CN102633938A - AM/BAMACB[7]/AMPS-Na copolymer and preparation method - Google Patents
AM/BAMACB[7]/AMPS-Na copolymer and preparation method Download PDFInfo
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- CN102633938A CN102633938A CN2012101309386A CN201210130938A CN102633938A CN 102633938 A CN102633938 A CN 102633938A CN 2012101309386 A CN2012101309386 A CN 2012101309386A CN 201210130938 A CN201210130938 A CN 201210130938A CN 102633938 A CN102633938 A CN 102633938A
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Abstract
The invention relates to an AM/BAMACB[7]/AMPS-Na copolymer as an oil-displacing agent in oil exploitation and a preparation method, which can satisfy the requirement for increasing injection liquid viscosity under the conditions of high temperature and high salt. The technical proposal provided by the invention is as follows: the copolymer is obtained by polymerizing three monomers, namely acrylamide AM, a complex BAMACB[7] of N-butyl amine methyl acrylate and seven-membered melon link, and 2-acrylamide-2-sodium methylacrylsulfonate AMPS-Na; and the AM/BAMACB[7]/AMPS-Na copolymer comprises the following components according to molar percentage: 80-85% of AM, 8-11% of BAMACB[7] and 4-8% of AMPS-Na. A preparation method comprises the following steps of: adding the monomers into a three-neck flask; preparing the monomers into 15% of solution by adding water; adding ammonium persulfate and sodium hydrogensulfite; under the protection of nitrogen, reacting at 80 DEG C for 4-5 h to obtain a colloid product; and washing, precipitating and drying by using absolute ethyl alcohol to obtain the AM/BAMACB[7]/AMPS-Na copolymer. The copolymer disclosed by the invention has the advantages of being simple and convenient in preparation method, moderate in reaction condition, good in thermal stability property and strong in salt tolerance and is used for oil field oil-displacing agents.
Description
Technical field
The present invention relates to a kind of AM/BAMACB [7]/AMPS-Na multipolymer and preparation method who is used for the petroleum recovering industry as oil-displacing agent.
Technical background
Fail the irreducible oil and the surplus oil of extraction to secondary oil recovery, carrying out TOR is the important method that improves RF, and wherein polymer flooding is the technology of extremely important and extensive enforcement in China's TOR.The partially hydrolyzed polyacrylamide of high molecular weight is widely used as the polymer flooding in the TOR, can improve the viscosity of injecting liquid in the oil field, adjust water-oil mobility ratio, improve oil reservoir nonuniformity, improve the sweep efficiency that injects liquid.But also there are some problems in partially hydrolyzed polyacrylamide in practical application, like temperature resistant antisalt poor performance etc.Along with the rising of reservoir temperature, WS increases, and the viscosity of polyacrylamide solution declines to a great extent, and can not satisfy increases the requirement of injecting fluid viscosity under high temperature, high salt condition.Therefore, exploitation temperature resistant antisalt polymkeric substance becomes the emphasis problem of domestic and international water-soluble polymers research and development.The present invention introduces seven yuan of melon rings of novel salt-resistant and writes a Chinese character in simplified form (CB [7]) and n-Butyl Amine 99 methacrylate (BAMA) complex compound monomer; 2-acrylamido-2-methyl propane sulfonic acid sodium writes a Chinese character in simplified form (AMPS-Na) and acrylic amide (AM) monomer is a raw material; Carry out copolymerization; Prepare AM/BAMACB [7]/AMPS-Na multipolymer, this multipolymer has temperature resistance and saline-alkaline tolerance preferably as the oil field oil-displacing agent.
Summary of the invention
The objective of the invention is: constantly raise in order to overcome reservoir temperature; The stratum salinity constantly increases; Existing polymer flooding can not well satisfy increases the requirement of injecting fluid viscosity under high temperature, the high salt condition, the spy provides a kind of AM/BAMACB [7]/AMPS-Na multipolymer and preparation method.
For achieving the above object; The present invention adopts following technical scheme: a kind of AM/BAMACB [7]/AMPS-Na multipolymer; It is characterized in that: this multipolymer is to write a Chinese character in simplified form AM by acrylic amide; The complex compound of n-Butyl Amine 99 methacrylate BAMA and seven yuan of melon ring CB [7] is write a Chinese character in simplified form BAMACB [7], and 2-acrylamido-2-methyl propane sulfonic acid sodium is write a Chinese character in simplified form three kinds of monomer polymerizations of AMPS-Na and got; The molar percentage of raw materials used component and partial properties are: the AM monomer is 80-85%; BAMACB [7] monomer is 8-11%; The 0.86g methylacrylic acid is dissolved in the 20ml deionized water; And add 0.73g butylamine solution slowly, and treat that butylamine adds restir half a hour fully, add seven yuan of melon rings of 9.96g and stirred at normal temperatures 24 hours; Filtration obtains clear filtrate and extracts with acetone and obtain white precipitate, refilters and obtains BAMACB [7] with a large amount of washing with acetones, oven dry; The AMPS-Na monomer is 4-8%, uses concentration to be 7-8 as NaOH solution titration 2-acrylamido-2-methyl propane sulfonic acid AMPS solution system of 4.0g/L to pH, promptly gets AMPS-Na solution; In the copolymer, oxygenant is used ammonium persulphate, and consumption is the 0.3-0.5% of monomer total mass, and reductive agent is used sodium sulfite anhy 96, and consumption is the 0.35-0.45% of monomer total mass.The structural formula of this multipolymer is:
Wherein the molar percentage of X is that the molar percentage of 80-85%, Y is 8-11%,
seven yuan of melon ring structures of symbolic representation unit.
The preparation method of a kind of AM/BAMACB [7]/AMPS-Na multipolymer: earlier in there-necked flask; Add 7.1g acrylic amide AM successively, the complex compound BAMACB [7] of 13.1g n-Butyl Amine 99 methacrylate and seven yuan of melon rings and 0.698g 2-acrylamido-2-methyl propane sulfonic acid sodium AMPS-Na; Add the 140mL deionized water then; Be made into monomer total mass percentage concentration and be 15% solution; After stirring treats that each monomer dissolves fully; Adding concentration is that ammonium persulphate 0.11mL and the concentration of 0.8g/mL is 0.7g/mL sodium sulfite anhy 96 0.11mL, and above-mentioned monomer consumption AM:BAMACB [7]: AMPS-Na three's mol ratio is 85:14.5:0.5; After mixing above-mentioned solution evenly at last; Inflated with nitrogen 20min removes oxygen, is 80 ℃ of reaction 4-5h down in temperature, gets the colloidal product; With absolute ethanol washing 3-5 time; Until white precipitate occurring, will be deposited in the baking oven 50 ℃ of bakings of constant temperature 24h after, make AM/BAMACB [7]/AMPS-Na multipolymer.
Compared with prior art, the present invention has following beneficial effect: the preparation method of ⑴ AM/BAMACB [7]/AMPS-Na multipolymer is simple and feasible, and reaction conditions is gentle; ⑵ make out in the laboratory novel anti salt group melon ring by oneself, not only strengthens the hydrophobic association effect of multipolymer, the port of melon ring by carbonyl institute around; Carbonyl can form the positively charged ion binding site; And thereby the hydrogen bond action through dipolar interaction and carbonyl comes positively charged ions such as calcium ion, mg ion in the bonding stratum to keep the viscosity of polymkeric substance in salts solution, and as additive for drilling fluid, thermal stability is good; The temperature resistance ability is strong, through still embodying good heat and salinity tolerance ability behind 220 ℃ of high temperature ageings.
Description of drawings
Fig. 1 is the IR Characterization figure of this copolymer A M/BAMACB [7]/AMPS-Na, and what X-coordinate was represented is wavelength, and what ordinate zou was represented is transmitance.
Fig. 2 is the influence graph of a relation of temperature to this polymers soln AV, and what X-coordinate was represented is temperature, the viscosity that ordinate zou is represented.
Fig. 3 is the influence graph of a relation of different concns salts solution to this polymers soln AV, and what X-coordinate was represented is salt solubility, and what ordinate zou was represented is viscosity.
Embodiment
Through embodiment the present invention is further specified below.
Embodiment 1The preparation method of AM/BAMACB [7]/AMPS-Na multipolymer
In the 250mL there-necked flask; Add 7.1g acrylic amide AM successively; 13.1g the complex compound BAMACB [7] of n-Butyl Amine 99 methacrylate and seven yuan of melon rings and 0.698g 2-acrylamido-2-methyl propane sulfonic acid sodium AMPS-Na; Add the 140mL deionized water then, be made into the monomer total mass concentration and be 15% solution, stir treat that monomer dissolves fully after; Adding concentration is that ammonium persulphate 0.11mL and the concentration of 0.8g/mL is 0.7g/mL sodium sulfite anhy 96 0.11mL, and AM:BAMACB [7]: AMPS-Na three's mol ratio is 85:14.5:0.5; After mixing above-mentioned solution evenly at last, inflated with nitrogen 20min removes oxygen, reacts 5h down at 80 ℃; The colloidal product, with absolute ethanol washing 4 times, until white precipitate occurring; After will being deposited in 50 ℃ of baking ovens baking 24h, make AM/BAMACB [7]/AMPS-Na multipolymer.
Press the intrinsic viscosity of the said standard test AM/BAMACB of GB12005.1-89 [7]/AMPS-Na multipolymer; According to the molecular weight of GB/T12005.10-92 standard test multipolymer, the molecular-weight average that records AM/BAMACB [7]/AMPS-Na multipolymer is M=8.67 * 10 again
5
Embodiment 2The IR Characterization of AM/BAMACB [7]/AMPS-Na multipolymer
This research adopts infrared spectroscopy that the various functional groups in AM/BAMACB [7]/AMPS-Na polymkeric substance have been carried out initial analysis.With the sample preparation of KBr compressing tablet, product is done IR spectroscopy with the Paragon100 type IR that PE company produces.
Main absorption peak as shown in Figure 1 is following: 3232cm
-1Be-CONH
2The stretching vibration peak of N-H key in (carboxamido-group), 1665cm
-1Be-CONH
2The stretching vibration peak of middle C=O key, 1130cm
-1And 1082cm
-1Be the sulfonic group vibration peak, 2 938cm
-1Long-chain methylene radical (CH has appearred in the place
2) charateristic avsorption band.3024 cm
-1With 2979 cm
-1Be the charateristic avsorption band of the methylene radical of melon ring, slightly move with respect to the absorption peak of pure melon ring.And 980 cm
-1With 938 cm
-1With 836 cm
-1It is the skeletal vibration absorption peak of melon ring.Thereby prove the structure that contains acrylic amide (AM) and 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and BAMACB [7] in this compound.
Embodiment 3The temperature tolerance effect of AM/BAMACB [7]/AMPS-Na multipolymer
In order to estimate the temperature resistant capability of AM/BAMACB [7]/AMPS-Na multipolymer, having done following experiment proves.With the acrylamide polymer of the product A M/BAMACB that obtains [7]/AMPS-Na multipolymer and purchase, be made into the salts solution that concentration is 2000mg/L respectively, detailed process is following: at first use the NaCl solution of deionized water compound concentration as 3000mg/L; Salts solution with preparation is made into the aqueous copolymers solution of 2000mg/L with the above-mentioned product A M/BAMACB that makes [7]/AMPS-Na again, the acrylamide polymer of buying also is made into the solution of 2000mg/L; At last will above two kinds of solution being made into, under differing temps, measure the changing conditions of solution AV, as shown in Figure 2, prove that AM/BAMACB [7]/AMPS-Na multipolymer that this invention makes than general acrylamide polymer, has temperature tolerance preferably.
Embodiment 4The salt resistance effect of AM/BAMACB [7]/AMPS-Na multipolymer
In order to estimate the saline-alkaline tolerance of AM/BAMACB [7]/AMPS-Na multipolymer, having done following experiment proves.Acrylamide polymer with the product A M/BAMACB that obtains [7]/AMPS-Na multipolymer and purchase; Be made into the salts solution that concentration is 2000mg/L respectively; Detailed process is following: with deionized water NaCl being configured to the salt brine solution of a series of concentration, respectively the acrylamide copolymer of AM/BAMACB [7]/AMPS-Na multipolymer and purchase being made into the copolymer solution that concentration is 2000mg/L with the salts solution of different concns, is under 25 ℃ the condition in temperature; Measure the AV changing conditions of the two; As shown in Figure 3, prove that AM/BAMACB [7]/AMPS-Na multipolymer that this invention makes than general acrylamide polymer, has salt resistance preferably.
Claims (2)
1. an AM/BAMACB [7]/AMPS-Na multipolymer; It is characterized in that: this multipolymer is to write a Chinese character in simplified form AM by acrylic amide, and the complex compound of n-Butyl Amine 99 methacrylate BAMA and seven yuan of melon ring CB [7] is write a Chinese character in simplified form BAMACB [7] and 2-acrylamido-2-methyl propane sulfonic acid sodium and write a Chinese character in simplified form three kinds of monomer polymerizations of AMPS-Na and get; The molar percentage and the partial properties of the raw materials used component of this polymkeric substance are: the AM monomer is 80-85%; BAMACB [7] monomer is 8-11%; The 0.86g methylacrylic acid is dissolved in the 20ml deionized water; And add 0.73g butylamine solution slowly, and treat that butylamine adds restir half a hour fully, add seven yuan of melon rings of 9.96g and stirred at normal temperatures 24 hours; Filtration obtains clear filtrate and extracts with acetone and obtain white precipitate, refilters and obtains BAMACB [7] with a large amount of washing with acetones, oven dry; The AMPS-Na monomer is 4-8%, uses the NaOH solution titration 2-acrylamido-2-methyl propane sulfonic acid AMPS solution of concentration as 4.0g/L, to system pH be 7-8, promptly make AMPS-Na; Oxygenant is used ammonium persulphate, and consumption is the 0.3-0.5% of monomer total mass, and reductive agent is used sodium sulfite anhy 96, and consumption is the 0.35-0.45% of monomer total mass.
2. preparation method of multipolymer according to claim 1; It is characterized in that: in there-necked flask, add the complex compound BAMACB [7] and the 0.698g 2-acrylamido-2-methyl propane sulfonic acid sodium AMPS-Na of 7.1g acrylic amide AM, 13.1g n-Butyl Amine 99 methacrylate and seven yuan of melon rings successively earlier; Add the 140mL deionized water then; Be made into monomer total mass percentage concentration and be 15% solution; After stirring treats that each monomer dissolves fully; Adding concentration is that ammonium persulphate 0.11mL and the concentration of 0.8g/mL is 0.7g/mL sodium sulfite anhy 96 0.11mL, and above-mentioned monomer consumption AM:BAMACB [7]: AMPS-Na three's mol ratio is 85:14.5:0.5; After mixing above-mentioned solution evenly at last; Inflated with nitrogen 20min removes oxygen, is 80 ℃ of reaction 4-5h down in temperature, gets the colloidal product; With absolute ethanol washing 3-5 time; Until white precipitate occurring, will be deposited in the baking oven 50 ℃ of bakings of constant temperature 24h after, make AM/BAMACB [7]/AMPS-Na multipolymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804149A (en) * | 2015-04-16 | 2015-07-29 | 西南石油大学 | Preparation method of AA (acrylic acid)/AM (acrylamide)/AMPS (2-acrylamido-2-methylpropane sulfonic acid)/MAH (maleic anhydride)-beta-CD (cyclodextrin) quaternary oil displacement agent |
| CN112876619A (en) * | 2021-02-05 | 2021-06-01 | 江苏奥莱特新材料股份有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| US3806367A (en) * | 1972-06-01 | 1974-04-23 | Bitz Lab Inc | Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents |
| CN102268123A (en) * | 2011-06-10 | 2011-12-07 | 陕西国防工业职业技术学院 | Method for preparing super absorbent material for plugging during oil field drilling |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3806367A (en) * | 1972-06-01 | 1974-04-23 | Bitz Lab Inc | Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents |
| CN102268123A (en) * | 2011-06-10 | 2011-12-07 | 陕西国防工业职业技术学院 | Method for preparing super absorbent material for plugging during oil field drilling |
Non-Patent Citations (2)
| Title |
|---|
| 孙焕泉等: "NaCl存在下SDBS与超高相对分子质量AM-AA-AMPS三元共聚物的相互作用", 《石油学报（石油加工）》, vol. 27, no. 1, 28 February 2011 (2011-02-28) * |
| 杨小华等: "AMPS聚合物及钻井液体系研究与应用", 《石油与天然气化工》, vol. 30, no. 3, 30 June 2001 (2001-06-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804149A (en) * | 2015-04-16 | 2015-07-29 | 西南石油大学 | Preparation method of AA (acrylic acid)/AM (acrylamide)/AMPS (2-acrylamido-2-methylpropane sulfonic acid)/MAH (maleic anhydride)-beta-CD (cyclodextrin) quaternary oil displacement agent |
| CN112876619A (en) * | 2021-02-05 | 2021-06-01 | 江苏奥莱特新材料股份有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
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