CN104448120A - Acrylamide copolymer and preparation method and application thereof - Google Patents
Acrylamide copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an acrylamide copolymer and a preparation method and an application thereof, wherein the acrylamide copolymer contains an acrylamide structural unit and a structural unit A shown in a formula (I), the viscosity average molecular weight of the acrylamide copolymer is more than 30 millions, M1 is sodium or potassium. The invention also discloses a preparation method of the acrylamide copolymer, and an application of the acrylamide copolymer as an oil displacement agent, the acrylamide copolymer of the present invention has the advantage of high temperature resistance, and has good tackifying effect under high ore degree, the acrylamide copolymer can be widely used in petrochemical industry filed, and especially is taken as an oil-displacement agent for tertiary recovery.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and preparation method thereof, and acrylamide copolymer is as the application of oil-displacing agent.
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).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 the hydrolysis of AMPS unit, although along with hydrolysis reaction, in multipolymer, acrylic acid structure unit ratio increases, and improves its Thermo-sensitive and salt sensitivity energy, but because AMPS is 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.
Therefore, the temperature resistant antisalt how improving acrylamide copolymer is further still the problem needing solution badly.
Summary of the invention
The object of the invention is to overcome the defect that the polymer oil-displacing agent temperature resistant antisalt performance of prior art is poor, acrylamide copolymer that a kind of temperature resistant antisalt performance is good and its preparation method and application is provided.
An aspect of of the present present invention provides a kind of acrylamide copolymer, and wherein, this acrylamide copolymer contains the structural unit A shown in acrylamide structural unit and formula (I), and the viscosity-average molecular weight of described acrylamide copolymer is more than 3,000 ten thousand,
Wherein, M
1for sodium or potassium.
The present invention provides a kind of preparation method of acrylamide copolymer on the other hand, under this preparation method is included in solution polymerization condition, under initiator exists, makes monomer mixture carry out polyreaction, obtains acrylamide copolymer; Wherein, described monomer mixture contains acrylamide and monomer C, and described monomer C is the monomer of structure shown in formula (IV), M
1for sodium or potassium;
After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of gained acrylamide copolymer is more than 3,000 ten thousand.
Present invention also offers the application of aforesaid propylene amide copolymer provided by the invention 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 hydrophobic interaction of a methyl around amide group in acrylamide monomers provided by the invention and a phenyl and space steric effect 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, the sulfonic group in this monomer is insensitive to divalent salts ion, therefore improves the anti-salt property of this acrylamide copolymer; Again because acrylamide monomers has larger volume, copolymer chain is not easily occurred curling, thus make this acrylamide copolymer reach the effect with thickening.
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.
According to a kind of acrylamide copolymer provided by the invention, wherein, this acrylamide copolymer contains the structural unit A shown in acrylamide structural unit and formula (I), and the viscosity-average molecular weight of described acrylamide copolymer can be more than 3,000 ten thousand,
Wherein, M
1can be sodium or potassium.
According to the present invention, in the preferred case, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of described acrylamide structural unit can be 1-99 % by mole, the content of described structural unit A can be 1-99 % by mole, and the viscosity-average molecular weight of described acrylamide copolymer can be 3,000 ten thousand-3,550 ten thousand; Preferably, the content of described acrylamide structural unit can be 80-97.5 % by mole, and the content of described structural unit A can be 2.5-20 % by mole, and the viscosity-average molecular weight of described acrylamide copolymer can be 3,100 ten thousand-3,500 ten thousand.
According to the present invention, in the preferred case, described acrylamide copolymer also contains formula (II) and/or the structural unit B shown in formula (III),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3can be identical or not identical, can be the alkyl of C1-C4 separately; M
2and M
3can be identical or not identical, can be sodium or potassium separately.
According to the present invention, preferably, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of described acrylamide structural unit can be 1-98 % by mole, the content of described structural unit A can be 1-98 % by mole, and the content of described structural unit B can be 0.1-40 % by mole; Preferably, the content of described acrylamide structural unit can be 60-87.5 % by mole, and the content of described structural unit A can be 10-30 % by mole, and the content of described structural unit B can be 12.5-40 % by mole.
According to the present invention, additionally provide a kind of preparation method of acrylamide copolymer, under this preparation method is included in solution polymerization condition, under initiator exists, makes monomer mixture carry out polyreaction, obtain acrylamide copolymer; Wherein, described monomer mixture contains acrylamide and monomer C, and described monomer C is for having the monomer of structure shown in formula (IV), M
1can be sodium or potassium;
After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of gained acrylamide copolymer can be more than 3,000 ten thousand.
According to the present invention, the consumption of the present invention to acrylamide and monomer C does not have particular requirement, preferably, with the total mole number of monomer in described monomer mixture for benchmark, the consumption of described acrylamide can be 1-99 % by mole, the consumption of described monomer C can be 1-99 % by mole, and after the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of gained acrylamide copolymer can be 3,100 ten thousand-3,500 ten thousand.
According to the present invention, can also contain monomer D in described monomer mixture, described monomer D can for having the monomer of structure shown in formula V,
Wherein, R
1it can be the alkylidene group of C1-C4; R
2and R
3can be identical or not identical, can be the alkyl of C1-C4 separately; M
2can be sodium or potassium.
According to the present invention, with the total mole number of monomer in described monomer mixture for benchmark, the consumption of described acrylamide can be 1-98 % by mole, and the consumption of described monomer C can be 60-87.5 % by mole, and the consumption of described monomer D can be 0.1-40 % by mole; Preferably, the consumption of described acrylamide is 60-80 % by mole, and the consumption of described monomer C can be 2.5-20 % by mole, and the consumption of described monomer D can be 10-30 % by mole.
According to certain invention, in the preferred case, the method is also included in after monomer mixture carries out polyreaction, under hydrolysising condition, contact being polymerized the acrylamide copolymer obtained with inorganic alkaline compound, hydrolysising condition makes the acrylamide structural unit partial hydrolysis in multipolymer become to have the unit of structure shown in formula (III)
Wherein, M
3can be sodium or potassium.
According to the present invention, it can thus be appreciated that, acrylamide copolymer of the present invention had both comprised the polymkeric substance that acrylamide and structure monomer copolymer are as shown in the formula (I) formed, also comprise the polymkeric substance that acrylamide, structure monomer as shown in the formula (I) and other temperature resistant antisalt monomers (such as 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid salt) are obtained by reacting under condition of copolymer, also comprise the hydrolysate that aforementioned copolymer is formed by hydrolysis reaction.Those skilled in the art can know, and by hydrolysis, some acrylamide structural unit is transformed into acrylate structural unit.
According to the present invention, because the acrylamide structural unit partial hydrolysis be used in the acrylamide copolymer making polymerization obtain by described inorganic alkaline compound compound provided by the invention becomes sodium acrylate structural unit, the various inorganic alkaline compound compounds that can realize above-mentioned purpose that described inorganic alkaline compound compound can be commonly used for this area, can be selected from sodium hydroxide, potassium hydroxide and sodium carbonate one or more.The consumption of described inorganic alkaline compound can carry out appropriate selection according to the hydrolysis degree of acrylamide copolymer, meets service requirements be as the criterion to make the hydrolysis degree of acrylamide copolymer.
According to method of the present invention, the present invention does not have particular requirement to the condition that acrylamide polymer is hydrolyzed, as long as make the acrylamide structural unit partial hydrolysis in acrylamide copolymer become acrylate structural unit, preferably, described hydrolysising condition comprises: hydrolysis temperature can be 50-110 DEG C, and hydrolysis time can be 0.5-6h; Further, hydrolysis temperature can be preferably 55-105 DEG C, and hydrolysis time can be 1-5.5h; Further, hydrolysis temperature can be preferably 70-90 DEG C; Hydrolysis time can be 1-4 hour.
According to method of the present invention, preferably, inorganic alkaline compound consumption makes acrylamide copolymer degree of hydrolysis can be 10-30%.
According to the present invention, the condition of described polyreaction can be the condition of this area routine, and such as described solution polymerization carries out in the presence of an inert gas, and described solution polymerization condition comprises: temperature can be-10 DEG C to 20 DEG C, time can be 1-20 hour, and pH value can be 4-12; Preferably, temperature can be-7 DEG C to 15 DEG C, and the time can be 3-8 hour, and pH value can be 5-10.
According to the present invention, described initiator can be the various radical initiator in this area, preferably, described initiator comprises water-soluble azo series initiators, amine reduction auxiliary agent, sulfite reducing agent and oxygenant, and with 100 weight parts monomers mixtures for benchmark, the consumption of water-soluble azo series initiators can be 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of amine reduction auxiliary agent can be 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of sulfite reducing agent can be 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of oxygenant can be 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part.
According to the present invention, preferably, described water-soluble azo series initiators can be 2,2 '-azo (2-amidine propane) dihydrochloride, 2,2 '-azo (2-tetrahydroglyoxaline propane) dihydrochloride and 4, one or more in 4 '-azo two (4-cyanopentanoic acid), are preferably 2,2 '-azo (2-amidine propane) dihydrochloride; Described sulfite reducing agent can be water-soluble sulfite, be preferably in ammonium sulphite, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite and sodium bisulfite one or more, be more preferably in ammonium sulphite, potassium sulfite and sodium bisulfite one or more; Described oxygenant can be one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, is preferably ammonium persulphate and/or Potassium Persulphate; Described amine reduction auxiliary agent can be N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, N, N '-dimethyl piperazine, tetramethyl-urea element, N, N-dimethyl urea element, N, N, N ', N '-Tetramethyl Ethylene Diamine, one or more in N, N-dimethyl-ethylenediamine, are preferably N, N, N ', N '-Tetramethyl Ethylene Diamine.
According to the present invention, when described polyreaction starts, described polyreaction is carried out in water, and the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture can be 0.15-0.4:1, most preferably is 0.2-0.3:1.
According to the present invention, the present invention also can comprise the acrylamide based copolymer prepared is carried out granulation, drying, crushes and screens and pack.Described granulation, drying, pulverizing, screening and packaging are the ordinary skill in the art.
According to the present invention, the present invention is to the method for drying and condition without particular requirement, and under preferable case, can adopt hot air seasoning, described warm air drying temperature is 40-110 DEG C, is preferably 70-90 DEG C; The time of warm air drying is 0.2-4 hour, is preferably 0.5-2 hour.
Present invention also offers the acrylamide copolymer obtained according to aforesaid method.
Present invention also offers the application of aforesaid propylene amide copolymer in oil-displacing agent.
In following examples, the performance test of product adopts following methods to carry out:
1, solid content is measured according to the method specified in GB12005.2-89;
2, dissolution time is measured according to the method specified in GB12005.8-89;
3, intrinsic viscosity is measured according to the method specified in GB12005.1-89;
4, formula M=([η]/K) is adopted according to the method specified in GB12005.10-92
1/ αcalculate the viscosity-average molecular weight of polymkeric substance, wherein, K=4.75 × 10
-3, α=0.80, [η] is intrinsic viscosity;
5, the apparent viscosity of aqueous solutions of polymers is at the temperature of 95 DEG C, use Brookfield viscometer determining;
6, the filtration ratio of the aqueous solution of polymkeric substance, insolubles content and AM residual monomer content is measured according to Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard Q/SH1020 1572-2006;
7, aged viscosity retention rate: the solution with the salt solution of salinity 32000mg/L, polymkeric substance being made into 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 aged viscosity retention rate:
Aged 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, 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., and 2,2 '-azo (2-amidine propane) dihydrochloride business available from Aldrich Co.
Embodiment 1
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof
927.09 kilograms of acrylamides (AM) and 948.84 kilograms of acrylamide monomers C(are added wherein, M in batching kettle
1for sodium), 7503.72 kilograms of deionized waters, 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 water-soluble azo initiator 2,2 '-azo (2-amidine propane) dihydrochloride 18.76 grams and reduction auxiliary agent N, N, N ', N '-Tetramethyl Ethylene Diamine 18.76 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 18.76 grams and ammonium persulphate 18.76 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 130.43 kilogram sodium hydroxide grain alkali and contacts, at temperature 90 DEG C, be hydrolyzed 4h, after secondary granulation, by crushing and screening and be packaged to be 20-80 object product.The viscosity-average molecular weight of this acrylamide copolymer is 3,520 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Embodiment 2
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof.
1108.85 kilograms of AM and 116.4 kilogram acrylamide monomers C(is added wherein, M in batching kettle
1for sodium), 2858.92 kilograms of deionized waters, 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 water-soluble azo initiator 2,2 '-azo (2-amidine propane) dihydrochloride 612.63 grams and reduction auxiliary agent N, N, N ', N '-Tetramethyl Ethylene Diamine 612.63 grams, logical high pure nitrogen deoxygenation 0.5h, add sodium bisulfite 612.63 grams and ammonium persulphate 612.63 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.Mediated with 64 kilogram sodium hydroxide grain alkali by the little micelle obtained and contact, under temperature 70 C, be hydrolyzed 1h, 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 product.The viscosity-average molecular weight of this acrylamide copolymer is 3,380 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Embodiment 3
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof.
1080.4 kilograms of AM and 245.6 kilograms of temperature resistant antisalt monomer C(are added wherein, M in batching kettle
1for potassium), 3978 kilograms of deionized waters, under whipped state, control solution temperature 0 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is pumped in polymeric kettle, add water-soluble azo initiator 2,2 '-azo (2-amidine propane) dihydrochloride 200 grams and reduction auxiliary agent 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.Mediated with 192 kilogram sodium hydroxide grain alkali by the little micelle obtained and contact, at temperature 85 DEG C, be hydrolyzed 1.5h, 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 product.The viscosity-average molecular weight of this acrylamide copolymer is 3,450 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Embodiment 4
The present embodiment is for illustration of acrylamide copolymer provided by the invention and preparation method thereof.
Same process condition is adopted with embodiment 1, except adding AM and acrylamide monomers C in monomer mixture, also add 2-acrylamide-2-methylpro panesulfonic acid (AMPS), with the total mole number of monomer in monomer mixture for benchmark, the consumption of acrylamide is 80 % by mole, acrylamide monomers C consumption is 10 % by mole, and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) consumption is 10 % by mole.The viscosity-average molecular weight of this acrylamide copolymer is 3,100 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Embodiment 5
Same process condition is adopted 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 and contact, at temperature 90 DEG C, be hydrolyzed the step of 4h.The viscosity-average molecular weight of this acrylamide copolymer is 3,200 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Comparative example 1
Same process condition is adopted with embodiment 1,2-acrylamide-2-methylpro panesulfonic acid (AMPS) is changed into unlike by acrylamide monomers C, the acrylamide copolymer viscosity-average molecular weight obtained is 2,900 ten thousand, and the basic physical and chemical index of this acrylamide copolymer is as shown in table 1.
Table 1
The acrylamide copolymer that table 2 is prepared for embodiment 1-5 and comparative example 1-2 is 1500mg/L in concentration, and salinity is under 30000mg/L, the temperature variant relation of solution apparent viscosity.
Table 2
| Temperature | 25℃ | 45℃ | 60℃ | 80℃ | 95℃ |
| Embodiment 1 | 46.3 | 40.5 | 34.0 | 27.3 | 25.5 |
| Comparative example 1 | 32.8 | 28.1 | 24.1 | 18.4 | 16.9 |
| Embodiment 2 | 38.5 | 34.1 | 29.6 | 24.0 | 22.0 |
| Embodiment 3 | 40.8 | 36.2 | 31.3 | 26.8 | 23.5 |
| Embodiment 4 | 35.7 | 32.0 | 27.2 | 21.3 | 18.5 |
| Embodiment 5 | 37.4 | 33.3 | 28.0 | 22.1 | 20.0 |
The data of associative list 1 and table 2 are known, the acrylamide copolymer molecular weight product that embodiment 1 obtains can reach 3,520 ten thousand, and comparative example 1 obtains acrylamide copolymer molecular weight product and is only 2,900 ten thousand, the molecular weight of copolymer that embodiment 1 obtains compared with comparative example 1 improves nearly 6,200,000; At 95 DEG C, the apparent viscosity of the acrylamide copolymer product that embodiment 1 obtains is 25.5mPas, and the apparent viscosity that comparative example 1 obtains acrylamide copolymer product is 16.9mPas, embodiment 1 improves 8.6mPas compared with the apparent viscosity of the multipolymer that comparative example 1 obtains.Illustrate that acrylamide monomers provided by the invention is more conducive to improving the apparent viscosity under the molecular weight of multipolymer and hot conditions than 2-acrylamide-2-methylpro panesulfonic acid.
By embodiment 1 compared with embodiment 4, except AM and acrylamide monomers C in embodiment 4, also add 2-acrylamide-2-methylpro panesulfonic acid (AMPS).The molecular weight obtaining acrylamide copolymer product is 3,100 ten thousand, and corresponding 95 DEG C of corresponding meter observing viscosities are 18.5mPas, lower than the index result of embodiment 1.
By embodiment 1 compared with embodiment 5, the molecular weight obtaining acrylamide copolymer product in embodiment 5 is 3,150 ten thousand, and 95 DEG C of corresponding meter observing viscosities improve 20.0mPas, lower than the index result of embodiment 1.Apparent viscosity under suitably introducing sodium acrylate structural unit has the molecular weight and hot conditions being more conducive to improving multipolymer is described in copolymer structure.
In addition, analyze acrylamide copolymer of the present invention at concentration 1500mg/L, salinity is 30000mg/L, temperature is respectively 25 DEG C, 45 DEG C, 60 DEG C, 80 DEG C, the apparent viscosity under 95 DEG C of conditions, the temperature resistant antisalt performance of known acrylamide copolymer provided by the invention is good.
Claims (15)
1. an acrylamide copolymer, is characterized in that, this acrylamide copolymer contains the structural unit A shown in acrylamide structural unit and formula (I), and the viscosity-average molecular weight of described acrylamide copolymer is more than 3,000 ten thousand,
Wherein, M
1for sodium or potassium.
2. acrylamide copolymer according to claim 1, wherein, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of described acrylamide structural unit is 1-99 % by mole, the content of described structural unit A is 1-99 % by mole, and the viscosity-average molecular weight of described acrylamide copolymer is 3,000 ten thousand-3,550 ten thousand; Preferably, the content of described acrylamide structural unit is 80-97.5 % by mole, and the content of described structural unit A is 2.5-20 % by mole, and the viscosity-average molecular weight of described acrylamide copolymer is 3,100 ten thousand-3,500 ten thousand.
3. acrylamide copolymer according to claim 1, wherein, described acrylamide copolymer also contains formula (II) and/or the structural unit B shown in formula (III),
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3identical or different, be the alkyl of C1-C4 separately; M
2and M
3identical or different, be sodium or potassium separately.
4. the acrylamide copolymer according to claim 1 or 3, wherein, with the total mole number of structural unit in described acrylamide copolymer for benchmark, the content of described acrylamide structural unit is 1-98 % by mole, the content of described structural unit A is 1-98 % by mole, and the content of described structural unit B is 0.1-40 % by mole; Preferably, the content of described acrylamide structural unit is 60-87.5 % by mole, and the content of described structural unit A is 10-30 % by mole, and the content of described structural unit B is 12.5-40 % by mole.
5. a preparation method for acrylamide copolymer, under this preparation method is included in solution polymerization condition, under initiator exists, makes monomer mixture carry out polyreaction, obtains acrylamide copolymer; Wherein, described monomer mixture contains acrylamide and monomer C, and described monomer C is the monomer of structure shown in formula (IV), M
1for sodium or potassium;
After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of gained acrylamide copolymer is more than 3,000 ten thousand.
6. method according to claim 5, wherein, with the total mole number of monomer in described monomer mixture for benchmark, the consumption of described acrylamide is 1-99 % by mole, the consumption of described monomer C is 1-99 % by mole, and after the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of gained acrylamide copolymer is 3,100 ten thousand-3,500 ten thousand.
7. method according to claim 5, wherein, also contains monomer D, described monomer D for having the monomer of structure shown in formula (V) in described monomer mixture,
Wherein, R
1for the alkylidene group of C1-C4; R
2and R
3identical or different, be the alkyl of C1-C4 separately; M
2for sodium or potassium.
8. method according to claim 7, wherein, with the total mole number of monomer in described monomer mixture for benchmark, the consumption of described acrylamide is 1-98 % by mole, the consumption of described monomer C is 60-87.5 % by mole, and the consumption of described monomer D is 0.1-40 % by mole; The consumption of preferred described acrylamide is 60-80 % by mole, and the consumption of described monomer C is 2.5-20 % by mole, and the consumption of described monomer D is 10-30 % by mole.
9. according to the method in claim 5-8 described in any one, wherein, the method is also included in after monomer mixture carries out polyreaction, under hydrolysising condition, contact being polymerized the acrylamide copolymer obtained with inorganic alkaline compound, hydrolysising condition makes the acrylamide structural unit partial hydrolysis in multipolymer become to have the unit of structure shown in formula (III)
Wherein, M
3for sodium or potassium.
10. method according to claim 9, wherein, described hydrolysising condition comprises: hydrolysis temperature is 50-110 DEG C, and hydrolysis time is 0.5-6h.
11. methods according to claim 5, 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, and the time is 1-20 hour, and pH value is 4-12.
12. methods according to claim 5, wherein, described initiator comprises water-soluble azo series initiators, amine reduction auxiliary agent, sulfite reducing agent and oxygenant, and with 100 weight parts monomers mixtures for benchmark, the consumption of water-soluble azo series initiators is 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of amine reduction auxiliary agent is 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of sulfite reducing agent is 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; The consumption of oxygenant is 0.0001-0.1 weight part, is preferably 0.001-0.05 weight part; Described water-soluble azo series initiators is 2,2 '-azo (2-amidine propane) dihydrochloride, 2,2 '-azo (2-tetrahydroglyoxaline propane) dihydrochloride and 4, one or more in 4 '-azo two (4-cyanopentanoic acid), be preferably 2,2 '-azo (2-amidine propane) dihydrochloride; Described amine reduction auxiliary agent is N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, N, N '-dimethyl piperazine, tetramethyl-urea element, N, N-dimethyl urea element, N, N, N ', N '-Tetramethyl Ethylene Diamine, one or more in N, N-dimethyl-ethylenediamine, are preferably N, N, N ', N '-Tetramethyl Ethylene Diamine; Described sulfite reducing agent is water-soluble sulfite, is preferably one or more in ammonium sulphite, potassium sulfite and sodium bisulfite; Described oxygenant is one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, is preferably ammonium persulphate and/or Potassium Persulphate.
13. methods according to claim 5, wherein, described polyreaction is carried 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.
The acrylamide copolymer that method in 14. claim 5-13 described in any one is obtained.
Acrylamide based copolymer in 15. claim 1-4 and 14 described in any one is as the application of oil-displacing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310421080.3A CN104448120A (en) | 2013-09-16 | 2013-09-16 | Acrylamide copolymer and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106543351A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
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| EP0112921A1 (en) * | 1982-06-24 | 1984-07-11 | MITSUI TOATSU CHEMICALS, Inc. | Process for preparing amidoalkanesulfonic acid derivatives |
| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| CN102746441A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Acrylamide terpolymer and polymer and preparation method and application thereof |
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| EP0112921A1 (en) * | 1982-06-24 | 1984-07-11 | MITSUI TOATSU CHEMICALS, Inc. | Process for preparing amidoalkanesulfonic acid derivatives |
| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106543351A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
| CN106543351B (en) * | 2015-09-21 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
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