CN106608944A - Temperature-resistant thickening agent copolymerization association compound and preparation method thereof - Google Patents
Temperature-resistant thickening agent copolymerization association compound and preparation method thereof Download PDFInfo
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- CN106608944A CN106608944A CN201510683658.1A CN201510683658A CN106608944A CN 106608944 A CN106608944 A CN 106608944A CN 201510683658 A CN201510683658 A CN 201510683658A CN 106608944 A CN106608944 A CN 106608944A
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- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title abstract 4
- 239000002562 thickening agent Substances 0.000 title abstract 3
- 125000002091 cationic group Chemical group 0.000 claims abstract description 89
- 229920000768 polyamine Polymers 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 238000010276 construction Methods 0.000 claims description 43
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000010792 warming Methods 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 150000004292 cyclic ethers Chemical class 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 5
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 5
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 4
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 11
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 abstract 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000706 filtrate Substances 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000005553 drilling Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000012530 fluid Substances 0.000 description 16
- NZQQFMVULBBDSP-FPLPWBNLSA-N bis(4-methylpentan-2-yl) (z)-but-2-enedioate Chemical compound CC(C)CC(C)OC(=O)\C=C/C(=O)OC(C)CC(C)C NZQQFMVULBBDSP-FPLPWBNLSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003643 water by type Substances 0.000 description 11
- 239000013067 intermediate product Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000230 xanthan gum Substances 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- 235000010493 xanthan gum Nutrition 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a temperature-resistant thickening agent copolymerization association compound and a preparation method thereof. The copolymerization association compound contains a structural unit A, a structural unit B and a structural unit C, the structural unit A is N,N-dimethylacrylamide, the structural unit B is an amphoteric monomer methacryloyloxyethyl-N,N-dimethylpropanesulfonate (DMAPS), and the structural unit C is an ion association body of the structural unit B and cationic polyamine; and based on the total amount of the copolymerization association compound, the content of the N,N-dimethylacrylamide is 10-75% by weight, preferably 30-65% by weight, the total content of the amphoteric monomer is 8-55% by weight, preferably 20-60% by weight, and the content of the cationic polyamine is 1-50% by weight, preferably 3-40% by weight. Temperature resistance of the thickening agent prepared by the method can reach 150 DEG C, anti-NaCl concentration is saturated, and anti-CaCl2 concentration reaches 20%; and meanwhile, excellent shale inhibition performance and filtrate loss controllability are furthermore achieved.
Description
Technical field
The present invention relates to polymer for drilling fluid and preparation method thereof in Process of Oil Well Drilling, more particularly to a kind of drilling fluid high temperature resistant anticalcium viscosifier and preparation method thereof.
Background technology
In drilling process, in order to ensure that drilling fluid has higher viscosity and good rheological characteristic under low solid phase, it usually needs add viscosifier to improve the viscosity of drilling fluid.Drilling fluid tackifier is the very long high molecular weight water soluble polymer of strand, and viscosifier also tend to also serve as shale control agent except playing viscosifying action（Coating agent）, fluid loss additive and flow pattern modifier etc..Therefore, be often conducive to improving the rheological characteristic of drilling fluid using viscosifier, be also beneficial to wellbore stability.
Drilling fluid tackifier is of paramount importance one kind in drilling well auxiliary agent, is broadly divided into natural plant and synthesis two big class of macromolecule, is ensureing drilling fluid safe construction, taking the aspects such as abrasive band bits have important function.But existing drilling fluid tackifier such as xanthan gum, 80A51
Deng, construction at high temperature needs are not well positioned to meet, most of viscosifier Efficient Adhesive Promotion under the conditions of higher than 150 DEG C declines rapidly, even disappears completely.In terms of salt resistance, anti- high calcium chloride concentration also drilling fluid field problem demanding prompt solution, current almost polymer of the not anti-calcium chloride concentration more than 15% in conventional viscosifier, thus tackifier for drilling fluid heat resistance conventional at present and anti-calcium and anti-salt performance tend not to take into account.
CN102372818A
With anticalcium polymeric viscosifiers disclosed in CN102464761A, mainly obtained by sulfonation group or hydrophobic group being introduced in acrylamide copolymer, can only meet calcium ion concentration and be not higher than 2000mg/L
Cryogenic conditions under（Less than 100 DEG C）Use demand.High temperature resistant viscosifier disclosed in CN101955564A, CN103113518A and CN102127401A, the resistance to elevated temperatures of viscosifier are obviously improved, and heatproof reaches more than 200 DEG C；Anti-calcium and anti-salt performance is not referred to, but speculates that anti-calcium and anti-salt performance is not improved from monomer used and preparation method.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of anticalcium viscosifier copolymerization associated complex and preparation method thereof.Up to 150 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl to the viscosifier heatproof that the inventive method is obtained2Concentration is up to 20%.Higher apparent viscosity is maintained after high temperature ageing, while also having preferable yield value.
The invention provides a kind of heat-resistance type viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, the construction unit A is N, N- DMAAs, the construction unit B be zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate（DMAPS）, the construction unit C is the ion association body of construction unit B and cationic polyamine, and on the basis of the total amount of the copolymerization associated complex, the content of the N,N-DMAA is 10-75 weight %, preferably 30-65 weight %；The total content of the zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 8-55 weight %, preferably 20-60 weight %；The content of the cationic polyamine is 1-50 weight %, preferably 3-40 weight %；The copolymerization associated complex is 40-70mPas in 150 DEG C of apparent viscosities after aging 16 hours.
According to the viscosifier copolymerization associated complex that the present invention is provided, the structural formula of the construction unit A N,N-DMAAs is：
Formula（I）, the construction unit B zwitterionic monomers methylacryoyloxyethyl-N, the structural formula of N- dimethyl propylene sulfonate (DMAPS) is：Formula（II）, the construction unit C has the structure shown in following formula：
Formula（III）
Wherein, dotted line ... represents ion association, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structure：Formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, integers of the t for 1-5, integers of the z for 0-5；
N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 0.5-2mmol/g.Further preferably the kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree are 0.5-1.5mmol/g.
Above-mentioned cationic polyamine can balance anion with corresponding with multiple nitrogen cations for various, and under preferable case, the cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
T, n, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10.When x is 0, formula（V）End diamidogen is represented, y is preferably the integer of 1-7；When x is not equal to 0, and during y=2, formula（V）Represent polyethylene polyamine, integers of the x for 1-10.
Wherein the definition of substituent group and subscript with it is identical above.
Specifically, the cationic polyamine can be obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours to be reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide are 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
It should be noted that although temperature range 50-120 DEG C before heating up is overlapped with temperature range 80-150 DEG C after intensification, the temperature of the latter must be higher than the former temperature.
Can be by adding hydrochloric acid come terminating reaction.The addition of hydrochloric acid is preferably hydrochloric acid：End amine=1-3：1（Mol ratio）.
Under preferable case, the end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
Under preferable case, the cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
Under preferable case, the haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
According to the copolymerization associated complex that the present invention is provided, under preferable case, the weight average molecular weight of the copolymerization associated complex is 500,000-500 ten thousand, more preferably 1,000,000-300 ten thousand.
In the present invention, copolymerization associated complex had both included the structure formed by copolymerization in referring to polymer, also include the structure formed by ion association, wherein construction unit A, construction unit B are formed by copolymerization, construction unit B and cationic polyamine are combined together by ion association, form construction unit C.Dotted line ... in each structural formula represents ion association.
In the present invention, the total content of the various versions that the content of copolymerization associated complex cationic polyamine is provided by cationic polyamine in referring to copolymerization associated complex, including the amount of the cationic polyamine for forming copolymerization associated complex, also including the amount of the cationic polyamine for not forming copolymerization associated complex.
The means of testing grasped due to inventor is limited and/or limitation based on existing means of testing, the present invention each construction unit of copolymerization associated complex content be only capable of testing be construction unit corresponding with monomer content, and the content of construction unit C can not be measured, the amount of the zwitterionic structural elements for participating in associating and have neither part nor lot in association can not be measured, the content of i.e. above-mentioned zwitterionic structural elements includes associating to form the zwitterionic structural elements i.e. content of construction unit B of construction unit C with cationic polyamine, also include content not with the zwitterionic structural elements to form construction unit C that associate with cationic polyamine.
In the present invention, the content of each construction unit can be determined by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
In the present invention, the alkyl of the C1-C5 can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, one or more in neopentyl.The substituent group of the alkyl of the C1-C5 can for example be halogen or hydroxyl.
According to the copolymerization associated complex that the present invention is provided, it is conventional covalent polymerization methodses between wherein construction unit A, construction unit B, pass through Covalent bonding together between i.e., and construction unit C then by its anion and cation respectively with construction unit B on cation and anion become the construction unit of copolymerization associated complex with ion association, so as to its network structure is introduced in copolymerization associated complex so that copolymerization associated complex has higher shear force and heat-resistant salt-resistant.Above-mentioned ion association can by by its with obtained by carrying out being simply mixed the mixture for obtaining by the copolymerization associated complex and cationic polyamine between construction unit A, construction unit B and measure the greatest differences of its shear force and heat-resistant salt-resistant under the same conditions and speculate with reference to the principles of chemistry.
In the present invention, the content of each construction unit can be determined by way of content of monomer calculating or nuclear magnetic resonance, NMR before and after reaction are with reference to infrared spectrum analysiss.
The present invention also provides a kind of preparation method of above-mentioned heat-resistance type viscosifier copolymerization associated complex, and the preparation method is comprised the following steps：
（1）Inorganic salt is mixed with water, the inorganic salt solution of 2wt%～30wt% is prepared；
（2）Cationic polyamine and water are hybridly prepared into into cationic polyamine aqueous solution, the mass concentration of the cationic polyamine aqueous solution is 0.5%～3%；
（3）Methylacryoyloxyethyl-N is weighed,
N- dimethyl propylenes sulfonate and N, N- DMAA and step（1）In inorganic salt solution mixing, methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and N,N-DMAA monomer gross mass concentration are 5%～20%, and according to N,N-DMAA, methylacryoyloxyethyl-N,
On the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of N,N-DMAA is 10-75 weight %, preferably 30-65 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 15-65 weight %, preferably 20-60 weight %；N is passed through after fully dissolving20.5～1h of deoxygenation, while being warming up to 40～60 DEG C, adds 0.5～2h of initiator for reaction after 5～10min of constant temperature；
（4）By step（2）The cationic polyamine aqueous solution of preparation is added to step（3）In the product for obtaining, mix homogeneously is warming up to 50～70 DEG C simultaneously, continues reaction 3～5；On the basis of the total amount of N,N-DMAA, methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %；
（5）By step（4）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing is viscosifier through drying and after crushing.
The preparation method of the copolymerization associated complex provided according to the present invention, the environment that the anion and cation that one Main Function of the inorganic salt is to provide on zwitterionic structural elements is exchanged/associated with cation and anion on cationic polyamine, as long as therefore can provide above-mentioned environment inorganic salt may be used as the present invention inorganic salt.Under preferable case, the inorganic salt be ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, one or more in zirconates.The inorganic salt is preferably used in the form of a solution.
, by research it has furthermore been found that different types of inorganic salt, the solution concentration for reaching optimum efficiency is different for the present inventor, for example, when the inorganic salt is ammonium salt, the inorganic salt solution concentration is preferably 10wt%～30wt%；When the inorganic salt is calcium salt, magnesium salt, mantoquita, zinc salt, the inorganic salt solution concentration is preferably 5%～15%, more preferably 10%～15%；When the inorganic salt is aluminium salt, the inorganic salt solution concentration is preferably 2wt%～10wt%；When the inorganic salt is zirconates, described inorganic salt solution concentration is preferably 2wt%～5wt%.The concentration of above-mentioned inorganic salt solution only considers the amount of inorganic salt and its solvent, does not consider the amount of other materials such as monomer.
When the inorganic salt be ammonium salt when, be specifically as follows ammonium chloride, ammonium bromide, one or more of ammonium nitrate；When the inorganic salt is calcium salt, calcium chloride, calcium bromide are specifically as follows；When the inorganic salt be magnesium salt when, be specifically as follows magnesium chloride, magnesium bromide, magnesium sulfate, one or more of magnesium nitrate；When the inorganic salt be aluminium salt when, be specifically as follows aluminum chloride, aluminium bromide, aluminum sulfate, one or more of aluminum nitrate；When the inorganic salt be mantoquita when, be specifically as follows copper chloride, copper bromide, copper sulfate, one or more of copper nitrate；When the inorganic salt be zinc salt when, be specifically as follows zinc chloride, zinc bromide, one or more of zinc nitrate；When the inorganic salt be zirconates when, be specifically as follows zirconium chloride, zirconium bromide, zirconium oxychloride, one or more of zirconium nitrate.
The preparation method of the copolymerization associated complex provided according to the present invention, step（3）Carry out in the presence of initiator, the species and consumption of the initiator are referred to prior art to be carried out.Under preferable case, the initiator can be one or more in sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate..The consumption of the initiator is preferably the 0.3-0.7wt% of monomer total amount.
In the inventive method, the monomer gross mass concentration is the ratio of monomer mass and water gross mass.
The preparation method of the copolymerization associated complex provided according to the present invention, the cationic polyamine have following formula（i）Shown structure：
Formula（i）
Wherein, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structureFormula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, integers of the t for 1-5, integers of the z for 0-5；N, p are respectively the integer of 1-5, integers of the x for 0-10, integers of the y for 1-10；L, l ' and l ' ' value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 0.5-2mmol/g.
Above-mentioned cationic polyamine is referred to the preparation method of cationic polyamine polymer disclosed in CN103773332A and is prepared：By carrying out polyreaction and obtaining end amine, cyclic ethers and epoxy alkyl halide.The end amine can be the alkyl diamine that alkyl diamine such as carbon number is 1-6, concrete such as ethylenediamine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；Can also be polyamines polyene such as NH2-(CH2-CH2-NH)nIntegers of the H wherein n for 1-5, such as diethylenetriamine, triethylene tetramine or TEPA.The cyclic ethers can be cyclic ethers such as oxirane, expoxy propane, the epoxy butane that carbon number is 2-6.The epoxy alkyl halides can such as be epoxychloropropane, epoxy bromopropane or epoxy chlorobutane.But in order to ensure association and more preferable property of drilling fluid is obtained, the kinematic viscosity of the cationic polyamine should be controlled to 100-500mm2/ s, cationic degree should be controlled to 0.5-2mmol/g.Kinematic viscosity and cationic degree can be controlled by controlling the addition of cyclic ethers and epoxy alkyl halide within the above range.Usually control end amine and the mol ratio of cyclic ethers are 1：（2-4）.End amine is 1 with the mol ratio of epoxy alkyl halide：（0.2-0.7）.Other reaction conditions and operation are referred to above-mentioned prior art to be carried out.
The cationic polyamine is preferably used as an aqueous solution, and the concentration of cationic polyamine aqueous solution is preferably 0.5-3wt%, and the wherein amount of water is the total Water in reaction system.
According to the method that the present invention is provided, step（6）The purpose of products therefrom washing with acetone is to remove unreacted component, and dry temperature can be 100-120 DEG C, and the dry time can be 16-24 hours.
Compared with prior art, the viscosifier copolymerization associated complex that the present invention is provided and preparation method thereof advantage is as follows：
（1）The copolymerization associated complex that the present invention is provided, by containing N with certain proportion simultaneously, N- DMAA construction units, zwitterionic structural elements and cationic polyamine construction unit, and cationic polyamine construction unit has specific kinematic viscosity and cationic degree, during so that the copolymerization associated complex being used as drilling fluid tackifier, gained drilling fluid is not only after high temperature ageing with good apparent viscosity, but also there is preferable shear force, and heatproof, at least up to more than 150 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl2Concentration is up to 20%.
（2）In the preparation method of viscosifier copolymerization associated complex of the present invention, phase is by using high concentration inorganic salt solution before the reaction, sulfonic group zwitterionic monomer can be made to combine to form special construction with inorganic salt, as the presence of metal ion in inorganic salt causes the structure of sulfonic group zwitterionic monomer more to stretch, substantially reduce during polymerization intermolecular sterically hindered, arrange monomer molecule even closer, considerably increase the molecular weight of polymer.Phase is by adding low molecular weight cationic polyamine after the reaction, further had an effect with the sulfonic group in zwitterionic monomer by the ammonium cation on low molecular weight cationic polyamine structure, form more stable network structure, strengthen the structural viscosity of polymer, while ensureing that viscosifier have good apparent viscosity, preferable shear force is provided with again.
（3）Viscosifier copolymerization associated complex prepared by the inventive method has long-chain branch and rigid annular group.In aqueous due to the presence of long-chain branch and rigid annular group, increased the sterically hindered of polymer, increase the hydrodynamic volume of polymer, the trend of polymer temperature influence fracture hydrolysis is caused to reduce, so as to improve the performance of its heatproof, at least up to 150 DEG C, what is had reaches 180 DEG C to heatproof.
Description of the drawings
Fig. 1 and Fig. 2 be respectively DMAPS infrared and1HNMR spectrograms.
Specific embodiment
The effect and effect of the inventive method are illustrated with reference to embodiment, but following examples do not constitute the restriction to the present invention program.The present invention is described further for the following examples.In following examples, kinematic viscosity adopts GB GB/T
265 oil product kinematic viscosity algoscopys and dynamic viscosity calculating method are measured；Cationic degree is measured using colloid titration method；Apparent viscosity and yield value are determined by six fast rotating cylinder viscometer methods.Wherein, shear force represents the structural viscosity that system has, and shear force is bigger, illustrates that the performance of the suspension landwaste of drilling fluid is better.
In the embodiment of the present invention and comparative example, DMAPS monomers used can be prepared as follows：
Weigh 785g dimethylaminoethyl methacrylates to pour in reactor, be then placed in thermostat water bath, heat and start stirring.The PS of 122g being weighed again, being added directly in dimethylaminoethyl methacrylate, reaction temperature is 55 DEG C, and the crude product of DMAPS is obtained after stirring reaction 2h.DMAPS crude products are transferred in large stretch of filter paper and are wrapped, be positioned in Soxhlet extraction device, the use of ethanol is solvent extraction 2.5h, extracting after finishing is placed on filter paper bag in drying baker, dry at 35 DEG C, finally gives pure DMAPS monomers.The infrared spectrum of the DMAPS and hydrogen nuclear magnetic spectrogram are respectively as depicted in figs. 1 and 2.
In the embodiment of the present invention and comparative example, cationic polyamine used is prepared as follows：
In 1000mL four round flask, add 60g ethylenediamines, 70 DEG C are warming up under agitation, then gradually Deca 116g expoxy propane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxychloropropane, controlling reaction temperature are 90-150 DEG C, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of ethylenediamine:1, reaction 4h obtains cationic polyamine 1.The kinematic viscosity of cationic polyamine 1 is 330mm2/ s, cationic degree are 1.8mmol/g.
Wherein, R9、R9’、R10、R10' it is respectively following formula（IV-1）Shown structure
Formula（IV-1）
In 1000mL four round flask, add 60g hexamethylene diamines, 70 DEG C are warming up under agitation, then gradually Deca 116g oxirane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxy bromopropane, controlling reaction temperature are 90-150 DEG C, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of hexamethylene diamine:1, reaction 4h obtains cationic polyamine 2.The kinematic viscosity of cationic polyamine 2 is 460mm2/ s, cationic degree are 1.9 mmol/g.
In 1000mL four round flask, add 60g triolefin tetramines, 70 DEG C are warming up under agitation, then gradually Deca 116g epoxy butane, controlling reaction temperature 60-100 DEG C, 95 DEG C are warming up to after reaction 1h, gradually Deca 185g epoxy chlorobutane, controlling reaction temperature is 90-150, when thickening behavior occurs in question response system, hydrochloric acid is added after at least maintaining half an hour, hydrochloric acid is 2 with the mol ratio of triolefin tetramine:1, reaction 4h obtains cationic polyamine 3.The kinematic viscosity of cationic polyamine 3 is 410 mm2/ s, cationic degree are 1.5 mmol/g.
Embodiment 1
Weigh 440g NaCl to be dissolved in 1650g deionized waters；Weigh 28g DMAPS, 90g again respectively
DMAM is dissolved in NaCl solution；Reactor is transferred to after fully dissolving, N is passed through2Deoxygenation 1h, while being warming up to 55 DEG C, adds 0.45g Ammonium persulfate .s, obtains intermediate product after reaction 2h after keeping 30min.Again 20g cationic polyamines 1 are dissolved in 100g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 65 DEG C, continue reaction 4 hours.Precipitate is obtained with acetone precipitation.Crush after 24h is dried at 110 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Embodiment 2
Weigh 112g CaCl2It is dissolved in 910g deionized waters；Weigh 56g DMAPS again respectively, 78g DMAM are dissolved in CaCl2In solution；Reactor is transferred to after fully dissolving, N is passed through2Deoxygenation 1h, while being warming up to 60 DEG C, adds 0.45g sodium peroxydisulfates, reaction 1h to obtain intermediate product after keeping 30min.Again 20g cationic polyamines 2 are dissolved in 100g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue reaction 3 hours.Precipitate is obtained with acetone precipitation.Crush after 24h is dried at 120 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Embodiment 3
Weigh 40g AlCl3It is dissolved in 660g deionized waters；Weigh 84g DMAPS again respectively, 70g DMAM are dissolved in AlCl3In solution；Reactor is transferred to after fully dissolving, N is passed through2Deoxygenation 0.5h, while being warming up to 60 DEG C, adds 0.54g potassium peroxydisulfates, obtains intermediate product after reaction 1.5h after keeping 30min.Again 25g cationic polyamines 3 are dissolved in 100g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 65 DEG C, continue reaction 4 hours.Precipitate is obtained with acetone precipitation.Crush after 16h is dried at 120 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Embodiment 4
Weigh 19g ZrCl4It is dissolved in 368g deionized waters；Weigh 28g DMAPS again respectively, 90g DMAM are dissolved in ZrCl4In solution；Reactor is transferred to after fully dissolving, N is passed through2Deoxygenation 1h, while being warming up to 55 DEG C, adds 0.30g sodium peroxydisulfates, reaction 1h to obtain intermediate product after keeping 1h.Again 10g cationic polyamines 2 are dissolved in 50g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue reaction 4.5 hours.Precipitate is obtained with acetone precipitation.Crush after 20h is dried at 110 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Comparative example 1（It is not added with inorganic salt）
56g DMAPS, 78g are weighed respectively
DMAM is transferred to reactor after being completely dissolved in 910g deionized waters, is passed through N2Deoxygenation 1h, while being warming up to 50 DEG C, adds 0.45g sodium peroxydisulfates, reaction 1h to obtain intermediate product after keeping 30min.Again 20g cationic polyamines 2 are dissolved in 100g deionized waters and are configured to cationic polyamine solution, then cationic polyamine solution is added into intermediate product, mix homogeneously, while being warming up to 70 DEG C, continue reaction 3 hours.Precipitate is obtained with acetone precipitation.Crush after 24h is dried at 120 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Comparative example 2（It is not added with cationic polyamine）
Weigh 112g CaCl2It is dissolved in 1010g deionized waters；Weigh 56g DMAPS again respectively, 78g DMAM are dissolved in CaCl2In solution；Reactor is transferred to after fully dissolving, N is passed through2Deoxygenation 1h, while being warming up to 70 DEG C, adds 0.45g sodium peroxydisulfates, obtains gelatinous solid, obtain precipitate with acetone precipitation after reaction 5h after keeping 30min.Crush after 24h is dried at 120 DEG C, it is final to obtain DMAPS/DMAM viscosifier.
Comparative example 3
By commercially available purchase viscosifier 80A51.
Comparative example 4
By commercially available purchase viscosifier xanthan gum.
Above-described embodiment and comparative example evaluate thickening property using the base slurry of saliferous calcic, and concrete evaluation methodology is as follows：
Base slurry is prepared：In 1000mL water, add 40g calcium bentonites and 5g sodium carbonate, high-speed stirred 20min that maintenance 24h is placed under room temperature, fresh water-based slurry is obtained；Continuously add 200g CaCl2, high-speed stirred 20min, placement maintenance 24h under room temperature obtain evaluating with containing 20% CaCl2Base is starched.
Evaluation methodology：The base slurry of 350mL is measured, and adds 2% viscosifier, high-speed stirred 20min its apparent viscosity to be surveyed after room temperature maintenance 24h.Again after aging 16h at 150 DEG C, apparent viscosity is determined again, calculate apparent viscosity conservation rate.
1 different viscosifier temperature-resistant anti-salt anticalcium performance comparison tables of table
| Apparent viscosity after high temperature ageing, mPa s | Apparent viscosity conservation rate, % | Yield value after high temperature ageing, mPa s | |
| Embodiment 1 | 52 | 91.6 | 21 |
| Embodiment 2 | 60 | 93.9 | 27 |
| Embodiment 3 | 56 | 93.3 | 24 |
| Embodiment 4 | 63 | 93.9 | 25 |
| Comparative example 1 | 22 | 54.4 | 5 |
| Comparative example 2 | 36 | 71.8 | 9 |
| Comparative example 3 | 6 | 18.8 | 1 |
| Comparative example 4 | 8 | 11.1 | 1 |
Note：The dosage of 4 xanthan gum of comparative example is 0.5%.
From the result of table 1 can be seen that the present invention viscosifier after high temperature ageing apparent viscosity conservation rate it is higher, illustrate preferable heatproof and salt resistant character；And yield value is also in preferable level after high temperature ageing, it is ensured that drilling fluid system rock of taking under the high temperature conditions carries grittiness energy.
Claims (19)
1. a kind of heat-resistance type viscosifier copolymerization associated complex, the copolymerization associated complex contains construction unit A, construction unit B and construction unit C, and the construction unit A is N,N-DMAA, the construction unit B be zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate（DMAPS）, the construction unit C is the ion association body of construction unit B and cationic polyamine, and on the basis of the total amount of the copolymerization associated complex, the content of the N,N-DMAA is 10-75 weight %, preferably 30-65 weight %；The total content of the zwitterionic monomer methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 8-55 weight %, preferably 20-60 weight %；The content of the cationic polyamine is 1-50 weight %, preferably 3-40 weight %；The copolymerization associated complex is 40-70mPas in 150 DEG C of apparent viscosities after aging 16 hours.
2. according to the copolymerization associated complex described in claim 1, it is characterised in that：The construction unit C has the structure shown in following formula：
Formula（III）
Wherein, dotted line ... represents ion association, X-For inorganic anion；R、R9、R9’、R10、R10' it is respectively following formula（IV）Shown structure：Formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, integers of the t for 1-5, integers of the z for 0-5；N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；L, l ' and l " value cause the cationic polyamine kinematic viscosity be 100-500mm2/ s, cationic degree are 0.5-2mmol/g.
3. according to the copolymerization associated complex described in claim 2, it is characterised in that：The kinematic viscosity of the cationic polyamine is 150-450mm2/ s, cationic degree are 0.5-1.5mmol/g.
4. according to the copolymerization associated complex described in claim 1, it is characterised in that：The cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
T, n, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；When x is 0, formula（V）End diamidogen is represented, y is preferably the integer of 1-7；When x is not equal to 0, and during y=2, formula（V）Represent polyethylene polyamine, integers of the x for 1-10.
5. according to the copolymerization associated complex described in claim 1, it is characterised in that：The cationic polyamine is obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours to be reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide are 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
6. according to the copolymerization associated complex described in claim 5, it is characterised in that：The end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
7. according to the copolymerization associated complex described in claim 5, it is characterised in that：The cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
8. according to the copolymerization associated complex described in claim 5, it is characterised in that：The haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
9. according to the copolymerization associated complex described in any claim in claim 1-8, it is characterised in that：The weight average molecular weight of the copolymerization associated complex is 500,000-500 ten thousand, preferably 1,000,000-300 ten thousand.
10. as described in any claim in claim 1-9 heat-resistance type viscosifier copolymerization associated complex preparation method, the preparation method comprises the following steps：
（1）Inorganic salt is mixed with water, the inorganic salt solution of 2wt%～30wt% is prepared；
（2）Cationic polyamine and water are hybridly prepared into into cationic polyamine aqueous solution, the mass concentration of the cationic polyamine aqueous solution is 0.5%～3%；
（3）Weigh methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and N, N- DMAA and step（1）In inorganic salt solution mixing, methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and N, N- dimethacrylamide monomers total mass concentration is 5%～20%, and according to N,N-DMAA, methylacryoyloxyethyl-N, on the basis of the total amount of N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of N,N-DMAA is 10-75 weight %, preferably 30-65 weight %；The consumption of methylacryoyloxyethyl-N, N- dimethyl propylene sulfonate is 15-65 weight %, preferably 20-60 weight %；N is passed through after fully dissolving20.5～1h of deoxygenation, while being warming up to 40～60 DEG C, adds 0.5～2h of initiator for reaction after 5～10min of constant temperature；
（4）By step（2）The cationic polyamine aqueous solution of preparation is added to step（3）In the product for obtaining, mix homogeneously is warming up to 50～70 DEG C simultaneously, continues reaction 3～5；On the basis of the total amount of N,N-DMAA, methylacryoyloxyethyl-N, N- dimethyl propylenes sulfonate and cationic polyamine, the consumption of cationic polyamine is 1-50 weight %, preferably 3-40 weight %；
（5）By step（4）The product for obtaining is washed with acetone soln, and the solid sediment obtained after washing is viscosifier through drying and after crushing.
11. in accordance with the method for claim 10, it is characterised in that：The inorganic salt be ammonium salt, calcium salt, magnesium salt, mantoquita, zinc salt, aluminium salt, one or more in zirconates.
12. according to the method described in claim 10 or 11, it is characterised in that：The inorganic salt is used in the form of a solution, and the inorganic salt be ammonium salt when, the inorganic salt solution concentration be 10wt%～30wt%；When the inorganic salt is calcium salt, magnesium salt, mantoquita, zinc salt, the inorganic salt solution concentration is 5%～15%, preferably 10%～15%；When the inorganic salt is aluminium salt, the inorganic salt solution concentration is 2wt%～10wt%；When the inorganic salt is zirconates, described inorganic salt solution concentration is 2wt%～5wt%.
13. in accordance with the method for claim 10, it is characterised in that：The initiator is sodium peroxydisulfate, potassium peroxydisulfate, one or more in Ammonium persulfate., the 0.3-0.7wt% of the consumption of the initiator for monomer total amount.
14. in accordance with the method for claim 10, it is characterised in that：The cationic polyamine has following formula（i）Shown structure：
Formula（i）
Wherein, X-For inorganic anion；R、R9、R9`、R10、R10` is respectively following formula（IV）Shown structural formula（IV）, wherein, R11For H, substituted or unsubstituted C1-C5 alkyl, integers of the t for 1-5, integers of the z for 0-5；
N, p are respectively the integer of 1-5；Integers of the x for 0-10, integers of the y for 1-10；It is 100-500mm that the value of l, l` and l`` causes the kinematic viscosity of the cationic polyamine2/ s, cationic degree are 0.5-2mmol/g.
15. in accordance with the method for claim 14, it is characterised in that：The cationic polyamine is by formula（V）Shown end amine and formula（VI）Shown cyclic ethers and formula（VII）Shown haloalkylene oxide is obtained by condensation reaction
。
16. in accordance with the method for claim 15, it is characterised in that：The cationic polyamine is obtained by following methods：Mol ratio to Deca cyclic ethers in the amine of end, cyclic ethers and end amine at stirring condition and 50-120 DEG C is 2-4：1,1-4 hours to be reacted after completion of dropwise addition, 80-150 DEG C is then heated to, Deca haloalkylene oxide under stirring condition, haloalkylene oxide are 0.2-0.7 with the mol ratio of end amine：1,1-4 hours are reacted after completion of dropwise addition, then terminating reaction.
17. in accordance with the method for claim 16, it is characterised in that：The end amine be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, one or more in TEPA.
18. in accordance with the method for claim 16, it is characterised in that：The cyclic ethers is oxirane, expoxy propane, one or more in tetrahydrofuran.
19. in accordance with the method for claim 16, it is characterised in that：The haloalkylene oxide is epoxychloropropane, epoxy bromopropane, one or more in epoxy chlorobutane.
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