be it is known in the art, details are not described herein.
The step of a preferred embodiment of the invention, the preparation method of the acrylamide copolymer includes：
1) acrylamide monomers D, surface active monomer E and fluorochemical monomer F and water are mixed to form monomer mixture water
Solution is 6-10 with the pH that alkali adjusts the aqueous solution；
2) complexing agent aqueous solution and other adjuvant water solutions are added into the aqueous solution of step 1), stir evenly；
3) be passed through nitrogen flooding oxygen 20-40 minutes to the reaction system of step 2), 0-10 DEG C at a temperature of, be added oxidation also
Former initiator continues to stop after leading to nitrogen 3-10 minutes, under nitrogen protection, make until solution retrogradation, that is, start polymerization reaction
The reaction maintains 6-8 hours；
4) reaction is warming up to 50-70 DEG C, the reaction was continued under nitrogen protection 4-6 hours, obtains polymer blob of viscose；
5) polymer blob of viscose is cut, is granulated, is crushed and is sieved, obtain acrylamide copolymer product.
In step 2), the complexing agent aqueous solution is preferably the EDTA-2Na aqueous solution that concentration is 0.5-2.5 weight %, institute
Stating other adjuvant water solutions is preferably the aqueous solution of urea that concentration is 0.5-2.5 weight %.
In step 3), the Oxidizing and Reducing Agents in the redox initiator is preferably added as an aqueous solution,
The concentration of aqueous oxidizing agent solution can be 0.1-3 weight %, and the concentration of reducing agent aqueous solution can be 0.1-3 weight %.
According to the third aspect of the present invention, the present invention provides the acrylamide based copolymers prepared by the above method.
In the present invention, the structure of obtained acrylamide based copolymer can be characterized by IR spectrum.Pass through
IR optical spectroscopy arrives, 3342cm-1It is nearby-NH2Characteristic absorption peak, 1039cm-1And 1230cm-1It is nearby sulfonic acid group
Characteristic absorption peak, 1124cm-1It is nearby-CF3Characteristic absorption peak, it is seen then that the copolymer of synthesis contains structural unit A, structure
Unit B and structural unit C, namely acrylamide based copolymer of the invention has been synthesized using this method.
Since above-mentioned preparation method will be copolymerized the structural unit of the monomer E and fluorochemical monomer F of energy with surface-active
It is introduced on polyacrylamide strand, on the one hand the acrylamide copolymer has the thickening of water soluble polymer
Property and viscoplasticity；On the other hand the acrylamide copolymer has certain surface-active, by emulsification increase-volume and reduces table
The characteristics such as face tension increase the displacement efficiency of polymer.
According to the fourth aspect of the present invention, the present invention provides acrylamide based copolymer the answering as oil displacement agent
With.
Acrylamide based copolymer heat resistance and salt tolerance with higher of the invention, the aqueous copolymers solution is in high temperature height
Higher viscosity is still kept under salt；In addition, the acrylamide based copolymer also has lower surface tension and interfacial tension, because
This also has good surface-active, increase-volume emulsification and washing oil ability, therefore is suitable as oil displacement agent use.
In following embodiment and comparative example, the performance test of product is carried out using following methods：
1, it is measured according to method specified in People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008
The intrinsic viscosity of polymer.
2, polymer viscosity average molecular weigh method according to specified in SY/T5862-2008, using formula M=([η]/
0.000373)1.515To calculate, wherein M is viscosity average molecular weigh, and [η] is intrinsic viscosity.
3, the apparent viscosity of polymer solution is the salt with salinity 25000mg/L (wherein calcium ions and magnesium ions are 800mg/L)
Polymer is made into the solution of 1500mg/L by water, and with Brookfield viscosimeter (use ULA rotor) at 80 DEG C, shear velocity is
7.34s-1Under the conditions of measure.
4, with the surface of DCAT-21 surface tension instrument test polymer aqueous solution (concentration 1500mg/L) at 25 DEG C
Power.
In following embodiment, acrylamide is commercially available from Bao Mo biochemical industry limited liability company, 2- acrylamido 14
Alkyl sulfonic acid is made according to document：The glad surface active monomer 2- acrylamido tetradecane sulfonic acid of Yu Yaming, Gao Baojiao, Wang Rui
Research [J] the colloid and polymer of synthesis and its micellization behavior of sodium, 2005,23 (4):26-2.
In following embodiment and comparative example, the concentration of EDTA-2Na aqueous solution and aqueous solution of urea is 1 weight %.
Embodiment 1
The present embodiment is for illustrating acrylamide based copolymer and preparation method thereof of the invention.
17.98 grams of acrylamides, 2.0 grams of 2- acrylamido myristyl sulfonic acid and 0.02g are added in polymerization bottle
Perfluoro hexyl ethyl propylene acid esters (shown in structure such as formula (7), is purchased from lark prestige Reagent Company), and 60 grams of deionized waters are added, match
At the aqueous solution of monomer mixture, then adjusting pH with sodium hydroxide is 6.0.It is water-soluble that EDTA-2Na is successively added into the polymerization bottle
Liquid 1.0g, aqueous solution of urea 0.5g, stirs evenly.Polymerization bottle is put into water bath with thermostatic control, leads to high pure nitrogen deoxygenation 30 minutes, adds
Enter persulfate aqueous solution (concentration is 0.1 weight %) 3g and aqueous solution of sodium bisulfite (concentration is 0.1 weight %) 1.5g, in
0 DEG C of initiator for reaction continues logical nitrogen and stops after five minutes, under nitrogen protection, polymerization reaction 6 hours.It is warming up to 50 DEG C of continuation
Reaction 8 hours, obtains blob of viscose；Acrylamide based copolymer is obtained after the blob of viscose is cut, is granulated, crushes and is sieved, it should
The property of acrylamide based copolymer is listed in Table 1 below.
Embodiment 2
The present embodiment is for illustrating acrylamide based copolymer and preparation method thereof of the invention.
The complete of 18.8 grams of acrylamides, 0.2 gram of 2- acrylamido myristyl sulfonic acid and 1.0g is added in polymerization bottle
Fluorine decyl butyl propyleneglycol acid esters (shown in structure such as formula (8), is purchased from lark prestige Reagent Company), and 60 grams of deionized waters are added, are made into
The aqueous solution of monomer mixture, then adjusting pH with sodium hydroxide is 7.2.EDTA-2Na aqueous solution is successively added into the polymerization bottle
1.0g, aqueous solution of urea 0.5g, stirs evenly.Polymerization bottle is put into water bath with thermostatic control, leads to high pure nitrogen deoxygenation 30 minutes, is added
Ammonium persulfate aqueous solution (concentration is 0.1 weight %) 10g and bisulfite aqueous solutions of potassium (concentration is 0.1 weight %) 5.0g, in 5
DEG C initiator for reaction continues logical nitrogen and stops after five minutes, under nitrogen protection, polymerization reaction 6 hours.It is warming up to 55 DEG C of continuation
Reaction 7 hours, obtains blob of viscose.Acrylamide based copolymer is obtained after the blob of viscose is cut, is granulated, crushes and is sieved, it should
The property of acrylamide based copolymer is listed in Table 1 below.
Embodiment 3
The present embodiment is for illustrating acrylamide based copolymer and preparation method thereof of the invention.
The complete of 18.5 grams of acrylamides, 1.0 grams of 2- acrylamido myristyl sulfonic acid and 0.5g is added in polymerization bottle
Fluorine octyl ethyl propylene acid esters (shown in structure such as formula (9), is purchased from lark prestige Reagent Company), and 60 grams of deionized waters are added, are made into
The aqueous solution of monomer mixture, then adjusting pH with sodium hydroxide is 10.0.It is water-soluble that EDTA-2Na is successively added into the polymerization bottle
Liquid 2.0g, aqueous solution of urea 0.5g, stirs evenly.Polymerization bottle is put into water bath with thermostatic control, leads to high pure nitrogen deoxygenation 30 minutes, adds
Enter ammonium persulfate aqueous solution (concentration is 0.1 weight %) 8.0g and aqueous solution of sodium bisulfite (concentration is 0.1 weight %) 4.0g,
In 10 DEG C of initiator for reaction, continues logical nitrogen and stop after five minutes, under nitrogen protection, polymerization reaction 8 hours.It is warming up to 70 DEG C
The reaction was continued 5 hours, obtains blob of viscose.Acrylamide copolymerization is obtained after the blob of viscose is cut, is granulated, crushes and is sieved
The property of object, the acrylamide based copolymer is listed in Table 1 below.
Embodiment 4
The present embodiment is for illustrating acrylamide based copolymer and preparation method thereof of the invention.
18.98 grams of acrylamides, 1.0 grams of 2- acrylamido myristyl sulfonic acid and 0.02g is added such as in polymerization bottle
60 grams of deionized waters are added in fluorochemical monomer shown in formula (7), are made into the aqueous solution of monomer mixture, then adjust pH with sodium carbonate
It is 7.0.EDTA-2Na aqueous solution 0.2g is successively added into the polymerization bottle, aqueous solution of urea 0.2g is stirred evenly.By polymerization bottle
Be put into water bath with thermostatic control, lead to high pure nitrogen deoxygenation 30 minutes, be added ammonium persulfate aqueous solution (concentration is 0.1 weight %) 5.0g and
Aqueous solution of sodium bisulfite (concentration is 0.1 weight %) 2.5g continues logical nitrogen and stops after five minutes in 10 DEG C of initiator for reaction,
Under nitrogen protection, polymerization reaction 7 hours.Being warming up to 60 DEG C, the reaction was continued 6 hours, obtains blob of viscose；The blob of viscose is cut,
Acrylamide based copolymer is obtained after being granulated, crush and sieving, the property of the acrylamide based copolymer is listed in Table 1 below.
Embodiment 5
Acrylamide copolymer is prepared according to the method for embodiment 1, the difference is that with the 2- acrylamide of phase homogenous quantities
Base dodecyl sodium sulfonate is (according to document：The synthesis of Wang Xiangying, Tong Ruili .2- acrylamido dodecane sulfonic acid sodium and its micella
Change behavioral study [J] Hunan University of Technology journal, 2007,21 (2):68-71 is made) instead of the 2- acrylamide in embodiment 1
Base myristyl sulfonic acid, so that acrylamide based copolymer be made, the property of the acrylamide based copolymer is listed in Table 1 below.
Embodiment 6
The present embodiment is for illustrating acrylamide based copolymer and preparation method thereof of the invention.
17 grams of acrylamides, 2.5 grams of 2- acrylamido myristyl sulfonic acid and 0.5g such as formula (7) are added in polymerization bottle
Shown in fluorochemical monomer, 60 grams of deionized waters are added, are made into the aqueous solution of monomer mixture, then adjusts pH with sodium hydroxide and is
8.0.EDTA-2Na aqueous solution 0.3g is successively added into the polymerization bottle, aqueous solution of urea 0.3g is stirred evenly.Polymerization bottle is put
Enter in water bath with thermostatic control, leads to high pure nitrogen deoxygenation 30 minutes, be separately added into persulfate aqueous solution 6.0g and sodium hydrogensulfite is water-soluble
Liquid 3.0g continues logical nitrogen and stops after five minutes in 15 DEG C of initiator for reaction, under nitrogen protection, polymerization reaction 7 hours.Heating
To 60 DEG C, the reaction was continued 5 hours, obtains blob of viscose；Acrylamide is obtained after the blob of viscose is cut, is granulated, crushes and is sieved
The property of copolymer, the acrylamide based copolymer is listed in Table 1 below.
Comparative example 1
Acrylamide copolymer is prepared according to the method for embodiment 1, the difference is that not using fluorochemical monomer, and propylene
The dosage of amide is 18g, so that acrylamide based copolymer be made, the property of the acrylamide based copolymer is listed in Table 1 below.
Comparative example 2
Acrylamide copolymer is prepared according to the method for embodiment 1, the difference is that the dosage of fluorochemical monomer is 1.5g,
And the dosage of acrylamide is 16.5g, so that acrylamide based copolymer be made, the property of the acrylamide based copolymer is listed in
In table 1.
Comparative example 3
Acrylamide copolymer is prepared according to the method for embodiment 1, the difference is that surface active monomer is not used, and
The dosage of acrylamide is 19.98g, so that acrylamide based copolymer be made, the property of the acrylamide based copolymer is listed in
In table 1.
Table 1
As can be seen from Table 1, pass through the surface active monomer and functional fluoropolymer of the certain dosage of introducing in method of the invention
Monomer, prepared acrylamide based copolymer molecular weight with higher, the apparent viscosity with higher under high salinity,
Therefore there is preferable temperature-resistant anti-salt performance.In addition, the copolymer also shows excellent surface-active.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of acrylamide based copolymer, which is characterized in that the acrylamide based copolymer contains structural unit A, structure list
First B and structural unit C, wherein the structural unit A is the unit with structure shown in formula (1), and the structural unit B is tool
There is the unit of structure shown in formula (2), the structural unit C is the unit with structure shown in formula (3), and with the acrylamide
In based copolymer on the basis of the total weight of structural unit, the content of the structural unit A is 85-98.9 weight %, the structure
The content of unit B is 1-10 weight %, and the content of the structural unit C is 0.1-5 weight %；The acrylamide based copolymer
Viscosity average molecular weigh be 23,000,000-3,000 ten thousand,
Wherein, R1-R3It is identical or different, it is each independently hydrogen or the alkyl of C1-C4, M is hydrogen, sodium or potassium, and p is the whole of 8-16
Number, m are the integer of 2-4, and n is the integer of 3-9.
2. acrylamide based copolymer according to claim 1, wherein the viscous equal molecule of the acrylamide based copolymer
Amount is 24,000,000-2,800 ten thousand.
3. acrylamide based copolymer according to claim 1 or 2, wherein R1-R3It is each independently selected from hydrogen or methyl,
M is hydrogen, p 10-14.
4. a kind of preparation method of acrylamide based copolymer, the preparation method include the following steps：In solution polymerization item
Under part, in the presence of initiator, monomer mixture is made to carry out polymerization reaction in water, which is characterized in that the monomer mixture
It is the monomer with structure shown in formula (4) containing monomer D, monomer E and monomer F, the monomer D, the monomer E is with formula
(5) monomer of structure shown in, the monomer F are the monomer with structure shown in formula (6), and with the gross weight of the monomer mixture
On the basis of amount, the dosage of the monomer D is 85-98.9 weight %, and the dosage of the monomer E is 1-10 weight %, the monomer F
Dosage be 0.1-5 weight %；The solution polymerization condition makes the viscosity average molecular weigh of resulting polymers after polymerization reaction
It is 23,000,000-3,000 ten thousand,
Wherein, R1’-R3' identical or different, it is each independently hydrogen or the alkyl of C1-C4, M ' is hydrogen, sodium or potassium, and p ' is 8-16
Integer, m ' be 2-4 integer, n ' be 3-9 integer.
5. according to the method described in claim 4, wherein, the solution polymerization condition makes gained polymerization after polymerization reaction
The viscosity average molecular weigh of object is 24,000,000-2,800 ten thousand.
6. according to the method described in claim 4, wherein, R1’-R3' it is each independently selected from hydrogen or methyl, M ' is hydrogen, and p ' is 8-
14。
7. according to the method described in claim 4, wherein, the initiator is selected from redox series initiators, and the oxidation is also
Former series initiators include Oxidizing and Reducing Agents, and the dosage of the oxidant is the 0.01-0.1 of the total weight of monomer mixture
Weight %, the dosage of the reducing agent are the 0.005-0.05 weight % of the total weight of monomer mixture.
8. according to the method described in claim 7, wherein, the oxidant is selected from benzoyl peroxide, hydrogen peroxide, tert-butyl
At least one in bis- (hydrogen peroxide) hexanes of hydrogen peroxide, 2,5- dimethyl -2,5, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate
Kind；The reducing agent is selected from ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, Asia
Potassium acid sulfate, sodium thiosulfate, potassium thiosulfate, rongalite, sodium hydrogensulfite, N, N- dimethylethanolamine, N, N- dimethyl
Piperazine, tetramethylurea and N, N, N ', at least one of N '-tetramethylethylenediamine.
9. the method according to any one of claim 4-8, wherein the polymerization reaction in the presence of an inert gas into
Row, the solution polymerization condition include：Temperature is 0-70 DEG C, and the time is 10-14 hours, pH 6-10.
10. the method according to any one of claim 4-8, wherein the polymerization reaction includes two successively carried out
A stage：The reaction condition of first stage includes：Temperature is 0-10 DEG C, and the time is 6-8 hours；The reaction condition packet of second stage
It includes：Temperature is 50-70 DEG C, and the time is 4-6 hours.
11. the method according to any one of claim 4-8, wherein the polymerization reaction complexing agent and/or other
It is carried out in the presence of auxiliary agent；The dosage of the complexing agent is the 0.01-0.1 weight % of the total weight of monomer mixture, it is described its
The dosage of his auxiliary agent is the 0.01-0.1 weight % of the total weight of monomer mixture；The complexing agent is selected from ethylenediamine tetra-acetic acid two
At least one of sodium, citric acid, citrate and poly- hydroxy acrylic acid；Other described auxiliary agents are selected from urea, sodium formate, isopropyl
At least one of pure and mild sodium hypophosphite.
12. the acrylamide based copolymer of any one of claim 4-11 the method preparation.
13. application of the acrylamide based copolymer as oil displacement agent described in any one of claim 1-3 and 12.
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| CN104211855A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method and application thereof |
| CN104448130A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof |
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| CN104211855A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method and application thereof |
| CN104448130A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant copolymer for oilfield, and preparation method and application thereof |
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