CN104628610A - Acrylamide monomer, as well as preparation method and application thereof - Google Patents
Acrylamide monomer, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an acrylamide monomer, as well as a preparation method and an application thereof. The monomer has a structure as shown in a formula (1), wherein R1 is alkyl of C1-C8, R2 is hydrogen or alkyl of C1-C4, and M1 and M2 are respectively at least one of hydrogen, potassium and sodium independently. Experiments indicate that an acrylamide copolymer prepared by polymerizing the monomer has relatively high molecular weight and excellent temperature-resistance, salt-resistance and shearing resistance, and can be used as an oil-displacing agent for tertiary recovery of a high temperature and high salinity reservoir.
Description
Technical field
The present invention relates to a kind of acrylamide monomers and its preparation method and application.
Background technology
Polymer flooding mainly by injecting the polymers soln of certain scale, increases displacing fluid viscosity, reduces oil-reservoir water phase permeability and reduces mobility ratio, adjustment intake profile, to reach the object improving sweeping phase volume, and then improve recovery ratio.As main polymer oil-displacing agent, water-soluble portion hydro-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, be mainly reflected in exploitation high temperature and high salt oil deposit time high temperature, high salt, shearing and obtain solution time dissolved oxygen compound action HPAM soltion viscosity is significantly reduced, cause oil displacement efficiency not remarkable.
For above-mentioned performance shortcomings, researchist has carried out a large amount of study on the modification to HPAM.Wherein, by acrylamide and temperature resistant antisalt monomer copolymerization, introducing temperature resistant antisalt group in HPAM multipolymer, is an important channel of enhancing product performance.The temperature resistant antisalt monomer developed comprises sulfonic acid type monomer, hydrophobic association monomer and zwitterionic monomer etc.Such as be entitled as " the low temperature synthesis of AMPS/AM multipolymer and performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) use properties that can significantly improve HPAM with 2-acrylamide-2-methylpro panesulfonic acid (AMPS) sulfonic acid type monomer and acrylamide copolymerization is reported in article.But correlative study " pyrohydrolysis of water-soluble AM/AA/AMPS multipolymer " (Zhu Linyong, applied chemistry, 2000,17,2) also find simultaneously, under the hot conditions of 90 DEG C, by the Molecular modelling effect closing on vinylformic acid (AA) unit, also there is hydrolysis reaction in AMPS unit, and in multipolymer, acrylic acid structure unit ratio increases, improve its Thermo-sensitive and salt sensitivity energy, because which limit the application under the high temperature and high salt condition of this kind of polymkeric substance more than hydrolysis temperature.Hydrophobic associated polymer utilizes molecular structure to make its viscosity really have obvious thickening effectiveness at normal temperatures, but its extemporaneous preparation requirement fresh water or heating dissolution, make troubles to construction, in addition this base polymer also exists and easily blocks stratum, shortcoming (Wang Zhonghua, meticulous and specialty chemicals, 2006 of tolerance difference under high temperature and high salt condition, 14,24).Amphoteric ion copolymer has the salt consistence energy of polyamphoteric electrolyte uniqueness, but because there is positive charge in its structure, there is adsorption, add loss with surface of stratum negative charge.
Therefore from molecular designing angle, exploitation temperature resistant antisalt performance is good, and the temperature resistant antisalt monomer being easy to generate high molecular weight product will be the long-standing issues that HPAM enters study on the modification.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of acrylamide monomers and preparation method thereof is provided.
The invention provides a kind of acrylamide monomers, wherein, this monomer has the structure shown in formula (1):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
Present invention also offers a kind of preparation method of acrylamide monomers, wherein, the method comprises: be under the condition of-5 DEG C to 30 DEG C in temperature, and the monomer of structure shown in the monomer of structure formula (2) Suo Shi, formula (3) and sulphonating agent are reacted 2-16 hour,
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1for at least one in hydrogen, potassium and sodium.
Present invention also offers a kind of acrylamide polymer, this acrylamide polymer contains the structural unit shown in formula (4):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
Present invention also offers the application of aforesaid propylene amide polymer in polymer oil-displacing agent.
Experiment shows that acrylamide monomers of the present invention carries out being polymerized the acrylamide copolymer obtained and still have higher apparent viscosity under high temperature, high ore deposit degree and high shear rate, thus has excellent temperature resistant antisalt and anti-shear performance.This may be due to amide group in acrylamide monomers of the present invention around the hydrophobic interaction of alkyl and space steric effect greatly improve the anti-hydrolytic performance of monomer self under hot conditions.In addition, the disulfonic acid base in this monomer is insensitive to divalent salts ion, thus further increases the anti-salt property of the acrylamido copolymer solution of synthesis.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide monomers, wherein, this monomer has the structure shown in formula (1):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
In the present invention, the alkyl of described C1-C4 can be straight chain, also can be side chain.The example of the alkyl of described C1-C4 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.
In the present invention, the alkyl of described C1-C8 can be straight chain, also can be side chain.The example of the alkyl of described C1-C8 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-thmethylpropyl, 1, 2, 2-thmethylpropyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-Ethyl-2-Methyl propyl group, n-heptyl and n-octyl.
In the present invention, in order to when preparing acrylamide copolymer, obtain the product of high conversion further, under preferable case, in the acrylamide monomers shown in formula (1), described R
1for the alkyl of C1-C4, R
2for hydrogen or methyl, M
1for hydrogen or sodium.
Present invention also offers a kind of preparation method of acrylamide monomers, wherein, the method comprises: be under the condition of-5 DEG C to 30 DEG C in temperature, and the monomer of structure shown in the monomer of structure formula (2) Suo Shi, formula (3) and sulphonating agent are reacted 2-16 hour,
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1for at least one in hydrogen, potassium and sodium.
The alkyl of described C1-C4 is all identical with foregoing description with the alkyl of C1-C8.
In the present invention, in order to the acrylamide monomers of the shown structure of the formula (1) obtaining high yield, under preferable case, R in the monomer of structure shown in formula (2)
1for the alkyl of C1-C4, M
1for hydrogen or sodium; R in the monomer of structure shown in formula (3)
2for hydrogen or methyl; Further preferably, shown in formula (2), the monomer of structure is single sulfonation iso-butylene, and shown in formula (3), the monomer of structure is vinyl cyanide.
In the present invention, the structure of described single sulfonation iso-butylene is as the formula (5):
According to the present invention, the present invention is to the not special requirement of the kind of sulphonating agent, in prior art, various sulphonating agent all can realize object of the present invention, consider that the sulphonating agent with strongly-acid and strong oxidizing property can improve the productive rate of reaction, preferably, described sulphonating agent is sulfuric acid or the oleum of concentration 95-150 % by weight.
According to the present invention, in order to obtain the acrylamide monomers of high yield, under preferable case, described reaction comprises two stages of carrying out successively: the first stage is under temperature is the condition of-5 DEG C to 10 DEG C, the monomer of the monomer of structure formula (2) Suo Shi with structure formula (3) Suo Shi is contacted, obtains the first solution; And lower than under the condition of 10 DEG C, in the first obtained solution, add sulphonating agent, make the first solution and sulphonating agent react 1-8 hour, obtain the second solution; Subordinate phase, for adding water in the second obtained solution, is under the condition of 10-30 DEG C in temperature, continues reaction 1-8 hour.
In the present invention, after formula (2) Suo Shi, the monomer of structure, the monomer of formula (3) depicted structure and sulphonating agent react, in the acrylamide monomers of structure shown in the formula (1) obtained, M
2for hydrogen, those skilled in the art can know, and works as M
2during for hydrogen, the acidity of described acrylamide monomer is comparatively strong, easily in the course of the polymerization process causes corrosion to polymeric kettle, needs to neutralize product.
Therefore, under preferable case, described method is also included in after the monomer of structure, the monomer of formula (3) depicted structure and sulphonating agent shown in formula (2) react, and the reaction product obtained and inorganic alkaline compound is reacted, generates corresponding an alkali metal salt.
In the present invention, described inorganic alkaline compound be preferably in sodium hydroxide, potassium hydroxide and sodium carbonate one or more, more preferably sodium hydroxide.
Under normal circumstances, the inorganic alkaline compound used makes the monomer of structure shown in formula (1) at M
2during for hydrogen, the pH value of the solution be mixed with is 4-12, is preferably 6-9.
According to the present invention, the mol ratio of the present invention to the monomer of structure shown in the monomer of structure formula (2) Suo Shi, sulphonating agent and formula (3) is not particularly limited, as long as the acrylamide monomers of structure shown in the formula that obtains (1) can be realized, under preferable case, the mol ratio of the monomer of the monomer of structure shown in formula (2), sulphonating agent and formula (3) depicted structure is 1:0.8-1.2:5-25, more preferably 1:1-1.2:10-20.
In the present invention, be easy to make acrylamide monomers of the present invention store, under preferable case, described method comprises further is undertaken filtering, wash and drying by above-mentioned reaction products therefrom.
Described filtration, washing and oven dry are the method for ability routine, do not repeat them here.
According to the preferred embodiment of the present invention, the preparation method of acrylamide monomers of the present invention can comprise the following steps:
(1) under whipped state, joined by the monomer of structure formula (2) Suo Shi in the monomer of structure shown in excessive formula (3), obtain the first solution, the temperature controlling the first solution is-5 DEG C to 10 DEG C.In the first solution, slowly add sulphonating agent, control reacting liquid temperature and be no more than 10 DEG C in adition process, reaction 1-8 hour, obtains the second solution.
(2) in the second solution, add suitable quantity of water, under normal temperature condition, continue reaction 1-8 hour, static, there is crystal to separate out.
(3) shown in the formula (3) that elimination is excessive, the monomer of structure, obtains thick product, and is washed 2-3 time by thick product with the monomer of structure formula (3) Suo Shi, and vacuum-drying obtains target product.
According to the present invention, inventive point of the present invention is mainly to provide above-mentioned acrylamide monomers, and the method for synthesizing described acrylamide monomers can be the method for this area routine, the structure example of the acrylamide monomers synthesized by method of the present invention is as passed through Infrared Characterization, in infrared spectrum, 1185cm
-1near be the charateristic avsorption band of sulfonic acid group, 1650cm
-1near be the absorption peak of alkene, 1740cm
-1near be the charateristic avsorption band of ester group, 3340cm
-1near be the charateristic avsorption band of amide group, and at 2250cm
-1near do not occur which illustrating the charateristic avsorption band of itrile group method of the present invention and synthesized target product.Therefore, in the examples below, no longer further described acrylamide monomers is characterized.
Present invention also offers a kind of acrylamide polymer, this acrylamide polymer contains the structural unit shown in formula (4):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
According to the present invention, the preparation method of described acrylamide polymer can be the method for this area routine, such as, the monomer of structure shown in acrylamide monomer, formula (1) can be carried out polyreaction under solution polymerization condition, under initiator exists.
In order to increase the temperature resistant antisalt performance of acrylamide polymer further, under preferable case, described preparation method also comprises: under hydrolysising condition, is contacted by the acrylamide polymer of polyreaction gained with inorganic alkaline compound, makes the degree of hydrolysis of polymkeric substance reach 10-30%.
Well known to a person skilled in the art and be, by hydrolysis, the acrylamide structural unit in described acrylamide polymer is partially converted into acrylate structural unit.In the present invention, described degree of hydrolysis refers to that the mole number of acrylate structural unit accounts for the per-cent of the total mole number of the structural unit of acrylamide polymer of the present invention.According to the present invention, described degree of hydrolysis is determined by the consumption of inorganic alkaline compound.
Those skilled in the art can know, and by regulating the consumption of inorganic alkaline compound, can obtain the acrylamide polymer of different degree of hydrolysis.
In the present invention, the mole number of described inorganic alkaline compound equals the mole number of acrylate structural unit.
Present invention also offers the application of aforesaid propylene amide polymer in polymer oil-displacing agent.
Below, by following examples, the present invention will be described in more detail.
In the examples below, single sulfonation iso-butylene available from Aldrich Co, acrylamide is purchased from Bao Mo biochemical industry limited-liability company, 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., 2,2 '-azo diisobutyl amidine dihydrochloride business available from Aldrich Co.
Embodiment 1
The present embodiment is for illustration of acrylamide monomers provided by the invention and preparation method thereof
Under whipped state, in temperature-controlled glass reactor, add 530 grams of vinyl cyanide, 136 grams of single sulfonation iso-butylenes, in whipping process, the temperature of system is controlled at-5 DEG C, after stirring, drip the vitriol oil 100 grams that concentration is 98%, maintain temperature of reaction system below 10 DEG C.React after 1 hour, add suitable quantity of water, under normal temperature condition, continue reaction 1 hour.After filtration, washing, dry obtain pure monomer, product yield is 95.5%.
Embodiment 2
The present embodiment is for illustration of acrylamide monomers provided by the invention and preparation method thereof.
Under whipped state, in temperature-controlled glass reactor, add 1060 grams of vinyl cyanide, 136 grams of single sulfonation iso-butylenes, in whipping process, the temperature of system is controlled at 5 DEG C, after stirring, drip the vitriol oil 117.6 grams that concentration is 98%, maintain temperature of reaction system below 10 DEG C.React after 1 hour, add suitable quantity of water, under normal temperature condition, continue reaction 8 hours.After filtration, washing, dry obtain pure monomer, product yield is 96%.
Embodiment 3
The present embodiment is for illustration of acrylamide monomers provided by the invention and preparation method thereof.
Under whipped state, in temperature-controlled glass reactor, add 636 grams of vinyl cyanide, 136 grams of single sulfonation iso-butylenes, in whipping process, the temperature of system is controlled at 5 DEG C, after stirring, drip the vitriol oil 107.8 grams that concentration is 98%, maintain temperature of reaction system below 10 DEG C.React after 1 hour, add suitable quantity of water, under normal temperature condition, continue reaction 6 hours.After filtration, washing, dry obtain pure monomer, product yield is 97%.
Embodiment 4
The present embodiment is for illustration of acrylamide monomers provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares acrylamide monomers, difference is, the oleum with 120% replaces concentration to be the vitriol oil of 98%, and the consumption of oleum is 96 grams, after filtration, washing, dry obtain pure monomer, the yield of product is 95.7%.
Embodiment 5
The present embodiment is for illustration of acrylamide monomers provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares acrylamide monomers, and difference is, reacts after 6 hours under normal temperature condition, is after 7 further by the pH value of sodium hydroxide regulation system, and after filtration, washing, oven dry obtain pure monomer, and the yield of product is 94%.
Experimental example
Add 1000 grams of acrylamides, the acrylamide monomers 10 grams of embodiment 1 gained and 3030 grams of water in the reactor, under whipped state, control solution temperature 15 DEG C, add sodium hydroxide solution and regulate pH to 9.Add 1010 milligram 2,2 '-azo diisobutyl amidine dihydrochloride and 1010 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 1010 milligrams of sodium bisulfites and 1010 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in reactor, in 2 hours reaction times, obtain acrylamide copolymer.The acrylamide copolymer obtained is taken out, is become the little micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 90 DEG C, be hydrolyzed 1 hour, after secondary granulation, under 70 DEG C of hot blast conditions, drying 2 hours, obtains 20-80 object acrylamide copolymer by crushing and screening.Calculate according to charging capacity and determine, in acrylamide copolymer, shown in acrylamide structural unit, acrylate structural unit and formula (4), the mass ratio of structural unit is 799:265:10.The viscosity-average molecular weight of resulting polymers is 2,600 ten thousand, and the apparent viscosity of polymers soln is 16.5mPa.s.
Comparative example
Method experimentally described in example prepares acrylamide copolymer, difference is, the acrylamide monomers obtained by embodiment 1 is replaced with the 2-acrylamide-2-methylpro panesulfonic acid of equal mass, the viscosity-average molecular weight of resulting polymers is 2,200 ten thousand, and the apparent viscosity of polymers soln is 11.5mPa.s.
In above experimental example and comparative example: the intrinsic viscosity of polymkeric substance measures according to the method specified in People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008; Polymkeric substance viscosity-average molecular weight, according to the method specified in SY/T5862-2008, adopts formula M=([η]/0.000373)
1.515calculate, wherein, M is viscosity-average molecular weight, and [η] is intrinsic viscosity; The apparent viscosity of polymers soln is after polymkeric substance being made into the solution of 1500mg/L with the salt solution of salinity 32000mg/L, with Brookfield viscometer at 95 DEG C, and 7.34s
-1measure under condition.
As can be seen from above experimental example and comparative example, acrylamide polymer synthesized by acrylamide monomers of the present invention has the high feature of molecular weight, the acrylamide copolymer obtained still has higher apparent viscosity under high temperature, high ore deposit degree and high shear rate, illustrate that acrylamide polymer of the present invention has excellent temperature resistant antisalt performance and resistant to shearing performance, can as high temperature and high salt oil deposit Flooding Agent for EOR.
Claims (11)
1. an acrylamide monomers, wherein, this monomer has the structure shown in formula (1):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
2. acrylamide monomers according to claim 1, wherein, described R
1for the alkyl of C1-C4, R
2for hydrogen or methyl, M
1for hydrogen or sodium.
3. a preparation method for acrylamide monomers, is characterized in that, the method comprises: be under the condition of-5 DEG C to 30 DEG C in temperature, and the monomer of structure formula (2) Suo Shi, the monomer of formula (3) depicted structure and sulphonating agent are reacted 2-16 hour,
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1for at least one in hydrogen, potassium and sodium.
4. method according to claim 3, wherein, described R
1for the alkyl of C1-C4, R
2for hydrogen or methyl, M
1for hydrogen or sodium.
5. method according to claim 3, wherein, sulfuric acid or the oleum of described sulphonating agent to be concentration be 95-150 % by weight.
6. method according to claim 3, wherein, described reaction comprises two stages of carrying out successively: the first stage is under temperature is the condition of-5 DEG C to 10 DEG C, is contacted by the monomer of the monomer of structure formula (2) Suo Shi with structure formula (3) Suo Shi, obtains the first solution; And lower than under the condition of 10 DEG C, in the first obtained solution, add sulphonating agent, make the first solution and sulphonating agent react 1-8 hour, obtain the second solution; Subordinate phase, for adding water in the second obtained solution, is under the condition of 10-30 DEG C in temperature, continues reaction 1-8 hour.
7. method according to claim 3, wherein, described method is included in after the monomer of structure, the monomer of formula (3) depicted structure and sulphonating agent shown in formula (2) react further, the reaction product obtained and inorganic alkaline compound is reacted.
8. method according to claim 7, wherein, described inorganic alkaline compound is at least one in sodium hydroxide, potassium hydroxide and sodium carbonate.
9. according to the method in claim 3-8 described in any one, wherein, monomer, the sulphonating agent of structure shown in formula (2) are 1:0.8-1.2:5-25 with the mol ratio of the monomer of formula (3) depicted structure, preferably 1:1-1.2:10-20.
10. an acrylamide polymer, wherein, this acrylamide polymer contains the structural unit shown in formula (4):
Wherein, R
1for the alkyl of C1-C8, R
2for the alkyl of hydrogen or C1-C4, M
1and M
2be at least one in hydrogen, potassium and sodium independently of one another.
11. application of acrylamide polymer according to claim 10 in polymer oil-displacing agent.
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Citations (4)
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|---|---|---|---|---|
| JPH01134449A (en) * | 1987-11-20 | 1989-05-26 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, its production method, and its use |
| JP2008210541A (en) * | 2007-02-23 | 2008-09-11 | Hitachi Maxell Ltd | Battery separator, and nonaqueous electrolyte battery |
| CN104448122A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
-
2013
- 2013-11-15 CN CN201310573774.9A patent/CN104628610B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01134449A (en) * | 1987-11-20 | 1989-05-26 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, its production method, and its use |
| JP2008210541A (en) * | 2007-02-23 | 2008-09-11 | Hitachi Maxell Ltd | Battery separator, and nonaqueous electrolyte battery |
| CN104448122A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
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| Title |
|---|
| DRAGAN, STELA ET AL: "Polyelectrolyte complexes. II. Specific aspects of the formation of polycation/dye/polyanion complexes", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》, vol. 37, no. 4, 31 December 1999 (1999-12-31) * |
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