US20190359753A1 - Sulfonate lycine type hydrophobic associated polymer and preparation method thereof - Google Patents
Sulfonate lycine type hydrophobic associated polymer and preparation method thereof Download PDFInfo
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- US20190359753A1 US20190359753A1 US16/068,898 US201716068898A US2019359753A1 US 20190359753 A1 US20190359753 A1 US 20190359753A1 US 201716068898 A US201716068898 A US 201716068898A US 2019359753 A1 US2019359753 A1 US 2019359753A1
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 55
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 19
- 150000003839 salts Chemical class 0.000 abstract description 13
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- -1 quaternary ammonium cations Chemical class 0.000 description 3
- 0 [1*]C(C)(CC(C)(CCC(CC(C)C(N)=O)C(=O)O[Na])C(=O)NCCC[N+](C)(C)CCCS(=O)(=O)[O-])C(=O)N(CC)CC1=CC=CC=C1 Chemical compound [1*]C(C)(CC(C)(CCC(CC(C)C(N)=O)C(=O)O[Na])C(=O)NCCC[N+](C)(C)CCCS(=O)(=O)[O-])C(=O)N(CC)CC1=CC=CC=C1 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C09K8/84—Compositions based on water or polar solvents
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Definitions
- the present invention relates to a sulfonate lycine type hydrophobic associated polymer for an oilfield to increase a recovery rate and perform acid fracturing, and a preparation method thereof.
- hydrophobic associated polymer For a hydrophobic associated polymer, a small amount of hydrophobic groups are introduced to copolymer molecular chains, such that the solution of the hydrophobic associated polymer has efficient viscosifying property, excellent salt resistance, and better temperature resistance and shear resistance, and is widely applied to increase a recovery rate and perform acid fracturing for an oilfield.
- the temperature resistance and salt resistance of the hydrophobic associated polymer still need to be improved.
- Sulfonate betaine monomer is a kind of polymerizable functional monomer which contains equal number of quaternary ammonium cations and sulfonate anions and is not easily affected by pH and inorganic electrolytes.
- the molecules of the sulfonate betaine monomer are electrically neutral and have good chemical thermal stability and strong hydration capabilities, and copolymers of the sulfonate betaine monomer exhibit an obvious anti-polyelectrolyte behavior.
- polybetaine had short-range attraction and remote repulsion, and the apparent viscosity of an aqueous solution of the polybetaine increased with the increase of the concentration of external electrolyte (such as NaCl), showing an obvious anti-polyelectrolyte behavior, such that the polymer has better salt resistance.
- external electrolyte such as NaCl
- acrylamide as a main monomer
- allyl long-chain alkyl quaternary ammonium salt as a hydrophobic monomer
- sulfonate betaine as a functional monomer to perform terpolymerization to produce the sulfonate betaine type hydrophobic associated polymer which has temperature resistance and salt resistance properties and still has higher viscosity at 85° C.
- An objective of the present invention is to provide a sulfonate lycine type hydrophobic associated polymer which integrates the advantages of a two-tailed hydrophobic associated polymer and the advantages of a lycine type polymer, such that the properties of the polymer, such as temperature resistance, salt resistance and hydrolysis resistance are improved.
- the sulfonate lycine type hydrophobic associated polymer can be used as an oil-displacing agent or an acid fracturing thickener for increasing a crude oil recovery rate in oilfield development and overcome the defects and deficiencies of the prior art.
- Another objective of the present invention is to provide a preparation method of the sulfonate lycine type hydrophobic associated polymer.
- a sulfonate betaine monomer into polymer molecular chains, the properties of the hydrophobic associated polymers, such as viscosifying property, temperature resistance, salt resistance, and hydrolysis resistance, can be significantly improved.
- the method is reliable in principle and simple in operation and has a broad market prospect.
- the present invention provides the following technical solution.
- a sulfonate lycine type hydrophobic associated polymer has the following structural formula:
- x, y, m, and n are percentages of structural units, where x is 75 to 85%, m is 0.01 to 1.0%, n is 0.01 to 0.5%, and y is 1-x-m-n; a, b are numbers of structural units, where a is 11, 13 or 15, and b is 1 or 2; R 1 is CH 3 or H.
- the polymer has a viscosity average molecular weight of 100 to 10,000,000.
- a preparation process of the sulfonate lycine type hydrophobic associated polymer comprises the following steps: firstly, mixing acrylamide and acrylic acid in an aqueous solution; adjusting pH of the system to be around 6 to 8; adding 3-(dimethyl amino propyl methacrylamide) propanesulfonate, N-aryl-N-alkyl (methyl) acrylamide and lauryl sodium sulfate and stirring till the solution is clear; and after nitrogen is introduced for deoxidization, adding a photoinitiator azobis (isobutylamidine hydrochloride) (v5) for performing polymerization under photoinitiation conditions to prepare the sulfonate lycine type hydrophobic associated polymer.
- a photoinitiator azobis isobutylamidine hydrochloride
- the preparation method of the sulfonate lycine type hydrophobic associated polymer sequentially comprises the following steps:
- the photoinitiator is azobis (isobutylamidine hydrochloride) (v50).
- the present invention has the following beneficial effects: the two-tailed hydrophobic monomer with an acrylamide structure is similar to the acrylamide structure and easily copolymerized with main monomer acrylamide; by the introduction of a benzene ring, the hydrolysis of amide groups can be effectively inhibited, and meanwhile the rigidity of molecular chains can be increased and the temperature resistance of the polymer can be improved; by the introduction of a long-chain alkyl group, the favorable hydrophobic association effect of the polymer is achieved; the two-tailed structure of the hydrophobic monomer effectively inhibits of the hydrolysis of amide groups and improve the hydrophobic association effect.
- the properties of the hydrophobic associated polymer such as viscosifying property, temperature resistance, salt resistance, and hydrolysis resistance, can be significantly improved.
- the sulfonate lycine type hydrophobic associated polymer of the present invention can be used as an oil-displacing agent or an acid fracturing thickener for increasing a crude oil recovery rate in oilfield development, and has a broad market prospect.
- FIG. 1 is an infrared spectrum of a sulfonate lycine type hydrophobic associated polymer.
- FIG. 2 is a viscosity-concentration relationship curve of the sulfonate lycine type hydrophobic associated polymer.
- FIG. 3 is a viscosity-salinity relationship curve of the sulfonate lycine type hydrophobic associated polymer.
- FIG. 4 is a viscosity-aging days relationship curve of the sulfonate lycine type hydrophobic associated polymer.
- FIG. 1 is an infrared spectrum of the polymer synthesized in the example 1.
- a characteristic absorption peak of stretching vibration of N—H of primary amide appears at 3408 cm ⁇ 1 ; characteristic absorption peaks of antisymmetric stretching vibration and symmetrical stretching vibration of methylene appear at 2981 cm ⁇ 1 and 2897 cm ⁇ 1 ; a characteristic absorption peak of carbonyl appears at 1640 cm ⁇ 1 ; a stretching vibration peak of a benzene ring skeleton appears at 1531 cm ⁇ 1 ; an in-plane bending vibration absorption peak of methylene appears at 1398 cm ⁇ 1 ; a stretching vibration absorption peak of C—N in quaternary ammonium salt appears at 1320 cm ⁇ 1 ; symmetrical and asymmetric vibration absorption peaks of —SO3 ⁇ appear at 1088 cm ⁇ 1 and 1049 cm ⁇ 1 ; an out-of-plane rocking characteristic peak of primary amide-NH 2 appears at 615 cm ⁇ 1 .
- the polymer synthesized in the example 1 is prepared into polymer solutions of different concentrations.
- a viscosity-concentration relationship curve of the polymer is measured at room temperature and at a shear rate of 7.34 s ⁇ 1 (as shown in FIG. 2 ).
- the sulfonate lycine type hydrophobic associated polymer has lower critical association concentration and a good viscosifying effect which reaches 743.7 mPa ⁇ s at 2000 mg/L.
- the prepared hydrophobic associated polymer is prepared into a 2000 mg/L polymer solution at different salinities.
- a change relationship of the apparent viscosity of the polymer solution along with the salinity is measured at room temperature and at a shear rate of 7.34 s ⁇ 1 (as shown in FIG. 3 ).
- the apparent viscosity of the polymer presents a trend of decrease-increase-decrease, and the viscosity of the polymer solution can still be maintained at 50% or more under high salinity 120,000 of NaCl, showing a favorable salt resistance effect.
- the anti-aging property of the polymer synthesized in the example 1 is evaluated.
- the prepared hydrophobic associated polymer is prepared into a 2000 mg/L polymer solution, deoxidant is added to the solution and then the mixture is placed in a vial, and sealed.
- the mixture is aged in a 90° C. oven, and the viscosity of the polymer solution is measured at regular time.
- the viscosity is stable after the polymer solution is aged for about 30 d.
- the viscosity of the polymer solution can still be maintained at 60 mPa ⁇ s or more, showing good resistance to temperature, salt and aging.
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Abstract
Description
- This application is the national phase entry of International Application No. PCT/CN2017/085328, filed on May 22, 2017, which is based upon and claims priority to Chinese Patent Application No. 201710342023.4, filed on May 16, 2017, the entire contents of which are incorporated herein by reference.
- The present invention relates to a sulfonate lycine type hydrophobic associated polymer for an oilfield to increase a recovery rate and perform acid fracturing, and a preparation method thereof.
- For a hydrophobic associated polymer, a small amount of hydrophobic groups are introduced to copolymer molecular chains, such that the solution of the hydrophobic associated polymer has efficient viscosifying property, excellent salt resistance, and better temperature resistance and shear resistance, and is widely applied to increase a recovery rate and perform acid fracturing for an oilfield. However, for a high temperature and high salinity reservoir, the temperature resistance and salt resistance of the hydrophobic associated polymer still need to be improved.
- For a two-tailed hydrophobic monomer containing a long-chain alkyl group and a benzene ring (Wu Xiaoyan et al. A Surface-active Two-tailed Hydrophobic Associated Acrylamide Copolymer. Guangdong Chemical Industry, 2014, 41(22): 42-44; Pu Wanfen et al. Synthesis and Property Evaluation of Two-tailed Acrylamide Type Hydrophobic Associated Polymer. Modern Chemicals, 2016(4):117-120), by the introduction of the benzene ring, the temperature resistance and hydrolysis resistance of the polymer are effectively improved; by the introduction of the long-chain alkyl group, the hydrophobic association effect of the polymer is improved favorably; a main structure of acrylamides is adopted to make the hydrophobic monomer easy to polymerize with main monomer acrylamide; the two-tailed structure effectively improves the hydrolysis resistance and hydrophobic association effect of the hydrophobic monomer. Therefore, the synthesized hydrophobic associated polymer achieves the purposes of resistance to heat, salt and hydrolysis.
- Sulfonate betaine monomer is a kind of polymerizable functional monomer which contains equal number of quaternary ammonium cations and sulfonate anions and is not easily affected by pH and inorganic electrolytes. The molecules of the sulfonate betaine monomer are electrically neutral and have good chemical thermal stability and strong hydration capabilities, and copolymers of the sulfonate betaine monomer exhibit an obvious anti-polyelectrolyte behavior. In 2002, LOWE A B et al. found that polybetaine had short-range attraction and remote repulsion, and the apparent viscosity of an aqueous solution of the polybetaine increased with the increase of the concentration of external electrolyte (such as NaCl), showing an obvious anti-polyelectrolyte behavior, such that the polymer has better salt resistance. In 2012, Ding Wei, et al. used 3-(dimethylamino propyl acrylamide) propanesulfonate to copolymerize with acrylamide to obtain a copolymer P(AM-DMAPAAS) whose viscosity in saline water is higher than that in distilled water and whose viscosity in a salt solution containing divalent ions (Mg2+ or Ca2+) is larger than that in a monovalent ion salt solution (Na+ or K+) and increases with the increase of the salinity of the solution. In 2015, Chen Hong, et al. used acrylamide as a main monomer, allyl long-chain alkyl quaternary ammonium salt as a hydrophobic monomer, and sulfonate betaine as a functional monomer to perform terpolymerization to produce the sulfonate betaine type hydrophobic associated polymer which has temperature resistance and salt resistance properties and still has higher viscosity at 85° C.
- An objective of the present invention is to provide a sulfonate lycine type hydrophobic associated polymer which integrates the advantages of a two-tailed hydrophobic associated polymer and the advantages of a lycine type polymer, such that the properties of the polymer, such as temperature resistance, salt resistance and hydrolysis resistance are improved. The sulfonate lycine type hydrophobic associated polymer can be used as an oil-displacing agent or an acid fracturing thickener for increasing a crude oil recovery rate in oilfield development and overcome the defects and deficiencies of the prior art.
- Another objective of the present invention is to provide a preparation method of the sulfonate lycine type hydrophobic associated polymer. By the introduction of a sulfonate betaine monomer into polymer molecular chains, the properties of the hydrophobic associated polymers, such as viscosifying property, temperature resistance, salt resistance, and hydrolysis resistance, can be significantly improved. The method is reliable in principle and simple in operation and has a broad market prospect.
- To fulfill said technical objectives, the present invention provides the following technical solution.
- A sulfonate lycine type hydrophobic associated polymer has the following structural formula:
- in the formula, x, y, m, and n are percentages of structural units, where x is 75 to 85%, m is 0.01 to 1.0%, n is 0.01 to 0.5%, and y is 1-x-m-n; a, b are numbers of structural units, where a is 11, 13 or 15, and b is 1 or 2; R1 is CH3 or H.
- The polymer has a viscosity average molecular weight of 100 to 10,000,000.
- A preparation process of the sulfonate lycine type hydrophobic associated polymer comprises the following steps: firstly, mixing acrylamide and acrylic acid in an aqueous solution; adjusting pH of the system to be around 6 to 8; adding 3-(dimethyl amino propyl methacrylamide) propanesulfonate, N-aryl-N-alkyl (methyl) acrylamide and lauryl sodium sulfate and stirring till the solution is clear; and after nitrogen is introduced for deoxidization, adding a photoinitiator azobis (isobutylamidine hydrochloride) (v5) for performing polymerization under photoinitiation conditions to prepare the sulfonate lycine type hydrophobic associated polymer.
- The preparation method of the sulfonate lycine type hydrophobic associated polymer sequentially comprises the following steps:
- (1) adding acrylamide and acrylic acid to distilled water and stirring uniformly, adjusting pH to 6 to 8 with sodium hydroxide, adding 3-(dimethylamino propyl methacrylamide) propanesulfonate, hydrophobic monomer N-aryl-N-alkyl (methyl) acrylamide and a surfactant lauryl sodium sulfate and stirring till the solution is clear, wherein the total mass percentage of reaction monomers is 25 to 28.5 wt %, in which acrylamide accounts for 20-21.5 wt %, acrylic acid accounts for 3.5-5 wt %, 3-(dimethylamino propyl methacrylamide) propanesulfonate accounts for 0.2-1.0 wt %, N-aryl-N-alkyl (methyl) acrylamide accounts for 0.2-0.6 wt % and lauryl sodium sulfate accounts for 0.4-0.8 wt %;
- (2) introducing nitrogen for 15 min to remove dissolved oxygen in water;
- (3) adding a photoinitiator and reacting for 3 to 5 h at 10 to 30° C. under a photoinitiation device to obtain viscous white colloid, i.e., the sulfonate lycine type hydrophobic associated polymer.
- The photoinitiator is azobis (isobutylamidine hydrochloride) (v50).
- Compared with the prior art, the present invention has the following beneficial effects: the two-tailed hydrophobic monomer with an acrylamide structure is similar to the acrylamide structure and easily copolymerized with main monomer acrylamide; by the introduction of a benzene ring, the hydrolysis of amide groups can be effectively inhibited, and meanwhile the rigidity of molecular chains can be increased and the temperature resistance of the polymer can be improved; by the introduction of a long-chain alkyl group, the favorable hydrophobic association effect of the polymer is achieved; the two-tailed structure of the hydrophobic monomer effectively inhibits of the hydrolysis of amide groups and improve the hydrophobic association effect.
- By the introduction of a sulfonate betaine monomer into polymer molecular chains, the properties of the hydrophobic associated polymer, such as viscosifying property, temperature resistance, salt resistance, and hydrolysis resistance, can be significantly improved.
- The sulfonate lycine type hydrophobic associated polymer of the present invention can be used as an oil-displacing agent or an acid fracturing thickener for increasing a crude oil recovery rate in oilfield development, and has a broad market prospect.
-
FIG. 1 is an infrared spectrum of a sulfonate lycine type hydrophobic associated polymer. -
FIG. 2 is a viscosity-concentration relationship curve of the sulfonate lycine type hydrophobic associated polymer. -
FIG. 3 is a viscosity-salinity relationship curve of the sulfonate lycine type hydrophobic associated polymer. -
FIG. 4 is a viscosity-aging days relationship curve of the sulfonate lycine type hydrophobic associated polymer. - The present invention is described below in detail according to the drawings and the examples.
- weighing acrylamide (10 g), acrylic acid (2.5 g), adding distilled water and stirring uniformly, and adjusting pH to 7; then, adding 3-(dimethylamino propyl methacrylamide) propanesulfonate (0.1 g), N-aryl-N-lauryl methacrylamide and lauryl sodium sulfate (0.3 g), then adding a certain amount of distilled water such that the total mass of the solution reaches 50 g, and stirring till the solution is clear; introducing nitrogen for 15 min to remove dissolved oxygen in water; and adding an initiator v50 (0.1-0.2 wt % of total monomer mass), placing under a photoinitiation device, and reacting for 3 h.
- weighing acrylamide (10 g), acrylic acid (2.5 g), adding distilled water and stirring uniformly, and adjusting pH to 7; then, adding 3-(dimethylamino propyl methacrylamide) propanesulfonate (0.1 g), N-aryl-N-lauryl methacrylamide (0.1 g) and lauryl sodium sulfate (0.3 g), then adding a certain amount of distilled water such that the total mass of the solution reaches 50 g, and stirring till the solution is clear; introducing nitrogen for 15 min to remove dissolved oxygen in water; and adding an initiator v50 (0.1-0.2 wt % of total monomer mass), placing under a photoinitiation device, and reacting for 3 h.
-
FIG. 1 is an infrared spectrum of the polymer synthesized in the example 1. - As can be seen from
FIG. 1 , a characteristic absorption peak of stretching vibration of N—H of primary amide appears at 3408 cm−1; characteristic absorption peaks of antisymmetric stretching vibration and symmetrical stretching vibration of methylene appear at 2981 cm−1 and 2897 cm−1; a characteristic absorption peak of carbonyl appears at 1640 cm−1; a stretching vibration peak of a benzene ring skeleton appears at 1531 cm−1; an in-plane bending vibration absorption peak of methylene appears at 1398 cm−1; a stretching vibration absorption peak of C—N in quaternary ammonium salt appears at 1320 cm−1; symmetrical and asymmetric vibration absorption peaks of —SO3− appear at 1088 cm−1 and 1049 cm−1; an out-of-plane rocking characteristic peak of primary amide-NH2 appears at 615 cm−1. - The polymer synthesized in the example 1 is prepared into polymer solutions of different concentrations. A viscosity-concentration relationship curve of the polymer is measured at room temperature and at a shear rate of 7.34 s−1 (as shown in
FIG. 2 ). As can be seen fromFIG. 2 , the sulfonate lycine type hydrophobic associated polymer has lower critical association concentration and a good viscosifying effect which reaches 743.7 mPa·s at 2000 mg/L. - A study is made for the sensitivity to salt of the polymer synthesized in the example 1. The prepared hydrophobic associated polymer is prepared into a 2000 mg/L polymer solution at different salinities. A change relationship of the apparent viscosity of the polymer solution along with the salinity is measured at room temperature and at a shear rate of 7.34 s−1 (as shown in
FIG. 3 ). As can be seen fromFIG. 3 , with the increase of NaCl concentration, the apparent viscosity of the polymer presents a trend of decrease-increase-decrease, and the viscosity of the polymer solution can still be maintained at 50% or more under high salinity 120,000 of NaCl, showing a favorable salt resistance effect. - The anti-aging property of the polymer synthesized in the example 1 is evaluated. The prepared hydrophobic associated polymer is prepared into a 2000 mg/L polymer solution, deoxidant is added to the solution and then the mixture is placed in a vial, and sealed. The mixture is aged in a 90° C. oven, and the viscosity of the polymer solution is measured at regular time.
- As can be seen from
FIG. 4 , the viscosity is stable after the polymer solution is aged for about 30 d. At a temperature of 90° C. and a salinity (NaCl) of 10×104 mg/L, the viscosity of the polymer solution can still be maintained at 60 mPa·s or more, showing good resistance to temperature, salt and aging.
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CN113563863A (en) * | 2021-09-02 | 2021-10-29 | 成都理工大学 | Gas-solid-liquid three-phase fracturing fluid system and using method thereof |
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CN105439909B (en) * | 2015-11-19 | 2017-05-10 | 中国石油天然气股份有限公司 | Glycine betaine sulfonate and glycine betaine sulfonate type hydrophobic polymer as well as production method and application thereof |
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CN113563863A (en) * | 2021-09-02 | 2021-10-29 | 成都理工大学 | Gas-solid-liquid three-phase fracturing fluid system and using method thereof |
CN117143283A (en) * | 2023-10-26 | 2023-12-01 | 东营市百扬石油科技有限责任公司 | Salt-resistant fracturing fluid thickening agent and preparation method thereof |
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