CN104628942B - A kind of acrylamide copolymer and its preparation method and application - Google Patents
A kind of acrylamide copolymer and its preparation method and application Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010276 construction Methods 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 28
- 239000011591 potassium Substances 0.000 claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 28
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 110
- 239000000203 mixture Substances 0.000 claims description 28
- -1 2,2'-azo diisobutyl amidine Chemical class 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000003638 reducing agent Substances 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000001118 alkylidene group Chemical group 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 9
- KWYHDKDOAIKMQN-UHFFFAOYSA-N Tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 230000001590 oxidative Effects 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L Potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 claims description 2
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 claims description 2
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Ammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M Potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- VLYFRFHWUBBLRR-UHFFFAOYSA-L potassium;sodium;carbonate Chemical compound [Na+].[K+].[O-]C([O-])=O VLYFRFHWUBBLRR-UHFFFAOYSA-L 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 238000004026 adhesive bonding Methods 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 abstract description 22
- 150000003839 salts Chemical class 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000000243 solution Substances 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000033228 biological regulation Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- 239000000693 micelle Substances 0.000 description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Acrylamido-2-methylpropane sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 150000003926 acrylamides Chemical class 0.000 description 5
- 238000006392 deoxygenation reaction Methods 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 238000009818 secondary granulation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 230000001404 mediated Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- INWATCUTVADDFP-UHFFFAOYSA-N [K].OS(=O)(=O)C=CC1=CC=CC=C1 Chemical compound [K].OS(=O)(=O)C=CC1=CC=CC=C1 INWATCUTVADDFP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000302 molecular modelling Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- RVJXHBDUWYVGQD-UHFFFAOYSA-N potassium;prop-1-en-2-ylbenzene Chemical compound [K].CC(=C)C1=CC=CC=C1 RVJXHBDUWYVGQD-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- RTJKEOKLFIWBTE-UHFFFAOYSA-N CC(=C)C1=CC=CC=C1.[S] Chemical compound CC(=C)C1=CC=CC=C1.[S] RTJKEOKLFIWBTE-UHFFFAOYSA-N 0.000 description 1
- 229920002456 HOTAIR Polymers 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N N',N'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ODBSOAATZFAZCB-UHFFFAOYSA-N prop-1-en-2-ylbenzene;sodium Chemical compound [Na].CC(=C)C1=CC=CC=C1 ODBSOAATZFAZCB-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003385 sodium Chemical group 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention discloses a kind of acrylamide copolymer and its preparation method and application, this acrylamide copolymer contains the construction unit shown in formula (1) and the construction unit shown in formula (2), wherein, R1And R2It is each independently hydrogen or the alkyl of C1 C4, R3For the alkyl of C1 C8, M1And M2It is each independently at least one in hydrogen, potassium and sodium；And in described acrylamide copolymer on the basis of the total mole number of construction unit, the content of the construction unit shown in formula (1) is 30 99 moles of %, the content of the construction unit shown in formula (2) is 1 70 moles of %；The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000 3,700 ten thousand.The temperature-resistant anti-salt product using the acrylamide copolymer of the present invention has the advantages that molecular weight is high, and the acrylamide copolymer of the present invention has significantly thickening advantage, can be as high temperature and high salt oil deposit Flooding Agent for EOR.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and its preparation method and application.
Background technology
Polymer flooding, mainly by injecting the polymer solution of certain scale, increases displacing fluid viscosity, fall
Low oil-reservoir water phase permeability reduces mobility ratio, adjusts intake profile, to reach to improve displacing phase volume
Purpose, and then improve recovery ratio.
As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA) (HPAM) is at conventional oil reservoir
In tertiary oil recovery (EOB) technology, obtain large-scale promotion and application, sent out for oilfield stable production and volume increase
Wave important function.Along with the minimizing of conventional reservoir reserve, high temperature and high salt oil deposit makes the application of HPAM
It is faced with many difficult problems, molten in high temperature, high salt and solution when being mainly reflected in exploitation high temperature and high salt oil deposit
The compound action solving oxygen generation makes HPAM solution viscosity be greatly reduced, and causes HPAM oil displacement efficiency
The most notable.Research shows, when temperature is higher than 70 DEG C, and the acylamino-hydrolysis of HPAM generates carboxyl and shows
Writing aggravation, when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution2+、Mg2+Ion is raw
Become precipitation, make solution viscosity lose.Additionally, at high temperature, there is dissolved oxygen in oxygen and solution in air
Time, main polymer chain fracture also can be caused to make solution viscosity be remarkably decreased.
It is total to acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS)
Aggregate into bipolymer relatively HPAM in heat-resistant salt-resistant performance really to increase, as entitled
" the low temperature synthesis of AMPS/AM copolymer and performance " (Chang Zhiying, polymer material science and engineering,
1997,13,16) described in article.But, entitled " water solublity AM/AA/AMPS copolymer
Pyrohydrolysis " (Zhu Linyong, applied chemistry, 2000,17,2) research finds, at the height of 90 DEG C
Under the conditions of temperature, being subject to close on the Molecular modelling effect of acrylic acid (AA) unit, AMPS unit is also sent out
Raw hydrolysis, although as hydrolysis, in copolymer, acrylic acid structure unit ratio increases, and improves
Its Thermo-sensitive and the quick performance of salt, but owing to AMPS the most easily hydrolyzes, therefore limit this
Application under the conditions of base polymer high temperature and high salt more than hydrolysis temperature.
Therefore, improve the temperature-resistant anti-salt performance of acrylamide copolymer the most further to be still and need solution badly
Problem.
Summary of the invention
It is an object of the invention to overcome the drawbacks described above of prior art, it is provided that a kind of acrylamide copolymer
And its preparation method and application.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains formula (1) institute
Construction unit shown in the construction unit shown and formula (2), and with structure in described acrylamide copolymer
On the basis of the total mole number of unit, the content of the construction unit shown in formula (1) is 30-99 mole of %, formula
(2) content of the construction unit shown in is 1-70 mole of %, it is preferable that the structure list shown in formula (1)
The content of unit is 50-97.5 mole of %, and the content of the construction unit shown in formula (2) is 2.5-50 mole of %；
The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000-3,700 ten thousand, preferably 32,000,000-3600
Ten thousand,
Wherein, R1And R2It is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or methyl；R3
Alkyl for the alkyl of C1-C8, preferably C1-C4；M1And M2Be each independently hydrogen, potassium and
At least one in sodium, preferably potassium or sodium.
Present invention also offers the preparation method of a kind of acrylamide copolymer, the method includes: at solution
Under polymeric reaction condition, in the presence of initiator, monomer mixture is made to carry out polyreaction；Wherein, institute
State the monomer of structure shown in the monomer and formula (6) that monomer mixture contains structure shown in formula (5)；With institute
Stating in monomer mixture on the basis of the total mole number of monomer, shown in formula (5), the content of the monomer of structure is
30-99 mole of %, shown in formula (6), the content of the monomer of structure is 1-70 mole of %；Preferably, formula (5)
The content of the monomer of shown structure is 50-97.5 mole of %, and shown in formula (6), the content of the monomer of structure is
2.5-50 mole of %；The condition of described solution polymerization make resulting polymers after polyreaction viscous all
Molecular weight is 31,000,000-3,700 ten thousand, preferably 32,000,000-3,600 ten thousand,
Wherein, R1' and R2' it is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or methyl；R3’
Alkyl for the alkyl of C1-C8, preferably C1-C4；M1' and M2' be each independently hydrogen, potassium and
At least one in sodium, preferably potassium or sodium.
The invention provides by the acrylamide copolymer obtained by above method.
Present invention also offers the application as oil displacement agent of the aforesaid propylene amide copolymer.
The acrylamide copolymer that the present invention provides is the most high temperature resistant, and has under the degree of high ore deposit well
Efficient Adhesive Promotion, can be widely used in petrochemical industry, especially as the application of Flooding Agent for EOR.
Tracing it to its cause may dredging for alkyl around amide groups in the acrylamide copolymer of the present invention and phenyl
The space steric effect of water effect and disulfonic acid base significantly limit under hot conditions carboxyl to amide
The Molecular modelling hydrolysis of base, therefore improves the anti-hydrolytic performance of this acrylamide copolymer；Additionally,
Two sulfonic groups in this copolymer are insensitive to divalent salts ion, therefore improve this acrylamide copolymerization
The anti-salt property of thing；Due to the structure of acrylamide copolymer, there is bigger volume again, make copolymerization owner
Chain is not susceptible to curling, so that this acrylamide copolymer has reached the effect with thickening.
The temperature-resistant anti-salt product of the acrylamide copolymer of the present invention have water-soluble good, residual monomer content is low
The feature high with molecular weight, particularly under salinity 32000mg/L, the hot conditions of 95 DEG C, solution
Apparent viscosity up to more than 22mPa.s, and the apparent viscosity of commercially available high molecular weight polyacrylamide solution
It is only 8.9mPa.s.As can be seen here, relatively commercially available prod, the acrylamide copolymer of the present invention has significantly
Thickening advantage, can be as high temperature and high salt oil deposit Flooding Agent for EOR.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains formula (1) institute
Construction unit shown in the construction unit shown and formula (2), and with structure in described acrylamide copolymer
On the basis of the total mole number of unit, the content of the construction unit shown in formula (1) is 30-99 mole of %, formula
(2) content of the construction unit shown in is 1-70 mole of %, it is preferable that the structure list shown in formula (1)
The content of unit is 50-97.5 mole of %, and the content of the construction unit shown in formula (2) is 2.5-50 mole of %；
The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000-3,700 ten thousand, preferably 32,000,000-3600
Ten thousand,
Wherein, R1And R2It is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or methyl；R3
Alkyl for the alkyl of C1-C8, preferably C1-C4；M1And M2Be each independently hydrogen, potassium and
At least one in sodium, preferably potassium or sodium.
According to the present invention, described acrylamide copolymer is possibly together with shown in formula (3) and/or formula (4)
Construction unit:
Wherein, R4、R5And R6It is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or methyl；
R7Alkylidene for the alkylidene of C1-C8, preferably C1-C4；M3For in hydrogen, potassium and sodium at least
One, preferably potassium or sodium；M4For potassium or sodium.
In the present invention, the alkyl of described C1-C4 can be straight chain, it is also possible to be side chain.Described
The example of the alkyl of C1-C4 may include that methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkyl of described C1-C8 can be straight chain, it is also possible to be side chain.Described
The example of the alkyl of C1-C8 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just oneself
Base, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,2-dimethylbutyl, 1,3-dimethyl
Butyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,
1,1,2-thmethylpropyl, 1,2,2-thmethylpropyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-ethyl-2-
Methyl-propyl, n-heptyl and n-octyl.
In the present invention, the alkylidene of described C1-C8 can be straight or branched, described C1-C8's
The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene,
Sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tert-butyl group, sub-n-pentyl, isoamylidene, sub-uncle penta
Base, sub-neopentyl, sub-n-hexyl, sub-n-heptyl and sub-n-octyl.Described alkylidene refers to that alkane loses
Removing the residue after two hydrogen atoms, said two hydrogen atom can be that two hydrogen on same carbon atom are former
Son, it is also possible to two hydrogen atoms on different carbon atoms, can be straight chains, it is also possible to be side chain,
Such as, described ethylidene can be-CH2CH2-or-CH (CH3)-。
The content of the construction unit shown in formula (3) and/or formula (4) is not specially required by the present invention,
Such as, in described acrylamide copolymer on the basis of the total mole number of construction unit, shown in formula (1)
The content of construction unit be 30-90 mole of %, the structural unit content shown in formula (2) is that 1-40 rubs
You are %, and the structural unit content shown in formula (3) and/or formula (4) is 3-60 mole of %；Preferably, formula
(1) content of the construction unit shown in is 50-87.5 mole of %, and the construction unit shown in formula (2) contains
Amount is 2.5-20 mole of %, and the structural unit content shown in formula (3) and/or formula (4) is 6-35 mole
%。
Present invention also offers the preparation method of a kind of acrylamide copolymer, the method includes: at solution
Under polymeric reaction condition, in the presence of initiator, monomer mixture is made to carry out polyreaction；Wherein, institute
State the monomer of structure shown in the monomer and formula (6) that monomer mixture contains structure shown in formula (5)；With institute
Stating in monomer mixture on the basis of the total mole number of monomer, shown in formula (5), the content of the monomer of structure is
30-99 mole of %, shown in formula (6), the content of the monomer of structure is 1-70 mole of %；Preferably, formula (5)
The content of the monomer of shown structure is 50-97.5 mole of %, and shown in formula (6), the content of the monomer of structure is
2.5-50 mole of %；The condition of described solution polymerization make resulting polymers after polyreaction viscous all
Molecular weight is 31,000,000-3,700 ten thousand, preferably 32,000,000-3,600 ten thousand,
Wherein, R1' and R2' it is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or methyl；R3’
Alkyl for the alkyl of C1-C8, preferably C1-C4；M1' and M2' be each independently hydrogen, potassium and
At least one in sodium, preferably potassium or sodium.
In the present invention, in order to make the acrylamide copolymer of described polyreaction gained obtain higher turning
Rate, it is further preferred that the monomer of structure shown in formula (6) is the monomer of structure shown in formula (9):
Wherein, M1' and M2' it is each independently potassium or sodium.
A preferred embodiment of the invention, the preparation process of the monomer of structure shown in formula (6)
As follows:
(1) under stirring, the concentrated sulphuric acid of 98% is slowly added in the acrylonitrile of excess,
To the first solution, the temperature controlling mixed liquor is-5 DEG C to 10 DEG C.Be slowly added in the first solution α-
Methyl styrenesulfonic acid sodium or α-methyl styrene potassium sulfonate, control reacting liquid temperature not in adition process
More than 10 DEG C, react 1-8 hour, obtain the second solution.
(2) in the second solution, add suitable quantity of water, under normal temperature condition, continue reaction 1-8 hour, add
The pH entering sodium hydroxide or potassium hydroxide regulation system is 5-10, static, has crystal to separate out.
(3) filter off the acrylonitrile of excess, obtain thick product, and with acrylonitrile, thick product is washed 2-3
Secondary, vacuum drying obtains target product.
Wherein, the α-methyl styrene sodium sulfonate in step (1), α-methyl styrene potassium sulfonate are permissible
It is to be respectively through sodium hydroxide, potassium hydroxide regulation system pH by α-methyl styrene sulphur aqueous acid
5-10 obtains.
According to the present invention, the primary object of the present invention is that shown in offer formula (6), the monomer of structure is
Temperature-resistant anti-salt monomer, makes the acrylamide polymer of synthesis have at higher temperature and salinity
Preferably Efficient Adhesive Promotion, and the method for the monomer of structure shown in synthesis type (6) can be this area routine
Method, the monomer of structure shown in the formula (6) of present invention synthesis such as can pass through Infrared Characterization,
In infrared spectrum, 1500cm-1Near be the characteristic absorption peak of phenyl ring, 1185cm-1Neighbouring is sulfonic acid group
Characteristic absorption peak, 1650cm-1Near be the absworption peak of alkene, 1740cm-1Near be the feature of ester group
Absworption peak, 3340cm-1Near be the characteristic absorption peak of amide group, and at 2250cm-1Near do not go out
The characteristic absorption peak of existing itrile group, this illustrates that method of the present invention has synthesized target product.Therefore,
In the examples below, the most further the monomer of structure shown in formula (6) is characterized.
In the present invention, on the premise of reaching the purpose of the present invention, in order to reduce reaction cost further,
Under preferable case, described monomer mixture possibly together with the monomer of structure shown in formula (7),
Wherein, R4’、R5' and R6' it is each independently the alkyl of hydrogen or C1-C4, preferably hydrogen or first
Base；R7' it is the alkylidene of C1-C8, the alkylidene of preferably C1-C4；M3' it is in hydrogen, potassium and sodium
At least one, preferably potassium or sodium.It is further preferred that the monomer of structure is 2-third shown in formula (7)
Acrylamide base-2-methyl propane sulfonic acid (AMPS).
According to the present invention, the description of the alkylidene of the alkyl of C1-C4, the alkyl of C1-C8 and C1-C8 is equal
Same as described above.
The content of the monomer of structure shown in formula (7) is not specially required by the present invention, for instance, it is preferred that
In described monomer mixture on the basis of the total mole number of monomer, shown in formula (5), the monomer of structure contains
Amount is 30-98 mole of %, and the content of the monomer of structure shown in formula (6) is 1-40 mole of %, formula (7)
The content of the monomer of shown structure is 0.1-35 mole of %；It is further preferred that structure shown in formula (5)
The content of monomer be 70-97.5 mole of %, shown in formula (6), the content of the monomer of structure is 1-20 mole
%, shown in formula (7), the content of the monomer of structure is 1-20 mole of %.
According to the present invention, described solution polymerization is carried out in water, when described solution polymerization starts,
There is no particular limitation for the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture,
Can change in wider scope, under preferable case, the weight of described monomer mixture and water and monomer
The ratio of the gross weight of mixture is 0.15-0.4:1, more preferably 0.2-0.3:1.
In the present invention, described initiator can be the various initiator in this area.Such as, described initiator
Azo series initiators and/or oxidoreduction body class initiator, preferably azo series initiators and oxygen can be selected from
Change reduction series initiators.The consumption of described azo series initiators can be the gross weight of monomer mixture
0.0001-0.1 weight %, preferably 0.001-0.05 weight %；The consumption of described oxidoreduction series initiators
Can be 0.0002-0.3 weight % of the gross weight of monomer mixture, preferably 0.003-0.15 weight %；
Described azo series initiators is water-soluble azo series initiators, and described oxidoreduction series initiators includes oxidation
Agent and reducing agent, described reducing agent can be inorganic reducing agent and/or organic reducing agent, and described oxidant
Can be 0.1-1:1 with the weight ratio of described reducing agent.
In the present invention, described water-soluble azo series initiators can be selected from 2,2'-azo diisobutyl amidine two
Hydrochlorate, 2,2'-azo [2-(2-imidazoline-2-base) propane] dihydrochloride and 4,4'-azo are double (4-cyanopentanoic acid)
In at least one, preferably 2,2'-azo diisobutyl amidine dihydrochloride.
In the present invention, described oxidant can be selected from Ammonium persulfate., sodium peroxydisulfate and potassium peroxydisulfate
At least one, preferably Ammonium persulfate. and/or potassium peroxydisulfate.
In the present invention, described reducing agent can be inorganic reducing agent and/or organic reducing agent, is preferably
Inorganic reducing agent and organic reducing agent.Described inorganic reducing agent can be selected from ammonium sulfite, potassium sulfite,
At least one in sodium sulfite, ammonium bisulfite, Potassium acid sulfite and sodium sulfite, is preferably Asia
At least one in ammonium sulfate, potassium sulfite and sodium sulfite；Described organic reducing agent is preferably amine
Reducing agent, described amine reducing agent can be N, N-dimethylethanolamine, N, N-dimethyl propanol amine,
N, N-lupetazin, tetramethylurea, N, N-dimethyl urea element, N, N, N ', N '-tetramethylethylenediamine and
At least one in N, N-dimethyl-ethylenediamine, preferably N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, the condition of described solution polymerization can be the condition that this area is conventional.Such as,
Described solution polymerization is carried out in the presence of an inert gas, and described polymeric reaction condition may include that temperature
Degree, for-10 DEG C to 20 DEG C, is preferably-7 DEG C to 15 DEG C；Time is 1-20 hour, preferably 3-8 hour；
PH value is 4-12, preferably 5-10.
In the present invention, described noble gas is the gas not reacted with raw material and product, such as may be used
Think at least one in the conventional nitrogen in this area or the periodic table of elements in group 0 element gas, preferably
For nitrogen.
According to the present invention, described method also includes: under hydrolysising condition, is polymerized by gained after polyreaction
Thing contacts with inorganic alkaline compound, and the condition of described hydrolysis makes the some acrylamide in polymer tie
The unit of structure shown in a unit hydrolysis accepted way of doing sth (8) of structure shown in structure unit i.e. formula (1):
Wherein, M4' it is potassium or sodium.
In the present invention, described inorganic alkaline compound can be commonly used in the art various is capable of
State purpose inorganic alkaline compound, it is preferable that described inorganic alkaline compound is selected from sodium hydroxide, hydrogen-oxygen
Change at least one in potassium and sodium carbonate.
According to the present invention, the condition of described hydrolysis can be the condition that this area is conventional.Such as, described water
The condition solved may include that temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hour,
It is preferably 1-4 hour；After the condition of described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers is
10-30%。
According to the present invention, degree of hydrolysis refers to that the molal quantity of the construction unit shown in formula (8) accounts for the present invention's
The percentage ratio of the total mole number of the construction unit of acrylamide copolymer.In the present invention, degree of hydrolysis is by nothing
The consumption of machine alkali compounds determines.
Those skilled in the art could be aware that, by regulating the consumption of inorganic alkaline compound, and can
To obtain the acrylamide copolymer of different degree of hydrolysis.
In the present invention, the molal quantity of described inorganic alkaline compound is equal to the structure list shown in formula (8)
The molal quantity of unit.
In the present invention, in order to obtain the acrylamide copolymer product being dried further, under preferable case,
Described method also includes being dried said method gained acrylamide copolymer.
According to the present invention, dry method and condition without particular/special requirement, such as, described are dried by the present invention
Method hot-air seasoning, described hot air drying temperature can be used can be 40-110 DEG C, be preferably
70-90℃；The described dry time can be 0.2-4 hour, preferably 0.5-2 hour.
The present invention one preferred embodiment in, the preparation method bag of described acrylamide copolymer
Include following steps:
(1) acrylamide monomer, temperature-resistant anti-salt monomer and water are mixed to form comonomer aqueous solution,
Regulate pH to 5-10 with inorganic alkaline compound, control solution temperature-10 DEG C to 20 DEG C；
(2) in comonomer aqueous solution, logical nitrogen carries out deoxygenation, controls oxygen content in solution and is less than
1mg/L, preferably smaller than 0.2mg/L；
(3) under logical condition of nitrogen gas, add composite initiation system to monomer solution, carry out adiabatic poly-
Close, obtain copolymer gel；
(4) copolymer gel is carried out a pelletize, hydrolysis, secondary granulation, is dried, pulverizes and sieves
Get the acrylamide copolymer product of temperature-resistant anti-salt.
According to the present invention, in step (1), described temperature-resistant anti-salt monomer is Chinese style of the present invention (6) institute
Show the monomer of structure, it is also possible to containing the monomer of structure, described inorganic alkaline compound shown in formula (7)
For regulating the pH value of comonomer aqueous solution.Described inorganic alkaline compound can be sodium hydroxide,
At least one in potassium hydroxide and sodium carbonate, preferably sodium hydroxide.
Present invention also offers the acrylamide copolymer prepared according to said method.
Additionally, present invention also offers the application in oil displacement agent of the described acrylamide copolymer.
Below, by following example, the present invention will be described in more detail.
In following example, the performance test of product uses following methods to carry out:
1, according to regulation in People's Republic of China's oil and gas industry standard SY/T5862-2008
Method measures the solid content of polymer, dissolution time, filtration ratio, AM residual monomer content and characteristic
Viscosity number.
2, polymer viscosity-average molecular weight is according to the method for regulation in SY/T5862-2008, uses formula
M=([η]/0.000373)1.515Calculating, wherein, M is viscosity-average molecular weight, and [η] is intrinsic viscosity.
3, the apparent viscosity of polymer solution is to be made into by polymer with the saline of salinity 32000mg/L
The solution of 1500mg/L, with Brookfield viscometer at 95 DEG C, 7.34s-1Under the conditions of measure.
4, polymer solution antioxygen thermal ageing test is according to the method for regulation in SY/T5862-2008, uses
Polymer is made into the solution of 1500mg/L by the saline of salinity 32000mg/L, by oxygen content in solution
Except to required value, by the polymer solution that obtains at a temperature of 95 DEG C, after aging 3 months, use
Brookfield viscometer measures the apparent viscosity that polymer solution is at 95 DEG C, calculates apparent by below equation
Viscosity retention ratio:
Apparent viscosity retention rate %=aging post-consumer polymer solution apparent viscosity/aging prepolymer solution table
See viscosity × 100%.
In following example, acrylamide is commercially available from Bao Mo biochemical industry limited company, 2-acryloyl
Amido-2-methyl propane sulfonic acid commercially available from Xiamen Changtian Enterprise Co., Ltd., 2,2'-azo diisobutyl amidine disalts
Hydrochlorate is commercially available from Aldrich.In the examples below, in the monomer of structure shown in formula (6), R2’
It is hydrogen, R3' it is methyl (that is, the monomer of structure shown in formula (9)).
Embodiment 1
Acrylamide copolymer that the present embodiment provides for the present invention is described and preparation method thereof.
(1) preparation of the monomer of structure shown in formula (6)
In temperature-controlled glass reactor, add 1060 kilograms of acrylonitrile, under stirring, drip concentration
It is the concentrated sulphuric acid 200 kilograms of 98%, mixed liquor is cooled to-5 DEG C, after stirring, drip Alpha-Methyl
Sodium styrene sulfonate 440 kilograms, maintains temperature of reaction system below 10 DEG C.After reacting 1 hour, add
Enter suitable quantity of water, after continuing reaction under normal temperature condition 4 hours, further by sodium hydroxide regulation system
After pH value is 7, obtaining pure monomer through filtering, wash, drying, the yield of product is 93.9%.
This monomer is monomer (wherein, the M of structure shown in formula (6)1' and M2' be sodium).
(2) preparation of acrylamide polymer
Structure shown in 927.09 kilograms of acrylamides, 1281.42 kilograms of formulas (6) is added in batching kettle
Monomer and 8834.04 kilograms of deionized waters, under stirring, control solution temperature-7 DEG C with chilled brine,
Add sodium hydroxide regulation pH to 5.Being pumped into by monomer solution in polymeric kettle, add 2,2'-azo two is different
Butyl amidine dihydrochloride 22.08 grams and N, N, N ', N '-tetramethylethylenediamine 22.08 grams, logical high pure nitrogen
Deoxygenation 0.5h, adds sodium sulfite 22.08 grams and Ammonium persulfate. 22.08 grams, continues logical nitrogen until gathering
Close thermocouple in still to start to warm up, response time 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, compress with 0.3MPa
The copolymer colloid obtained is extruded by air, is become the little micelle of 4-6 millimeter by granulator granulation.Will
The little micelle arrived and 130.43 kilogram sodium hydroxide grain alkali mediate contact, hydrolyze 4h at temperature 90 DEG C,
After secondary granulation, by crushing and screening and be packaged to be the acrylamide copolymer product of 20-80 mesh,
The performance of product is as shown in table 1.Calculate according to inventory and determine, so that described acrylamide copolymer to be tied
On the basis of the total mole number of structure unit, the content of the construction unit shown in formula (1) is 60 moles of %, formula
(2) structural unit content shown in is 20 moles of %, and the structural unit content shown in formula (4) is 20
Mole %.
Comparative example 1
Same process condition is used, except for the difference that, by the monomer of structure shown in formula (6) with embodiment 1
Change the 2-acrylamide-2-methylpro panesulfonic acid of same molar into, thus obtain acrylamide copolymer and produce
Product, the performance of product is as shown in table 1.
Embodiment 2
(1) preparation of the monomer of structure shown in formula (6)
Adding 636 kilograms of acrylonitrile in temperature-controlled glass reactor, under stirring, dropping concentration is
The concentrated sulphuric acid of 98% 107.8 kilograms, is cooled to 5 DEG C by mixed liquor, after stirring, drips Alpha-Methyl
236 kilograms of styrene sulfonic acid potassium, maintains temperature of reaction system below 10 DEG C.After reacting 1 hour, add
Enter suitable quantity of water, after continuing reaction under normal temperature condition 6 hours, with the pH value of potassium hydroxide regulation system
After being 7, obtaining pure monomer through filtering, wash, drying, the yield of product is 95.5%.This monomer
It is monomer (wherein, the M of structure shown in formula (6)1' and M2' be potassium).
(2) preparation of acrylamide polymer
The list of structure shown in 1108.85 kilograms of acrylamides, 170 kilograms of formulas (6) is added in batching kettle
Body and 2983.98 kilograms of deionized waters, under stirring, control solution temperature 15 DEG C with chilled brine,
Add sodium hydroxide regulation pH to 10.Being pumped into by monomer solution in polymeric kettle, add 2,2'-azo two is different
Butyl amidine dihydrochloride 639.42 grams and N, N, N ', N '-tetramethylethylenediamine 639.42 grams, logical High Purity Nitrogen
Gas deoxygenation 0.5h, adds sodium sulfite 639.42 grams and Ammonium persulfate. 639.42 grams, continues logical nitrogen straight
To polymeric kettle, thermocouple starts to warm up, response time 3h.Open Polycondensation Reactor and Esterification Reactor ball valve, use 0.3MPa
The copolymer colloid obtained is extruded by compressed air, is become the little micelle of 4-6 millimeter by granulator granulation.
The little micelle obtained and 64 kilogram sodium hydroxide grain alkali are mediated contact, under temperature 70 C, hydrolyze 1h,
After secondary granulation, under the conditions of 70 DEG C of hot blasts, it is dried 2h, by crushing and screening and being packaged to be 20-80
Purpose acrylamide copolymer product, the performance of product is as shown in table 1.Calculate according to inventory and determine,
In described acrylamide copolymer on the basis of the total mole number of construction unit, the structure shown in formula (1)
The content of unit is 87.5 moles of %, and the structural unit content shown in formula (2) is 2.5 moles of %, formula (4)
Shown structural unit content is 10 moles of %.
Embodiment 3
Acrylamide copolymer that the present embodiment provides for the present invention is described and preparation method thereof.
(1) preparation of the monomer of structure shown in formula (6)
In temperature-controlled glass reactor, add 1060 kilograms of acrylonitrile, under stirring, drip concentration
It is the concentrated sulphuric acid 117.6 kilograms of 98%, mixed liquor is cooled to 5 DEG C, after stirring, drip α-first
236 kilograms of base styrene sulfonic acid potassium, maintains temperature of reaction system below 10 DEG C.After reacting 1 hour,
Add suitable quantity of water, after continuing reaction under normal temperature condition 8 hours, with the pH of sodium hydroxide regulation system
After value is 7, obtaining pure monomer through filtering, wash, drying, the yield of product is 94.5%.This is single
Body is monomer (wherein, the M of structure shown in formula (6)1' it is sodium, M2' be potassium).
(2) preparation of acrylamide polymer
The list of structure shown in 1080.4 kilograms of acrylamides, 327.2 kilograms of formulas (6) is added in batching kettle
Body and 4222.8 kilograms of deionized waters, under stirring, control solution temperature 0 DEG C with chilled brine, add
Enter sodium hydroxide regulation pH to 10.Monomer solution is pumped in polymeric kettle, add 2,2'-azo two isobutyl
Base amidine dihydrochloride 200 grams and N, N, N ', N '-tetramethylethylenediamine 200 grams, logical high pure nitrogen deoxygenation
0.5h, adds sodium sulfite 150 grams and Ammonium persulfate. 200 grams, continues logical nitrogen until heat in polymeric kettle
Galvanic couple starts to warm up, response time 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, incite somebody to action by 0.3MPa compressed air
The copolymer colloid arrived extrudes, and is become the little micelle of 4-6 millimeter by granulator granulation.The little glue that will obtain
Grain is mediated with 192 kilogram sodium hydroxide grain alkali and is contacted, and hydrolyzes 1.5h, through secondary granulation at temperature 85 DEG C
After, under the conditions of 70 DEG C of hot blasts, it is dried 2h, by crushing and screening and be packaged to be the propylene of 20-80 mesh
Amide copolymer product, the performance of product is as shown in table 1.Calculate according to inventory and determine, with described third
In acrylamide copolymer on the basis of the total mole number of construction unit, containing of the construction unit shown in formula (1)
Amount is 65 moles of %, and the structural unit content shown in formula (2) is 5 moles of %, the knot shown in formula (4)
Structure unit content is 30 moles of %.
Embodiment 4
Use with embodiment 1 use same process condition, except that, in monomer mixture possibly together with
2-acrylamide-2-methylpro panesulfonic acid (AMPS), in monomer mixture, the total mole number of monomer is as base
Standard, the consumption of acrylamide is 80 moles of %, and the consumption of the monomer of structure shown in formula (6) is 10 to rub
Your consumption of %, 2-acrylamide-2-methylpro panesulfonic acid is 10 moles of %, thus obtains acrylamide altogether
Copolymer product, the performance of product is as shown in table 1.Calculate according to inventory and determine, with described acrylamide
In copolymer on the basis of the total mole number of construction unit, the content of the construction unit shown in formula (1) is 60
Mole %, the structural unit content shown in formula (2) is 10 moles of %, the construction unit shown in formula (3)
Content is 10 moles of %, and the structural unit content shown in formula (4) is 20 moles of %.
Embodiment 5
Use and use same process condition with embodiment 1, except for the difference that, without hydrolysis, the most do not enter
The little micelle obtained and 130.43 kilogram sodium hydroxide grain alkali being mediated in row embodiment 1 contacts, in temperature
Hydrolyze the step of 4h at spending 90 DEG C, thus obtain acrylamide copolymer product, the performance of product such as table
Shown in 1.Calculate according to inventory and determine, with in described acrylamide copolymer total mole of construction unit
On the basis of number, the content of the construction unit shown in formula (1) is 80 moles of %, the knot shown in formula (2)
Structure unit content is 20 moles of %.
Embodiment 6
Use the monomer of structure shown in process conditions formula (6) same as in Example 1.
Structure shown in 430.34 kilograms of acrylamides, 1281.42 kilograms of formulas (6) is added in batching kettle
Monomer and 6847.04 kilograms of deionized waters, under stirring, control solution temperature-7 DEG C with chilled brine,
Add sodium hydroxide regulation pH to 5.Being pumped into by monomer solution in polymeric kettle, add 2,2'-azo two is different
Butyl amidine dihydrochloride 17.12 grams and N, N, N ', N '-tetramethylethylenediamine 17.12 grams, logical high pure nitrogen
Deoxygenation 0.5h, adds sodium sulfite 17.12 grams and Ammonium persulfate. 17.12 grams, continues logical nitrogen until gathering
Close thermocouple in still to start to warm up, response time 8h.Open Polycondensation Reactor and Esterification Reactor ball valve, compress with 0.3MPa
The copolymer colloid obtained is extruded by air, is become the little micelle of 4-6 millimeter by granulator granulation.Will
The little micelle arrived and 74.51 kilogram sodium hydroxide grain alkali mediate contact, hydrolyze 4h, warp at temperature 90 DEG C
After secondary granulation, by crushing and screening and be packaged to be the acrylamide copolymer product of 20-80 mesh, produce
The performance of product is as shown in table 1.Calculate according to inventory and determine, with structure in described acrylamide copolymer
On the basis of the total mole number of unit, the content of the construction unit shown in formula (1) is 45 moles of %, formula (2)
Shown structural unit content is 35 moles of %, and the structural unit content shown in formula (4) is 20 moles of %.
Table 1
Understanding in conjunction with table 1 data, the molecular weight of the acrylamide copolymer product that embodiment 1 obtains is permissible
Reach 35,800,000, and comparative example 1 obtains acrylamide copolymer molecular weight product and is only 29,500,000, in fact
Executing example 1 molecular weight of copolymer that relatively comparative example 1 obtains and improve nearly 6,300,000, corresponding 95 DEG C of apparent viscosities carry
High 9.7mPa s.Illustrate that acrylamide copolymer that the present invention provides is than acrylamide and 2-acrylamido
-2-methyl propane sulfonic acid polymerization gained acrylamide copolymer be more beneficial for improve copolymer molecular weight and
Apparent viscosity under hot conditions.
By embodiment 1 compared with Example 4, except shown in acrylamide and formula (6) in embodiment 4
Outside the monomer of structure, it is also added into 2-acrylamide-2-methylpro panesulfonic acid.Obtain acrylamide copolymer
The molecular weight of product is 31,500,000, and corresponding 95 DEG C of corresponding meter observing viscosities are 18.7mPa s, less than embodiment
The index result of 1, but also there is higher molecular weight and apparent viscosity.
By embodiment 1 compared with Example 5, embodiment 5 obtains dividing of acrylamide copolymer product
Son amount be 32,600,000,95 DEG C of corresponding meter observing viscosities be 20.2mPa s, less than the index result of embodiment 1.
Illustrate to be suitably introduced into acrylates construction unit in copolymer structure to have and be more beneficial for improving copolymer
Apparent viscosity under molecular weight and hot conditions.
The temperature-resistant anti-salt performance being understood the acrylamide copolymer that the present invention provides by data in table 1 is good,
Can be as high temperature and high salt oil deposit Flooding Agent for EOR.
Claims (28)
1. an acrylamide copolymer, it is characterised in that this acrylamide copolymer contains formula (1)
Construction unit shown in shown construction unit and formula (2), and so that described acrylamide copolymer to be tied
On the basis of the total mole number of structure unit, the content of the construction unit shown in formula (1) is 30-99 mole of %,
The content of the construction unit shown in formula (2) is 1-70 mole of %；Gluing all of described acrylamide copolymer
Molecular weight is 31,000,000-3,700 ten thousand,
Wherein, R1And R2It is each independently the alkyl of hydrogen or C1-C4；R3Alkyl for C1-C8；
M1And M2It is each independently at least one in hydrogen, potassium and sodium.
Acrylamide copolymer the most according to claim 1, wherein, with described acrylamide altogether
In polymers on the basis of the total mole number of construction unit, the content of the construction unit shown in formula (1) is 50-97.5
Mole %, the content of the construction unit shown in formula (2) is 2.5-50 mole of %.
Acrylamide copolymer the most according to claim 1, wherein, described acrylamide copolymerization
The viscosity-average molecular weight of thing is 32,000,000-3,600 ten thousand.
Acrylamide copolymer the most according to claim 1, wherein, R1And R2Independently of one another
For hydrogen or methyl；R3Alkyl for C1-C4；M1And M2It is each independently potassium or sodium.
Acrylamide copolymer the most according to claim 1, wherein, described acrylamide copolymerization
Thing is possibly together with the construction unit shown in formula (3) and/or formula (4):
Wherein, R4、R5And R6It is each independently the alkyl R of hydrogen or C1-C47Alkylene for C1-C8
Base；M3For at least one in hydrogen, potassium and sodium；M4For potassium or sodium.
Acrylamide copolymer the most according to claim 5, wherein, R4、R5And R6The most solely
It is on the spot hydrogen or methyl；R7Alkylidene for C1-C4；M3For potassium or sodium.
Acrylamide copolymer the most according to claim 5, wherein, with described acrylamide altogether
In polymers on the basis of the total mole number of construction unit, the content of the construction unit shown in formula (1) is 30-90
Mole %, the structural unit content shown in formula (2) is 1-40 mole of %, formula (3) and/or formula (4)
Shown structural unit content is 3-60 mole of %.
Acrylamide copolymer the most according to claim 6, wherein, with described acrylamide altogether
In polymers on the basis of the total mole number of construction unit, the content of the construction unit shown in formula (1) is 50-87.5
Mole %, the structural unit content shown in formula (2) is 2.5-20 mole of %, formula (3) and/or formula (4)
The unit content of shown structure is 6-35 mole of %.
9. a preparation method for acrylamide copolymer, the method includes: at solution polymerization bar
Under part, in the presence of initiator, monomer mixture is made to carry out polyreaction；Wherein, described monomer mixing
Thing contains the monomer of structure shown in the monomer of structure shown in formula (5) and formula (6)；Mix with described monomer
In thing on the basis of the total mole number of monomer, shown in formula (5), the content of the monomer of structure is 30-99 mole of %,
Shown in formula (6), the content of the monomer of structure is 1-70 mole of %；The condition of described solution polymerization makes
After polyreaction the viscosity-average molecular weight of resulting polymers be 31,000,000-3,700 ten thousand,
Wherein, R1' and R2' it is each independently the alkyl of hydrogen or C1-C4；R3' it is the alkyl of C1-C8；
M1' and M2' it is each independently at least one in hydrogen, potassium and sodium.
Method the most according to claim 9, wherein, with monomer total in described monomer mixture
On the basis of molal quantity, shown in formula (5), the content of the monomer of structure is 50-97.5 mole of %, formula (6)
The content of the monomer of shown structure is 2.5-50 mole of %.
11. methods according to claim 9, wherein, the condition of described solution polymerization makes
After polyreaction, the viscosity-average molecular weight of resulting polymers is 32,000,000-3,600 ten thousand.
12. methods according to claim 9, wherein, R1' and R2' it is each independently hydrogen or first
Base；R3' it is the alkyl of C1-C4；M1' and M2' it is each independently potassium or sodium.
13. methods according to claim 9, wherein, described monomer mixture is possibly together with formula (7)
The monomer of shown structure,
Wherein, R4’、R5' and R6' it is each independently the alkyl of hydrogen or C1-C4；R7' it is C1-C8's
Alkylidene；M3' it is at least one in hydrogen, potassium and sodium.
14. methods according to claim 13, wherein, R4’、R5' and R6' be each independently
Hydrogen or methyl；R7' it is the alkylidene of C1-C4；M3' it is potassium or sodium.
15. methods according to claim 13, wherein, with monomer in described monomer mixture
On the basis of total mole number, shown in formula (5), the content of the monomer of structure is 30-98 mole of %, formula (6)
The content of the monomer of shown structure is 1-40 mole of %, and shown in formula (7), the content of the monomer of structure is 0.1-35
Mole %.
16. methods according to claim 15, wherein, with monomer in described monomer mixture
On the basis of total mole number, shown in formula (5), the content of the monomer of structure is 70-97.5 mole of %, formula (6)
The content of the monomer of shown structure is 1-20 mole of %, and shown in formula (7), the content of the monomer of structure is 1-20
Mole %.
17. methods according to claim 9, wherein, described solution polymerization is carried out in water,
The weight of described monomer mixture is 0.15-0.4:1 with the ratio of water and the gross weight of monomer mixture.
18. methods according to claim 17, wherein, described solution polymerization enters in water
OK, the weight of described monomer mixture is 0.2-0.3:1 with the ratio of water and the gross weight of monomer mixture.
19. methods according to claim 9, wherein, described initiator is selected from azo series initiators
With oxidoreduction series initiators, the gross weight that consumption is monomer mixture of described azo series initiators
0.0001-0.1 weight %, the gross weight that consumption is monomer mixture of described oxidoreduction series initiators
0.0002-0.3 weight %；Described azo series initiators is water-soluble azo series initiators, and described oxidation is also
Former series initiators includes that Oxidizing and Reducing Agents, described reducing agent are inorganic reducing agent and/or organic reducing
Agent, and the weight ratio of described oxidant and described reducing agent is 0.1-1:1.
20. methods according to claim 19, wherein, described water-soluble azo series initiators selects
From 2,2'-azo diisobutyl amidine dihydrochloride, 2,2'-azo [2-(2-imidazoline-2-base) propane] dihydrochloride
With at least one in 4,4'-azo double (4-cyanopentanoic acid)；Described oxidant is selected from Ammonium persulfate., over cure
At least one in acid sodium and potassium peroxydisulfate；Described inorganic reducing agent selected from ammonium sulfite, potassium sulfite,
At least one in sodium sulfite, ammonium bisulfite, Potassium acid sulfite and sodium sulfite；Described organic
Reducing agent selected from N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, four
MU, N, N-dimethyl urea element, N, N, N ', N '-tetramethylethylenediamine and N, in N-dimethyl-ethylenediamine
At least one.
21. methods according to claim 9, wherein, described solution polymerization is at noble gas
In the presence of carry out, described solution polymerization condition includes: temperature is-10 DEG C to 20 DEG C；Time is 1-20
Hour；PH value is 4-12.
22. methods according to claim 21, wherein, described solution polymerization condition includes:
Temperature is-7 DEG C to 15 DEG C；Time is 3-8 hour；PH value is 5-10.
23. according to the method described in any one in claim 9-22, and wherein, described method is also wrapped
Include: under hydrolysising condition, resulting polymers after polyreaction is contacted with inorganic alkaline compound, described
The condition of hydrolysis makes structure shown in an acrylamide construction unit partial hydrolysis accepted way of doing sth (8) in polymer
Unit:
Wherein, M4' it is potassium or sodium.
24. methods according to claim 23, wherein, described inorganic alkaline compound is selected from hydrogen
At least one in sodium oxide, potassium hydroxide and sodium carbonate.
25. methods according to claim 23, wherein, described hydrolysising condition includes: temperature is
50-110℃；Time is 0.5-6 hour；Described hydrolysis makes the hydrolysis of resulting polymers after polyreaction
Degree is 10-30%.
26. methods according to claim 25, wherein, described hydrolysising condition includes: temperature is
70-90℃；Time is 1-4 hour.
The acrylamide copolymer that in 27. claim 9-25, method described in any one prepares.
In 28. claim 1-8 and 27, the acrylamide copolymer described in any one is as oil displacement agent
Application.
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| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, its production method, and its use |
| CN101528888A (en) * | 2006-10-23 | 2009-09-09 | 美国海博公司 | Functional polymer for enhanced oil recovery |
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| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| JP2007177154A (en) * | 2005-12-28 | 2007-07-12 | Toagosei Co Ltd | Acrylic acid copolymer, its production method, and its use |
| CN101528888A (en) * | 2006-10-23 | 2009-09-09 | 美国海博公司 | Functional polymer for enhanced oil recovery |
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