CN117777372A - Comb-shaped betaine type amphoteric ion polymer viscosity reducing agent and preparation method thereof - Google Patents
Comb-shaped betaine type amphoteric ion polymer viscosity reducing agent and preparation method thereof Download PDFInfo
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- CN117777372A CN117777372A CN202211160762.9A CN202211160762A CN117777372A CN 117777372 A CN117777372 A CN 117777372A CN 202211160762 A CN202211160762 A CN 202211160762A CN 117777372 A CN117777372 A CN 117777372A
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 57
- 150000002500 ions Chemical class 0.000 title claims abstract description 48
- 229960003237 betaine Drugs 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims 12
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 238000005553 drilling Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- -1 vinyl tertiary amine Chemical class 0.000 claims description 32
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 229940117986 sulfobetaine Drugs 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 4
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 claims description 4
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 4
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 abstract description 18
- 150000003839 salts Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000005461 lubrication Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000015784 hyperosmotic salinity response Effects 0.000 description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 101000832669 Rattus norvegicus Probable alcohol sulfotransferase Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 125000003142 tertiary amide group Chemical group 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of oilfield chemistry in petroleum industry, and particularly relates to a comb-shaped betaine type zwitterionic polymer viscosity reducer and a preparation method thereof, wherein the preparation method comprises the following steps: the betaine type amphoteric ion monomer is adopted to replace the traditional anionic monomer and cationic monomer, so that the amphoteric ion polymer with zero net charge is obtained, and the salt resistance of the polymer can be improved; and the amphoteric ion monomer and nonionic monomer are subjected to free radical polymerization reaction to obtain a polymer with a comb-shaped structure, which has the effects of lubrication and internal friction reduction, good adsorption performance, hydrolysis resistance and thermal stability, so that the dispersion viscosity reduction capability of the viscosity reducer under the conditions of high temperature and high salt is further improved, the viscosity reducer is resistant to Wen Dayu ℃ and the salt resistance is more than 30%, the high-temperature stability of the water-based drilling fluid is improved, the fluid loss of the drilling fluid is reduced, and compared with sulfonated materials, the material cost is lower and the environment is more friendly.
Description
Technical Field
The invention belongs to the field of oilfield chemistry in petroleum industry, and particularly relates to a comb-shaped betaine type zwitterionic polymer viscosity reducer and a preparation method thereof.
Background
At present, three technical methods for solving the problem of controlling the rheological property of the high-temperature high-density water-based drilling fluid are mainly adopted. Firstly, low molecular polymer viscosity reducing agents such as XY-27, tannic acid, sulfonated tannin, synthetic linear copolymer AA/AMPS/DMDAAC and derivatives thereof are added into water-based drilling fluid, but the low molecular polymers have the problem of insufficient high temperature salt resistance (the temperature resistance is lower than 200 ℃ and the salt resistance is less than 10 percent), so that the low molecular polymer viscosity reducing agents are difficult to adapt to the drilling of high temperature deep wells and ultra-deep wells and high temperature salt paste layers. The second method is to add iron ore powder or micro-manganese and other high-density weighting materials to reduce the solid phase content of the drilling fluid, but the iron ore powder has the defects of serious abrasion to drilling tools, easy sedimentation and the like, and the micro-manganese weighting materials can better control the rheological property of the drilling fluid, but have the defects of high cost (needing import) and poor compatibility. The third method is to use organic salt for weighting and further reduce the solid phase content, such as cesium formate, but the cost is extremely high.
Aiming at the problems of corresponding defects of the three methods, the prior art also proposes to adopt a betaine type amphoteric ion compound as a drilling fluid additive to solve the problem of difficult control of the rheological property of the high-temperature high-density water-based drilling fluid, and the drilling fluid prepared by using the betaine type amphoteric ion compound has the advantages of high temperature resistance, stable rheological property and low fluid loss. For example, a zwitterionic polymer, a method for preparing the same and applications thereof are proposed in chinese patent publication No. CN114163573a, in which a nonionic monomer, a cationic monomer, an anionic monomer and a zwitterionic monomer are dispersed in deionized water to obtain a polymerized monomer of the zwitterionic polymer; and regulating the pH value to 7, and adding an initiator for treatment to obtain the amphoteric ion polymer. In the method, the double functions of adsorption and hydration of the cationic groups are utilized; and a large number of hydration groups such as amide groups and sulfonic groups can form a compact hydration layer around clay particles to prevent and delay contact between water molecules and the clay surface, so that the aim of preventing hydration expansion of the clay particles is fulfilled. The method forms a polymerThe amount of polymer used as a fluid loss agent, however, the following drawbacks remain in the process: the temperature resistance is only 180 ℃, and the ultra-high temperature (more than 200 ℃) ultra-deep well drilling requirement cannot be met; the molecular weight is large, the viscosity is increased, the method is suitable for preparing low-density water-based drilling fluid, and the high density (2.0 g/cm) cannot be met 3 Above) rheological control requirements of water-based drilling fluids; for conventional zwitterionic polymers, the net charge is not equal to 0, and there is no inverse polyelectrolyte effect.
Disclosure of Invention
Aiming at the problems, the invention provides a comb-shaped betaine type zwitterionic polymer viscosity reducer to solve the problems of insufficient temperature resistance and salt tolerance, unsatisfactory viscosity reduction dispersion and flocculation removal effects and the like of the conventional linear polymer viscosity reducer, so as to achieve the aim of effectively solving the problem of rheological regulation and control of high-temperature high-density water-based drilling fluid.
The specific technical scheme is as follows:
in one aspect, the invention provides a preparation method of a comb-shaped betaine type amphoteric ion polymer viscosity reducer, which comprises the following steps:
preparing a sulfobetaine type amphoteric ion monomer by taking a vinyl tertiary amine monomer and 1, 3-propyl sultone as raw materials;
and carrying out free radical polymerization reaction on the sulfobetaine type amphoteric ion monomer and the nonionic monomer to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent with zero net charge.
Further, the preparation of the sulfobetaine type zwitterionic monomer comprises the following steps:
mixing vinyl tertiary amine monomer, polymerization inhibitor and solvent, and stirring to obtain mixed solution;
dispersing 1, 3-propyl sultone into a solvent to form a first solution, dropwise adding the first solution into the mixed solution, and carrying out heating reaction until a white crystal product is separated out;
and washing and drying the white crystal product by using a mixed solvent in sequence to obtain the sulfobetaine type amphoteric ion monomer.
Further, the proportion of the vinyl tertiary amine monomer and the polymerization inhibitor is as follows: adding 0.20-0.22 mol of vinyl tertiary amine monomer into every 100-150 mL of solvent, wherein the mass volume ratio of the polymerization inhibitor to the solvent is 0.01-0.03%;
the mol ratio of the vinyl tertiary amine monomer to the 1, 3-propyl sultone is 1-1.1:1, a step of;
the input ratio of the 1, 3-propyl sultone to the solvent is as follows: adding 0.2mol of 1, 3-propyl sultone into each 30-40 mL of solvent;
the solvent is acetone, the mixed solvent is a mixture of acetone and diethyl ether, and the volume ratio of the acetone to the diethyl ether is 2:1.
further, the vinyl tertiary amine monomer comprises one of N- (3-dimethylaminopropyl) methacrylamide, 4-vinylpyridine or methacryloxyethyl dimethylamine;
the mass ratio of the sulfobetaine type amphoteric ion monomer to the nonionic monomer is as follows: 7-8: 9 to 10;
wherein the nonionic monomers comprise allyl polyoxyethylene ether, N-alkyl acrylamide and vinyl heterocyclic monomers.
Further, the stirring time is 10-30min;
the dripping time is 1-3 h;
the heating reaction condition is that the reaction is carried out for 20-24 hours at 50-80 ℃.
Further, the free radical polymerization reaction of the sulfobetaine type amphoteric ion monomer and the nonionic monomer comprises the following steps:
sequentially adding the sulfobetaine type amphoteric ion monomer, allyl polyoxyethylene ether, N-alkyl acrylamide and vinyl heterocyclic monomer into water to form a second solution;
and (3) uniformly stirring the second solution, heating to 70-80 ℃ under the condition of introducing nitrogen, adding an initiator and a molecular weight regulator to initiate polymerization, and reacting for 1-3 hours to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducer.
Further, the second solution comprises the following raw materials in parts by weight: 5-10 parts of sulfobetaine type amphoteric ion monomer, 0.1-1 part of allyl polyoxyethylene ether, 1-5 parts of N-alkyl acrylamide, 1-5 parts of vinyl heterocyclic monomer and 180 parts of water;
the initiator is 0.5-1 part, and the molecular weight regulator is 0.1-0.5 part.
Further, the N-alkyl acrylamide comprises one of N, N-dimethyl acrylamide or N, N-diethyl acrylamide;
the vinyl heterocyclic monomer comprises one of N-vinyl pyrrolidone or N-vinyl caprolactam.
Further, the initiator is ammonium persulfate, and the molecular weight regulator is dodecyl mercaptan.
On the other hand, the invention also provides the comb-shaped betaine type zwitterionic polymer viscosity reducing agent prepared by the preparation method, the net charge of the zwitterionic polymer viscosity reducing agent is zero, and the weight average molecular weight is lower than 20000g/Mol.
The comb-shaped betaine type zwitterionic polymer viscosity reducer can be applied to petroleum drilling.
The invention has the beneficial effects that:
the betaine type amphoteric ion monomer is adopted to replace the traditional anionic monomer and cationic monomer, so that the amphoteric ion polymer with zero net charge is obtained, and the salt resistance of the polymer can be improved; the amphoteric ion monomer and the nonionic monomer are subjected to free radical polymerization reaction, the nonionic monomer comprises allyl polyoxyethylene ether, N-alkyl acrylamide and vinyl heterocyclic monomer, wherein the allyl polyoxyethylene ether is of a long chain structure and is high in hydrophobicity, so that a product is provided with a long hydrophobic side chain and is of a comb structure, a comb-structured polymer is adsorbed on the surface of solid-phase particles, the long comb-shaped side chain stretches to a solvent to form a sufficiently thick solvation layer, the steric hindrance between the solid-phase particles is increased, solid-solid friction is converted into friction between polymer 'comb teeth', and the hydrophobicity of a tooth chain is added to play a role in lubrication and internal friction reduction; meanwhile, the N-alkyl acrylamide provides tertiary amide groups, so that the product has good adsorption performance and hydrolysis resistance; the vinyl heterocyclic monomer improves the rigidity of a polymer molecular chain, gives the product good thermal stability, and the combined action of the substances further improves the dispersion viscosity reducing capability of the viscosity reducing agent under the high-temperature and high-salt condition;
compared with the existing polymer viscosity reducer, the viscosity reducer has excellent temperature resistance and salt resistance, the temperature resistance is Wen Dayu ℃ and is more than 30%, the high-temperature stability of water-based drilling fluid can be improved, the fluid loss of the drilling fluid is reduced, and compared with sulfonated materials, the cost of the used materials is lower and the environment is more friendly.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart for preparing a comb-betaine zwitterionic polymer viscosity reducer in an embodiment of the invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a comb-shaped betaine type zwitterionic polymer viscosity reducing agent and a preparation method thereof, which are used for solving the problems of insufficient temperature resistance and salt tolerance, unsatisfactory viscosity reducing dispersion and flocculation removing effects and the like of the conventional linear polymer viscosity reducing agent.
As shown in FIG. 1, the preparation of the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent is carried out in two steps, wherein the first step of reaction is the preparation of a sulfobetaine type amphoteric ion monomer, and the second step of reaction is the free radical polymerization of one of the products of the first step of reaction serving as a monomer and a screened nonionic monomer to obtain a final target product.
The method comprises the following specific steps:
the first step of reaction: preparation of sulfobetaine type zwitterionic monomer.
Weighing polymerization inhibitor, 0.20-0.22 mol of vinyl tertiary amine monomer and 100-150 mL of solvent acetone, adding into a 250mL three-neck flask, and stirring and mixing for 10-30min to obtain mixed solution; wherein the mass volume ratio of the polymerization inhibitor to the solvent is 0.01-0.03%.
Weighing 0.2mol of 1, 3-propyl sultone, adding the 1, 3-propyl sultone into 30-40 mL of solvent acetone, transferring the solvent acetone into a constant pressure low liquid funnel, slowly dripping the solvent acetone into the mixed liquid in the previous step, and finishing the adding within 1-3 hours; reacting for 20-24 h at 50-80 ℃ until white crystal products are separated out;
repeatedly washing the precipitated white crystal product with a mixed solvent of acetone and diethyl ether, and drying in a vacuum oven to constant weight to obtain the sulfobetaine type zwitterionic monomer, wherein the volumes of the acetone and the diethyl ether are 2:1.
preferably, the vinyl tertiary amine monomer comprises one of N- (3-dimethylaminopropyl) methacrylamide, 4-vinylpyridine or methacryloxyethyl dimethylamine;
the polymerization inhibitor is preferably catechol.
And the second step of reaction: and (3) preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent.
Adding 5-10 parts of sulfobetaine type amphoteric ion monomer, 0.1-1 part of allyl polyoxyethylene ether, 1-5 parts of N-alkyl acrylamide and 1-5 parts of vinyl heterocyclic monomer into 180 parts of water in turn, stirring uniformly, introducing nitrogen to remove oxygen, heating to 70-80 ℃, adding 0.5-1 part of initiator ammonium persulfate and 0.1-0.5 part of molecular weight regulator to initiate polymerization, and reacting for 1-3 hours to obtain viscous liquid, namely the comb-type betaine type amphoteric ion low molecular weight polymer with zero net charge, namely the viscosity reducer.
The mass ratio of the sulfobetaine type amphoteric ion monomer to the nonionic monomer is as follows: 7-8: 9 to 10.
Preferably, the N-alkyl acrylamide comprises one of N, N-dimethyl acrylamide or N, N-diethyl acrylamide;
preferably, the vinyl heterocyclic monomer comprises one of N-vinyl pyrrolidone or N-vinyl caprolactam;
the molecular weight regulator is dodecyl mercaptan.
The above preparation process is described in detail with reference to specific examples.
Example 1
The first step of reaction: preparation of sulfobetaine type zwitterionic monomer.
Weighing 0.22mol of N- (3-dimethylaminopropyl) methacrylamide, 0.02% polymerization inhibitor catechol and 120mL of solvent acetone, adding into a 250mL three-neck flask, and stirring and mixing for 20min to obtain a mixed solution;
weighing 0.2mol of 1, 3-propyl sultone, adding the solution into 30mL of solvent acetone, transferring the solution into a constant pressure low liquid funnel, slowly dripping the solution into the mixed solution in the previous step, and finishing the addition within 2 hours; reacting at 60 ℃ for 21h until white crystal products are separated out;
repeatedly washing the precipitated white crystal product with a mixed solvent of acetone and diethyl ether, and drying in a vacuum oven until the weight is constant to obtain the sulfobetaine type zwitterionic monomer DMAPAS.
And the second step of reaction: and (3) preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent.
Adding 7.2 parts of DMAPAS, 0.8 part of allyl polyoxyethylene ether, 4 parts of N-alkyl acrylamide and 5 parts of N-vinyl pyrrolidone into 180 parts of water in turn, stirring uniformly, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 0.52 part of initiator persulfuric acid and 0.17 part of molecular weight regulator dodecyl mercaptan to initiate polymerization, and reacting for 2 hours to obtain the comb-shaped betaine type amphoteric polymer viscosity reducer WNTHIN-1.
Example 2
The first step of reaction: preparation of sulfobetaine type zwitterionic monomer.
Weighing 0.21mol of 4-vinylpyridine, 0.01% of polymerization inhibitor catechol and 100mL of solvent acetone, adding into a 250mL three-neck flask, and stirring and mixing for 10min to obtain a mixed solution;
weighing 0.2mol of 1, 3-propyl sultone, adding the solution into 20mL of solvent acetone, transferring the solution into a constant pressure low liquid funnel, slowly dripping the solution into the mixed solution in the previous step, and finishing the addition within 2 hours; reacting for 24 hours at 80 ℃ until white crystal products are separated out;
repeatedly washing the precipitated white crystal product with a mixed solvent of acetone and diethyl ether for 5 times, and drying in a vacuum oven to constant weight to obtain the sulfobetaine type zwitterionic monomer 4-VPPS.
And the second step of reaction: and (3) preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent.
Adding 8 parts of 4-VPPS, 1 part of allyl polyoxyethylene ether, 3 parts of N, N diethyl acrylamide and 5 parts of N-vinyl caprolactam into 180 parts of water in sequence, stirring uniformly, introducing nitrogen to remove oxygen, heating to 75 ℃, adding 0.74 part of initiator persulfuric acid and 0.35 part of molecular weight regulator dodecyl mercaptan to initiate polymerization, and reacting for 3 hours to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducer WNTHIN-2.
Example 3
The first step of reaction: preparation of sulfobetaine type zwitterionic monomer.
0.22mol of methacryloxyethyl dimethylamine, 0.03 percent of polymerization inhibitor catechol and 125mL of solvent acetone are weighed and added into a 250mL three-neck flask, and the mixture is stirred and mixed for 30min to obtain a mixed solution;
weighing 0.2mol of 1, 3-propyl sultone, adding the solution into 30mL of solvent acetone, transferring the solution into a constant pressure low liquid funnel, slowly dripping the solution into the mixed solution in the previous step, and finishing the addition within 2 hours; reacting for 20 hours at 55 ℃ until white crystal products are separated out;
repeatedly washing the precipitated white crystal product with a mixed solvent of acetone and diethyl ether for 5 times, and drying in a vacuum oven to constant weight to obtain the sulfobetaine type zwitterionic monomer DMAPS.
And the second step of reaction: and (3) preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent.
Adding 7.5 parts of DMAPS, 0.5 part of allyl polyoxyethylene ether, 5 parts of N, N-dimethylacrylamide and 4 parts of N-vinyl pyrrolidone into 174 parts of water in sequence, stirring uniformly, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 0.65 part of initiator persulfuric acid and 0.25 part of molecular weight regulator dodecyl mercaptan to initiate polymerization, and reacting for 2.5 hours to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent WNTHIN-3.
Test example 1
The viscosity performance of the comb betaine zwitterionic polymer viscosity reducers prepared in examples 1-3 was evaluated in a composite brine slurry (300 mL clear water+0.3% anhydrous sodium carbonate+7% bentonite+15% evaluation soil+0.5% CaCl 2 +4% nacl), and the results are shown in table 1.
TABLE 1 viscosity reducing effect of different Polymer viscosity reducing Agents in composite brine-based slurries (200 ℃ C., 16 h)
In the table, AV means apparent viscosity, PV means plastic viscosity, Φ 100 Refers to the reading measured by a six-degree viscometer at 100 rpm. As can be seen from Table 1, the prepared three comb-shaped betaine type amphoteric ion polymer viscosity reducers have good viscosity reducing capability after being aged at a high temperature of 200 ℃ in the composite brine slurry, and the effect is superior to that of the conventional amphoteric viscosity reducer XY-27 and anionic polymer sulfonated tannin, so that the viscosity reducing capability is excellent, and the temperature and salt resisting capability is good.
Test example 2
In view of the optimal viscosity performance of the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent WNTHIN-3, the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent is applied to a high-temperature high-density water-based drilling fluid system (1% base slurry, 0.3% NaOH, 0.8% polymer filtrate reducer, 3% KFT, 2% SMP-2, 4% SPNH, 4% HPAN-NH 4 +5% KCL+3% Polymer blocking agent+5% sulfonated asphaltCyan+0.5% sodium sulfite+4% calcium carbonate+barite (density 2.2 g/cm) 3 ) The viscosity reducing effect was further tested and the results are shown in table 2.
TABLE 2 Effect of viscosity reducing Agents on high Density Water-based drilling fluid System Performance
Note that: YP refers to dynamic shear force, Φ 6 And phi is 3 The readings measured by a six-degree viscometer at 6rpm and 3rpm, respectively. As can be seen from Table 2, the viscosity of the high-density water-based system without the viscosity-reducing agent is higher, and the high-density water-based system has serious thickening phenomenon after aging at high temperature (200 ℃ and 16 hours) and is expressed as sharp increase of viscosity shear force. However, after a small amount of viscosity reducing agent WNTHIN-3 is added, the viscosity of the system is reduced before aging, the thickening phenomenon after aging is greatly improved, and the filtration loss of drilling fluid is reduced to be within 10mL, which indicates that the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent WNTHIN-3 has good dispersing and deflocculating capability, and can improve the high temperature resistance and colloid stability of the drilling fluid system.
As can be seen from the results of the combination of the examples 1-3 and the test examples 1-2, the comb-shaped betaine type zwitterionic polymer viscosity reducer prepared by the preparation method provided by the invention has good viscosity reducing capability, can be well dispersed and deflocculated, and has good temperature resistance and salt tolerance.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. The preparation method of the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent is characterized by comprising the following steps of:
preparing a sulfobetaine type amphoteric ion monomer by taking a vinyl tertiary amine monomer and 1, 3-propyl sultone as raw materials;
and carrying out free radical polymerization reaction on the sulfobetaine type amphoteric ion monomer and the nonionic monomer to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducing agent with zero net charge.
2. The method for preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducer according to claim 1, wherein,
the preparation of the sulfobetaine type zwitterionic monomer comprises the following steps:
mixing vinyl tertiary amine monomer, polymerization inhibitor and solvent, and stirring to obtain mixed solution;
dispersing 1, 3-propyl sultone into a solvent to form a first solution, dropwise adding the first solution into the mixed solution, and carrying out heating reaction until a white crystal product is separated out;
and washing and drying the white crystal product by using a mixed solvent in sequence to obtain the sulfobetaine type amphoteric ion monomer.
3. The method for preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducer according to claim 2, wherein,
the input proportion of the vinyl tertiary amine monomer and the polymerization inhibitor is as follows: adding 0.20-0.22 mol of vinyl tertiary amine monomer into every 100-150 mL of solvent, wherein the mass volume ratio of the polymerization inhibitor to the solvent is 0.01-0.03%;
the mol ratio of the vinyl tertiary amine monomer to the 1, 3-propyl sultone is 1-1.1:1, a step of;
the input ratio of the 1, 3-propyl sultone to the solvent is as follows: adding 0.2mol of 1, 3-propyl sultone into each 30-40 mL of solvent;
the solvent is acetone, the mixed solvent is a mixture of acetone and diethyl ether, and the volume ratio of the acetone to the diethyl ether is 2:1.
4. the method for preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducer according to claim 1, wherein,
the vinyl tertiary amine monomer comprises one of N- (3-dimethylaminopropyl) methacrylamide, 4-vinylpyridine or methacryloxyethyl dimethylamine;
the mass ratio of the sulfobetaine type amphoteric ion monomer to the nonionic monomer is as follows: 7-8: 9 to 10;
wherein the nonionic monomers comprise allyl polyoxyethylene ether, N-alkyl acrylamide and vinyl heterocyclic monomers.
5. The method for preparing the comb-shaped betaine type amphoteric ion polymer viscosity reducer according to claim 2, wherein,
the stirring time is 10-30min;
the dripping time is 1-3 h;
the heating reaction condition is that the reaction is carried out for 20-24 hours at 50-80 ℃.
6. The method for preparing a comb-shaped betaine type zwitterionic polymer viscosity reducing agent according to claim 4, characterized in that,
the free radical polymerization reaction of the sulfobetaine type amphoteric ion monomer and the nonionic monomer comprises the following steps:
sequentially adding the sulfobetaine type amphoteric ion monomer, allyl polyoxyethylene ether, N-alkyl acrylamide and vinyl heterocyclic monomer into water to form a second solution;
and (3) uniformly stirring the second solution, heating to 70-80 ℃ under the condition of introducing nitrogen, adding an initiator and a molecular weight regulator to initiate polymerization, and reacting for 1-3 hours to obtain the comb-shaped betaine type amphoteric ion polymer viscosity reducer.
7. The method for preparing a comb-shaped betaine type zwitterionic polymer viscosity reducing agent according to claim 6, characterized in that,
the second solution comprises the following raw materials in parts by weight: 5-10 parts of sulfobetaine type amphoteric ion monomer, 0.1-1 part of allyl polyoxyethylene ether, 1-5 parts of N-alkyl acrylamide, 1-5 parts of vinyl heterocyclic monomer and 180 parts of water;
the initiator is 0.5-1 part, and the molecular weight regulator is 0.1-0.5 part.
8. The method for preparing a comb-shaped betaine type zwitterionic polymer viscosity reducing agent according to claim 6 or 7, characterized in that,
the N-alkyl acrylamide comprises one of N, N-dimethyl acrylamide or N, N-diethyl acrylamide;
the vinyl heterocyclic monomer comprises one of N-vinyl pyrrolidone or N-vinyl caprolactam.
9. The method for preparing a comb-shaped betaine type zwitterionic polymer viscosity reducing agent according to claim 6 or 7, characterized in that,
the initiator is ammonium persulfate, and the molecular weight regulator is dodecyl mercaptan.
10. A comb-shaped betaine-type zwitterionic polymer viscosity reducing agent prepared by the preparation method according to any one of claims 1 to 9, wherein the net charge of the zwitterionic polymer viscosity reducing agent is zero, and the weight average molecular weight is lower than 20000g/Mol.
11. Use of the comb-betaine zwitterionic polymer viscosity-reducing agent according to claim 10 in oil drilling.
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