CN104211855B - A kind of acrylamide copolymer and preparation method thereof and application - Google Patents
A kind of acrylamide copolymer and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of acrylamide copolymer and its preparation method and application, this acrylamide copolymer contains the structural unit A with structure shown in formula (1), the structural unit B with structure shown in formula (2) and has the structural unit C of structure shown in formula (3), and with the gross weight of structural unit in acrylamide copolymer for benchmark, the content of structural unit A is 5-95 % by weight, the content of structural unit B is 2.5-90 % by weight, and the content of structural unit C is 0.05-5 % by weight; The viscosity-average molecular weight of acrylamide copolymer is 20,000,000-30,000,000.Multipolymer of the present invention has higher apparent viscosity under high temperature, high salinity condition, and excellent resistance to gentle anti-salt property, can improve the recovery ratio of oil greatly.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and preparation method thereof, and described acrylamide copolymer is as the application of polymer oil-displacing agent.
Background technology
In recent years, along with deepening continuously of China's oil-field development, in Produced Liquid, water ratio rises gradually, and part oil field composite water cut even reaches more than 90%.For improving oil recovery factor further, the tertiary oil recovery technologies such as polymer flooding, binary combination flooding oil (alkali-polymkeric substance), ternary composite oil-displacing (alkali, surfactant and polymer) are successively widely used in east main force oil fields such as grand celebration, the Liaohe River, huge port, triumpies, and achieve significant oil increasing precipitation effect and good economic and social benefits.Current Polymer Used For Oil Displacement mainly partially hydrolyzed polyacrylamide, but at high temperature can there is the chain rupture of obvious molecular chain due to partially hydrolyzed polyacrylamide (HPAM), cause its viscosity significantly to reduce, be thus not suitable with high-temperature oil reservoir.
Hydrophobic associated water-soluble polymer is on polyacrylamide molecular chain, introduce a small amount of special hydrophobic functional group, hydrophobic grouping its become side base or the side chain of polymer molecular chain.Therefore, polymer molecule in aqueous, there is some strength but reversible physical association due to the hydrophobic interaction of hydrophobic grouping and electrostatic, hydrogen bond or van der Waals interaction in intermolecular automatic generation, thus form huge 3 D stereo mesh space structure.This makes hydrophobic associated polymer still have higher viscosity under lower molecular weight and low concentration.
Fluorine-containing modified amphoteric water-soluble polymer refers to the class water-soluble polymers introducing perfluor hydrophobic grouping and negative ions group on polymer hydrophilicity macromolecular chain.In water-soluble polymers, introduce hydrophobic grouping, utilize the heat resistance and salt tolerance of hydrophobic grouping to be the important channel of improving polymkeric substance heat-resistant salt-resistant performance.Hydrophobic grouping can form Interpolymer Association effect and increase the hydrodynamic volume of polymer molecule, and the viscosity of solution exponentially increases with the increase of polymer concentration, even higher in the viscosity ratio pure water of polymkeric substance in salt solution.Current great majority research all concentrates on hydrocarbon hydrophobic chain modified water-soluble polymer.Fluorocarbon chain is used for modified water-soluble polymer and there is not yet report.
Summary of the invention
For the defect existed in prior art, provide that a kind of molecular weight is high, apparent viscosity is high, the acrylamide copolymer of heat-resisting and good salt tolerance and its preparation method and application.
The present inventor is found by research, and fluorocarbon chain, compared with the hydrocarbon chain of equal length, has lower cohesive energy density(CED) and surface energy, and its heat resistance and salt tolerance comparatively hydrocarbon chain is stronger.Therefore itself and acrylamide monomer are carried out copolymerization, the multipolymer obtained has tackifying and the heat and salt resistance of raising; And due to the introducing of hydrophobic monomer containing fluorocarbon chain, in the long-term cycle uses, the tackifying of polymkeric substance can be improved, keep the entanglement capability of polymer molecular chain, improve the visco-elasticity of polymkeric substance, thus improve oil displacement efficiency.Based on this, complete the present invention.
The invention provides a kind of acrylamide copolymer, wherein, this acrylamide copolymer contains the structural unit A with structure shown in formula (1), the structural unit B with structure shown in formula (2) and has the structural unit C of structure shown in formula (3), and with the gross weight of structural unit in described acrylamide copolymer for benchmark, the content of described structural unit A is 5-95 % by weight, the content of described structural unit B is 2.5-90 % by weight, and the content of described structural unit C is 0.05-5 % by weight; The viscosity-average molecular weight of described acrylamide copolymer is 20,000,000-30,000,000,
formula (1),
formula (2),
formula (3),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
Present invention also offers a kind of preparation method of allylamine multipolymer, this preparation method comprises under micellar copolymerization reaction conditions, under the existence of emulsifying agent, contacted with initiator by monomer mixture, the condition of contact makes the viscosity-average molecular weight of the multipolymer obtained be 20,000,000-30,000,000
Wherein, described monomer mixture contains acrylamide, the monomer D of the structure shown in (4) that has formula and have the monomer E of structure shown in formula (5), and with the gross weight of described monomer mixture for benchmark, the consumption of acrylamide is 5-95 % by weight, the consumption of described monomer D is 2.5-90 % by weight, and the consumption of described monomer E is 0.05-5 % by weight;
formula (4),
formula (5),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
Present invention also offers a kind of preparation method of described acrylamide copolymer, the method comprises the steps:
(1) acrylamide, the monomer D with structure shown in formula (4) and the monomer E with structure shown in formula (5) are made into the aqueous solution, are 6-10 by alkali adjust ph, then add emulsifying agent, obtain the mixture containing monomer;
(2) sequestrant and solubility promoter are joined that step (1) obtains containing in the mixture of monomer;
(3) at 10 DEG C ~ 15 DEG C temperature, under nitrogen protection, initiator is joined in the mixture that step (2) obtains, is polymerized and is warmed up to 40 DEG C ~ 60 DEG C after 4 ~ 8 hours, continue polymerization 4 ~ 6 hours,
formula (4),
formula (5),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
In addition, the present invention also provides the acrylamide copolymer prepared by aforesaid method.And described acrylamide copolymer is as the application of polymer oil-displacing agent.
The multipolymer that the present invention obtains has high viscosity-average molecular weight, and the viscosity-average molecular weight of polymkeric substance obtained in embodiment 1-4 all can reach 23,000, more than 000; The solution of the 1000mg/L be mixed with the salt solution that salinity is 30,000mg/L is 7.34s in shearing rate
-1temperature is under the condition of 25 DEG C, there is the apparent viscosity value up to 40.5mPas, be under the condition of 85 DEG C in temperature, also the viscosity number of 18-21mPas is still had, illustrate that polymkeric substance of the present invention still has high apparent viscosity under high salt high temperature and shear conditions, compared with the copolymer not containing fluorocarbon chain Third monomer, the apparent viscosity at its viscosity-average molecular weight and 25 DEG C and 85 DEG C is all improved largely.
Embodiment
The invention provides a kind of acrylamide copolymer, wherein, this acrylamide copolymer contains the structural unit A with structure shown in formula (1), the structural unit B with structure shown in formula (2) and has the structural unit C of structure shown in formula (3), and with the gross weight of structural unit in described acrylamide copolymer for benchmark, the content of described structural unit A is 5-95 % by weight, the content of described structural unit B is 2.5-90 % by weight, and the content of described structural unit C is 0.05-5 % by weight; The viscosity-average molecular weight of described acrylamide copolymer is 20,000,000-30,000,000,
formula (1),
formula (2),
formula (3),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.Preferably, with the gross weight of structural unit in described acrylamide copolymer for benchmark, the content of described structural unit A is 40-72 % by weight, and the content of described structural unit B is 25-55 % by weight, and the content of described structural unit C is 0.1-5 % by weight; R
1for the alkylidene group of C1-C2; R
2and R
3be the alkyl of C1-C2 independently of one another; M
1for H and/or Na; M is the integer of 2-3, and n is 4,6 or 8, and the viscosity-average molecular weight of described acrylamide copolymer is 23,000,000-27,000,000.
The present inventor finds under study for action, and the polymer oil-displacing agent that the ter-polymers be made up of specific structural unit B and structural unit C is made can obtain fabulous oil displacement efficiency, such as, m to be 2, n be 4,6 or 8, R1 be alkylidene group; R
2and R
3be methyl independently of one another; M
1for H and/or Na.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises under micellar copolymerization reaction conditions, under the existence of emulsifying agent, contacted with initiator by monomer mixture, the condition of contact makes the viscosity-average molecular weight of the multipolymer obtained be 20,000,000-30,000,000
Wherein, described monomer mixture contains acrylamide, the monomer D of the structure shown in (4) that has formula and have the monomer E of structure shown in formula (5), and with the gross weight of described monomer mixture for benchmark, the consumption of acrylamide is 5-95 % by weight, the consumption of described monomer D is 2.5-90 % by weight, and the consumption of described monomer E is 0.05-5 % by weight;
formula (4),
formula (5),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.Preferably, with the gross weight of described monomer mixture for benchmark, the consumption of acrylamide is 40-72 % by weight, and the consumption of monomer D is 25-55 % by weight, and the consumption of described monomer E is 0.1-5 % by weight; And R
1for the alkylidene group of C1-C2; R
2and R
3be the alkyl of C1-C2 independently of one another; M
1for H and/or Na; M is the integer of 2-3, and n is 4,6 or 8, and the condition of contact makes the viscosity-average molecular weight of the multipolymer obtained be 23,000,000-27,000,000.
The present inventor finds under study for action, and the polymer oil-displacing agent that the ter-polymers be made up of specific monomer D and monomer E is made can obtain fabulous oil displacement efficiency, and such as, to be 2, n be m 4,6 or 8, R
1for methylene radical; R
2and R
3be methyl independently of one another; M
1for H and/or Na.
According to the present invention, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is preferably 0.05-0.5:1, more preferably 0.15-0.4:1, most preferably is 0.2-0.4:1.
According to the present invention, the consumption of the present invention to initiator does not specially require, and preferably, the weight of described initiator can be the 0.001-0.1% of described monomer mixture gross weight.
Described initiator can be the various initiator in this area, as being selected from azo series initiators and redox series initiators, the consumption of described azo series initiators can be the 0-0.05 % by weight of the gross weight of monomer in monomer mixture, the consumption of described redox series initiators can be the 0-0.5 % by weight of the gross weight of monomer in monomer mixture, and the total amount of described azo series initiators and redox series initiators preferably meets: the consumption of described initiator is the 0.001-0.1 % by weight of the gross weight of monomer in monomer mixture.
In the present invention, preferably, described azo series initiators is selected from Diisopropyl azodicarboxylate, the two methylpent hydrochlorate, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride], more preferably 2,2 '-azo diisobutyl amidine hydrochloride, 2,2 '-azo two [at least one in 2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride and the two methylpent hydrochlorate of azo.
Described redox series initiators comprises Oxidizing and Reducing Agents, preferably, the weight ratio of described oxygenant and described reductive agent is 0.1-10:1, under meeting the condition of aforementioned proportion, the consumption of described oxygenant is preferably the 0.0001-0.01 % by weight of the gross weight of monomer in monomer mixture, more preferably 0.001-0.05 % by weight; Preferably, described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide, at least one more preferably in ammonium persulphate, Potassium Persulphate and Sodium Persulfate; The consumption of described reductive agent is preferably the 0.0001-0.01 % by weight of the gross weight number of monomer in monomer mixture, is preferably the 0.001-0.05 % by weight of the gross weight number of monomer in monomer mixture; Described reductive agent can be inorganic reducing agent and/or organic reducing agent (chainextender), preferably, described inorganic reducing agent is selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate and vat powder, more preferably sodium bisulfite and/or S-WAT; Described organic reducing agent is preferably selected from N, N '-dimethyl quadrol, N, N '-dimethyl propylene diamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N-dimethyl amine, 3-methylamino-propylamine, Dimethylaminoethyl Methacrylate, at least one in N-(3-dimethylamino-propyl) Methacrylamide, most preferably be N, N '-dimethyl quadrol, N, N '-dimethyl propylene diamine and N, N, N ', N ' at least one in-Tetramethyl Ethylene Diamine.
According to the present invention, the consumption of described emulsifying agent is not particularly limited, can change in wider scope, as long as described emulsifying agent and oil are mixed to form oil phase, under preferable case, with the gross weight of described monomer mixture for benchmark, the consumption of described emulsifying agent can be 1.5-8.5 % by weight, more preferably 2-3 % by weight.
According to the present invention, described emulsifying agent can be the various emulsifying agent for letex polymerization in this area, such as, can be alkylaryl sulfonate surfactants.Described alkylaryl sulfonate surfactants can be one or more in dodecyl diphenyl oxide sodium sulfonate, dialkyl diphenyl ether disulfonic acid sodium and sodium dialkyl diphenyl ether monosulfonate.
According to the present invention, described polyreaction can also be carried out under various auxiliary agent exists; Described auxiliary agent can be selected from sequestrant and/or solubility promoter; With the gross weight of monomer in described monomer mixture for benchmark, the consumption of described sequestrant can be 0-2 % by weight, be preferably 0.0001-1 % by weight, the consumption of described solubility promoter can be 0-2 % by weight, be preferably 0.0001-1 % by weight, preferably, the consumption of described sequestrant and solubility promoter makes: with the gross weight of monomer in described monomer mixture for benchmark, and the consumption of described auxiliary agent is 0.0001-4 % by weight; Described sequestrant is preferably at least one in disodium ethylene diamine tetraacetate (EDTA), Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic, more preferably EDTA and/or Citrate trianion, described Citrate trianion can be such as Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate etc.; Described solubility promoter is preferably selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite, is preferably urea and/or sodium formiate.
The present inventor finds, under there is the condition of above-mentioned various initiator and auxiliary agent at the same time, can obtain the polymkeric substance that viscosity-average molecular weight is very high.
According to the present invention, the condition of described micellar copolymerization reaction can be the condition of this area routine, and as carried out in the presence of an inert gas, the pH value of the reaction system of described micellar copolymerization reaction is 4-11, and described micellar copolymerization reaction is carried out in an inert atmosphere; The condition of described micellar copolymerization reaction can comprise: temperature is 0 DEG C-80 DEG C, is preferably 4-60 DEG C; Time is 1-32 hour, is preferably 11-28 hour; PH value is 5-13, is preferably 6-10.Described pH value regulates by adding acid, and described acid is preferably mineral acid, and described mineral acid is preferably at least one in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid.When there being AMPS in comonomer, alkali regulation system pH value need be added, described alkali can be mineral alkali or organic amine compound, as being selected from least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, thanomin and trolamine, is preferably sodium hydroxide.
The present inventor finds under study for action, take following condition can obtain the polymkeric substance of ultra-high molecular weight: namely, preferably, described polyreaction comprises two stages of carrying out successively, the reaction conditions of first stage comprises: temperature is 10-15 DEG C, and the time is 1-10 hour; The reaction conditions of subordinate phase comprises: temperature is 35-60 DEG C, and the time is 2-14 hour.
Present invention also offers a kind of preparation method of described acrylamide copolymer, the method comprises the steps:
(1) acrylamide, the monomer D with structure shown in formula (4) and the monomer E with structure shown in formula (5) are made into the aqueous solution, are 6-10 by alkali adjust ph, then add emulsifying agent, obtain the mixture containing monomer;
(2) sequestrant and solubility promoter are joined that step (1) obtains containing in the mixture of monomer;
(3) at 10 DEG C ~ 15 DEG C temperature, under nitrogen protection, initiator is joined in the mixture that step (2) obtains, is polymerized and is warmed up to 40 DEG C ~ 60 DEG C after 4 ~ 8 hours, continue polymerization 4 ~ 6 hours,
formula (4),
formula (5),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
Present invention also offers the acrylamide copolymer obtained according to aforesaid method.
Acrylamide copolymer provided by the invention, owing to having high viscosity-average molecular weight and apparent viscosity, thus when oil drilling is exploited, more effectively can infiltrate oil reservoir rock gap, thus improves oil recovery factor.Therefore, present invention also offers the application of described acrylamide polymer in oil-displacing agent.Described acrylamide polymer of the present invention can be used for oil recovering as oil-displacing agent.
Below, by following examples, the present invention will be described in more detail.
In following examples, the composition of molecular structural formula and structural unit adopts quantitatively
13c composes mensuration.
The reagent etc. used in following examples, comparative example and test case is commercially available product.
Embodiment 1
12.0g acrylamide, 7.8g2-acrylamide-2-methylpro panesulfonic acid and 0.2g had the hydrophobic monomer (m=2 of structure shown in formula (5), n=4) join in polyreaction bottle, add deionized water 50.0g to dissolve, adding sodium hydroxide again regulates pH to be 8.1, then add 0.5g Sodium dodecylbenzene sulfonate, after abundant stirring and emulsifying, add the EDTA-2Na aqueous solution 1.0g of 1%, the aqueous solution of urea 0.5g of 1% successively.
Polyreaction bottle is put into water bath with thermostatic control, logical nitrogen flooding oxygen is after 30 minutes, add the bisulfite aqueous solutions of potassium 2.0g of the persulfate aqueous solution 4.0g and 0.1% of 0.1% again, in 10 DEG C of initiation reactions, continue logical nitrogen to stop after five minutes, polyreaction, after 4 hours, is warming up to 50 DEG C and continues reaction 6 hours, obtain blob of viscose.Take out blob of viscose, cutting, granulation, pulverize, sieve to obtain white temperature resistant antisalt Polymer Used For Oil Displacement P1.
Wherein, acrylamide weight ratio is 60%, 2-acrylamide-2-methylpro panesulfonic acid mass ratio is 39%, and hydrophobic monomer (n=4) is 1%.The molecular weight of polymkeric substance is 27,000,000 after tested, and apparent viscosity is 52.0mPas.
Infrared spectroscopy IR mensuration is carried out to P1, result as shown in Figure 1, wherein, 3324.4cm
-1for-NH
2vibration absorption peak, 3202.8cm
-1for-NH-vibration absorption peak; 2929.8cm
-1for-CH
2-symmetry and asymmetric stretching vibration absorption peak, 1685.9cm
-1for the stretching vibration peak of-C=O, 1458.0cm
-1for typical-CH
2-scissoring vibration; 1305.2cm
-1, 1188.4cm
-1and 1041.2cm
-1for-SO
3-symmetrical and asymmetric vibration absorption peak; 1159.0cm
-1for the stretching vibration peak of-C-F.The charateristic avsorption band of three kinds of structural units all appears in infrared spectra, shows that this multipolymer is made up of these three kinds of structural units.Recording its viscosity-average molecular weight Mv by viscosimetry is 27,000,000.Wherein, formula (6) and x, y and z only indicate type and the number of structural unit, do not represent the mode of connection of structural unit.
formula (6), wherein n=4.
Comparative example 1
Acrylamide based copolymer is prepared according to the method for embodiment 1, unlike, do not add the monomer of structure shown in formula (5), thus obtain the copolymer DP1 of AM and AMPS, recording its viscosity-average molecular weight is 17,000,000.
Embodiment 2
9.9g acrylamide, 10.0g2-acrylamide-2-methylpro panesulfonic acid and 0.1g had the hydrophobic monomer (m=2 of structure shown in formula (5), n=6) join in polyreaction bottle, add deionized water 50.0g to dissolve, adding sodium hydroxide again regulates pH to be 7.5, then add 0.5g Sodium dodecylbenzene sulfonate, after abundant stirring and emulsifying, add the EDTA-2Na aqueous solution 1.0g of 1%, the aqueous solution of urea 1.0g of 1% successively.
Polyreaction bottle is put into water bath with thermostatic control, logical nitrogen flooding oxygen is after 30 minutes, add the bisulfite aqueous solutions of potassium 2.0g of the ammonium persulfate aqueous solution 5.0g and 0.1% of 0.1%, in 10 DEG C of initiation reactions, continue logical nitrogen to stop after five minutes, polyreaction, after 6 hours, is warming up to 50 DEG C and continues reaction 6 hours, obtain blob of viscose.Take out blob of viscose, cutting, granulation, pulverize, sieve to obtain white temperature resistant antisalt Polymer Used For Oil Displacement P2.The molecular weight of polymkeric substance is 23,000,000 after tested, and apparent viscosity is 40.5mPas.
Wherein the proportion of acylamide is 49.5%, 2-acrylamide-2-methylpro panesulfonic acid mass ratio is 50%, and hydrophobic monomer (n=6) is 0.5%.
Comparative example 2
Acrylamide based copolymer is prepared according to the method for embodiment 2, unlike, do not add the monomer of structure shown in formula (5), thus obtain the copolymer DP2 of AM and AMPS, recording its viscosity-average molecular weight is 16,000,000.
Embodiment 3
13.98g acrylamide, 6.0g2-acrylamide-2-methylpro panesulfonic acid and 0.02g had the hydrophobic monomer (m=2 of structure shown in formula (5), n=8) join in polyreaction bottle, add deionized water 50.0g to dissolve, adding sodium hydroxide again regulates pH to be 9.5, then add 0.5g Sodium dodecylbenzene sulfonate, after abundant stirring and emulsifying, add the EDTA-2Na aqueous solution 2.0g of 1%, the aqueous solution of urea 0.5g of 1% successively.
Polyreaction bottle is put into water bath with thermostatic control, logical nitrogen flooding oxygen is after 30 minutes, add the aqueous solution of sodium bisulfite 5.0g of the ammonium persulfate aqueous solution 10g and 0.1% of 0.1%, in 15 DEG C of initiation reactions, continue logical nitrogen to stop after five minutes, polyreaction, after 8 hours, is warming up to 55 DEG C and continues reaction 5 hours, obtain blob of viscose.Take out blob of viscose, cutting, granulation, pulverize, sieve to obtain white temperature resistant antisalt Polymer Used For Oil Displacement.The molecular weight of polymkeric substance is 24,000,000 after tested, and apparent viscosity is 43.2mPas.
Wherein the proportion of acylamide is 69.9%, 2-acrylamide-2-methylpro panesulfonic acid mass ratio is 30%, and hydrophobic monomer (n=8) is 0.1%.
Comparative example 3
Acrylamide based copolymer is prepared according to the method for embodiment 3, unlike, do not add the monomer of structure shown in formula (5), thus obtain the copolymer DP3 of AM and AMPS, recording its viscosity-average molecular weight is 14,000,000.
Embodiment 4
9.8g acrylamide, 10.0g2-acrylamide-2-methylpro panesulfonic acid and 0.2g had the hydrophobic monomer (m=2 of structure shown in formula (5), n=4) join in polyreaction bottle, add deionized water 50.0g to dissolve, adding sodium hydroxide again regulates pH to be 8.5, then add 0.5g Sodium dodecylbenzene sulfonate, after abundant stirring and emulsifying, add the EDTA-2Na aqueous solution 0.2g of 1%, the aqueous solution of urea 0.2g of 1% successively.
Polyreaction bottle is put into water bath with thermostatic control, logical nitrogen flooding oxygen is after 30 minutes, add the aqueous solution of sodium bisulfite 3.0g of the ammonium persulfate aqueous solution 6.0g and 0.1% of 0.1%, in 10 DEG C of initiation reactions, continue logical nitrogen to stop after five minutes, polyreaction, after 8 hours, is warming up to 50 DEG C and continues reaction 4 hours, obtain blob of viscose.Take out blob of viscose, cutting, granulation, pulverize, sieve to obtain white temperature resistant antisalt Polymer Used For Oil Displacement P4.The molecular weight of polymkeric substance is 26,000,000 after tested, and apparent viscosity is 49.8mPas.
Wherein the proportion of acylamide is 49%, 2-acrylamide-2-methylpro panesulfonic acid mass ratio is 50%, and hydrolysis monomer (n=4) is 1%.
Test case 1
The intrinsic viscosity of polymer P 1-P4 and DP1-DP3 measures according to GB12005.1-89 For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M
η=([η]/K)
1/ α, wherein K=4.5 × 10
-3, α=0.80 calculates; The apparent viscosity of aqueous solutions of polymers is 7.34s by BROOKFIELDDV-III viscosity apparatus in rotating speed perseverance
-1, temperature is carry out mensuration under the condition of 25 DEG C and 85 DEG C to obtain, and wherein, test condition comprises: polymer concentration is 1500mg/L, and solution total mineralization is 30,000mg/L.Test result is as shown in table 1.
Table 1
| M η(×10 4) | η 25(mPa·s) | η 85(mPa·s) | |
| P1 | 2700 | 52 | 28.4 |
| P2 | 2600 | 49.8 | 26.5 |
| P3 | 2400 | 43.2 | 21.6 |
| P4 | 2500 | 47.0 | 24.2 |
| DP1 | 1700 | 22.5 | 11.9 |
| DP2 | 1600 | 20.6 | 10.8 |
| DP3 | 1400 | 18.4 | 9.6 |
M in table 1
ηthe viscosity-average molecular weight of representation polymer, η
25represent the apparent viscosity of aqueous solutions of polymers at 25 DEG C, η
85represent the apparent viscosity of aqueous solutions of polymers at 85 DEG C.Compared by the data of embodiment 1-4 and the data of comparative example 1-3, can find out adopt its aqueous solution of polymer P 1-P4 of preparing of method of the present invention at normal temperatures (25 DEG C) there is very high apparent viscosity, and when it is in high temperature (85 DEG C), high salinity (30, still can keep very high apparent viscosity under condition 000mg/L), illustrate that the polymkeric substance prepared by the present invention has good temperature resistant antisalt performance.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. an acrylamide copolymer, it is characterized in that, this acrylamide copolymer contains the structural unit A with structure shown in formula (1), the structural unit B with structure shown in formula (2) and has the structural unit C of structure shown in formula (3), and with the gross weight of structural unit in described acrylamide copolymer for benchmark, the content of described structural unit A is 5-95 % by weight, the content of described structural unit B is 2.5-90 % by weight, and the content of described structural unit C is 0.05-5 % by weight; The viscosity-average molecular weight of described acrylamide copolymer is 20,000,000-30,000,000,
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
2. multipolymer according to claim 1, wherein, with the gross weight of structural unit in described acrylamide copolymer for benchmark, the content of described structural unit A is 40-72 % by weight, the content of described structural unit B is 25-55 % by weight, and the content of described structural unit C is 0.1-5 % by weight;
R
1for the alkylidene group of C1-C2; R
2and R
3be the alkyl of C1-C2 independently of one another; M
1for H and/or Na; M is the integer of 2-3, and n is 4,6 or 8, and the viscosity-average molecular weight of described acrylamide copolymer is 23,000,000-27,000,000.
3. multipolymer according to claim 2, wherein, R
1for methylene radical; R
2and R
3be methyl independently of one another; M
1for H and/or Na; M is 2, n is 4,6 or 8.
4. the preparation method of acrylamide copolymer described in a claim 1, this preparation method comprises under micellar copolymerization reaction conditions, under the existence of emulsifying agent, contacted with initiator by monomer mixture, the condition of contact makes the viscosity-average molecular weight of the multipolymer obtained be 20,000,000-30,000,000
Wherein, described monomer mixture contains acrylamide, the monomer D of the structure shown in (4) that has formula and have the monomer E of structure shown in formula (5), and with the gross weight of described monomer mixture for benchmark, the consumption of acrylamide is 5-95 % by weight, the consumption of described monomer D is 2.5-90 % by weight, and the consumption of described monomer E is 0.05-5 % by weight;
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another;
M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
5. method according to claim 4, wherein, with the gross weight of described monomer mixture for benchmark, the consumption of acrylamide is 40-72 % by weight, and the consumption of described monomer D is 25-55 % by weight, and the consumption of described monomer E is 0.1-5 % by weight, and,
R
1for the alkylidene group of C1-C2; R
2and R
3be the alkyl of C1-C2 independently of one another; M
1for H and/or Na; M is the integer of 2-3, and n is 4,6 or 8, and the condition of contact makes the viscosity-average molecular weight of the multipolymer obtained be 23,000,000-27,000,000.
6. method according to claim 4, wherein, R
1for methylene radical; R
2and R
3be methyl independently of one another; M
1for H and/or Na; M is 2, n is 4,6 or 8.
7. method according to claim 4, wherein, described micellar copolymerization reaction is carried out under auxiliary agent exists, and described auxiliary agent is selected from sequestrant and/or solubility promoter; With the gross weight of monomer in described monomer mixture for benchmark, the consumption of described sequestrant is 0-2 % by weight, the consumption of described solubility promoter is 0-2 % by weight, and with the gross weight of monomer in described monomer mixture for benchmark, the consumption of described auxiliary agent is 0.0001-4 % by weight; Described sequestrant is selected from least one in disodium ethylene diamine tetraacetate, Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic; Described solubility promoter is selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite.
8. method according to claim 7, wherein, with the gross weight of monomer in described monomer mixture for benchmark, the consumption of described sequestrant is 0.0001-1 % by weight.
9. method according to claim 7, wherein, with the gross weight of monomer in described monomer mixture for benchmark, the consumption of described solubility promoter is 0.0001-1 % by weight.
10. method according to claim 4, wherein, the pH value of the reaction system of described micellar copolymerization reaction is 4-11, and described micellar copolymerization reaction is carried out in an inert atmosphere; Described micellar copolymerization reaction comprises two stages of carrying out successively: the reaction conditions of first stage comprises: temperature is 10-15 DEG C, and the time is 1-10 hour; The reaction conditions of subordinate phase comprises: temperature is 35-60 DEG C, and the time is 2-14 hour.
The preparation method of acrylamide copolymer described in 11. 1 kinds of claims 1, the method comprises the steps:
(1) acrylamide, the monomer D with structure shown in formula (4) and the monomer E with structure shown in formula (5) are made into the aqueous solution, are 6-10 by alkali adjust ph, then add emulsifying agent, obtain the mixture containing monomer;
(2) sequestrant and solubility promoter are joined that step (1) obtains containing in the mixture of monomer;
(3) at 10 DEG C ~ 15 DEG C temperature, under nitrogen protection, initiator is joined in the mixture that step (2) obtains, is polymerized and is warmed up to 40 DEG C ~ 60 DEG C after 4 ~ 8 hours, continue polymerization 4 ~ 6 hours,
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3be the alkyl of C1-C4 independently of one another; M
1for at least one in H, Na and K; M is the integer of 2-5, and n is the integer of 4-10.
12. acrylamide copolymers obtained according to the method in claim 4-11 described in any one.
Acrylamide copolymer in 13. claim 1-3 and 12 described in any one is as the application of polymer oil-displacing agent.
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| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101392041A (en) * | 2008-10-24 | 2009-03-25 | 中国海洋大学 | Hydrophobic associating polymer containing capsaicine and sulfonic group and preparation method thereof |
| CN101463116A (en) * | 2009-01-12 | 2009-06-24 | 成都理工大学 | Non-linear associating water-soluble quadripolymer, and preparation and use thereof |
| CN101519473A (en) * | 2009-03-31 | 2009-09-02 | 山东大学 | Method for preparing fluorine-containing modified amphoteric water-soluble polymer |
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| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101392041A (en) * | 2008-10-24 | 2009-03-25 | 中国海洋大学 | Hydrophobic associating polymer containing capsaicine and sulfonic group and preparation method thereof |
| CN101463116A (en) * | 2009-01-12 | 2009-06-24 | 成都理工大学 | Non-linear associating water-soluble quadripolymer, and preparation and use thereof |
| CN101519473A (en) * | 2009-03-31 | 2009-09-02 | 山东大学 | Method for preparing fluorine-containing modified amphoteric water-soluble polymer |
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