CN104250348B - A kind of acrylamide based copolymer and its preparation method and application - Google Patents
A kind of acrylamide based copolymer and its preparation method and application Download PDFInfo
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- CN104250348B CN104250348B CN201310269900.1A CN201310269900A CN104250348B CN 104250348 B CN104250348 B CN 104250348B CN 201310269900 A CN201310269900 A CN 201310269900A CN 104250348 B CN104250348 B CN 104250348B
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 81
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000010276 construction Methods 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims description 223
- 239000000203 mixture Substances 0.000 claims description 59
- 239000012071 phase Substances 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000003638 reducing agent Substances 0.000 claims description 34
- -1 2,2 '-azo diisobutyl Chemical group 0.000 claims description 33
- 239000003999 initiator Substances 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000839 emulsion Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 125000001118 alkylidene group Chemical group 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 16
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000002738 chelating agent Substances 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 150000001409 amidines Chemical class 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000001590 oxidative Effects 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 210000000481 Breast Anatomy 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
- HLBBKKJFGFRGMU-UHFFFAOYSA-M Sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M Rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L Sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- ZGKNDXOLMOFEJH-UHFFFAOYSA-M Sodium hypophosphite Chemical compound [Na+].[O-]P=O ZGKNDXOLMOFEJH-UHFFFAOYSA-M 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims 1
- 229960003330 Pentetic Acid Drugs 0.000 claims 1
- LLJZKKVYXXDWTB-UHFFFAOYSA-N acetic acid;sodium Chemical compound [Na].[Na].CC(O)=O LLJZKKVYXXDWTB-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001603 reducing Effects 0.000 abstract description 32
- 239000004927 clay Substances 0.000 abstract description 11
- 229910052570 clay Inorganic materials 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000005755 formation reaction Methods 0.000 abstract description 10
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 125000002883 imidazolyl group Chemical group 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- 239000012530 fluid Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 206010022114 Injury Diseases 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229920002907 Guar gum Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000665 guar gum Substances 0.000 description 6
- 229960002154 guar gum Drugs 0.000 description 6
- 235000010417 guar gum Nutrition 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 229940001607 sodium bisulfite Drugs 0.000 description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-Dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N DABCO Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 229940051841 POLYOXYETHYLENE ETHER Drugs 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000001476 alcoholic Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000036961 partial Effects 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 description 3
- LBCZOTMMGHGTPH-UHFFFAOYSA-N 2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCO)C=C1 LBCZOTMMGHGTPH-UHFFFAOYSA-N 0.000 description 3
- 241001272567 Hominoidea Species 0.000 description 3
- 210000001834 NPE Anatomy 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N Nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 2
- 241000040710 Chela Species 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M Tetramethylammonium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 229940057402 UNDECYL ALCOHOL Drugs 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N Undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- YWQITIOCTIOTGV-UHFFFAOYSA-N [O].C(C1=CC=CC=C1)C1=C(C=CC=C1)O Chemical compound [O].C(C1=CC=CC=C1)C1=C(C=CC=C1)O YWQITIOCTIOTGV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000903 blocking Effects 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
- 238000010411 cooking Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000004576 sand 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-Dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- GASMGDMKGYYAHY-UHFFFAOYSA-N 2-methylidenehexanamide Chemical compound CCCCC(=C)C(N)=O GASMGDMKGYYAHY-UHFFFAOYSA-N 0.000 description 1
- JCUDAMKYTWVICI-UHFFFAOYSA-N 4-benzyl-2,3-dimethylphenol Chemical compound C1=C(O)C(C)=C(C)C(CC=2C=CC=CC=2)=C1 JCUDAMKYTWVICI-UHFFFAOYSA-N 0.000 description 1
- 241001088417 Ammodytes americanus Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OGGXGZAMXPVRFZ-UHFFFAOYSA-N Cacodylic acid Chemical compound C[As](C)(O)=O OGGXGZAMXPVRFZ-UHFFFAOYSA-N 0.000 description 1
- 229960004256 Calcium Citrate Drugs 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H Calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 240000002275 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N Dodecanol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N Isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- 229920000126 Latex Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229960003975 Potassium Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K Potassium citrate Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- JNYAEWCLZODPBN-CTQIIAAMSA-N Sorbitan Chemical compound OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- ZRDXIILBYDTYOA-UHFFFAOYSA-N azane;phosphonous acid Chemical compound N.OPO ZRDXIILBYDTYOA-UHFFFAOYSA-N 0.000 description 1
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 210000004027 cells Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000593 degrading Effects 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002829 reduced Effects 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 239000012266 salt solution Substances 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002522 swelling Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- BKEOXUSOEGMVTL-UHFFFAOYSA-N trimethyl-$l^{3}-bromane Chemical compound CBr(C)C BKEOXUSOEGMVTL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000011791 tripotassium citrate Substances 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- 239000011778 trisodium citrate Substances 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
Abstract
The invention discloses a kind of acrylamide based copolymer and its preparation method and application.Described acrylamide based copolymer contains construction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described construction unit C is the construction unit shown in formula (3) and/or the construction unit shown in formula (4), and described construction unit D is the construction unit shown in formula (5)；The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000 1,500 ten thousand.The acrylamide based copolymer drag reducing efficiency that the present invention provides is high, salt tolerance high shear performance high, anti-is good, good water solubility and clay stabilizer have good compatibility and low to formation damage.
Description
Technical field
The present invention relates to a kind of acrylamide based copolymer, two kinds of preparation methods of acrylamide based copolymer and described
Acrylamide based copolymer is as the application of drag reducer.
Background technology
Exploitation as Typical Representative shale gas (oily) resource of unconventional petroleum resources utilization has become as the whole world
One revolution in unconventional petroleum resources field, the development and utilization of current shale gas has become countries in the world and has paid close attention to emphatically and send out
The focus technology of exhibition.Owing to the ultimate attainment close oil-gas reservoirs such as shale gas reservoir have permeability extremely low (generally less than 0.5mD), frac pressure
High, easily cause the feature of formation damage." drag reduction water (slippery water) pressure break " technique must be used to exploit.
" drag reduction water (slippery water) pressure break " is the one of fracturing.(modifyed guar gum cross-links with the most conventional pressure break system
System) to compare, drag reduction water (slippery water) pressure break does not relies on high viscosity colloid and takes sand, but takes sand with high infusion discharge capacity, real
Now reservoir fracturing is reticulated the final purpose in crack.Compared with conventional pressure break system, drag reduction water (slippery water) pressure break is at cost
On have greater advantage while less to the injury on stratum.
Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, and in practice of construction, the addition of water-based drag reducer overcomes work
Make liquid frictional resistance in pipeline, it is ensured that the raising of infusion discharge capacity, make pressure act on to greatest extent press off stratum and
Extend formation fracture, currently available make water-based drag reducer mainly have guanidine glue and derivative, cellulose derivative, acrylamide
Base polymer.
At present, guanidine glue, drag reducer during cellulose and its derivates splits as drag reduction hydraulic pressure is used to improve to a certain extent
Infusion discharge capacity, the frictional resistance (US5697444, US5271466) reduced in pipeline, but still drag reduction hydraulic pressure cannot be met split
Requirement, have the disadvantage in that (1) resistance-reducing performance is limited mainly due to above-mentioned boiomacromolecule；(2) due to guanidine glue, cellulose
And derivative has a small amount of insoluble matter and easily damages stratum；(3) dissolution time is longer.
In drag reduction water pressing crack construction, use acrylamide copolymer (partial hydrolysis acrylamide or anionic more
Acrylamide copolymer) split as drag reduction hydraulic pressure in friction reducer, greatly enhance infusion discharge capacity, reduce in pipeline
Frictional resistance, but the drag reducer split as shale gas reservoir drag reduction hydraulic pressure uses, and there is following major defect: (1) is in order to reduce
" water-sensitive effect " in fracturing process, the hydration swelling of clay composition in suppression shale, it is necessary to add little molecule in fracturing fluid
Cationic clay stabilizer (such as potassium chloride, tetramethyl ammonium chloride etc.).Partial hydrolysis acrylamide or anionic acrylamide
Copolymer and product emulsion thereof are poor with the compatibility of above-mentioned clay stabilizer, easily produce precipitation；(2) partial hydrolysis acryloyl
Amine or anionic acrylamide copolymer use anti-filtration property poor as the drag reducer that shale gas reservoir drag reduction hydraulic pressure splits, this
Kind of drag reduction water fracturing fluid easily leak-off is in the middle of stratum；(3) heat and salt resistance is poor, especially contains at high salinity high divalent ion
Under the conditions of amount, molecular structure is unstable, and resistance reducing effect declines very fast.
Patent US20090298721A1 discloses the formula of a kind of drag reduction water fracturing fluid: in 1000 gallons of deionized water
Add 0.5 gallon of acrylic acidcoacrylamide thing (FR-56TM) etc. anionic acrylamide copolymer emulsion as subtracting
Resist, adds the complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, and this drag reduction water fracturing fluid has excellent resistance-reducing performance,
Indoor average resistance-reducing yield reaches 65.0%, and salt tolerance (the especially tolerance to divalent calcium ions) has been had a certain degree of improvement,
But this kind of drag reduction hydraulic pressure splits system and uses as shale gas drag reduction water fracturing fluid, and there are the following problems: (1) is stable with organic clay
The compatibility of agent (such as tetramethyl ammonium chloride etc.) and alcohol is poor, easily produces precipitation；(2) anti-filtration property is poor, this kind of drag reduction
Water fracturing fluid easily leak-off is in the middle of stratum；(3) in practice of construction, " water-sensitive effect " is notable；(4) easily " water blocking " is produced；
(5) resistance to high speed shear poor performance, unstable under high speed shear effect, resistance-reducing yield declines quickly；(6) heat-resistant salt-resistant is poor,
Especially under the conditions of high salinity high divalent ion content, molecular structure is unstable, and resistance reducing effect declines very fast；(7) it is difficult to fall
Solve, easily cause permanent type to injure the finest and close shale formation, pollute stratum, then affect oil and gas production.
Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, cationic high-molecular amount
Acrylamide copolymer also has been reported that as drag reducer (US356226, US3868328), and this kind of structure copolymer is with steady with clay
Determining agent (such as KCl) compatibility preferable, preferable with the compatibility of alcohol, " water-sensitive effect " be not notable, is difficult to " water blocking ", but this type of fall resistance
The big molecule of agent is not easy to degraded, easily fine and close shale is caused possible permanent damage.
Therefore, improve the resistance to high speed shear performance of drag reducer the most further, improve fracturing fluid to the inhibition of clay and
Anti-leak-off, the stability improving the drag reducing efficiency under high salt shear conditions has degradability simultaneously, reduces polymer pair
The injury on stratum is still a yet unresolved issue.
Summary of the invention
It is an object of the invention to overcome the defect of prior art, it is provided that a kind of drag reducing efficiency is high, salt tolerance high shear high, anti-
Good, the good water solubility of energy and clay stabilizer have good compatibility, have degradability and acrylamide little to formation damage
Copolymer and its preparation method and application.
The present invention provides a kind of acrylamide based copolymer, and wherein, described acrylamide based copolymer contains construction unit
A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described
Construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3) and/or formula (4) institute
The construction unit shown, described construction unit D is the construction unit shown in formula (5)；And so that described acrylamide based copolymer to be tied
On the basis of the total mole number of structure unit, the content of described construction unit A is 5-95 mole of %, and the content of described construction unit B is
2.5-90 mole of %, the content of described construction unit C is 0.5-90 mole of %, and the content of described construction unit D is that 0.0001-1 rubs
You are %；The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand；
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4；R3Alkylidene for C1-C4
Or connecting key；R4Straight or branched alkylidene for C1-C20；R6And R7Be each independently H or C1-C20 straight chain or
Branched alkyl, and R6And R7It is asynchronously H；R9Straight chain branched alkyl for C1-C20；R11、R12、R11' and R12' independently of one another
Straight or branched alkyl for C1-C4；X-For Cl-, Br-, I-, SCN-Or
The present invention also provides for the preparation method of a kind of acrylamide based copolymer, and this preparation method is included in the solution of alkene
Under polymeric reaction condition, in the presence of initiator, a kind of monomer mixture is made to carry out polymerisation, wherein, described list in water
Body mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in formula (6), and described monomer F is formula
(7) monomer shown in, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is
Monomer shown in formula (10), in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95
Mole %, the content of described monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and described monomer H contains
Amount is 0.0001-1 mole of %；The condition of described solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation
It is 5,000,000-1,500 ten thousand,
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4；R3Alkylidene for C1-C4
Or connecting key；R4Straight or branched alkylidene for C1-C20；R6And R7Be each independently H or C1-C20 straight chain or
Branched alkyl, and R6And R7It is asynchronously H；R9Straight chain branched alkyl for C1-C20；R11、R12、R11' and R12' independently of one another
Straight or branched alkyl for C1-C4；X-For Cl-, Br-, I-, SCN-Or
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method includes aqueous phase
It is mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, in the presence of initiator, by this reversed-phase emulsion with oil phase
Carrying out polymerisation, described aqueous phase is the aqueous solution containing monomer mixture, and described oil phase contains organic solvent and emulsifying agent, its
In, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in above-mentioned formula (6),
Described monomer F is the monomer shown in above-mentioned formula (7), and described monomer G is the monomer shown in above-mentioned formula (8) and/or above-mentioned formula (9) institute
The structures alone shown, described monomer H is the monomer shown in above-mentioned formula (10), with the total mole number of monomer in described monomer mixture
On the basis of, the content of described monomer E is 5-95 mole of %, and the content of described monomer F is 2.5-90 mole of %, and described monomer G contains
Amount is 0.5-90 mole of %, and the content of described monomer H is 0.0001-1 mole of %；The condition of described emulsion polymerization makes polymerization
After reaction, the viscosity average molecular weigh of resulting polymers is 5,000,000-1,500 ten thousand.
Additionally, present invention also offers the application as drag reducer of the described acrylamide based copolymer.
In the described acrylamide based copolymer that the present invention provides, by the construction unit containing azo group is passed through
The method of copolymerization, is incorporated on the macromolecular chain containing acrylamide construction unit and cationic monomer construction unit, by control
Polymerizing condition processed obtains the copolymer of suitable molecular weight so that this acrylamide based copolymer has self-degradation, relatively low
Under formation temperature, (generally higher than 60 DEG C) can realize from degrading, it is possible to decrease the injury to stratum, and this acrylamide is altogether simultaneously
Polymers has higher drag reducing efficiency under high salt shear conditions, and has higher with clay stabilizer (such as KCl and NaCl)
Compatibility.Thus obtain the present invention.
And, the acrylamide based copolymer of present invention water insoluble matter content when as drag reducer is the most less；With help
Row's agent (such as methyl alcohol) has preferable compatibility.
Specifically, the viscosity average molecular weigh of the acrylamide based copolymer prepared in embodiment 1-6 can reach 500-1500 ten thousand；
Insolubles content in water is only 0.01 weight %；Under the shear rate of 2500rpm, this polymer does not produces at water/alcoholic solution
Raw precipitation, can be completely dissolved；The acrylamide based copolymer prepared in embodiment 1-6 is dissolved in concentration is 2 weight %, 4 weights
Measure in NaCl or the KCl solution of %, 8 weight %, 10 weight %, 12 weight %, be configured to the molten of 500mg/L and 1000mg/L
Liquid, drag reducing efficiency all can reach more than 60%；Under conditions of lower ground layer temperature (more than 60 DEG C), this polymer can be carried out certainly
Degraded, the injury to stratum is less than 10%.
Additionally, preparation method (solution polymerization process and the emulsion polymerization) tool of the acrylamide based copolymer of present invention offer
There are simplicity and the high advantage of monomer conversion.
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 described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
(1) acrylamide based copolymer
The present invention provides a kind of acrylamide based copolymer, and wherein, described acrylamide based copolymer contains construction unit
A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described
Construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3) and/or formula (4) institute
The construction unit shown, described construction unit D is the construction unit shown in formula (5)；And so that described acrylamide based copolymer to be tied
On the basis of the total mole number of structure unit, the content of described construction unit A can be 5-95 mole of %, preferably 10-70 mole %, more
It is preferably 50-70 mole of %；The content of described construction unit B is 2.5-90 mole of %, preferably 5-60 mole %, more preferably 20-
40 moles of %；The content of described construction unit C is 0.5-90 mole of %, preferably 5-30 mole %, more preferably 5-20 mole %, institute
The content stating construction unit D is 0.0001-1 mole of %, preferably 0.001-0.5 mole %, more preferably 0.005-0.2 mole %；
The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand,
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4, under preferable case, R1For H
Or methyl, R2、R5And R8It is each independently H, R10And R10' it is methyl；R3For alkylidene or the connecting key of C1-C4, preferably
For connecting key or methylene；R4For the straight or branched alkylidene of C1-C20, under preferable case, R4For C1-C5 straight chain or
Chain alkylidene, more preferably ethylidene, such as-CH2CH2-；R6And R7It is each independently the straight or branched alkane of H or C1-C20
Base, and R6And R7It is asynchronously H, under preferable case, R6And R7It is each independently the straight or branched alkyl of H or C1-C5,
And R6And R7Be asynchronously H, further preferably in the case of, R6And R7It is each independently H, methyl, ethyl, isopropyl or uncle
Butyl, and R6And R7It is asynchronously H；R9For the straight or branched alkyl of C1-C20, the straight or branched alkyl of preferably C1-C5,
More preferably methyl, ethyl, isopropyl or the tert-butyl group；R11、R12、R11' and R12' it is each independently the straight chain of C1-C4
Or branched alkyl, preferably methyl；X-For Cl-, Br-, I-, SCN-OrIt is preferably Br-。
In the present invention, described R3For the nitrogen-atoms on the imidazole ring in connecting key expression (2) directly with
InGroup connects.
In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
Described alkylidene refer to alkane lose two hydrogen atoms after residue, said two hydrogen atom can be same carbon
Two hydrogen atoms on atom, 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)-。
In the present invention, described alkylidene can be straight chain, it is also possible to be side chain.The straight or branched of described C1-C20
The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-Zhong Ding
Base, isobutylidene, the sub-tert-butyl group, sub-n-pentyl, isoamylidene, sub-tertiary pentyl, sub-neopentyl, sub-n-hexyl, sub-n-heptyl, Asia
N-octyl, sub-positive decyl, sub-dodecyl, sub-cetyl and alkylene eicosyl.
The present inventor finds under study for action, by specific construction unit A, construction unit B, construction unit C and knot
The acrylamide quadripolymer of structure cells D composition can obtain fabulous resistance reducing effect.Preferably, R is worked as1For H or methyl,
R2、R5And R8It is each independently H, R3For connecting key or methylene, R6And R7It is each independently the straight chain of H or C1-C5
Or branched alkyl, and R6And R7It is asynchronously H, R9Straight or branched alkyl for C1-C5；R10、R10’、R11、R12、R11' and R12’
It is each independently methyl；X-For Br-.That is, described construction unit A is the construction unit shown in formula (1), wherein, R1For H or first
Base, described construction unit B is the construction unit shown in formula (11) and/or the construction unit shown in formula (12), described construction unit C
For the one in formula (13), formula (14), formula (15) and the construction unit shown in formula (16), described construction unit D is formula (17) institute
The construction unit shown,
Wherein, R4For the straight or branched alkylidene of C1-C5, more preferably ethylidene, such as-CH2CH2-。
(2) solution polymerization process
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method is included in alkene
Solution polymerization under the conditions of, in the presence of initiator, make a kind of monomer mixture carry out polymerisation in water, wherein,
Described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in formula (6), described list
Body F is the monomer shown in formula (7), and described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), described
Monomer H is the monomer shown in formula (10), and in described monomer mixture on the basis of the total mole number of monomer, described monomer E's
Content is 5-95 mole of %, preferably 10-70 mole %, more preferably 50-70 mole %；The content of described monomer F is that 2.5-90 rubs
You are %, preferably 5-60 mole %, more preferably 20-40 mole %；The content of described monomer G is 0.5-90 mole of %, preferably 5-
30 moles of %, more preferably 5-20 mole %, the content of described monomer H is that 0.0001-1 mole of %, preferably 0.001-0.5 rub
You are %, more preferably 0.005-0.2 mole %；After the condition of described polymerisation makes polymerisation, the viscous of resulting polymers is divided equally
Son amount is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand；
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4, under preferable case, R1For H
Or methyl, R2、R5And R8It is each independently H, R10And R10' it is methyl；R3For alkylidene or the connecting key of C1-C4, preferably
For connecting key or methylene；R4For the straight or branched alkylidene of C1-C20, under preferable case, R4For C1-C5 straight chain or
Chain alkylidene, more preferably ethylidene, such as-CH2CH2-；R6And R7It is each independently the straight or branched alkane of H or C1-C20
Base, and R6And R7It is asynchronously H, under preferable case, R6And R7It is each independently the straight or branched alkyl of H or C1-C5,
And R6And R7Be asynchronously H, further preferably in the case of, R6And R7It is each independently H, methyl, ethyl, isopropyl or uncle
Butyl, and R6And R7It is asynchronously H；R9For the straight or branched alkyl of C1-C20, the straight or branched alkyl of preferably C1-C5,
More preferably methyl, ethyl, isopropyl or the tert-butyl group；R11、R12、R11' and R12' it is each independently the straight chain of C1-C4
Or branched alkyl, preferably methyl；X-For Cl-, Br-, I-, SCN-OrIt is preferably Br-。
According to the present invention, when described polymerisation starts, the weight of described monomer mixture and water and monomer mixture
The various ratios that the ratio of gross weight is known to those skilled in the art, usually, the weight of described monomer mixture and water
Can be 0.05-0.5:1, preferably 0.15-0.4:1 with the ratio of the gross weight of monomer mixture.
According to the present invention, described initiator can be the various initiator in this area.Such as, selected from azo series initiators and oxygen
Change reduction series initiators.In described monomer mixture on the basis of the total mole number of monomer, the consumption of described azo series initiators
For 0-10 mole of %, the consumption of described redox series initiators is 0-10 mole of %, and described azo initiator and redox
Total consumption of initiator is the most satisfied: total consumption of described initiator is the total mole number of monomer in monomer mixture
0.0001-10 mole of %.
In the present invention, it is preferable that described azo series initiators be selected from 2,2 '-azo diisobutyl amidine hydrochloride and/or 2,
2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
Described redox series initiators includes Oxidizing and Reducing Agents, it is preferable that described oxidant and described reducing agent
Mol ratio be 0.5-3.5:1, under conditions of meeting aforementioned proportion, the consumption of described oxidant can be single in monomer mixture
0.0001-0.01 mole of % of the total mole number of body, the preferably 0.001-0.008 of the total mole number of monomer in monomer mixture
Mole %；Under preferable case, described oxidant is selected from least in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide
Kind, more preferably ammonium persulfate and/or potassium peroxydisulfate；The consumption of described reducing agent can be monomer in monomer mixture
0.0001-0.005 mole of % of total mole number, preferably in monomer mixture, the 0.001-0.004 of the total mole number of monomer rubs
You are %；Described reducing agent can be inorganic reducing agent (helping reducing agent), it is preferable that described inorganic reducing agent is selected from bisulfite
At least one in sodium, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and urea, further
It is preferably sodium hydrogensulfite and/or sodium thiosulfate.
In the present invention, needing to particularly point out ground, described monomer H simultaneously works as the effect of chain extender in the course of the polymerization process,
This is because two the double bond groups that have in described monomer H may participate in polymerisation, it is similar to " bridge formation ".
It addition, the injury of the acrylamide based copolymer layer over the ground of present invention offer reduces, this is likely due to this polymerization
Thing has azo group, easily occurs from degradation reaction (more than 60 DEG C) at a temperature of relatively low stratum.
According to the present invention, described solution polymerization can also be carried out in the presence of various auxiliary agents, and described auxiliary agent can select
At least one in chelating agent and other auxiliary agents；In described monomer mixture on the basis of the total mole number of monomer, described chela
The consumption of mixture is 0-2 mole of %, preferably 0.0001-1 mole %, more preferably 0.0001-0.05 mole of %, described its
The consumption of his auxiliary agent can be 0-2 mole of %, preferably 0.0001-1 mole %, more preferably 0.0001-0.2 mole of %；Excellent
The consumption of selection of land, described chelating agent and other auxiliary agents makes: in described monomer mixture on the basis of the total mole number of monomer, institute
The consumption stating auxiliary agent is 0.0001-4 mole of %.
According to the present invention, described chelating agent can be selected from disodium ethylene diamine tetraacetate (EDTA), triethylenediamine pentaacetic acid,
At least one in citric acid, citrate and poly-hydroxy acrylic acid, more preferably EDTA, citrate and triethylenediamine
At least one in pentaacetic acid, described citrate can be potassium citrate, sodium citrate, calcium citrate and ammonium citrate etc..
According to the present invention, other auxiliary agents described can be selected from urea, sodium formate, isopropanol, trimethyl bromine
Change at least one in ammonium and sodium hypophosphite, preferably urea and/or sodium formate.
It was found by the inventors of the present invention that under conditions of existing concurrently with above-mentioned various initiator and auxiliary agent, solution polymerization process
The acrylamide based copolymer that viscosity average molecular weigh is controlled can be obtained.
According to the present invention, the condition of described solution polymerization can be the condition that this area is conventional.Such as, described solution
Polymerisation is carried out in the presence of an inert gas, and polymeric reaction condition may include that temperature is 0-50 DEG C, and the time is that 1-24 is little
Time, pH value is 5-13；Under preferable case, temperature is 4-45 DEG C, and the time is 4-24 hour, and pH value is 5-9.Described pH value can be led to
Cross addition acid or alkali be adjusted, described acid is preferably inorganic acid, described inorganic acid be preferably hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and
At least one in phosphoric acid；Described alkali can be inorganic base or organic amine compound, such as, can be selected from NaOH, hydrogen-oxygen
Change at least one in potassium, ammoniacal liquor, methylamine, ethamine, monoethanolamine and triethanolamine, preferably NaOH.
The present inventor finds under study for action, takes following condition can improve the molecular weight of polymer further:
I.e., it is preferable that the process of described solution polymerization includes the three phases carried out successively: the reaction condition bag of first stage
Including: temperature is 0-10 DEG C, preferably 4-10 DEG C, the time is 1-15 hour, preferably 3-10 hour；The reaction condition of second stage
Including: temperature is 15-30 DEG C, preferably 20-30 DEG C, and the time is 3-8 hour, preferably 3-5 hour；The reaction bar of phase III
Part includes: temperature is 35-50 DEG C, preferably 35-45 DEG C, and the time is 2-14 hour, preferably 2-12 hour.
Additionally, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and monomer H
When reacting, it is possible to improve the resistance reducing effect of the polymer of gained further.Preferably, R is worked as1For H or methyl, R2、R5With
R8It is each independently H, R3For connecting key or methylene, R6And R7It is each independently the straight or branched of H or C1-C5
Alkyl, and R6And R7It is asynchronously H；R9Straight or branched alkyl for C1-C5；R10、R10’、R11、R12、R11' and R12' the most only
It it is on the spot methyl；X-For Br-.That is, described monomer E is the monomer shown in formula (6), wherein, R1For H or methyl, described monomer F is
Monomer shown in formula (18) and/or the monomer shown in formula (19), described monomer G is formula (20), formula (21), formula (22) and formula (23)
The shown one in monomer, described monomer H is the monomer shown in formula (24),
Wherein, R4For the straight or branched alkylidene of C1-C20, under preferable case, R4Straight or branched alkylene for C1-C5
Base, more preferably ethylidene, such as-CH2CH2-。
(3) reversed emulsion polymerization
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method includes aqueous phase
It is mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, in the presence of initiator, by this reversed-phase emulsion with oil phase
Carrying out polymerisation, described aqueous phase is the aqueous solution containing monomer mixture, and described oil phase contains organic solvent and emulsifying agent, its
In, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in above-mentioned formula (6),
Described monomer F is the monomer shown in above-mentioned formula (7), and described monomer G is shown in the monomer shown in above-mentioned formula (8) and/or formula (9)
Structures alone, described monomer H is the monomer shown in above-mentioned formula (10), and with the total mole number of monomer in described monomer mixture is
Benchmark, the content of described monomer E is 5-95 mole of %, preferably 10-70 mole %, more preferably 50-70 mole %；Described monomer F
Content be 2.5-90 mole of %, preferably 5-60 mole %, more preferably 20-40 mole %；The content of described monomer G is 0.5-
90 moles of %, preferably 5-30 mole %, more preferably 5-20 mole %, the content of described monomer H is 0.0001-1 mole of %, preferably
For 0.001-0.5 mole of %, more preferably 0.005-0.2 mole %；The condition of described polymerisation makes gained after polymerisation
The viscosity average molecular weigh of polymer is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand；The choosing of monomer shown in formula (6)-formula (10)
Select identical with described above, do not repeat them here.
According to the present invention, described aqueous phase is the aqueous solution containing monomer mixture.The weight of described monomer mixture and water
Selection with the ratio of the gross weight of monomer mixture is identical with described above, does not repeats.
According to the present invention, the part by weight of described aqueous phase and oil phase is had no particular limits, if make described aqueous phase with
Oil phase is thoroughly mixed to form reversed-phase emulsion, and under preferable case, the part by weight of described aqueous phase and oil phase is 1:0.1-2, enters
One step is preferably 1:0.3-0.8.
According to the present invention, described organic solvent can be this area various for emulsion polymerization mutual exclusive with water non-
Polarity or the little organic solvent of polarity, such as, can be toluene, dimethylbenzene, hexane, hexamethylene, normal heptane, isomery paraffin, isomery
At least one in alkane, gasoline, kerosene and white oil, under preferable case, described organic solvent is selected from toluene, dimethylbenzene, just
At least one in heptane, isoparaffin, hexamethylene and kerosene.
According to the present invention, described oil phase contains organic solvent and emulsifying agent.The most special to the consumption of described organic solvent
Requirement, can change in wider scope, as long as described organic solvent and emulsifying agent are mixed to form oil phase, preferably feelings
Under condition, on the basis of the gross weight of described emulsion, the consumption of described organic solvent can be 10-60 weight %, more preferably
20-35 weight %.
According to the present invention, described emulsifying agent can be the various nonionic emulsifier for emulsion polymerization in this area, example
As being sorbitan fatty acid ester, APES, isomeric alcohol polyethenoxy ether, lauryl alcohol polyethylene glycol oxide
Ether, methyl glycol fatty acid ester, laureth, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, polyoxyethylene lose
Water sorbitan fatty acid fat, sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyethenoxy ether, fat
At least one in alcohol APEO and aliphatic amine polyoxyethylene ether.Under preferable case, described emulsifying agent is selected from Sorbitan
Alcohol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzyl
Phenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol and benzyl
At least one in dimethyl phenol APEO, is further preferably be made up of above two or two or more emulsifying agents
Hydrophilic lipophilic balance is the compound emulsifying agent of 5-9, such as, can be sorbitan fatty acid ester and Nonyl pheno
Ether.
According to the present invention, the consumption of described emulsifying agent is not particularly limited, can change in wider scope, only
Described emulsifying agent and described organic solvent is wanted to be mixed to form oil phase, under preferable case, with the gross weight of described emulsion as base
Standard, the consumption of described emulsifying agent can be 1-15 weight %, more preferably 2-10 weight %.
According to the present invention, described initiator can be various initiators in this area, and the selection of described initiator is with above
Describing identical, here is omitted.
In the present invention, under preferable case, first azo series initiators can be added aqueous phase, then be mixed to form anti-phase breast with oil phase
Liquid, then contacts reversed-phase emulsion with redox series initiators, by redox initiator initiated polymerization.
According to the present invention, described polymerisation can also be carried out in the presence of various auxiliary agents, and described auxiliary agent can be selected from chela
At least one in mixture and other auxiliary agents, the selection of described auxiliary agent is identical with described above, and here is omitted.
According in the present invention, the charging not particularly requirement on opportunity to described chelating agent, as long as making chelating agent and metal
Ion generation chelation, so that copolymer is played static stabilization, can select to add or in oil phase at aqueous phase
Add, under preferable case, in order to make chelating agent play stably more fully effect, addition chelating agent in aqueous phase can be selected.
According to the present invention, the selection of described chelating agent is identical with described above, and here is omitted.
Equally, it was found by the inventors of the present invention that under conditions of existing concurrently with above-mentioned various initiator and auxiliary agent, anti-phase breast
Liquid polymerization can obtain the acrylamide based copolymer that viscosity average molecular weigh is controlled and dissolution velocity is fast.
According to the present invention, the condition of described emulsion polymerization can be the condition that this area is conventional.Described polymerisation
The selection of condition is identical with described above, and here is omitted.
Equally, the present inventor finds under study for action, takes following condition can improve dividing of polymer further
Son amount: i.e., it is preferable that the process of described emulsion polymerization includes two stages carried out successively: the reaction bar of first stage
Part includes: temperature is 0-20 DEG C, preferably 5-10 DEG C, and the time is 1-15 hour, preferably 1-5 hour；The reaction of second stage
Condition includes: temperature is 20-50 DEG C, preferably 25-45 DEG C, and the time is 2-8 hour, preferably 2-5 hour.
According to the present invention, the method is additionally included in described polymerisation products therefrom and phase inversion agent after described polymerisation
Contact, so that described polymerisation products therefrom quickly dissolves in fracturing fluid is applied in water.Described phase inversion agent is permissible
The various phase inversion agent being polymerized for emulsion for this area, as long as making the water solubility of described polymerisation products therefrom increase,
Can be such as polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzylphenol
APEO, phenethyl phenol polyethenoxy ether, isomery ten alcohol APEO, isomery undecyl alcohol APEO, isomery ten
At least one in the nonionic emulsifier of triol APEO and aliphatic amine polyoxyethylene ether, under preferable case, described
Phase inversion agent is selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEO, isomery undecyl alcohol polyoxyethylene
At least one in ether, isomerous tridecanol polyoxyethylene ether, NPE and OPEO.
According to the present invention, the consumption not particularly requirement to described phase inversion agent, as long as described polymerisation institute can be made
Obtaining product quickly to dissolve in water in fracturing fluid is applied, the consumption of described phase inversion agent makes: with the gross weight of described emulsion
On the basis of amount, the consumption of described phase inversion agent can be 0.5-10 weight %, preferably 1-4 weight %.
Additionally, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and monomer H
When reacting, it is possible to improve the resistance reducing effect of the polymer of gained further.For instance, it is preferred that work as R1For H or methyl, R3
For connecting key or methylene, R2、R5And R8It is each independently H, R6And R7Be each independently H or C1-C5 straight chain or
Branched alkyl, and R6And R7It is asynchronously H；R9Straight or branched alkyl for C1-C5；R10、R10’、R11、R12、R11' and R12' each
From independently be methyl；X-For Br-.That is, described monomer E is the monomer shown in formula (6), wherein, R1For H or methyl, described monomer
F is the monomer shown in formula (18) and/or the monomer shown in formula (19), and described monomer G is formula (20), formula (21), formula (22) and formula
(23) one in the monomer shown in, described monomer H is the monomer shown in formula (24), single shown in formula (6), formula (18)-formula (24)
The selection of body is identical with described above, does not repeats them here.
Additionally, present invention also offers the application in drag reducer of the described acrylamide based copolymer.Employing is the present invention carry
The described acrylamide based copolymer of confession is as fracturing fluid drag reducer, it is possible to obtain high and stable drag reducing efficiency, concrete application
The technology that method is well known to those skilled in the art.
Hereinafter will be described the present invention by embodiment.It should be appreciated that concrete reality described herein
The mode of executing is merely to illustrate and explains the present invention, is not limited to the present invention.
Intrinsic viscosity is measured according to GB12005.1-89 polyacrylamide Intrinsic Viscosity Measurements method；Glue and divide equally
Son amount is according to formula Mv=([η]/K)1\α, wherein K=4.5 × 10-3, α=0.80 calculates；Dissolution time presses GB12500.8-89
Being measured (sample quality is all based on straight polymer quality in sample), the powdered samples dissolution time recorded is respectively less than
20min, samples of latex dissolution time is respectively less than 5min；The composition of molecular structure and construction unit use IR spectrum and13C-NMR surveys
Fixed；Water insoluble matter content is pressed SY/T5862-1993 and is measured；Indoor drag reducing efficiency is pressed SY/T6376-2008 and is measured.
Monomer M1 shown in following embodiment Chinese style (25) is according to document (Efficient fixation of CO2into
cyclic carbonates catalyzed by hydroxyl-functionalized poly(ionic liquids),
RSCAdvances, 2013,3 (11), 3726-3732) described in method prepare, the monomer M3 shown in formula (28) is according to patent
Prepared by the method that WO2010033014A2 embodiment 3 is recorded.
Monomer M1 shown in following embodiment Chinese style (25) and the monomer M3 shown in formula (28) is public purchased from Sigma-Aldrich
Department, in addition, unless specifically indicated, the reagent etc. used in embodiment, comparative example and test case is commercially available product.
Embodiment 1
The present embodiment is for illustrating that the solution polymerization process that the present invention provides prepares acrylamide based copolymer.
Under room temperature, by the acrylamide (AM) of 4.26g, 77.04g formula (25) shown in M1 monomer, the N of 17.55g, N-
The M2 monomer shown in formula (26) of DMAA (purchased from Sigma-Aldrich company) and 1.16g (according to
Prepared by the method that in JP08217755A, embodiment 1 is recorded, the most identical), join in reaction bulb, add deionized water
566.72g, stirring makes monomer be completely dissolved, and stirs.The EDTA aqueous solution 5.5g of 1 weight % is added respectively in flask,
The 2 of 1 weight %, 2 '-azo diisobutyl amidine hydrochloride aqueous solution 2.1g, add the solution of sodium bisulfite 1.1g of 0.1 weight %,
Urea 0.12g, is sufficiently stirred for making it mix.Regulate to 7.5 with the sodium hydroxide solution pH of 10 weight %.At the beginning of control system
Beginning temperature, to 4 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1 weight % ammonium persulfate aqueous solution 0.45g, and continues letting nitrogen in and deoxidizing 20
Minute.Reactor is airtight, it is maintained at 4 DEG C, after reacting 8 hours, reacts 5 hours after temperature is risen to 20 DEG C, then by temperature
Rise to 45 DEG C react 2 hours, the gum-like product that obtain is taken out, through granulation, be dried, pulverize and can receive acrylamide copolymerization
Thing P1.
P1 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak；1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration, 1356cm-1With
1401cm-1Typical methyl symmetric curvature vibration absorption peak, 3100cm occur-1Place's small peak belongs to stretching of C=C-H on imidazole ring
Contracting vibration, 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretching vibration, 1508-1654cm-1Go out peak to return
Belong to C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3C-H flexural vibrations, 1034-1229cm-1
Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm-1Go out peak and belong to the vibration of imidazole ring Ar-H out-of plane bending.Can
To determine that the copolymer molecule obtained has the structure shown in formula (27), recording its viscosity-average molecular weight Mv by viscosity method is 670
Ten thousand, monomer conversion is more than 99.9%.Wherein, formula (27) and x1、x2、y1、y2、z1、z2Construction unit is only represented with u
Type and number, and do not indicate that the connected mode of construction unit.x1、x2、y1、y2、z1、z2True by inventory with the concrete numerical value of u
Fixed, the composition of molecular structural formula and construction unit uses quantitatively13C composes mensuration, wherein, (x1+x2): (y1+y2): (z1+z2): u=1:
6:2.95:0.05.
Comparative example 1
Prepare acrylamide based copolymer according to the method for embodiment 1, except for the difference that, be added without M1 monomer, N, N-diformazan
Base acrylamide and M2 monomer, by (3-acrylamido-3-methyl) butyl trimethyl chlorine of acrylamide Yu identical molal quantity
Change ammonium and carry out polymerisation, thus obtain bipolymer DP1, record its viscosity average molecular weigh MvIt is 14,010,000.
Embodiment 2
The present embodiment is for illustrating that the solution polymerization process that the present invention provides prepares acrylamide based copolymer.
By M3 monomer, the isopropyl ester of 16.96g and the 0.46g shown in the formula (28) of AM, 6.99g of 29.85g
The M2 monomer shown in formula (26) join in polymerization bottle, add 126.61g deionized water, stirring make monomer be completely dissolved, point
In flask, do not add the EDTA aqueous solution 4.65g of 1 weight %, add the 2 of 1 weight %, 2 '-azo diisobutyl amidine hydrochloric acid salt solution
Solution 1.23g, adds 0.1% solution of sodium bisulfite 1.15g, adds urea 0.11g, is sufficiently stirred for making it mix.With 10
The sodium hydroxide solution regulation pH to 7.1 of weight %.Control system initial temperature is to 10 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds
1 weight % ammonium persulfate aqueous solution 0.45g, and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 10 DEG C, reacts 3
After hour, it is warming up to 30 DEG C, after reacting 3 hours, is warming up to 35 DEG C and reacts 12 hours, the gum-like product obtained is taken out, through making
Grain, be dried, pulverize can receive acrylamide copolymer p 2.
P2 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak；1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration；1310cm-1Locate little
Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretch
Contracting vibration, 1508-1654cm-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3
C-H flexural vibrations, 1034-1229cm-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm-1Go out peak to belong to
Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (29), by glutinous
It is 5,700,000 that degree method records its viscosity-average molecular weight Mv, and monomer conversion is more than 99.9%.Wherein, formula (29) and x1、x2、y1、
y2、z1、z2Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x1、x2、y1、y2、
z1、z2Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively13C composes mensuration, its
In, x1、x2、y1、y2、z1、z2、u1And u2Numerical value be respectively (x1+x2): (y1+y2): (z1+z2): u=1:0.07:0.35:
0.003。
Embodiment 3
The present embodiment is for illustrating that the solution polymerization process that the present invention provides prepares acrylamide based copolymer.
Under room temperature, by the Methacrylamide of 25.53g, 57.79g formula (25) shown in M1 monomer, uncle N-of 4.58g
The M2 monomer shown in formula (26) of butylacrylamide and 0.002g joins in polymerization bottle, adds 131.85g deionized water, stirs
Mix and make monomer be completely dissolved, in flask, add the EDTA aqueous solution 11.63g of 1 weight % respectively, add the 2 of 1 weight %, 2 '-idol
Nitrogen diisobutyl amidine hydrochloride aqueous solution 2.13g, adds 0.1 weight % solution of sodium bisulfite 1.13g, adds urea 0.20g,
DTAB 0.01g, is sufficiently stirred for making it mix.PH is regulated with the sodium hydroxide solution of 10 weight %
To 7.3.Control system initial temperature, to 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1% ammonium persulfate aqueous solution 0.4g, and continues
Continuous letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 8 DEG C, after reacting 10 hours, is warming up to 25 DEG C, after reacting 4 hours,
It is warming up to 40 DEG C react 7 hours, the gum-like product that obtain is taken out, through granulation, be dried, pulverize and can receive acrylamide altogether
Polymers P3.
P3 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak；1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration, 1310cm-1Locate little
Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretch
Contracting vibration, 1508-1654cm-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3
C-H flexural vibrations, 1034-1229cm-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm-1Go out peak to belong to
Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (30), by glutinous
It is 8,150,000 that degree method records its viscosity-average molecular weight Mv, and monomer conversion is more than 99.9%.Wherein, formula (30) and x1、x2、y1、
y2、z1、z2Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x1、x2、y1、y2、
z1、z2Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively13C composes mensuration, its
In, (x1+x2): (y1+y2): (z1+z2): u=1:0.88:0.12:0.00002.
Embodiment 4
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide based copolymer.
(1) by the Methacrylamide of 5.11g, 77.04g formula (25) shown in M1 monomer, the N of 17.55g, N-diformazan
The M2 monomer shown in formula (26) of base acrylamide and 1.16g joins in configuration bottle, adds 164.56g deionized water, stirring
Make monomer be completely dissolved, in flask, add the EDTA aqueous solution 14.61g of 1 weight % respectively, add the 2 of 1 weight %, 2 '-azo
Diisobutyl amidine hydrochloride aqueous solution 1.03g, adds urea 0.15g, is sufficiently stirred for making it mix, with the hydrogen of 10 weight %
Sodium hydroxide solution regulation pH to 7.1, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, the most identical) 37.81g, alkyl
Phenol polyethenoxy ether (Igepal CA720, Sigma-Aldrich company, the most identical) 10g, 177.16g kerosene is mixed into oil
Phase, and the aqueous phase obtained in step (1) is joined in whole oil phase, form reversed-phase emulsion by mixing at a high speed and join reaction
In device.
(3) control system initial temperature 5 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite
0.25g, adds 1 weight % ammonium persulfate aqueous solution 1.0g and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 5
DEG C, after reacting 5 hours, it is warming up to 45 DEG C, reacts 2 hours.After question response temperature is cooled to room temperature, adds 20.25g nonyl phenol and gather
Oxygen vinethene (Sigma-Aldrich company, the most identical), obtains emulsion-formulated products with 80 mesh filter-cloth filterings.By reversed-phase emulsion
After product acetone and methanol mixed solvent are precipitated out, acrylamide copolymer p 4 can be obtained.
P4 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak, 1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration, 1356cm-1With
1401cm-1Typical methyl symmetric curvature vibration absorption peak, 3100cm occur-1Place's small peak belongs to stretching of C=C-H on imidazole ring
Contracting vibration, 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretching vibration, 1508-1654cm-1Go out peak to return
Belong to C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3C-H flexural vibrations, 1034-1229cm-1
Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm-1Go out peak and belong to the vibration of imidazole ring Ar-H out-of plane bending.Can
To determine that the copolymer molecule obtained has the structure shown in formula (31), recording its viscosity average molecular weigh Mv by viscosity method is 710
Ten thousand, monomer conversion is more than 99.9%.Wherein, formula (31) and x1、x2、y1、y2、z1、z2Construction unit is only represented with u
Type and number, and do not indicate that the connected mode of construction unit.x1、x2、y1、y2、z1、z2True by inventory with the concrete numerical value of u
Fixed, the composition of molecular structural formula and construction unit uses quantitatively13C composes mensuration, wherein, (x1+x2): (y1+y2): (z1+z2): u=1:
6:2.95:0.05.
Comparative example 2
Prepare acrylamide based copolymer according to the method for embodiment 4, except for the difference that, be added without M1 monomer, N, N-diformazan
Base acrylamide and M2 monomer, by (3-acrylamido-3-methyl) butyl front three of Methacrylamide Yu identical molal quantity
Ammonium chloride carries out polymerisation, thus obtains bipolymer DP2, records its viscosity average molecular weigh MvIt is 9,250,000.
Embodiment 5
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide based copolymer.
(1) by the Methacrylamide of 35.74g, 6.99g formula (28) shown in M3 monomer, 16.96g acrylic acid different
The M2 monomer shown in formula (26) of propyl diester and 0.46g joins in preparation bottle, adds 240.6g deionized water, and stirring makes monomer
It is completely dissolved, in flask, adds the EDTA aqueous solution 7.63g of 1 weight % respectively, add 1 weight % azo diisobutyl amidine hydrochloric acid
Saline solution 2.03g, adds urea 0.10g, is sufficiently stirred for making it mix, and regulates with the sodium hydroxide solution of 15 weight %
PH to 7.0, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60) 28.82g, APES (Igepal CA720)
10g, 116.44g kerosene is mixed into oil phase, and is all joined in oil phase by the aqueous phase obtained in step (1), by the most mixed
Even formation reversed-phase emulsion joins in reactor.
(3) control system initial temperature 10 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite
0.13g, adds 1 weight % ammonium persulfate aqueous solution 0.63g, and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, keep
At 10 DEG C, after reacting 1 hour, it is warming up to 25 DEG C, reacts 5 hours, after question response temperature is cooled to room temperature, add 9.31g nonyl
Phenol polyethenoxy ether, obtains emulsion-formulated products with 80 mesh filter-cloth filterings.By reversed-phase emulsion product acetone and methanol mixed solvent
After being precipitated out, acrylamide copolymer p 5 can be obtained.
P5 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak, 1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration, 1310cm-1Locate little
Peak belongs to the stretching vibration of C=C-H, 1356cm on imidazole ring-1And 1401cm-1Occur that the vibration of typical methyl symmetric curvature is inhaled
Receive peak, 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretching vibration, 1508-1654cm-1Go out peak ownership
C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3C-H flexural vibrations, 1034-1229cm-1Go out
Peak belongs to C=N stretching vibration on imidazole ring, 1260cm-1Go out peak and belong to C-O stretching vibration on ester bond, 625-911cm-1Go out
Peak belongs to the vibration of imidazole ring Ar-H out-of plane bending.May determine that the copolymer molecule obtained has the knot shown in formula (32)
Structure, recording its viscosity average molecular weigh Mv by viscosity method is 5,450,000, and monomer conversion is more than 99.9%.Wherein, formula (32) and
x1、x2、y1、y2、z1、z2Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x1、
x2、y1、y2、z1、z2Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively13C composes
Measure, wherein, (x1+x2): (y1+y2): (z1+z2): u=1:0.07:0.35:0.003.
Embodiment 6
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide based copolymer.
(1) by the acrylamide of 21.32g, 57.79g formula (25) shown in M1 monomer, the N-tert-butyl group propylene of 4.58g
The M2 monomer shown in formula (26) of acid amides and 0.002g joins in preparation bottle, adds 474.26g deionized water, and stirring makes monomer
It is completely dissolved, in flask, adds the EDTA aqueous solution 8.5g of 1 weight % respectively, add 1 weight % azo diisobutyl amidine hydrochloric acid
Saline solution 2.1g, adds urea 0.08g, DTAB 0.01g, is sufficiently stirred for making it mix, and uses
The sodium hydroxide solution regulation pH to 7.1 of 10 weight %, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60) 12.75g, APES (Igepal CA720,
Sigma-Aldrich company, the most identical) 10g, 147.84g kerosene is mixed into oil phase, and adds obtaining aqueous phase in step (1)
Enter in oil phase, form reversed-phase emulsion by mixing at a high speed and join in reactor.
(3) control system initial temperature 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite
0.18g, adds 1 weight % ammonium persulfate aqueous solution 1.3g and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 8
DEG C, after reacting 3 hours, it is warming up to 40 DEG C, reacts 4 hours, after question response temperature is cooled to room temperature, adds 7.39g nonyl phenol and gather
Oxygen vinethene, obtains emulsion-formulated products with 100 mesh filter-cloth filterings.Reversed-phase emulsion product acetone and methanol mixed solvent are precipitated
After out, acrylamide copolymer p 6 can be obtained.
P6 is carried out various mensuration, in IR spectrum, 1660cm-1And 1635cm-1Place occurs belonging to the acyl of amide groups respectively
Amine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is stretching of C-N in place
Contracting vibration absorption peak, 1170cm-1Occur in that M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration, 1310cm-1Locate little
Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm-1Place goes out peak and is respectively belonging to-CH2-、-CH3C-H stretch
Contracting vibration, 1508-1654cm-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm-1Go out peak and belong to-CH2-、-CH3
C-H flexural vibrations, 1034-1229cm-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm-1Go out peak to belong to
Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (33), by glutinous
It is 7,600,000 that degree method records its viscosity average molecular weigh Mv, and monomer conversion is more than 99.9%.Wherein, formula (33) and x1、x2、y1、
y2、z1、z2Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x1、x2、y1、y2、
z1、z2Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively13C composes mensuration, its
In, (x1+x2): (y1+y2): (z1+z2): u=1:0.88:0.12:0.00002.
Test case 1
Water-insoluble is to measure according to the method for regulation in SY/T5862-1993.By P1-P6, DP1, DP2 and hydroxypropyl
Guar gum (JXY wellfracturing hydroxypropyl melon rubber powder, Shandong Juxin Chemical Co., Ltd., the most identical) carry out water-soluble mensuration, knot
Fruit is as shown in table 1.
Table 1
From table 1 it follows that in the acrylamide copolymer p 1-P6 for preparing of two kinds of methods that provides of the present invention water is not
Molten thing content is the conventional hydroxypropyl guar gum cooking drag reducer significantly lower than in site operation, this explanation and hydroxypropyl guar gum ratio, uses
P1-P6 is low to the injury on stratum as shale gas pressure break drag reducer.
Test case 2
Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2, partially hydrolyzed polyacrylamide (PHPA) (HPAM, Zibo
Tian Jian Chemical Co., Ltd., trade mark TJY-1, viscosity average molecular weigh is 1000-1300 ten thousand, lower same) and be each slowly added to respectively
In water/alcoholic solution (using methyl alcohol in this test case) that volume ratio is 80/20 and 60/40, P1-P6, DP1, DP2 and part water
Solve the 0.01 weight %(sample quality that consumption is water/alcoholic solution of polyacrylamide based on straight polymer quality in sample), dissolve
Time is 30min, and result is as shown in table 2.
Table 2
From Table 2, it can be seen that acrylamide copolymer p 1-P6 prepared by two kinds of methods that the present invention provides is as page
Rock air pressure splits with drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), good with the compatibility of alcohol.
Test case 3
Under conditions of temperature is 25 DEG C, P1-P6, DP1, DP2, HPAM and hydroxypropyl guar gum are dissolved in respectively pure water and dense
Degree is in NaCl or the KCl solution of 2 weight %, 4 weight %, 8 weight %, 10 weight %, 12 weight %, the 500mg/L being configured to
With the solution (sample quality is based on straight polymer quality in sample) of 1000mg/L, then specify according in SY/T6376-2008
Method on GLM-1 pipeline frictional resistance determinator, measure the drag reducing efficiency of above-mentioned solution, (test condition: test section pipeline interior
Footpath is 8mm, a length of 9m of test section pipeline, and infusion discharge capacity is 30L/min), result is as shown in Table 3 and Table 4.
Table 3
Table 4
It can be seen that the acrylamide copolymer p 1-P6 for preparing of two kinds of methods that provides of the present invention from table 3 and table 4
As shale gas pressure break drag reducer, compared with hydroxypropyl guar gum, HPAM, DP1 and DP2, with clay stabilizer (e.g., KCl and
NaCl) compatibility is good, and anti-salt property is excellent.
Test case 4
The nocuity of rock core is pressed oil and gas industry standard SY/T5107-2005 " aqueous fracturing fluid performance by friction reducer
Evaluation method " in fracturing fluid filtrate matrix permeability of rock core infringement experiment is carried out, in the test of American core company formation damage
Testing on instrument (FDS-800), the matrix permeability of rock core is 2md.
P1-P6, DP1 and DP2 are dissolved in pure water respectively, and (sample quality is by sample to be configured to the solution of 1000mg/L
Interior straight polymer quality meter), under conditions of test temperature is 65 DEG C, preserve 24hr, in the formation damage test of American core company
System (FDS-800) is upper tests its nocuity to rock core, and result is as shown in table 5.
Table 5
As can be seen from Table 5, acrylamide copolymer p 1-P6 prepared by two kinds of methods that the present invention provides is to rock core
Injury significantly lower than in site operation the conventional comparative sample cooking drag reducer, this explanation uses P1-P6 as shale gas pressure break
Low to the injury on stratum with drag reducer.
Above-mentioned test result illustrates, the acrylamide based copolymer that the present invention provides insolubles content in water is only
0.01%；Under the shear rate of 2500rpm, can be dissolved completely in water/alcoholic solution, good with the compatibility of alcohol；Due to alcohol and
The compatibility of clay stabilizer (NaCl or KCl) improves, and improves anti-filtration property；And under conditions of high salt and high shear
Still there is high drag reducing efficiency；Under conditions of lower ground layer temperature (more than 60 DEG C), there is self-degradation, the injury to stratum
Low.Additionally, the preparation method of acrylamide based copolymer that the present invention provides has simplicity and the high advantage of monomer conversion.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The combination of energy illustrates the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (23)
1. an acrylamide based copolymer, it is characterised in that described acrylamide based copolymer contains construction unit A, structure
Unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described structure list
Unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3) and/or the knot shown in formula (4)
Structure unit, described construction unit D is the construction unit shown in formula (5)；And with construction unit in described acrylamide based copolymer
Total mole number on the basis of, the content of described construction unit A is 5-95 mole of %, and the content of described construction unit B is 2.5-90
Mole %, the content of described construction unit C is 0.5-90 mole of %, and the content of described construction unit D is 0.0001-1 mole of %；
The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand；
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4；R3For C1-C4 alkylidene or
Connecting key；R4Straight or branched alkylidene for C1-C20；R6And R7It is each independently the straight or branched of H or C1-C20
Alkyl, and R6And R7It is asynchronously H；R9Straight or branched alkyl for C1-C20；R11、R12、R11' and R12' be each independently
The straight or branched alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-Or
Acrylamide based copolymer the most according to claim 1, wherein, with structure list in described acrylamide based copolymer
On the basis of the total mole number of unit, the content of described construction unit A is 10-70 mole of %, and the content of described construction unit B is 5-60
Mole %, the content of described construction unit C is 5-30 mole of %, and the content of described construction unit D is 0.001-0.5 mole of %,
The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,000 ten thousand.
Acrylamide based copolymer the most according to claim 1, wherein, R1For H or methyl, R2、R5And R8The most independent
Ground is H, R3For connecting key or methylene, R6And R7It is each independently the straight or branched alkyl of H or C1-C5, and R6With
R7It is asynchronously H, R9For the straight or branched alkyl of C1-C5, R10、R10’、R11、R12、R11' and R12' it is each independently methyl,
X-For Br-。
4. a preparation method for acrylamide based copolymer, this preparation method is included in the solution polymerization condition of alkene
Under, in the presence of initiator, make a kind of monomer mixture carry out polymerisation in water, wherein, described monomer mixture contains
Monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in formula (6), and described monomer F is the list shown in formula (7)
Body, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is shown in formula (10)
Monomer, in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95 mole of %, described
The content of monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and the content of described monomer H is
0.0001-1 mole of %；After the condition of described solution polymerization makes polymerisation, the viscosity average molecular weigh of resulting polymers is
5000000-1,500 ten thousand,
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4；R3For C1-C4 alkylidene or
Connecting key；R4Straight or branched alkylidene for C1-C20；R6And R7It is each independently the straight or branched of H or C1-C20
Alkyl, and R6And R7It is asynchronously H；R9Straight or branched alkyl for C1-C20；R11、R12、R11' and R12' be each independently
The straight or branched alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-Or
5. a preparation method for acrylamide based copolymer, this preparation method includes aqueous phase and oil phase are mixed to form anti-phase breast
Liquid, then under the conditions of emulsion polymerization, in the presence of initiator, carries out polymerisation, described water by this reversed-phase emulsion
Being the aqueous solution containing monomer mixture mutually, described oil phase contains organic solvent and emulsifying agent, and wherein, described monomer mixture contains
Having monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in formula (6), and described monomer F is shown in formula (7)
Monomer, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is shown in formula (10)
Monomer, in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95 mole of %, institute
The content stating monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and the content of described monomer H is
0.0001-1 mole of %；After the condition of described emulsion polymerization makes polymerisation, the viscosity average molecular weigh of resulting polymers is
5000000-1,500 ten thousand,
Wherein, R1、R2、R5、R8、R10And R10' it is each independently the alkyl of H or C1-C4；R3For C1-C4 alkylidene or
Connecting key；R4Straight or branched alkylidene for C1-C20；R6And R7It is each independently the straight or branched of H or C1-C20
Alkyl, and R6And R7It is asynchronously H；R9Straight or branched alkyl for C1-C20；R11、R12、R11' and R12' be each independently
The straight or branched alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-Or
Preparation method the most according to claim 5, wherein, described aqueous phase is 1:0.1-2 with the weight ratio of oil phase.
Preparation method the most according to claim 6, wherein, described aqueous phase is 1:0.3-0.8 with the weight ratio of oil phase.
Preparation method the most according to claim 5, wherein, on the basis of the gross weight of described emulsion, described organic solvent
Consumption be 10-60 weight %, the consumption of described emulsifying agent is 1-15 weight %.
Preparation method the most according to claim 8, wherein, on the basis of the gross weight of described emulsion, described organic solvent
Consumption be 20-35 weight %, the consumption of described emulsifying agent is 2-10 weight %.
Preparation method the most according to claim 5, wherein, the method is gathered described after being additionally included in described polymerisation
Close reaction products therefrom to contact with phase inversion agent.
11. preparation methods according to claim 10, wherein, on the basis of the gross weight of described emulsion, described phase inversion agent
Consumption be 0.5-10 weight %.
12. preparation methods according to claim 11, wherein, on the basis of the gross weight of described emulsion, described phase inversion agent
Consumption be 1-4 weight %.
13. according to the preparation method described in claim 4 or 5, wherein, with the total mole number of monomer in described monomer mixture is
Benchmark, the content of described monomer E is 10-70 mole of %, and the content of described monomer F is 5-60 mole of %, the content of described monomer G
For 5-30 mole of %, the content of described monomer H is 0.001-0.5 mole of %；The condition of described polymerisation makes polymerisation
The viscosity average molecular weigh of rear resulting polymers is 5,000,000-1,000 ten thousand.
14. according to the preparation method described in claim 4 or 5, wherein, R1For H or methyl, R2、R5And R8It is each independently
H, R3For connecting key or methylene, R6And R7It is each independently the straight or branched alkyl of H or C1-C5, and R6And R7No
It is H, R simultaneously9Straight or branched alkyl for C1-C5；R10、R10’、R11、R12、R11' and R12' it is each independently methyl each
Independently be methyl；X-For Br-。
15. according to the preparation method described in claim 4 or 5, and wherein, the weight of described monomer mixture mixes with water and monomer
The ratio of the gross weight of thing is 0.05-0.5:1.
16. preparation methods according to claim 15, wherein, the weight of described monomer mixture and water and monomer mixture
The ratio of gross weight be 0.15-0.4:1.
17. according to the preparation method described in claim 4 or 5, and wherein, described initiator is gone back selected from azo series initiators and oxidation
Former series initiators, in described monomer mixture on the basis of the total mole number of monomer, the consumption of described azo series initiators is 0-
10 moles of %, the consumption of described redox series initiators is 0-10 mole of %, and total consumption of described initiator is 0.0001-
10 moles of %；Described azo series initiators is selected from the double [2-(2-of 2,2 '-azo diisobutyl amidine hydrochloride and/or 2,2 '-azo
Imidazoline-2-base) propane] dihydrochloride, described redox series initiators includes Oxidizing and Reducing Agents, described oxidant with
The mol ratio of described reducing agent is 0.5-3.5:1, and described oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and mistake
At least one in hydrogen oxide；Described reducing agent is at least one in inorganic reducing agent, rongalite, ascorbic acid and urea, institute
Stating inorganic reducing agent is at least in sodium hydrogensulfite, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite
Kind.
18. according to the preparation method described in claim 4 or 5, and wherein, described polymerisation is carried out in the presence of auxiliary agent, described
Auxiliary agent is at least one in chelating agent and other auxiliary agents；On the basis of the total mole number of described monomer mixture, described
The consumption of chelating agent is 0-2 mole of %, and the consumption of other auxiliary agents described is 0-2 mole of %, and with single in described monomer mixture
On the basis of the total mole number of body, total consumption of described auxiliary agent is 0.0001-4 mole of %；Described chelating agent is selected from ethylenediamine tetraacetic
At least one in acetic acid disodium, diethylenetriamine pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, described other help
Agent is at least one in urea, sodium formate, isopropanol, DTAB and sodium hypophosphite.
19. preparation methods according to claim 4, wherein, described solution polymerization is carried out in the presence of an inert gas,
Polymeric reaction condition includes: temperature is 0-50 DEG C, and the time is 1-24 hour, and pH value is 5-13.
20. preparation methods according to claim 5, wherein, described emulsion polymerization is carried out in the presence of an inert gas,
Polymeric reaction condition includes: temperature is 0-50 DEG C, and the time is 1-24 hour, and pH value is 5-13.
21. according to the preparation method described in claim 4 or 19, and wherein, the process of described solution polymerization includes entering successively
The three phases of row, the reaction condition of first stage includes: temperature is 0-10 DEG C, and the time is 1-15 hour；Second stage anti-
Answering condition to include: temperature is 15-30 DEG C, the time is 3-8 hour；The reaction condition of phase III includes: temperature is 35-50 DEG C,
Time is 2-14 hour.
22. according to the preparation method described in claim 5 or 20, and wherein, the process of described emulsion polymerization includes entering successively
In two stages of row, the reaction condition of first stage includes: temperature is 0-20 DEG C, and the time is 1-15 hour；Second stage anti-
Answering condition to include: temperature is 20-50 DEG C, the time is 2-8 hour.
Acrylamide based copolymer described in any one or by any one in claim 4-22 in 23. claims 1-3
The acrylamide based copolymer that method described in Xiang prepares is as the application of drag reducer.
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