CN105601805A - Hydrophobic associated polymer and preparation method thereof - Google Patents
Hydrophobic associated polymer and preparation method thereof Download PDFInfo
- Publication number
- CN105601805A CN105601805A CN201511018633.6A CN201511018633A CN105601805A CN 105601805 A CN105601805 A CN 105601805A CN 201511018633 A CN201511018633 A CN 201511018633A CN 105601805 A CN105601805 A CN 105601805A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- acrylamide
- monomer
- hydrophobic
- associated polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 172
- 229920000642 polymer Polymers 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 146
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 58
- -1 allyl alkyl quaternary ammonium salt Chemical class 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical class 0.000 claims abstract description 39
- 125000005250 alkyl acrylate group Chemical class 0.000 claims abstract description 26
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 14
- 229940048053 acrylate Drugs 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000003252 repetitive effect Effects 0.000 claims abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 10
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 229940047670 sodium acrylate Drugs 0.000 claims description 9
- 150000003871 sulfonates Chemical class 0.000 claims description 9
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- JRUSUOGPILMFBM-UHFFFAOYSA-N n,n-dioctylprop-2-enamide Chemical compound CCCCCCCCN(C(=O)C=C)CCCCCCCC JRUSUOGPILMFBM-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940080818 propionamide Drugs 0.000 claims description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 3
- CFBQDVAZIXLOAR-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCC)C Chemical compound C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCC)C CFBQDVAZIXLOAR-UHFFFAOYSA-N 0.000 claims description 3
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002511 behenyl 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])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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000555 dodecyl gallate Substances 0.000 claims description 3
- 229940080643 dodecyl gallate Drugs 0.000 claims description 3
- 235000010386 dodecyl gallate Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 claims description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002460 pentacosyl 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])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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000001960 triggered effect Effects 0.000 claims description 3
- BRBUDLNOHBQTJM-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCCCC)C Chemical compound C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCCCC)C BRBUDLNOHBQTJM-UHFFFAOYSA-N 0.000 claims description 2
- LXPYCXSXQLWMMP-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCCCCC)C Chemical compound C(C=C)(=O)NC(C[Na])(CCCCCCCCCCCCCCCCCCCCCCC)C LXPYCXSXQLWMMP-UHFFFAOYSA-N 0.000 claims description 2
- BRUQQQPBMZOVGD-XFKAJCMBSA-N Oxycodone Chemical compound O=C([C@@H]1O2)CC[C@@]3(O)[C@H]4CC5=CC=C(OC)C2=C5[C@@]13CCN4C BRUQQQPBMZOVGD-XFKAJCMBSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical class [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- IXSXIMCFYLTCMM-UHFFFAOYSA-N n,n-didodecylprop-2-enamide Chemical class CCCCCCCCCCCCN(C(=O)C=C)CCCCCCCCCCCC IXSXIMCFYLTCMM-UHFFFAOYSA-N 0.000 claims description 2
- ZLSJVVLETDAEQY-UHFFFAOYSA-N n,n-dihexylprop-2-enamide Chemical compound CCCCCCN(C(=O)C=C)CCCCCC ZLSJVVLETDAEQY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims 1
- RZGZTQYTDRQOEY-UHFFFAOYSA-N 2-phenylethenone Chemical compound O=C=CC1=CC=CC=C1 RZGZTQYTDRQOEY-UHFFFAOYSA-N 0.000 claims 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000006467 substitution reaction Methods 0.000 abstract 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910001424 calcium ion Inorganic materials 0.000 description 15
- 229910001425 magnesium ion Inorganic materials 0.000 description 15
- 239000012266 salt solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000015784 hyperosmotic salinity response Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920000136 polysorbate Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- DBLNSVZHOZOZQX-UHFFFAOYSA-N n-tetradecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCNC(=O)C=C DBLNSVZHOZOZQX-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FDZUPHXVDHGJQR-UHFFFAOYSA-N 4,4-difluoroheptane Chemical compound CCCC(F)(F)CCC FDZUPHXVDHGJQR-UHFFFAOYSA-N 0.000 description 1
- HMRUVIQLLOKKNW-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCCCC)[Na] Chemical compound C(CCCCCCCCCCCCCCCCCCCCC)[Na] HMRUVIQLLOKKNW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- BKWMQCLROIZNLX-UHFFFAOYSA-N n-hexadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)C=C BKWMQCLROIZNLX-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention provides a hydrophobic associated polymer, comprising four repetitive units as follows, wherein y is equal to 0.001-0.2, z is equal to 0.005-0.3, m is equal to 0.03-0.2, and x plus y plus z plus m is equal to 1; A is a monomeric unit of a hydrophobic monomer; the hydrophobic monomer is selected from one or more of N-alkyl substituted acrylamide, alkyl acrylate, alkyl (meth) acrylate, fluoro-substitution alkyl acrylate, fluoro-substitution alkyl (meth) acrylate, allyl alkyl quaternary ammonium salt, acrylamide alkyl sulfoacid and acrylamide alkyl sulfonate; D is a monomer unit of a functional monomer. Compared with the prior art, the monomer unit of acrylamide in the polymer can provide hydrophilic groups; the monomeric unit of the hydrophobic monomer can provide hydrophobic lateral groups and provide viscoelasticity for a solution; a sodium acrylate unit can improve the solubleness of the hydrophobic associated polymer; the introduction of the monomer unit of the functional monomer can improve the temperature resistance and salt resistance of the polymer. The repetitive units are shown in the description.
Description
Technical field
The invention belongs to technical field of polymer, relate in particular to a kind of hydrophobic associated polymer and preparation side thereofMethod.
Background technology
In oil field development application technology, conventionally need to carry out rebuilding construction etc. to ground environment, need to makeCarry out mass transfer, conveying with the fluid of certain performance, by inject these fluids to stratum, by CucumberBring stratum into and produce work in order to transform ground environment, reach the object of oil-gas field development and volume increase. Meanwhile,Relevant application technology also requires these fluids itself also to possess some specific performance, for example thickening property,Viscoplasticity, drag reduction, permeability, the mobility ratio etc. of improving. Wherein, the most frequently used fluid is exactly the aqueous solution,It has the advantages such as source is wide, economy, constructability, natural or synthetic water-soluble by adding in waterProperty macromolecule, can obtain and have the above high performance aqueous solution. This class water soluble polymer has thickeningThe viscoplasticity that property is strong and good, and on strand, there are a lot of active groups, so that convection cell performance is enteredThe plurality of advantages such as row physics and chemical improvement possess easy construction simultaneously, and consumption is few, and cost is low, canFor bringing higher economic interests in oil field. Therefore, this class water soluble polymer is widely used in oil field skillIn art.
In prior art, the water soluble polymer of use mainly comprises natural or synthetic water-soluble high scoreSon. The yield and quality of natural polymer is owing to being subject to the restriction in season, area, and stability can notBe protected, and with respect to synthetic macromolecule, its consumption is large, easily biological-degradable, higher residue alsoEnvironment in meeting grievous injury stratum, brings many new problems to later development. At present, synthetic macromoleculeMost popular is polyacrylamide, although its various aspects of performance all can reach construction requirement,In pumping procedure, be easy to cause mechanical degradation, solution viscosity declines fast, simultaneously in some high temperature high mineralizationUnder degree reservoir media, polyacrylamide is salt tolerant not, and at high temperature very easily degraded, thereby causes every propertyCan significantly decline, and on the basis of its existing molecular structure, be difficult to further overcome, therefore,From polymer molecular structure, to its modification, to improve, it is anti-shearing, heat-resistant salt-resistant performance has been to compel at eyebrowEyelash.
For the problem of above-mentioned existence, researchers have proposed water-soluble hydrophobic associated polymerization on this basisThing. Water-soluble hydrophobic associated polymer (HAWSP) refer on polymer hydrophilicity macromolecular chain withThe water-soluble polymer of a small amount of hydrophobic grouping. In the aqueous solution, HAWSP concentration is higher than critical association concentrationAfter, macromolecular chain is assembled by hydrophobic association polymer effect, forms Interpolymer Association moving without chemical crosslinkingState physical cross-linked network, increases substantially solution viscosity. Meanwhile, adding also of some surfactantThe hydrophobic effect that can strengthen polymer molecule interchain, makes Interpolymer Association dynamic physical cross-linked network intensityIncrease, the supermolecule physical cross-linked network existing in HAWSP and surfactant solution also makes this moltenLiquid has the characteristic of frozen glue, thereby good viscoplasticity is provided. In addition, this supermolecule dynamic physical is crosslinkedNetwork have under high-rate of shear destroy and under low shear rate the feature of reversible recovery, make itStable performance, and possess excellent heatproof, salt tolerance, good shear thinning behavior, viscoplasticity etc. ThisSome excellent performances all show that hydrophobic associated polymer has that existing common oil field water dissolubility is high as an alternativeThe potentiality of molecule.
The present invention considers to provide a kind of new hydrophobic association polymer polymer.
Summary of the invention
In view of this it is good that, the technical problem to be solved in the present invention is to provide a kind of new salt resistant characterHydrophobic association polymer polymer and preparation method thereof.
The invention provides a kind of hydrophobic associated polymer, comprise following four repetitives:
Wherein, described y=0.001～0.2, z=0.005～0.3, m=0.03～0.2, x+y+z+m=1; DescribedA is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, acrylic acidThe alkyl acrylate that Arrcostab, alkyl methacrylate, fluorine replace, the methacrylic acid that fluorine replacesOne of Arrcostab, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid saltKind or multiple; Described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acidIn salt, the carbon number of alkyl is greater than 20; Described D is the monomeric unit of function monomer; Described function monomerBe selected to contain and hold sulfonic acid and the sulfonate derivatives thereof of thiazolinyl and contain the Hete rocyclic derivatives of holding thiazolinylIn one or more;
The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand.
Preferably, described y=0.001～0.1.
Preferably, described m=0.05～0.16.
Preferably, described N-alkyl-substituted acrylamide, alkyl acrylate, alkyl methacrylate,In the alkyl methacrylate that the alkyl acrylate that fluorine replaces and fluorine replace, the carbon number of alkyl is greater thanEqual 4.
Preferably, described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulphurIn hydrochlorate, the carbon number of alkyl is greater than 20 and is less than or equal to 40.
Preferably, described hydrophobic monomer be dodecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate,Metering system dodecyl gallate, methacrylic acid hexadecyl ester, octadecyl methacrylate, N-dodecyl thirdAlkene acid amides, N-cetyl acrylamide, 2-acrylamido-2-methyl pentacosyl sodium sulfonate, N-Octyl group propionamide, 2-acrylamido-2-methyl docosyl sodium sulfonate, 2-acrylamido-2 methylTetracosyl sodium sulfonate, N-myristyl acrylamide, N, N-dioctyl acrylamide, N, N-bis-is ownBase acrylamide, N, N-dioctylacrylamide, N, N-bis-dodecyl acrylamides, methyl-propTen difluoro heptan of olefin(e) acid hexafluoro butyl ester, acrylic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, acrylic acidEster, docosyl pi-allyl dichloride tetramethyl second two ammoniums, pentacosyl pi-allyl dibrominated tetramethylOne or more in base second two ammoniums and tetradecyl methylacrylate. Preferably, the carbon of described function monomerAtomicity is 2～20.
Preferably, described function monomer is 2-acrylamide-2-methylpro panesulfonic acid and sulfonate thereof, etheneIn base sulfonic acid and sulfonate thereof, styryl sulfonic acid and sulfonate and NVP oneKind or multiple.
The present invention also provides a kind of preparation method of hydrophobic associated polymer, comprising:
Under initator effect, acrylamide monomer, hydrophobic monomer and function monomer carry out copolyreaction,After hydrolysis, obtain hydrophobic associated polymer;
Or: under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator, hydrophobic listBody and function monomer carry out copolyreaction, obtain hydrophobic associated polymer; Or: under initator effect,Acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomer carry out copolyreaction, are dredgedWater association polymer;
Described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, alkyl acrylate, methacrylic acid alkaneThe alkyl acrylate that base ester, fluorine replace, alkyl methacrylate, the pi-allyl alkyl quaternary that fluorine replacesOne or more of ammonium salt, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt; Described pi-allylIn alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, the carbon number of alkyl is largeIn 20;
Described function monomer is selected to contain and holds sulfonic acid and the sulfonate derivatives thereof of thiazolinyl and contain endOne or more in the Hete rocyclic derivatives of thiazolinyl;
The molal quantity of described hydrophobic monomer is (0.001～0.2) with the ratio of total moles monomer: 1;
The molal quantity of described function monomer is (0.005～0.3) with the ratio of total moles monomer: 1.
The present invention also provides hydrophobic associated polymer at oilfield chemistry, water treatment, papermaking or mineral floatingApplication in field.
The invention provides a kind of hydrophobic associated polymer, comprise following four repetitives, described inY=0.001～0.2, z=0.005～0.3, m=0.03～0.2, x+y+z+m=1; Described A is hydrophobic monomerMonomeric unit; Described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, alkyl acrylate, methyl-propThe alkyl acrylate that olefin(e) acid Arrcostab, fluorine replace, alkyl methacrylate, the pi-allyl that fluorine replacesOne or more of alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt; DescribedIn pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, the carbon of alkyl is formerSubnumber is greater than 20; Described D is the monomeric unit of function monomer; Described function monomer is selected from and contains end thiazolinylSulfonic acid and sulfonate derivatives thereof and contain a kind of or many in the Hete rocyclic derivatives of holding thiazolinylKind; The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand. Compared with prior art, originallyInvention hydrophobic associated polymer is made up of four kinds of unit, the monomeric unit that hydrophilic unit is acrylamide, itsCan be hydrophobic association polymer hydrophilic group is provided, ensure that polymer has good water-soluble; Hydrophobic listUnit is the monomeric unit of hydrophobic monomer, and it can be hydrophobic associated polymer hydrophobic side group is provided, and ensures polymerizationThing chain has certain hydrophobic property, in water, between each hydrophobic side group, produces hydrophobic association effect, shapeBecome spacial framework, thereby provide necessary viscoplasticity for solution; PAA can improve hydrophobic associationThe dissolubility of polymer, improves the rheological property of polymer; Functional unit is the monomeric unit of function monomer,The introducing of these monomeric units can improve the heat-resistant salt-resistant performance of polymer; Above-mentioned four kinds of unit actings in conjunction,Temperature tolerance, salt tolerance and the anti-shear performance of hydrophobic associated polymer are improved.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the hydrophobic associated polymer that obtains in the embodiment of the present invention 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the hydrophobic associated polymer that obtains in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearlyChu, intactly description, obviously, described embodiment is only the present invention's part embodiment, and notWhole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art are not makingThe every other embodiment obtaining under creative work prerequisite, belongs to the scope of protection of the invention.
The invention provides a kind of hydrophobic associated polymer, comprise following four repetitives:
Wherein, described y=0.001～0.2, is preferably 0.001～0.15, and more preferably 0.001～0.1, more excellentElect 0.001～0.05 as, most preferably be 0.005～0.02; Described z=0.005～0.3, is preferably 0.05～0.2,Most preferably be 0.08～0.16; Described m=0.03～0.2, is preferably 0.05～0.16, then is preferably 0.1～0.16;X+y+z+m=1; Described m/ (x+m) is preferably 0.04～0.2, and more preferably 0.08～0.2.
Described A is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer be selected from N-alkyl-substituted acrylamide,The alkyl acrylate that alkyl acrylate, alkyl methacrylate, fluorine replace, the methyl that fluorine replacesAlkyl acrylate, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acidOne or more of salt, are preferably N-alkyl-substituted acrylamide, alkyl acrylate, methacrylic acidThe alkyl acrylate that Arrcostab, fluorine replace, alkyl methacrylate, the pi-allyl alkyl that fluorine replacesThe one of quaternary ammonium salt, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, more preferably N-alkylSubstituted acrylamide, alkyl acrylate, alkyl methacrylate, acrylamide alkyl sulfonic acid and thirdThe one of alkene acid amides alkylsulfonate; Described N-alkyl-substituted acrylamide, alkyl acrylate, methylAlkyl in the alkyl methacrylate that the alkyl acrylate that alkyl acrylate, fluorine replace and fluorine replaceCarbon number be preferably greater than or equal to 4, more preferably 4～40, then be preferably 4～30, then be preferably 10～20;Carbon atom in described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid saltNumber is greater than 20 and is less than or equal to 40, and more preferably 21～35, then be preferably 21～30; Third of described fluorine replacementThe number that in the alkyl methacrylate that olefin(e) acid Arrcostab and fluorine replace, fluorine replaces is preferably 4～10, more excellentElect 4～8 as; Hydrophobic monomer described in the present invention most preferably is dodecyl acrylate, Process Conditions of Cetane Acrylate, thirdOlefin(e) acid octadecyl ester, metering system dodecyl gallate, methacrylic acid hexadecyl ester, octadecyl methacrylate,N-dodecyl acrylamide, N-cetyl acrylamide 2-acrylamido-2-methyl pentacosylSodium sulfonate, N-octyl group propionamide, 2-acrylamido-2-methyl docosyl sodium sulfonate, 2-acrylamideBase-2 methyl tetracosyl sodium sulfonate, N-myristyl acrylamide, N, N-dioctyl acrylamide,N, N-dihexyl acrylamide, N, N-dioctylacrylamide, N, N-bis-dodecyl acrylamides,Hexafluorobutyl mathacrylate, acrylic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, acrylic acid tenDifluoro heptyl ester, docosyl pi-allyl dichloride tetramethyl second two ammoniums, pentacosyl pi-allyl dibromoOne or more in change tetramethyl second two ammonium tetradecyl methylacrylates.
Described D is the monomeric unit of function monomer; Described function monomer is selected from and contains the sulfnic acid derivatives of holding thiazolinylBiology and sulfonate derivatives thereof and contain one or more in the Hete rocyclic derivatives of holding thiazolinyl, described meritCarbon number that can monomer is preferably 2～20, and more preferably 2～15, then be preferably 2～10; In the present invention,Described function monomer most preferably is 2-acrylamide-2-methylpro panesulfonic acid and sulfonate thereof, vinyl sulfonic acidAnd a kind of or many in sulfonate, styryl sulfonic acid and sulfonate and NVPKind.
The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand, is preferably 100～1,500 ten thousand,More preferably 200～1,200 ten thousand, then be preferably 400～1,200 ten thousand, most preferably be 500～1,000 ten thousand.
Hydrophobic associated polymer of the present invention is made up of four kinds of unit, and hydrophilic unit is that acrylamide participates in copolymerizationForm, it can be hydrophobic association polymer hydrophilic group is provided, and ensures that polymer has good water-soluble;Hydrophobic units is that hydrophobic monomer participates in copolymerization formation, and it can be hydrophobic associated polymer hydrophobic side group is provided,Ensure that polymer chain has certain hydrophobic property, in water, between each hydrophobic side group, produce hydrophobic associationEffect, forms spacial framework, thereby provides necessary viscoplasticity for solution; PAA unit canImprove the dissolubility of hydrophobic associated polymer; Functional unit is that function monomer participates in copolymerization formation, and these are singleThe introducing of body unit can improve the heat-resistant salt-resistant performance of polymer; Above-mentioned four kinds of unit actings in conjunction, improveThe temperature tolerance of hydrophobic associated polymer, salt tolerance and anti-shear performance.
The present invention also provides a kind of preparation method of above-mentioned hydrophobic associated polymer, and the method is later waterThe mode of separating is introduced PAA, comprising: under initator effect, by acrylamide monomer, hydrophobic listBody and function monomer carry out copolyreaction, obtain hydrophobic associated polymer after hydrolysis; Described hydrophobic monomer choosingThe propylene replacing from N-alkyl-substituted acrylamide, alkyl acrylate, alkyl methacrylate, fluorineAlkyl methacrylate, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl that acid alkyl ester, fluorine replaceOne or more of sulfonic acid and acrylamide alkyl sulfonic acid salt; Described pi-allyl alkyl quaternary ammonium salts, acryloylIn amine alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, the carbon number of alkyl is greater than 20; Described function monomerBe selected to contain and hold sulfonic acid and the sulfonate derivatives thereof of thiazolinyl and contain the Hete rocyclic derivatives of holding thiazolinylIn one or more; The molal quantity of described hydrophobic monomer is (0.001～0.2) with the ratio of total moles monomer:1; The molal quantity of described function monomer is (0.005～0.3) with the ratio of total moles monomer: 1.
Wherein, described hydrophobic monomer and function monomer are all same as above, do not repeat them here; Described propyleneThe integral molar quantity of amide monomer, hydrophobic monomer and function monomer and the mol ratio of hydrophobic monomer are 1:(0.001～0.2), is preferably 1:(0.001～0.15), more preferably 1:(0.001～0.1), thenBe preferably 1:(0.001～0.05), most preferably be 1:(0.005～0.02); Rubbing of described function monomerThe total mol ratio of that number and monomer is (0.005～0.3): 1, be preferably (0.05～0.2): and 1, most preferablyFor (0.08～0.16): 1. Described initator is initator well known to those skilled in the art, there is noSpecial restriction, is preferably persulfate and sulfite oxidation reduction initiator system in the present invention; InstituteAlso state persulfate and sulfite oxidation reduction initiator system and be oxidation well known to those skilled in the artFormer initiator system, there is no special restriction, persulfate described in the present invention and sulphiteMass ratio is preferably (1～3): 1; In described initator, the quality of oxidant is total monomer quality0.05％～1％。
In the present invention, copolymerization can be undertaken by micell polymerization method or antiphase emulsifiable method again.
In the time that copolymerization process is micell polymerization method, preferably by acrylamide monomer, hydrophobic monomer and function listBody mixes, and preferably also adds surfactant, is heated to initiation temperature, then adds initator, is total toPoly-reaction. Wherein, described copolyreaction is preferably carried out in water; Described acrylamide monomer, hydrophobic listBody and function monomer total mass concentration in the aqueous solution is preferably 12%～35%, more preferably20%～35%, then be preferably 20%～30%; The pH value of mixing rear solution is preferably 4～10; Described tableSurface-active agent is preferably anion surfactant, more preferably dodecyl sodium sulfate, dodecyl sulphurOne or more in acid sodium and neopelex; Rubbing of described surfactant and hydrophobic monomerYou are than being preferably (2～20): 1, and more preferably (5～20): 1, most preferably be (8～15): 1; InstituteThe quality optimization of stating oxidant in initator is acrylamide monomer, hydrophobic monomer and function monomer gross mass0.05%～1%, more preferably 0.05%～0.6%, then be preferably 0.09%～0.4%; In described initatorThe mass ratio of persulfate and sulphite is (5:3)～(1:1), more preferably (4:3)～(1:1); Described initiation temperature is preferably 25 DEG C～65 DEG C, and more preferably 25 DEG C～50 DEG C, then be preferably 30 DEG C～40 DEG C; Described copolyreaction is preferably carried out under adiabatic condition; The time of described copolyreaction is preferably5～7h, more preferably, when rising and be no more than 1 DEG C in the temperature 30min of reaction system, reaction finishes.
In the time carrying out copolymerization by antiphase emulsifiable method, preferably carry out in accordance with the following methods: will gather propionamide listBody and function monomer are soluble in water, as water; Hydrophobic monomer is dissolved in oil solvent, preferably also addsEmulsifying agent, as oil phase; Water is mixed with oil phase, is heated to initiation temperature, then add initator,Carry out copolyreaction. Wherein, described oil solvent is oil solvent well known to those skilled in the art, andWithout special restriction, in the present invention, be preferably one or more in kerosene, white oil and atoleine, moreBe preferably kerosene; The oil-water ratio of described oil solvent and water is preferably (1～1.5): 1; Mixed solution after mixingMiddle total monomer concentration is preferably 20～35wt%, more preferably 25～30wt%; Described emulsifying agent is this areaEmulsifying agent known by the technical staff, there is no special restriction, and in the present invention, being preferably HLB value is 6～8Non-ionic surface active agent, more preferably Span class non-ionic surface active agent and/or Tween class are non-Ionic surface active agent, then be preferably Span class non-ionic surface active agent and Tween class non-ionic surfaceActivating agent, most preferably is Span-80 and Tween-20; Described Span class non-ionic surface active agent withThe mass ratio of Tween class non-ionic surface active agent is preferably (5～15): 2, and more preferably (6～10):2, most preferably be 8:2; The quality optimization of described emulsifying agent is 10%～20% of monomer gross mass, more excellentElect 12%～18% as, then be preferably 14%～18%; In described initator, the quality optimization of oxidant is single0.1%～0.5% of body gross mass, more preferably 0.1%～0.3%, then be preferably 0.1%～0.2%; Described drawingSend out temperature and be preferably 30 DEG C～45 DEG C, more preferably 35 DEG C～45 DEG C; The time of described copolyreaction is preferably5～7h, more preferably 4～6h; After adopting antiphase emulsifiable method copolymerization, preferably also carry out breakdown of emulsion processing. Copolymerization is anti-After should completing, preferably carry out granulation, be then hydrolyzed; The method of described granulation is art technologyThe method that personnel know, there is no special restriction; Described hydrolysis hydrolytic reagent used is this area skillThe hydrolytic reagent that art personnel know, there is no special restriction, and the present invention is preferably alkali metal hydroxide,More preferably potassium hydroxide and/or NaOH, then be preferably NaOH; The temperature of described hydrolysis is preferredBe 70 DEG C～100 DEG C, more preferably 80 DEG C～100 DEG C, then be preferably 90 DEG C～100 DEG C; Described hydrolysis timeBetween be preferably 1～3h; The degree of hydrolysis of described hydrolysis is preferably 4%～20%, and more preferably 5%～20%, thenBe preferably 10%～20%.
After hydrolysis, be preferably dried and obtain hydrophobic associated polymer; Described dry temperature is preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferably 0.5～3h, then be preferably 1～2h.
The present invention also provides a kind of front Hydrolyze method to prepare the method for above-mentioned hydrophobic associated polymer, comprising:Under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator, hydrophobic monomer and function listBody carries out copolyreaction, obtains hydrophobic associated polymer; Preferably after copolyreaction completely, continue slaking oneFix time, obtain hydrophobic associated polymer, described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, thirdThe alkyl acrylate that olefin(e) acid Arrcostab, alkyl methacrylate, fluorine replace, the methyl-prop that fluorine replacesOlefin(e) acid Arrcostab, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid saltOne or more; Described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkylIn sulfonate, the carbon number of alkyl is greater than 20; Described function monomer is selected to contain holds the sulfonic acid of thiazolinyl derivativeThing and sulfonate derivatives thereof and contain one or more in the Hete rocyclic derivatives of holding thiazolinyl; Described hydrophobicThe molal quantity of monomer is (0.001～0.2) with the ratio of total moles monomer: 1; Described function monomer moleNumber is (0.005～0.3) with the ratio of total moles monomer: 1.
Wherein, described acrylamide monomer, hydrophobic monomer, function monomer and initator are all same as above,Do not repeat them here; Described hydrolytic reagent is hydrolytic reagent well known to those skilled in the art, and it is special to there is noRestriction, in the present invention, be preferably alkali metal hydroxide, more preferably potassium hydroxide and/or NaOH,Be preferably again NaOH; The amount that described hydrolytic reagent adds is 0.4%～20% of monomer gross mass, more preferablyBe 1%～15%, then be preferably 2%～10%.
Copolymerization in front method for hydrolysis preparation can be undertaken by micell polymerization method or antiphase emulsifiable method again. ItsIn, described micell polymerization method and antiphase emulsifiable method are all same as above, just add acrylamide monomer withWhen hydrophobic monomer, add hydrolytic reagent, do not repeat them here.
After copolyreaction, preferably carry out granulation, dry, obtain hydrophobic associated polymer; Described granulationMethod is method well known to those skilled in the art, there is no special restriction; Described dry temperatureBe preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferably 0.5～3h, more excellentElect 1～2h as.
The present invention also provides a kind of method that adopts cohydrolysis to prepare above-mentioned hydrophobic associated polymer, comprising:Under initator effect, acrylamide monomer, function monomer, sodium acrylate monomers and hydrophobic monomer carry outCopolyreaction, obtains hydrophobic associated polymer; Described hydrophobic monomer be selected from N-alkyl-substituted acrylamide,The alkyl acrylate that alkyl acrylate, alkyl methacrylate, fluorine replace, the methyl that fluorine replacesAlkyl acrylate, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acidOne or more of salt; Described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkaneIn base sulfonate, the carbon number of alkyl is greater than 20; Described function monomer is selected from and contains the sulfnic acid derivatives of holding thiazolinylBiology and sulfonate derivatives thereof and contain one or more in the Hete rocyclic derivatives of holding thiazolinyl; Described dredgingThe molal quantity of aqueous monomer is (0.001～0.2) with the ratio of total moles monomer: 1; Rubbing of described function monomerYour number is (0.005～0.3) with the ratio of total moles monomer: 1.
Wherein, described hydrophobic monomer, function monomer and initator are all same as above, do not repeat them here;Preparing hydrophobic associated polymer at co-hydrolysis is that part propylene amide monomer sodium acrylate monomers is replacedGeneration, therefore total mole of described acrylamide monomer, sodium acrylate monomers, function monomer and hydrophobic monomerAmount is 1:(0.001～0.2 with the mol ratio of hydrophobic monomer), be preferably 1:(0.001～0.15), moreBe preferably 1:(0.001～0.1), then be preferably 1:(0.001～0.05), most preferably be 1:(0.005～0.02)The ratio of the total molal quantity of described sodium acrylate monomers and monomer is (0.03～0.2): 1, be preferably(0.05～0.16): 1, then be preferably (0.1～0.16): 1; Described acrylamide monomer and PAAThe mole that monomer is total and the mol ratio of sodium acrylate monomers are preferably 1:(0.04～0.2), more preferably1：(0.08～0.2)。
After copolyreaction, preferably carry out slaking, more preferably carry out granulation, dry, obtain hydrophobic association poly-Compound; The method of described granulation is method well known to those skilled in the art, there is no special restriction;Described dry temperature is preferably 80 DEG C～95 DEG C; The described dry time is preferably 0.5～4h, more preferablyBe 0.5～3h, then be preferably 1～2h.
The present invention adopts initator to prepare hydrophobic associated polymer, and composite initiator is decomposed to form list in waterBody free radical, monomer free radical and vinyl monomer carry out addition, form monomer free radical, i.e. spike;Then monomer free radical is opened the π key of other vinyl monomer molecules, adds and is shaped as new free radical. Like thisThe new radical reaction activity forming can not decay, and continues to carry out adding of interlock type with vinyl monomerBecome, and carry out in this manner chain propagation reaction. Between two chain free radicals, there is active collision,Double-basis cessation reaction occurs, and polymerisation finishes, and forms polymeric colloid.
The present invention also provide a kind of above-mentioned hydrophobic associated polymer at oilfield chemistry, water treatment, papermaking orApplication in mineral floating field.
In order to further illustrate the present invention, below in conjunction with embodiment to a kind of hydrophobic association provided by the inventionPolymer and preparation method thereof is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
By acrylamide monomer, function monomer 2-acrylamide-2-methyl propane sulfonic sodium and hydrophobic monomer propyleneAcid octadecyl ester feeds intake by the mol ratio of 85:14.2:0.8, adds in 5000mL beaker and dissolves preparation with pure waterBecome the mixed solution that total monomer is 25wt%, add ten in the ratio of 10 times of hydrophobic monomer molar concentrationsDialkyl benzene sulfonic acids sodium also stirs, and then beaker is put into 30 DEG C of water-baths and is incubated until solutionTemperature is 30 DEG C, adds ammonium persulfate and sodium hydrogensulfite composite initiator initiated polymerization, wherein persulfuric acidAmmonium and sodium hydrogensulfite mass ratio are 5:4, and ammonium persulfate dosage is 0.12% of monomer gross mass; Polymerization is anti-Should under adiabatic environment, carry out, insert thermometer monitoring polymerisation at reaction system center and carry out degree,In the time that being no more than 1 DEG C, temperature rise in 30min thinks that polymerisation completes substantially. After polymerisation completes 1H, takes out colloid, and colloid is cut into 3～5mm size particles, and hydrolytic reagent NaOH is according to 2.4g/100The amount of g colloid adds, and mixes, and transfers in polybag and seals, then constant temperature in constant temperature oven95 DEG C of hydrolysis 2h (should be noted that when sealing deaeration of trying one's best, and when retaining enough spaces and holding hydrolysisThe ammonia producing, while noting hydrolysis, sealing bag does not break). After being hydrolyzed, colloid is spread out and pavedOn 500 eye mesh screens, put into 90 DEG C of dry 40～90min of baking oven constant temperature, taking-up is sieved, and obtains hydrophobic formingClose polymer.
Utilize infrared spectrum to analyze the hydrophobic associated polymer obtaining in embodiment 1, obtain that it is redExternal spectrum figure as shown in Figure 1. As shown in Figure 1, in Fourier's infrared spectrogram, 3575cm-1With 3186cm-1Two places belong to respectively antisymmetric stretching vibration peak and the symmetrical stretching vibration peak of N-H key; 1674cm-1Belong to the stretching vibration peak of acid amides Ι with C=O, 1642cm-1Belonging to acid amides II shakes with the bending of N-HMoving peak; 1545cm-1And 1408cm-1Be respectively COO-Antisymmetric stretching vibration peak and symmetrical flexible shakingMoving peak, 1455cm-1Place belongs to the flexural vibrations peak of C-H; 1315cm-1For the stretching vibration of C-N keyPeak, 1172cm-1For the stretching vibration peak of S=O in sulfonic group; 1121cm-1For the flexible of C-O-C key shakesMoving peak.
Utilize nuclear magnetic resonance to analyze the hydrophobic associated polymer obtaining in embodiment 1, obtain its coreMagnetic resonance hydrogen spectrogram, as shown in Figure 2. As shown in Figure 2,6.88～7.68ppm is acrylamide and AMPSAmide groups (CONH2,-CONH-) the above chemical shift of hydrogen; 4.70ppm is solvent D2The upper hydrogen of OChemical shift; 3.52～3.55ppm is on acrylate alkyl chain and 2-acrylamide-2-methyl propane sulfonicMethylene hydrogen (CH on sodium side chain2) chemical shift; 2.11～2.23ppm is methine in molecular backboneThe chemical shift of hydrogen (CH-); 1.55～1.65ppm is methylene (CH on main chain2) chemical potential of hydrogenMove; 1.38ppm is methyl (CH on 2-acrylamide-2-methyl propane sulfonic sodium side chain3) chemical potential of hydrogenMove; 1.07～1.09ppm is methyl (CH on acrylate alkyl chain3) chemical shift of hydrogen.
The hydrophobic associated polymer obtaining in embodiment 1 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 96mPas.
Use Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 1To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 8,920,000.
Embodiment 2
According to the polymerization in embodiment 1 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 85.7:14.2:0.1 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 2 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 57mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 2Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 9,480,000.
Embodiment 3
According to the polymerization in embodiment 1 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 80.5:14.2:5 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 3 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 67mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 3Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 5,560,000.
Embodiment 4
According to the polymerization in embodiment 1 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 73.8:14.2:12 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 4 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 23mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 4Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 2,980,000.
Embodiment 5
According to the polymerization in embodiment 1 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 65.8:14.2:20 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 5 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 3.5mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 5Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 1,020,000.
Embodiment 6
According to the polymerization in embodiment 1 and step, change hydrophobic monomer into N-dodecyl acryloylAmine, obtains hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 6 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 115mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 6Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 1,262 ten thousand.
Embodiment 7
According to the polymerization in embodiment 1 and step, change hydrophobic monomer into 2-acrylamido-2 firstBase docosyl sodium sulfonate, obtains hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 7 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 44mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 7Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 4,890,000.
Embodiment 8
According to the polymerization in embodiment 1 and step, change hydrophobic monomer into docosyl pi-allylDibrominated tetramethyl second two ammoniums, obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 8 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 33mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 8Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 4,450,000.
Embodiment 9
According to the polymerization in embodiment 1 and step, change function monomer into SSS,To hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 9 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 78mPas.
Use Ubbelohde viscometer (0.55mm caliber) by GB/T12005.10-92 to obtaining in embodiment 9Hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 7,850,000.
Embodiment 10
According to the polymerization in embodiment 1 and step, function monomer is changed into sodium vinyl sulfonate,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 10 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 85mPas.
Use Ubbelohde viscometer (0.55mm caliber) to press GB/T12005.10-92 to obtaining in embodiment 10To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 8,600,000.
Embodiment 11
According to the polymerization in embodiment 1 and step, change function monomer into N-vinyl-2-pyrrolidinesKetone, obtains hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 11 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 72mPas.
Use Ubbelohde viscometer (0.55mm caliber) to press GB/T12005.10-92 to obtaining in embodiment 11To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 8,260,000.
Embodiment 12
According to the polymerization in embodiment 1 and step, change hydrophobic monomer into acrylic acid hexafluoro butyl ester,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 12 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 92mPas.
Use Ubbelohde viscometer (0.55mm caliber) to press GB/T12005.10-92 to obtaining in embodiment 12To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 9,230,000.
Embodiment 13
By acrylamide monomer, sodium acrylate monomers, function monomer 2-acrylamide-2-methyl propane sulfonic sodiumJoin in deionized water with hydrophobic monomer octadecyl acrylate, fully dissolve, this solution is as water;To add mass ratio in kerosene be the compound emulsifying agent of Span-80:Tween-20=8:2 composition and be stirred toFully dissolve, as oil phase. Under high-speed stirred, aqueous phase solution is added and in oil phase, carries out emulsification 20min,Then be transferred in 5000mL beaker, wherein monomer total mass concentration is 25%, acrylamide monomer,Sodium acrylate monomers, function monomer, with hydrophobic monomer octadecyl acrylate three mol ratio be 69:16:14.2:0.8, compound emulsifying agent additive capacity is total system quality 18%. When 40 DEG C of emulsion constant temperature, addEnter to account for potassium peroxydisulfate and the sodium hydrogensulfite composite initiator initiated polymerization of monomer mass 0.12%, wherein over cureAcid potassium and sodium hydrogensulfite mass ratio are 1:1, and reaction is carried out in 40 DEG C of water-baths, anti-after reaction 4～6hShould substantially complete, obtain white emulsion.
Add absolute ethyl alcohol to carry out breakdown of emulsion, precipitation, centrifugation the white emulsion obtaining, gained is heavyAbsolute ethanol washing 3 times of shallow lake thing, put into 95 DEG C of dry 1h of baking oven constant temperature, through pulverizing, sieving, obtainCertain particle diameter dry powder sample is hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 13 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 80mPas.
Utilize Ubbelohde viscometer (0.55mm caliber) according to GB/T12005.10-92 in embodiment 13The hydrophobic associated polymer obtaining is tested, and calculating its viscosity average molecular weigh is 8,070,000.
Embodiment 14
According to the polymerization in embodiment 14 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 94.2:5:0.8 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 14 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 124mPas.
Use Ubbelohde viscometer (0.55mm caliber) to press GB/T12005.10-92 to obtaining in embodiment 14To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 1,296 ten thousand.
Embodiment 15
According to the polymerization in embodiment 15 and step, by acrylamide monomer, function monomer 2-propyleneA mole proportioning for acid amides-2-methyl propane sulfonic acid sodium and hydrophobic monomer octadecyl acrylate changes 71.2:28:0.8 into,Obtain hydrophobic associated polymer.
The hydrophobic associated polymer obtaining in embodiment 15 is dissolved in to 20,000 salinities, calcium ions and magnesium ions concentrationIn the salt solution of 1000mg/L, be mixed with the solution of 0.2wt%, at 85 DEG C, 7.34s-1Sticky under shear rateDegree reaches 25mPas.
Use Ubbelohde viscometer (0.55mm caliber) to press GB/T12005.10-92 to obtaining in embodiment 15To hydrophobic associated polymer test, obtaining its viscosity average molecular weigh is 3,650,000.
Claims (10)
1. a hydrophobic associated polymer, comprises following four repetitives:
Wherein, described y=0.001～0.2, z=0.005～0.3, m=0.03～0.2, x+y+z+m=1; DescribedA is the monomeric unit of hydrophobic monomer; Described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, acrylic acidThe alkyl acrylate that Arrcostab, alkyl methacrylate, fluorine replace, the methacrylic acid that fluorine replacesOne of Arrcostab, pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid saltKind or multiple; Described pi-allyl alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acidIn salt, the carbon number of alkyl is greater than 20; Described D is the monomeric unit of function monomer; Described function monomerBe selected to contain and hold sulfonic acid and the sulfonate derivatives thereof of thiazolinyl and contain the Hete rocyclic derivatives of holding thiazolinylIn one or more;
The viscosity average molecular weigh of described hydrophobic associated polymer is 50～1,500 ten thousand.
2. hydrophobic associated polymer according to claim 1, is characterized in that, described iny＝0.001～0.1。
3. hydrophobic associated polymer according to claim 1, is characterized in that, described inm＝0.05～0.16。
4. hydrophobic associated polymer according to claim 1, is characterized in that, described N-alkyl is gotThe alkyl acrylate replacing for acrylamide, alkyl acrylate, alkyl methacrylate, fluorine withIn the alkyl methacrylate that fluorine replaces, the carbon number of alkyl is more than or equal to 4.
5. hydrophobic associated polymer according to claim 1, is characterized in that, described pi-allyl alkaneIn based quaternary ammonium salt, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, the carbon number of alkyl is greater than20 are less than or equal to 40.
6. hydrophobic associated polymer according to claim 1, is characterized in that, described hydrophobic monomerFor dodecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate, metering system dodecyl gallate, methylProcess Conditions of Cetane Acrylate, octadecyl methacrylate, N-dodecyl acrylamide, N-cetyl propyleneAcid amides, 2-acrylamido-2-methyl pentacosyl sodium sulfonate, N-octyl group propionamide, 2-acrylamido-2-methyl docosyl sodium sulfonate, 2-acrylamido-2 methyl tetracosyl sodium sulfonate, N-14Alkyl acrylamide, N, N-dioctyl acrylamide, N, N-dihexyl acrylamide, N, N-di-n-octylAcrylamide, N, N-bis-dodecyl acrylamides, Hexafluorobutyl mathacrylate, acrylic acid hexafluoroButyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, docosyl pi-allyl dichloroChange tetramethyl second two ammoniums, pentacosyl pi-allyl dibrominated tetramethyl second two ammoniums and methacrylic acid 14One or more in ester.
7. hydrophobic associated polymer according to claim 1, is characterized in that, described function monomerCarbon number be 2～20.
8. hydrophobic associated polymer according to claim 1, is characterized in that, described function monomerFor 2-acrylamide-2-methylpro panesulfonic acid and sulfonate, vinyl sulfonic acid and sulfonate thereof, styreneOne or more in base sulfonic acid and sulfonate thereof and NVP.
9. a preparation method for hydrophobic associated polymer, is characterized in that, comprising:
Under initator effect, acrylamide monomer, hydrophobic monomer and function monomer carry out copolyreaction,After hydrolysis, obtain hydrophobic associated polymer;
Or: under the condition existing at hydrolytic reagent, add the acrylamide triggered monomer of initator, hydrophobic listBody and function monomer carry out copolyreaction, obtain hydrophobic associated polymer;
Or: under initator effect, acrylamide monomer, sodium acrylate monomers, function monomer and thinAqueous monomer carries out copolyreaction, obtains hydrophobic associated polymer;
Described hydrophobic monomer is selected from N-alkyl-substituted acrylamide, alkyl acrylate, methacrylic acid alkaneThe alkyl acrylate that base ester, fluorine replace, alkyl methacrylate, the pi-allyl alkyl quaternary that fluorine replacesOne or more of ammonium salt, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt; Described pi-allylIn alkyl quaternary ammonium salts, acrylamide alkyl sulfonic acid and acrylamide alkyl sulfonic acid salt, the carbon number of alkyl is largeIn 20;
Described function monomer is selected to contain and holds sulfonic acid and the sulfonate derivatives thereof of thiazolinyl and contain endOne or more in the Hete rocyclic derivatives of thiazolinyl;
The molal quantity of described hydrophobic monomer is (0.001～0.2) with the ratio of total moles monomer: 1;
The molal quantity of described function monomer is (0.005～0.3) with the ratio of total moles monomer: 1.
10. hydrophobic associated polymer or the claim 9 described in any line of claim 1～8 is preparedThe application of hydrophobic associated polymer in oilfield chemistry, water treatment, papermaking or mineral floating field.
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| CN111808597A (en) * | 2019-10-29 | 2020-10-23 | 中国石油化工股份有限公司 | Composition for fluidity regulation and control, and preparation method and application thereof |
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| WO2017113773A1 (en) * | 2015-12-29 | 2017-07-06 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method therefor |
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| CN114835851A (en) * | 2022-07-04 | 2022-08-02 | 山东诺尔生物科技有限公司 | Temperature-resistant and salt-resistant polyacrylamide for oil displacement and preparation method and application thereof |
| CN114835851B (en) * | 2022-07-04 | 2022-09-02 | 山东诺尔生物科技有限公司 | Temperature-resistant and salt-resistant polyacrylamide for oil displacement and preparation method and application thereof |
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