CN103788295A - Two-step preparation method of acrylamide copolymer - Google Patents
Two-step preparation method of acrylamide copolymer Download PDFInfo
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- CN103788295A CN103788295A CN201210425813.6A CN201210425813A CN103788295A CN 103788295 A CN103788295 A CN 103788295A CN 201210425813 A CN201210425813 A CN 201210425813A CN 103788295 A CN103788295 A CN 103788295A
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- Prior art keywords
- monomer
- acrylamide
- formula
- preparation
- sodium
- Prior art date
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Links
- 229920006322 acrylamide copolymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 49
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 124
- 239000000203 mixture Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 23
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- -1 2-acrylamide-2-methylpro panesulfonic acid salt Chemical class 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000693 micelle Substances 0.000 claims description 12
- 229920006029 tetra-polymer Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001409 amidines Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- KGMXPXPXPAAUMD-UHFFFAOYSA-N propane;dihydrochloride Chemical compound Cl.Cl.CCC KGMXPXPXPAAUMD-UHFFFAOYSA-N 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 claims description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 abstract description 28
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 19
- 230000007062 hydrolysis Effects 0.000 abstract description 17
- 238000006073 displacement reaction Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000009818 secondary granulation Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 229920002401 polyacrylamide Polymers 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 229960001748 allylthiourea Drugs 0.000 abstract 1
- 239000011449 brick Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000009817 primary granulation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 11
- 229940047670 sodium acrylate Drugs 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000007601 warm air drying Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008126 allyl sulfides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 239000010865 sewage Substances 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a two-step preparation method of an acrylamide copolymer. The two-step preparation method is characterized in that by initiation of a novel low-temperature oxidation-reduction composite initiation system, acrylamide (AM), 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and allylthiourea undergo an aqueous solution adiabatic polymerization reaction, rubber bricks are subjected to primary granulation, the rubber granules are subjected to hydrolysis, the hydrolysis product is subjected to secondary granulation, and the granules are dried, crushed and screened so that the acrylamide copolymer is obtained. The acrylamide copolymer has good high-temperature oxidation resistance. The invention discloses the oxidation-resistant polyacrylamide oil-displacement agent and the preparation method thereof.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer preparation method.
Background technology
The development of petroleum engineering and technology, requirement farthest improves the recovery ratio in existing oil field.As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (HPAM), in conventional oil reservoir tertiary oil recovery (EOB) technology, has obtained large-scale promotion and application, for vital role has been brought into play in oilfield stable production and volume increase.Along with the minimizing of conventional reservoir reserve, high temperature and high salt oil deposit makes the application of HPAM be faced with many difficult problems, the compound action that in high temperature, high salt and solution while being mainly reflected in exploitation high temperature and high salt oil deposit, dissolved oxygen conditions produces significantly reduces HPAM soltion viscosity, causes HPAM oil displacement efficiency not remarkable.Research shows, when temperature is higher than 70 ℃, the reaction that the amide group hydrolysis of HPAM generates carboxyl significantly aggravates, when degree of hydrolysis reaches more than 40%, carboxyl be just easy to solution in Ca
2+, Mg
2+ion generates precipitation, makes soltion viscosity loss.In addition, at high temperature, the dissolved oxygen existing in airborne oxygen and solution can cause that main polymer chain fracture significantly declines soltion viscosity.
Really increase compared with HPAM in heat-resistant salt-resistant performance with acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization copolymer.As be entitled as " low temperature of AMPS/AM multipolymer synthetic and performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) reported and adopted oxidation-reduction trigger system to carry out the low temperature copolymerization of AMPS/AM, the viscosity-average molecular weight that obtains multipolymer is 10
6～10
7.Be entitled as " partial hydrolysis legal system is for high molecular weight water-soluble (acrylamide/vinylformic acid/2-acrylamide-2-methylpro panesulfonic acid) terpolymer " (Zhu Linyong, polymer journal, 2000,3,315), adopting low temperature hydrolysis reaction, is 10 by AM and AMPS multipolymer synthetic molecular weight
6terpolymer.No matter above-mentioned two kinds of methods are the generally (< 10 on the low side of polymericular weight that copolymerization method or copolymerization co-hydrolysis obtain
7), be difficult to be applicable to high temperature and high salt oil deposit.In addition, how guaranteeing that multipolymer has stronger heat resistanceheat resistant oxygen degradation property in oil recovery process, is the key that can this base polymer be applied to three class oil reservoir tertiary oil recoveries.
Form mechanism from thermal-oxidative degradation, sulfide in metal ion and the on-the-spot sewage of the introducings such as the residual initiators of polymerization process, the dissolved oxygen of process for preparation, preparation container and line of pipes all may produce living radical makes HPAM main polymer chain that chain fracture occur, and makes molecular weight and molecular weight.And raise with temperature, this free radical cracking effect aggravates all the more, make polymer solution viscosity loss in a large number at short notice, thus the use value of losing.The negatively influencing bringing to soltion viscosity for weakening this free radical cracking effect adds various stablizers conventionally in synthetic or process for preparation.Wherein, in order to improve the antioxygen property of HPAM, ordinary method is in the course of processing or in use procedure, to add small molecules, as Thiourea antioxidant stabilizer etc.Owing to there is very big difference in small molecules stablizer and macromolecule oil-displacing agent physicochemical property, in blowhole flow event, there is chromatographic fractionation effect, cause in actual use stablizer to add that consumption is large and service efficiency is low.JP74-27660 discloses the metal-salt small molecules stablizer that adds dithio amido class before HPAM micelle is dry, can prevent that product is crosslinked and degrade.In this invention, owing to being physical blending between the metal-salt small molecules stablizer of dithio amido class and HPAM, there will be in actual use between small molecules stablizer and macromolecule oil-displacing agent and can produce chromatographic fractionation effect, cause that stabilizing agent dosage is large and service efficiency is low.
Therefore, how further to improve the antioxygen property of oil-displacing agent under hot conditions and be still a problem of needing improvement badly.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, acrylamide copolymer that under a kind of ultra-high molecular weight, high temperature, antioxygen property is good and its preparation method and application is provided.
In displacement of reservoir oil polymer arts, antioxidant group is introduced on macromolecular chain by copolymerization mode, improve the antioxygen property of displacement of reservoir oil polymkeric substance, there is not yet relevant report, more do not report the multipolymer that applies it to acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization.The inventor finds through large quantity research, thiosinamine, acrylamide and 2-acrylamide-2-methylpro panesulfonic acid salt are carried out to copolymerization, the group with antioxygen function is connected on main polymer chain, in keeping the high molecular of existing acrylamide-2-acrylamide-2-methylpro panesulfonic acid multipolymer, improve the service efficiency of antioxidant group, significantly improved the antioxygen property of multipolymer under hot conditions.In actual use, owing to passing through covalent bonding between antioxidant group and main polymer chain, there will not be the chromatographic fractionation effect between small molecules stablizer and the macromolecule oil-displacing agent that adopts physical blending.Based on above discovery, complete the present invention.
First aspect present invention provides a kind of acrylamide copolymer, the structural unit E that this acrylamide copolymer contains structure shown in formula (11), the structural unit F of structure shown in formula (12), the structural unit H of structure shown in the structural unit G of structure shown in formula (13) and formula (14), in each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium.
Second aspect present invention provides a kind of preparation method of acrylamide copolymer,
Comprise the following steps:
The first step, prepare the first monomer mixture solution, with inorganic alkaline compound adjusting pH to 5-10, obtain the second monomer mixture solution, under solution polymerization condition, under initiator exists, make the second monomer mixture carry out polyreaction, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid;
Described the first monomer mixture contains monomer A, monomers B and monomer C, described monomer A is for having the monomer of structure shown in formula (1), described monomers B is for having the monomer of structure shown in formula (2), described monomer C is for having the monomer of structure shown in formula (3), described the second monomer mixture contains monomer A, monomer D and monomer C, described monomer A is for having the monomer of structure shown in formula (1), described monomer D is for having the monomer of structure shown in formula (4), described monomer C is for having the monomer of structure shown in formula (3), in each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium;
Second step, acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid that the first step is obtained is a granulated into after micelle, contact with alkali metal hydroxide, then crush and screen and obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylate/thiosinamine tetrapolymer through granulating and drying.
The viscosity-average molecular weight of the described acrylamide tetrapolymer obtaining is more than 2,000 ten thousand, in each structural formula, and R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium.
In described the first monomer mixture, the molar content of described monomer A is 1～99 part, and the molar content of described monomers B is 0.1～98 part, and the molar content of described monomer C is 0.001～5 part; Preferably, the molar content of described monomer A is 60～97.5 parts, and the molar content of described monomers B is 1～39 part, and the molar content of described monomer C is 0.01～1.5 part; The condition of described solution polymerization makes the viscosity-average molecular weight 3,000 ten thousand～3,500 ten thousand of resulting polymers after polyreaction, is preferably 3,200 ten thousand～3,350 ten thousand.
Third aspect present invention provides the application of the above-mentioned acrylamide copolymer of the present invention as oil-displacing agent.
Acrylamide copolymer of the present invention has high viscosity-average molecular weight, and the viscosity-average molecular weight that makes acrylamide copolymer in embodiment 1 all can reach more than 3,000 ten thousand; The apparent viscosity of 95 ℃ is 20.1mPas, the apparent viscosity retention rate (O of 3 months
2content is 8mg/L) be 88.3%, and in the situation that other conditions are identical, the acrylamide copolymer viscosity-average molecular weight that does not have the comparative example 1 of thiosinamine to prepare in monomer mixture is 2,850 ten thousand, and the apparent viscosity of 95 ℃ is 16.2mPas, 3 months apparent viscosity retention ratio (O
2content is 8mg/L) be only 16.7%.Illustrate that acrylamide copolymer of the present invention has good antioxygen property and high apparent viscosity concurrently, can realize good oil displacement efficiency.
Embodiment
The invention provides a kind of acrylamide copolymer, the structural unit E that this acrylamide copolymer contains structure shown in formula (1), the structural unit F of structure shown in formula (2), the structural unit H of structure shown in the structural unit G of structure shown in formula (3) and formula (4), the viscosity-average molecular weight of described acrylamide copolymer is more than 2,000 ten thousand;
The viscosity-average molecular weight of described acrylamide copolymer is more than 2,000 ten thousand;
In each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium.
In the present invention, described C
1～C
4the example of alkylidene group can include but not limited to: methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tertiary butyl, be preferably methylene radical.Described alkylidene group refers to that alkane loses two residues after hydrogen atom, and described two hydrogen atoms can be two hydrogen atoms on same carbon atom, two hydrogen atoms on also can different carbon atoms, it can be straight chain, also can be side chain, for example, described ethylidene can be-CH
2cH
2-or-CH (CH
3)-.
In the present invention, described alkyl can be straight chain, can be also side chain.Described C
1～C
4the example of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl.
According to the present invention, wherein, the present invention does not have special requirement to the content of E, F, G, H structural unit, preferably, mole number ratio in described acrylamide copolymer in structural unit is, described structural unit E is 1～99 part, and described structural unit F is 0.1～98 part, and described structural unit G is 0.001～5 part; Described structural unit H is 0.1～40 part; Preferably, described structural unit E is 50～92.5 parts, and described structural unit F is 1～39 part, and described structural unit G is 0.01～1.5 part; Described structural unit H is 5～30 parts; The viscosity-average molecular weight of described acrylamide copolymer is 3,000 ten thousand～3,500 ten thousand, is preferably 3,200 ten thousand～3,350 ten thousand.
The present inventor finds under study for action, can obtain good oil displacement efficiency good specific structural unit E, structural unit F, structural unit G and structural unit H when the quadripolymer being made up of is used for oil-displacing agent.Work as R
1for methylene radical; R
2and R
3identical, be methyl; M
1, M
2identical, be sodium, that is, structural unit B is that 2-acrylamide-2-methylpro panesulfonic acid sodium polymerization obtains, and structural unit D is sodium acrylate polymerization while obtaining, and oil displacement efficiency is good.
The present invention also provides a kind of preparation method of acrylamide copolymer,
Comprise the following steps:
The first step, prepare the first monomer mixture solution, with inorganic alkaline compound adjusting pH to 5-10, obtain the second monomer mixture solution, under solution polymerization condition, under initiator exists, make the second monomer mixture carry out polyreaction, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid;
Described the first monomer mixture contains monomer A, monomers B and monomer C, described monomer A is for having the monomer of structure shown in formula (1), described monomers B is for having the monomer of structure shown in formula (2), described monomer C is for having the monomer of structure shown in formula (3), described the second monomer mixture contains monomer A, monomer D and monomer C, described monomer A is for having the monomer of structure shown in formula (1), described monomer D is for having the monomer of structure shown in formula (4), described monomer C is for having the monomer of structure shown in formula (3), in each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium;
Second step, acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid that the first step is obtained is a granulated into after micelle, contact with alkali metal hydroxide, then crush and screen and obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylate/thiosinamine tetrapolymer through granulating and drying.
The viscosity-average molecular weight of the described acrylamide tetrapolymer obtaining is more than 2,000 ten thousand, in each structural formula, and R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium.Preferably, R
1for methylene radical; R
2and R
3be methyl; M
1for sodium., monomers B is 2-acrylamide-2-methylpro panesulfonic acid sodium.
According to the present invention, although the present invention does not have particular requirement to the consumption of described monomer A, B, C and D, preferably, in described the first monomer mixture, the molar content of described monomer A is 1～99 part, the molar content of described monomers B is 0.1～98 part, and the molar content of described monomer C is 0.001～5 part; Preferably, the molar content of described monomer A is 60～97.5 parts, and the molar content of described monomers B is 1～39 part, and the molar content of described monomer C is 0.01～1.5 part; The condition of described solution polymerization makes the viscosity-average molecular weight 3,000 ten thousand～3,500 ten thousand of resulting polymers after polyreaction, is preferably 3,200 ten thousand～3,350 ten thousand.
According to the present invention, the condition of described polyreaction can be the condition of this area routine.For example, described polyreaction is carried out under rare gas element exists, and described polymeric reaction condition can comprise: temperature is-10 ℃ to 20 ℃, and the time is 1～20 hour, and pH value is 4～12; Under preferable case, temperature is-7 ℃ to 15 ℃, and the time is 2～10 hours, and pH value is 6～9.
In the present invention, the B in described monomer mixture can be reacted and obtain with inorganic alkaline compound by sulfonic acid corresponding to monomers B.Described alkali inorganic alkaline compound can be selected from least one in sodium hydroxide, potassium hydroxide, sodium carbonate, is preferably sodium hydroxide.
According to the present invention, described initiator can be the various initiators in this area.For example, be selected from azo-initiator and/or redox body class initiator, be preferably azo-initiator and redox body class initiator.Take described 100 weight part the first monomer mixtures as benchmark, the consumption of described azo initiator is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part.
In the present invention, preferably, described azo-initiator is selected from Diisopropyl azodicarboxylate, 4,4 '-azo two (4-cyanopentanoic acid), 2, at least one in 2 '-azo diisobutyl amidine hydrochloride and azo diimidazole quinoline base propane dihydrochloride, more preferably 4,4 '-azo two (4-cyanopentanoic acid), 2, at least one in 2 '-azo diisobutyl amidine hydrochloride and azo diimidazole quinoline base propane dihydrochloride.
Described redox class initiator comprises Oxidizing and Reducing Agents, take described 100 weight part the first monomer mixtures as benchmark, and consumption 0.0001～0.1 weight part of described oxygenant, more preferably 0.001～0.05 weight part; Under preferable case, described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide, more preferably at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate; Described reductive agent can be inorganic reducing agent (helping reductive agent) and/or organic reducing agent (chainextender), be preferably the mixing reductive agent of inorganic reducing agent (helping reductive agent) and organic reducing agent (chainextender), take described 100 weight part the first monomer mixtures as benchmark, wherein, the consumption of described inorganic reducing agent is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part; Described inorganic reducing agent can be selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate, vat powder, xitix and urea, more preferably sodium bisulfite and/or S-WAT;
Take described 100 weight part the first monomer mixtures as benchmark, the consumption of described organic reducing agent is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part; The specific examples of described organic reducing agent can be, but not limited to as N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, N, N '-lupetazin, tetramethyl-urea element, N, N-dimethyl urea element, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N '-dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propylene diamine, 3-methylamino-propylamine and N, at least one in N-dimethyl-ethylenediamine; More preferably N, N '-dimethyl-1,3-propylene diamine and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine, more preferably N, N, N ', N '-Tetramethyl Ethylene Diamine; Described inorganic alkaline compound is sodium hydroxide or potassium hydroxide.
In a kind of preferred implementation of the present invention, described initiator is 2,2 '-azo diisobutyl amidine hydrochloride, Sodium Persulfate, sodium bisulfite and N, N, N ', N '-Tetramethyl Ethylene Diamine.
According to the present invention, when described polyreaction starts, the ratio of the gross weight of the weight of described the first monomer mixture and water and described the first monomer mixture is preferably 0.15～0.4:1, more preferably 0.2～0.3:1.
According to the present invention, the present invention also can comprise the acrylamide copolymer preparing is hydrolyzed, granulation, is dried, crushes and screens and pack.Wherein said granulation, dry, pulverizing, screening and packing are the ordinary skill in the art.
According to the present invention, described hydrolysising condition comprises: hydrolysis temperature is 50～110 ℃, and hydrolysis time is 0.5～6h, and more preferably hydrolysis temperature is 55～105 ℃, and hydrolysis time is 1～5.5h; Further selective hydrolysis temperature is 70～90 ℃; Hydrolysis time is 1～4 hour.
According to the present invention, the present invention without particular requirement, under preferable case, can adopt hot air seasoning to dry method and condition, and described warm air drying temperature is 40～110 ℃, is preferably 70～90 ℃; The time of warm air drying is 0.2～4 hour, is preferably 0.5～2 hour.
One of the present invention preferred embodiment in, the preparation method of described acrylamide copolymer comprises the steps:
(1) acrylamide, 2-acrylamide-2-methylpro panesulfonic acid and thiosinamine are mixed with deionized water, be made into acrylamide, 2-acrylamide-2-methylpro panesulfonic acid and thiosinamine total concn and be the solution of 20～30 % by weight (, the first monomer mixture solution), control solution temperature-10～20 ℃, with inorganic alkaline compound adjusting, pH to 4～12(is preferably 6～9), obtain acrylamide, 2-acrylamide-2-methylpro panesulfonic acid salt and thiosinamine monomer solution (, the second monomer mixture solution);
(2) acrylamide, 2-acrylamide-2-methylpro panesulfonic acid salt and the thiosinamine monomer solution that step (1) are obtained pump in polymeric kettle, add water-soluble azo initiator and amine reduction auxiliary agent, logical high pure nitrogen deoxygenation (time of passing into is 0.5～2 hour), add sulphite and persulphate, continue logical nitrogen until in polymeric kettle thermopair start to heat up, be-10 ℃ to 20 ℃ (being preferably-7 ℃ to 15 ℃) 1～20 hour reaction times (being preferably 2～10 hours) in temperature, obtain acrylamide copolymer;
(3) the acrylamide copolymer granulating from colloid by tablets press, step (2) being obtained becomes the little micelle of 4～6 millimeters; under hydrolysising condition; polymerization is obtained to acrylamide copolymer and contact with inorganic alkaline compound, hydrolysis temperature is 50～110 ℃, and hydrolysis time is 0.5～6 hour.
(4) copolymer colloid step (3) being obtained is dried 0.2～4 hour under 40～110 ℃ of hot blast conditions, by crushing and screening and be packaged to be powdery acrylamide copolymer.
The present invention also provides the acrylamide copolymer making according to aforesaid method.
In addition, the present invention also provides the application of described acrylamide copolymer in oil-displacing agent.
Below, by following examples, the present invention will be described in more detail
In following examples, the performance test of product adopts following methods to carry out:
Measure solid content according to the method stipulating in GB12005.2-89;
Measure dissolution time according to the method stipulating in GB12005.8-89;
Measure intrinsic viscosity according to the method stipulating in GB12005.1-89;
Adopt formula M=([η]/K) according to the method stipulating in GB12005.10-92
1/ αcalculate the viscosity-average molecular weight of polymkeric substance, wherein, K=4.75 × 10
-3, α=0.80, [η] is intrinsic viscosity;
Measure degree of hydrolysis according to the method stipulating in GB12005.6-89;
The apparent viscosity of aqueous solutions of polymers is at the temperature of 95 ℃, to use Brookfield viscometer determining;
Measure filtration ratio, insolubles content and the acrylamide residual monomer content of the aqueous solution of polymkeric substance according to the company standard Q/SH1020 1572-2006 of Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation;
Polymers soln antioxygen thermal ageing test method comprises: the solution that with the salt solution of salinity 32000mg/L, polymkeric substance is made into 1500mg/L, oxygen level in solution is removed to required value, by the polymers soln obtaining at 95 ℃ of temperature, after aging 3 months, apparent viscosity with Brookfield viscometer determining polymers soln at 95 ℃, calculate apparent viscosity retention ratio with following formula:
The aging post polymerization thing of apparent viscosity retention rate %=solution apparent viscosity/aging prepolymer solution apparent viscosity × 100%;
In following examples, acrylamide is purchased from Bao Mo biochemical industry limited-liability company, 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., 2,2 '-azo (2-amidine propane) dihydrochloride is purchased the company from Aldrich, and thiosinamine is purchased the company limited from Aldrich.
Embodiment 1
The present embodiment is used for explanation according to acrylamide copolymer of the present invention and preparation method thereof.
In batching kettle, add 869.56 kilograms of (12.233kmol) acrylamides, 1647.86 kilograms of (7.951kmol) 2-acrylamide-2-methylpro panesulfonic acids and 23.68 kilograms of (2.038mol) thiosinamines, 5929 kilograms of deionized waters, under whipped state, with chilled brine control solution temperature-7 ℃, add sodium hydroxide to regulate pH to 6.Monomer solution is pumped in polymeric kettle, add water-soluble azo initiator 2,12.706 grams of 2 '-azo (2-amidine propane) dihydrochlorides and reduction auxiliary agent N, N, N ', 12.706 grams of N '-Tetramethyl Ethylene Diamines, logical high pure nitrogen deoxygenation 0.5h, add 12.706 grams of 12.706 grams of sodium bisulfites and ammonium persulphates, continue logical nitrogen until in polymeric kettle thermopair start to heat up, reaction times 10h, obtains acrylamide copolymer (, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/thiosinamine terpolymer).Open Polycondensation Reactor and Esterification Reactor ball valve, by the acrylamide copolymer extrusion obtaining, become the little micelle of 4～6 millimeters with 0.3MPa pressurized air by granulator granulation.The little micelle obtaining is mediated and contacted with 81.55 kg of hydrogen sodium oxide grain alkali, under temperature 70 C, be hydrolyzed 1h, after secondary granulation, dry 2h under 70 ℃ of hot blast conditions, by crushing and screening and be packaged to be 20～80 object acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/thiosinamine tetrapolymers.Product performance are as follows: solid content >=89%, and dissolution time is less than 2h, at salinity 32000mg/L, 95 ℃ of temperature, concentration 1500mg/L, apparent viscosity 20.1mPas, filtration ratio 1.1, insolubles content 0.05%, acrylamide residual monomer 0.01%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, the apparent viscosity retention ratio of thermal ageing viscosity is listed in table 2.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare acrylamide copolymer, different is, do not add thiosinamine, obtain acrylamide copolymer (, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate terpolymer) product performance as follows: solid content >=89%, dissolution time is less than 2h, be the apparent viscosity 16.0mPas in the salt solution of 95 ℃ and when concentration is 1500mg/L in salinity 32000mg/L, temperature, filtration ratio 1.0, insolubles content 0.15%, acrylamide residual monomer 0.06%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, apparent viscosity retention ratio is listed in table 2.
Embodiment 2
The present embodiment is used for explanation according to acrylamide copolymer of the present invention and preparation method thereof.
In batching kettle, add 1530 kilograms of acrylamides, 45.752 kilograms of 2-acrylamide-2-methylpro panesulfonic acids and 6457 kilograms of deionized waters of 38.477 kilograms of allyl sulfides, under whipped state, with 15 ℃ of chilled brine control solution temperatures, add sodium hydroxide to regulate pH to 9.Monomer solution is pumped in polymeric kettle, add water-soluble azo initiator 2,807.11 grams of 2 '-azo (2-amidine propane) dihydrochlorides and reduction auxiliary agent N, N, N ', 807.11 grams of N '-Tetramethyl Ethylene Diamines, logical high pure nitrogen deoxygenation 0.5h, adds 807.11 grams of 807.11 grams of sodium bisulfites and ammonium persulphates, continue logical nitrogen until in polymeric kettle thermopair start to heat up, reaction times 2h, obtains acrylamide copolymer.Open Polycondensation Reactor and Esterification Reactor ball valve, by the acrylamide copolymer extrusion obtaining, become the little micelle of 4～6 millimeters with 0.3MPa pressurized air by granulator granulation.The little micelle obtaining is mediated and contacted with 44.15 kg of hydrogen sodium oxide grain alkali, under temperature 70 C, be hydrolyzed 1h, after secondary granulation, dry 2h under 70 ℃ of hot blast conditions, by crushing and screening and be packaged to be 20～80 object acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/thiosinamine tetrapolymers.Product performance are as follows: solid content >=89%, and dissolution time is less than 2h, at salinity 32000mg/L, 95 ℃ of temperature, concentration 1500mg/L, apparent viscosity 21.0mPas, filtration ratio 1.1, insolubles content 0.05%, acrylamide residual monomer 0.02%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, the apparent viscosity retention ratio of thermal ageing viscosity is listed in table 2.
Embodiment 3
The present embodiment is used for explanation according to acrylamide copolymer of the present invention and preparation method thereof.
In batching kettle, add 1200 kilograms of acrylamides, 874.21 kilograms of 2-acrylamide-2-methylpro panesulfonic acids and 0.245 kilogram of thiosinamine, 5186.13 kilogram deionized water, under whipped state, with 0 ℃ of chilled brine control solution temperature, add sodium hydroxide to regulate pH to 7.Monomer solution is pumped in polymeric kettle, add water-soluble azo initiator 2,188.9 grams of 2 '-azo (2-amidine propane) dihydrochlorides and reduction auxiliary agent N, N, N ', 188.9 grams of N '-Tetramethyl Ethylene Diamines, logical high pure nitrogen deoxygenation 0.5h, adds 188.9 grams of 188.9 grams of sodium bisulfites and ammonium persulphates, continue logical nitrogen until in polymeric kettle thermopair start to heat up, reaction times 4h, obtains acrylamide copolymer.Open Polycondensation Reactor and Esterification Reactor ball valve, by the acrylamide copolymer extrusion obtaining, become the little micelle of 4～6 millimeters with 0.6MPa pressurized air by granulator granulation.The little micelle obtaining is mediated and contacted with 253.24 kg of hydrogen sodium oxide grain alkali, at 85 ℃ of temperature, be hydrolyzed 1.5h, after secondary granulation, dry 2h under 70 ℃ of hot blast conditions, by crushing and screening and be packaged to be 20～80 object acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/thiosinamine tetrapolymers.Product performance are as follows: solid content >=89%, and dissolution time is less than 2h, at salinity 32000mg/L, 95 ℃ of temperature, concentration 1500mg/L, apparent viscosity 21.8mPas, filtration ratio 1.1, insolubles content 0.02%, acrylamide residual monomer 0.03%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, apparent viscosity retention ratio is listed in table 2.
Embodiment 4
The present embodiment is used for explanation according to acrylamide copolymer of the present invention and preparation method thereof.
Adopt the method preparation identical with embodiment 1, different is, initiator adopts 2,12.706 grams of 2 '-azo (2-amidine propane) dihydrochlorides, 12.706 grams of 12.706 grams of sodium bisulfites and ammonium persulphates, wherein, the product performance of the acrylamide copolymer particle obtaining are as follows: solid content >=89%, dissolution time is less than 2h, be the apparent viscosity 15.8mPas in the salt solution of 95 ℃ and when concentration is 1500mg/L in salinity 32000mg/L, temperature, filtration ratio 1.0, insolubles content 0.06%, acrylamide residual monomer 0.06%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, apparent viscosity retention ratio is listed in table 2.
Embodiment 5
The present embodiment is used for explanation according to acrylamide copolymer of the present invention and preparation method thereof.
Adopt the method identical with embodiment 1 to prepare acrylamide copolymer, different is, without hydrolysis, do not carry out the little micelle obtaining is mediated and being contacted with 81.55 kg of hydrogen sodium oxide grain alkali in embodiment 1, under temperature 70 C, be hydrolyzed the step of 1h, obtain acrylamide copolymer (, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/thiosinamine terpolymer) product performance as follows: solid content >=89%, dissolution time is less than 2h, at salinity 32000mg/L, temperature is the apparent viscosity 15.3mPas in the salt solution of 95 ℃ and when concentration is 1500mg/L, filtration ratio 1.0, insolubles content 0.08%, acrylamide residual monomer 0.05%.Wherein the data of viscosity-average molecular weight, apparent viscosity, monomer residual volume are listed in table 1, and under different oxygen, apparent viscosity retention ratio is listed in table 2.
Table 1
Table 2
The data of associative list 1 and table 2, embodiment 1 and embodiment 4 are contrasted, due to the change of initiator type, the viscosity-average molecular weight of the product that embodiment 1 obtains is increased to 3,250 ten thousand by 2,800 ten thousand of embodiment 4,95 ℃ of apparent viscosity are increased to 20.1mPas by 16.0mPas, and acrylamide residual monomer content is also reduced to 0.01 % by weight by 0.06 % by weight.
By embodiment 1 compared with embodiment 5, owing to having carried out rear hydrolysis operation in embodiment 1, in copolymer structure unit, introduce sodium acrylate structural unit, and in embodiment 5, do not carry out rear hydrolysis operation, in copolymer structure unit, there is no sodium acrylate structural unit, the viscosity-average molecular weight of the product that embodiment 1 obtains is increased to 3,250 ten thousand by 2,750 ten thousand of embodiment 5,95 ℃ of apparent viscosity are increased to 20.1mPas by 15.3mPas, and acrylamide residual monomer content is also reduced to 0.01 % by weight by 0.18 % by weight.
By embodiment 1 compared with comparative example 1, compared with employing the present invention prepares the acrylamide tetrapolymer preparing acrylamide copolymer with traditional method, the viscosity-average molecular weight of the product obtaining is increased to 3,250 ten thousand by 2,850 ten thousand, 95 ℃ of apparent viscosity are increased to 19.2mPas by 16.0mPas, antioxidant property significantly improves, for example, along with the increase of oxygen level, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate terpolymer apparent viscosity retention rate in comparative example 1 significantly reduces, O
2when content is 4mg/L, its apparent viscosity retention rate is 40.5%, and acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/thiosinamine tetrapolymer apparent viscosity retention rate in embodiment 1 is 90.2%, works as O
2when content reaches capacity oxygen level 8mg/L, acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate terpolymer apparent viscosity retention rate is 16.7%, and acrylamide/2-acrylamide-2-methylpro panesulfonic acid sodium/sodium acrylate/thiosinamine tetrapolymer apparent viscosity retention rate is 88.3%.Above result shows, acrylamide copolymer provided by the invention has high apparent viscosity and oxidation-resistance concurrently.
Claims (11)
1. a preparation method for acrylamide copolymer, comprises the following steps:
The first step, prepare the first monomer mixture solution, with inorganic alkaline compound adjusting pH to 5～10, obtain the second monomer mixture solution, under solution polymerization condition, under initiator exists, make the second monomer mixture carry out polyreaction, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid;
Described the first monomer mixture contains monomer A, monomers B and monomer C, and described monomer A is for having the monomer of structure shown in formula (1), and described monomers B is for having the monomer of structure shown in formula (2), and described monomer C is for having the monomer of structure shown in formula (3);
Described the second monomer mixture contains described monomer A, monomer D and described monomer C, and described monomer D is for having the monomer of structure shown in formula (4);
In described each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium;
Second step, acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/thiosinamine copolymer colloid that the first step is obtained is a granulated into after micelle, contact with alkali metal hydroxide, crush and screen through granulating and drying again, obtain acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylate/thiosinamine tetrapolymer.
2. preparation method according to claim 1, is characterized in that:
The structural unit H of structure shown in the structural unit G of structure shown in the structural unit F of structure, formula (13) and formula (14) shown in structural unit E that the acrylamide/2-acrylamide-2-methylpro panesulfonic acid salt/acrylate/thiosinamine tetrapolymer obtaining contains structure shown in formula (11), formula (12), the viscosity-average molecular weight of described acrylamide copolymer is more than 2,000 ten thousand;
In described each structural formula, R
1for C
1～C
4alkylidene group; R
2for C
1～C
4alkyl, R
3for C
1～C
4alkyl, R
2with R
3identical or different; M
1for sodium or potassium.
3. preparation method according to claim 2, is characterized in that:
In described each structural formula, R
1for methylene radical; R
2and R
3be methyl; M
1for sodium.
4. preparation method according to claim 1 and 2, is characterized in that:
In described the first monomer mixture, the molar content of described monomer A is 1～99 part, and the molar content of described monomers B is 0.1～98 part, and the molar content of described monomer C is 0.001～5 part; Preferably, the molar content of described monomer A is 60～97.5 parts, and the molar content of described monomers B is 1～39 part, and the molar content of described monomer C is 0.01～1.5 part; The condition of described solution polymerization makes the viscosity-average molecular weight 3,000 ten thousand～3,500 ten thousand of resulting polymers after polyreaction, is preferably 3,200 ten thousand～3,350 ten thousand.
5. preparation method according to claim 1 and 2, is characterized in that:
Described initiator is azo-initiator and/or redox class initiator, and take described 100 weight part the first monomer mixtures as benchmark, the consumption of described azo-initiator is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part; The consumption of the oxygenant of described redox class initiator is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part; The consumption of the inorganic reducing agent of described redox class is 0.0001～0.1 weight part, is preferably 0.001～0.05 weight part; The consumption of the organic reducing agent of described redox class is 0.0001～0.1 weight part, is preferably 0.0001～0.05 weight part.
6. preparation method according to claim 5, is characterized in that:
Described azo-initiator is selected from least one in following: 4, and 4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo diisobutyl amidine hydrochloride and azo diimidazole quinoline base propane dihydrochloride;
Described oxygenant is selected from least one in following: ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide;
Described inorganic reducing agent is selected from least one in following: sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate, vat powder, xitix and urea;
Described organic reducing agent is selected from least one in following: N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-lupetazin, N, N '-lupetazin, tetramethyl-urea element, N, N-dimethyl urea element, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N '-dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propylene diamine, 3-methylamino-propylamine and N, in N-dimethyl-ethylenediamine;
Described inorganic alkaline compound is sodium hydroxide or potassium hydroxide.
7. preparation method according to claim 1 and 2, is characterized in that:
Described the first step polyreaction is carried out under rare gas element exists, and described solution polymerization condition comprises: temperature is-10 ℃ to 20 ℃, preferably-7 ℃ to 15 ℃; Time is 1～20 hour, preferably 2～10 hours; PH value is 4～12, preferably 6～9.
8. preparation method according to claim 6, is characterized in that:
Described polyreaction is carried out in water, and the ratio of the gross weight of the weight of described the first monomer mixture and water and the first monomer mixture is 0.15～0.4:1; Be preferably 0.2～0.3:1.
9. preparation method according to claim 1 and 2, is characterized in that:
In second step, the temperature contacting with alkali metal hydroxide is 50～110 ℃, is preferably 70～90 ℃; The time of contact is 0.5～6 hour, is preferably 1～4 hour; Described alkali metal hydroxide is selected from least one in following: sodium hydroxide and potassium hydroxide.
10. the acrylamide copolymer that in claim 1～9, the preparation method described in any one makes.
11. acrylamide copolymers claimed in claim 10 are as the application of oil-displacing agent.
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| CN106397668A (en) * | 2016-08-31 | 2017-02-15 | 四川光亚聚合物化工有限公司 | Hydrophobic association polymer and preparation method thereof |
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| CN116063620A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide copolymer containing multi-branched long-chain structure, and preparation method and application thereof |
| CN117089019A (en) * | 2023-10-18 | 2023-11-21 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
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| CN104404824A (en) * | 2014-11-07 | 2015-03-11 | 安徽天润化学工业股份有限公司 | Star-shaped polymer papermaking dispersant and preparation method thereof |
| CN106478873A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
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| CN116063620A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide copolymer containing multi-branched long-chain structure, and preparation method and application thereof |
| CN116063620B (en) * | 2021-11-01 | 2024-03-26 | 中国石油化工股份有限公司 | Acrylamide copolymer containing multi-branched long-chain structure, and preparation method and application thereof |
| CN117089019A (en) * | 2023-10-18 | 2023-11-21 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
| CN117089019B (en) * | 2023-10-18 | 2024-01-02 | 山东诺尔生物科技有限公司 | Modified aqueous solution polyacrylamide flocculant and preparation method thereof |
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