CN106496400B - A kind of phosphorous terpolymer and preparation method thereof - Google Patents
A kind of phosphorous terpolymer and preparation method thereof Download PDFInfo
- Publication number
- CN106496400B CN106496400B CN201610971745.1A CN201610971745A CN106496400B CN 106496400 B CN106496400 B CN 106496400B CN 201610971745 A CN201610971745 A CN 201610971745A CN 106496400 B CN106496400 B CN 106496400B
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- Prior art keywords
- phosphorous
- monomer
- acid
- containing monomers
- terpolymer
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 113
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 19
- -1 washing assisant Substances 0.000 claims abstract description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011976 maleic acid Substances 0.000 claims description 22
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 21
- 229960003237 betaine Drugs 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-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 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 4
- BLYGFIYCEOLGRR-UHFFFAOYSA-N 3-(propylamino)propane-1-sulfonic acid Chemical compound CCCNCCCS(O)(=O)=O BLYGFIYCEOLGRR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003202 NH4 Inorganic materials 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- XYVLZAYJHCECPN-UHFFFAOYSA-L 6-aminohexyl phosphate Chemical compound NCCCCCCOP([O-])([O-])=O XYVLZAYJHCECPN-UHFFFAOYSA-L 0.000 claims description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 2
- 241000335053 Beta vulgaris Species 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- XUMBUIZXGGMMIM-ODZAUARKSA-N 2-aminoethanol;(z)-but-2-enedioic acid Chemical compound NCCO.OC(=O)\C=C/C(O)=O XUMBUIZXGGMMIM-ODZAUARKSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000003921 oil Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000003674 animal food additive Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 230000033228 biological regulation Effects 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 241001044369 Amphion Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical class PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000008719 thickening Effects 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
-
- 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
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- 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
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
-
- 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
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/385—Esters containing sulfur and containing nitrogen
-
- 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
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of phosphorous terpolymer and preparation method thereof, which is to be copolymerized to obtain in aqueous by phosphorous-containing monomers A, zwitterionic monomer B and unsaturated carboxylic acid monomer C.The present invention is water-soluble polymer, soaked because it is good, solubilising, scale removal, the performance such as slow setting and surface-active, available for chemical fibre, plastics, coating, oil, ceramics, biological medicine, washing assisant, cement matrix feed additives etc..
Description
Technical field
Generated the present invention relates to one kind by phosphorous-containing monomers unit, zwitterionic monomer unit and unsaturated carboxylic acid monomer unit
Aqueous polymer, and be related to the application of these high molecular polymers.
Background technology
High molecular surfactant all receives much concern all the time, soaks, disperses because it is good, solubilising, sterilizes, goes
The characteristics such as dirt, slow setting, before all there is wide application in chemical fibre, coating, daily use chemicals, ceramics, plastics, biological medicine and building materials
Scape.High molecular surfactant presses the difference of its structures alone, can be divided into cationic surface active agent, anionic surface
Activating agent, nonionic surface active agent and amphoteric ionic surfactant.Wherein amphoteric ionic surfactant due to
Be provided simultaneously with cation and anion in its structure, assign its unique performance, such as betaines amphion, acid and
Excellent stability is respectively provided with alkaline condition, nontoxic, irritation is small, soluble easily in water, and surface-active is strong, have thickening, sterilization,
Antistatic property, is a kind of environmentally protective good surface activating agent.
In oil-well cement and concrete-containing building material, organic phospho acid reagent is often used as slow setting, corrosion inhibiter, compared to traditional Portugal
Grape sodium saccharate, white sugar and citric acid, more preferably, but itself is not strong to the dispersibility of concrete, uses for its high temperature resistant, retarding effect
Concrete is be easy to cause when measuring big and glues weight, and dispersiveness is influenced substantially, with polycarboxylic acids diminishing in the high glue material of clay content
The compatibility of agent is improved and declined also with dosage.
The content of the invention
A kind of phosphorous terpolymer provided the purpose of the present invention is the deficiency for existing concrete retarder
And preparation method thereof, the construction unit containing phosphate group in the terpolymer, its retarding effect more preferably, dosage it is less, and
Include both sexes betaine type ion monomer in copolymer, the cation group on its quaternary ammonium salt makes it in the high glue material of clay content
In still there is good adaptability, and phosphoric acid, sulfonic acid and the carboxylic acid group in polymer have good adsorption capacity and point
The ability of dissipating, it is water-soluble good, good with polycarboxylate water-reducer compatibility, while there is good inhibition, detergency ability.
The object of the present invention is achieved like this：
A kind of phosphorous terpolymer, its feature are that it is to be based on phosphorous-containing monomers A, zwitterionic monomer B and unsaturation
The copolymer of carboxylic acid monomer C, the percentage that each monomer accounts for monomer gross mass are respectively：
Phosphorous-containing monomers A：10-60%
Zwitterionic monomer B：10-60%
Unsaturated carboxylic acid monomer C：10-80%
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In general formula (1), X O, NH, N-R1-Y；R1Represent the alkyl of 1-12 carbon atom, it is former containing O or N if necessary
Son, when containing O atom, R1It is polyoxyethylene groups, alkylether radicals, contains N atomic time, R1Represent polyvinylamine, polyethyleneimine
Amine, alkylamine etc., it is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M or-PHO3M2；M is
H, Na, K or NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, if necessary containing O or
Person's N atoms, it is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, one kind in itaconic acid or two kinds of mixing.
The phosphorous terpolymer, its feature be phosphorous-containing monomers A for two methylenephosphonic acid maleic acid monoester of monoethanolamine,
N- (amino-ethyl-phosphate)-maleic acid, N- (2- amino ethoxies ethyl-phosphate)-maleic acid, N- (amino
Hexyl-phosphate)-maleic acid, N- AminomethylphosphoniAcid Acids-maleic acid, N- aminoethyl phosphonic acids-maleic acid, N-
Ethylphosphonic acid-maleimide.
The phosphorous terpolymer, its feature are that zwitterionic monomer B is N, N- dimethyl-N-acryloyl ethoxies
Base-N- (3- sulfopropyls)-ammonium glycine betaine, N, N- dimethyl-N-acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, N, N- bis-
Methyl-N acrylamide propyl group-N- (2- carboxymethyls)-ammonium glycine betaine, N, N- dimethyl-N-acryloyloxyethyl-N- (methylphosphines
Acid)-ammonium glycine betaine.
The phosphorous terpolymer, its feature are that phosphorous-containing monomers A is N- (amino-ethyl-phosphate)-maleic acid
Acid amides, zwitterionic monomer B are N, N- dimethyl-N-acryloyloxyethyl-N- (methylphosphonic acid)-ammonium glycine betaine, unsaturated carboxylic
Acid monomers C is acrylic acid.
The phosphorous terpolymer, its feature are that phosphorous-containing monomers A is N- aminoethyl phosphonic acids-maleic acid,
Zwitterionic monomer B is N, N- dimethyl-N-acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, unsaturated carboxylic acid monomer C
For acrylic acid.
The phosphorous terpolymer, its feature are that phosphorous-containing monomers A is N- (2- amino ethoxies ethyls-phosphoric acid
Ester)-maleic acid, zwitterionic monomer B is N, N- dimethyl-N-acrylamide propyls-N- (2- carboxymethyls)-ammonium beet
Alkali, unsaturated carboxylic acid monomer C are acrylic acid.
A kind of preparation method of phosphorous terpolymer, its feature are that the polymer is by phosphorous-containing monomers A, amphion
Monomer B, unsaturated carboxylic acid monomer C and deionized water are added sequentially in reaction vessel, after stirring heating, add initiator and chain
Transfer agent, when insulation reaction 1-12 is small；The NaOH for adding 30% after reaction adjusts pH value to 6-8, and water use regulation is solid to be contained both
Obtain high molecular weight water soluble polymer；The percentage that each monomer accounts for monomer gross mass is respectively：Phosphorous-containing monomers A：10-60%；Both sexes
Ion monomer B：10-60%；Unsaturated carboxylic acid monomer C：10-80%；
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In general formula (1), X O, NH, N-R1-Y；R1Represent the alkyl of 1-12 carbon atom, it is former containing O or N if necessary
Son, it is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M、-OPHO3M2；M for H, Na, K,
NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, if necessary containing O or
Person's N atoms, it is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, one kind in itaconic acid or two kinds of mixing.
The preparation method of the phosphorous terpolymer, its feature be the initiator for thermal decomposition initiating or
Redox initiator；Thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide
One or more of mixing；Redox initiator is collectively constituted using thermal decomposition initiating and reducing agent, wherein thermally decomposing
Initiator is ammonium persulfate, one or more of mixing of potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, reduction
Agent is sodium hydrogensulfite, the one or more in potassium bisulfite, ferrous sulfate, sodium pyrosulfite, sodium hypophosphite, sodium formaldehyde sulfoxylate are mixed
Close.
The preparation method of the phosphorous terpolymer, its feature trigger in the thermal decomposition being added in reaction system
Agent dosage is the 0.1%-10.0% of monomer gross mass, and the reducing agent dosage being added in reaction system is monomer gross mass
0%-10%.
The preparation method of the phosphorous terpolymer, its feature are that chain-transferring agent used is isopropanol, sulfydryl
Ethanol, thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids and one kind in lauryl mercaptan or two kinds, chain-transferring agent dosage accounts for list
The 0%-6.0% of body gross mass.
The phosphorous terpolymer due to being a kind of water-soluble good high molecular polymer, have scattered, solubilising, decontamination,
The surface-actives such as slow setting, add available for chemical fibre, plastics, coating, oil, ceramics, biological medicine, washing assisant, cement-based material
Add agent etc..
Brief description of the drawings
Fig. 1 compares figure for hydration heat of cement experimental data.
Embodiment
Below with reference to specific embodiment, invention is described further, but any restrictions are not caused to invention.
Embodiment 1
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
Two methylenephosphonic acid maleic acid monoester of monoethanolamine, the N of monomer gross mass 30% of amount 30%, N- dimethyl-N -s acryloyloxyethyl-
N- (3- sulfopropyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 40% and the deionized water of monomer gross mass 60%, stirring rise
For temperature to 80 DEG C, the disposable ammonium persulfate for adding monomer gross mass 1%, when stirring insulation reaction 6 is small, adds the hydrogen-oxygen of 30wt%
Change sodium solution and adjust pH value to 6-8, water use regulation contains to 40% admittedly obtains phosphorous terpolymer aqueous solution P1.
Embodiment 2
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (amino-ethyl-phosphate)-maleic acid of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-acryloyl second
Epoxide-N- (methylphosphonic acid)-ammonium glycine betaine, the acrylic acid of monomer gross mass 40% and the deionized water of monomer gross mass 60%,
Stirring is warming up to 70 DEG C, the disposable ammonium persulfate for adding monomer gross mass 0.8%, and 1 interior dropwise addition when small contains monomer gross mass
0.8% aqueous solution of sodium bisulfite, when insulation reaction 4 is small after completion of dropwise addition, the sodium hydroxide solution for adding 30wt% is adjusted
For pH value to 6-8, water use regulation contains to 40% admittedly obtains phosphorous terpolymer aqueous solution P2.
Embodiment 3
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- aminoethyl phosphonic acids-maleic acid of amount 25%, the N of monomer gross mass 40%, N- dimethyl-N -s acrylamide propyl-
N- (sulfopropyl)-ammonium glycine betaine, the acrylic acid of monomer gross mass 35% and the deionized water of monomer gross mass 60%, stirring heating
To 70 DEG C, the disposable ammonium persulfate for adding monomer gross mass 1%, when insulation reaction 6 is small, the sodium hydroxide for adding 30wt% is molten
Liquid adjusts pH value to 6-8, and water use regulation contains to 40% admittedly obtains phosphorous terpolymer aqueous solution P3.
Embodiment 4
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (2- amino ethoxies ethyl-phosphate)-maleic acid of amount 15%, the N of monomer gross mass 35%, N- dimethyl-N -s
Acrylamide propyl-N- (2- carboxymethyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 50% and going for monomer gross mass 60%
Ionized water, stirring are warming up to 70 DEG C, the disposable ammonium persulfate and 0.2% mercaptopropionic acid for adding monomer gross mass 1%, insulation
React 6 it is small when, the sodium hydroxide solution for adding 30wt% adjusts pH value and arrives 6-8, and water use regulation is solid to be contained to 40% and obtain phosphorous ternary
Aqueous copolymers solution P4.
Embodiment 5
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (2- amino ethoxies ethyl-phosphate)-maleic acid of amount 20%, the N of monomer gross mass 15%, N- dimethyl-N -s
Acrylamide propyl-N- (2- carboxymethyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 65% and going for monomer gross mass 60%
Ionized water, stirring are warming up to 70 degree, the disposable ammonium persulfate and 0.4% mercaptopropionic acid for adding monomer gross mass 1%, insulation
React 4 it is small when, the sodium hydroxide solution for adding 30wt% adjusts pH value and arrives 6-8, and water use regulation is solid to be contained to 40% and obtain phosphorous ternary
Aqueous copolymers solution P5.
Embodiment 6
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
The two methylenephosphonic acid maleic acid monoester of monoethanolamine of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-methacryl second
Epoxide-N- (sulfopropyl)-ammonium glycine betaine, the methacrylic acid of monomer gross mass 40% and the deionization of monomer gross mass 60%
Water, stirring are warming up to 70 degree, the disposable ammonium persulfate and 0.15% mercaptopropionic acid for adding monomer gross mass 1.2%, insulation
React 6 it is small when, the sodium hydroxide solution for adding 30wt% adjusts pH value and arrives 6-8, and water use regulation is solid to be contained to 40% and obtain phosphorous ternary
Aqueous copolymers solution P6.
Embodiment 7
In the four-hole boiling flask equipped with blender, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- AminomethylphosphoniAcid Acids-maleic acid of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-acryloyloxyethyls-N-
(methylphosphonic acid)-ammonium glycine betaine, the methacrylic acid of monomer gross mass 40% and the deionized water of monomer gross mass 60%, stirring
70 degree are warming up to, the disposable ammonium persulfate and 0.3% mercaptopropionic acid for adding monomer gross mass 2%, when insulation reaction 6 is small,
The sodium hydroxide solution adjusting pH value for adding 30wt% is solid water-soluble containing phosphorous terpolymer is obtained to 40% to 6-8, water use regulation
Liquid P7.
Application examples
By the terpolymer in embodiment and common organic phospho acid retarder 1-hydroxy ethylidene-1,1-diphosphonic acid (abbreviation HEDP) into
Hydration heat of cement experiment is gone, experimental result is as shown in Figure 1, from hydration heat of cement Exotherm Time datagram, with blank water
Mud is compared, and the sample hydration exothermic heat appearance time for adding HEDP extends, and embodies the deferred action that HEDP delays hydrated cementitious,
Meanwhile exothermic peak also decreases, each phosphorous terpolymer in embodiment is compared with HEDP, when hydration heat peak occurs
Between it is longer, retarding effect is more preferably obvious, Slow setting time than HEDP extend 1-4.5 it is small when, significant effect.
Claims (10)
1. a kind of phosphorous terpolymer, it is characterised in that it is based on phosphorous-containing monomers A, zwitterionic monomer B and unsaturated carboxylic
The copolymer of acid monomers C, the percentage that each monomer accounts for monomer gross mass are respectively：
Phosphorous-containing monomers A：10-60%
Zwitterionic monomer B：10-60%
Unsaturated carboxylic acid monomer C：10-80%
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In general formula (1), X O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom of expression contains the miscellaneous of O or N atoms substitution
Alkylidene, it is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M、-OPHO3M2；M for H, Na,
K、NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4Taken for the alkyl of 1-6 carbon atom or containing O or N atoms
The miscellaneous alkylidene in generation, it is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or
CH2CH(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, one kind in itaconic acid or two kinds of mixing.
2. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is two methylenephosphonic acid of monoethanolamine
Maleic acid monoester, N- (amino-ethyl-phosphate)-maleic acid, N- (2- amino ethoxies ethyl-phosphate)-maleic acid
Acid amides, N- (Aminohexyl-phosphate)-maleic acid, N- AminomethylphosphoniAcid Acids-maleic acid, N- aminoethyl phosphonic acids-horse
Come sour acid amides, N- ethylphosphonic acids-maleimide.
3. phosphorous terpolymer according to claim 1, it is characterised in that zwitterionic monomer B is N, N- dimethyl-
N- acryloyloxyethyls-N- (3- sulfopropyls)-ammonium glycine betaine, N, N- dimethyl-N-acrylamide propyl-N- (sulfopropyl)-ammonium
Glycine betaine, N, N- dimethyl-N-acrylamide propyls-N- (2- carboxymethyls)-ammonium glycine betaine, N, N- dimethyl-N-acryloyl second
Epoxide-N- (methylphosphonic acid)-ammonium glycine betaine.
4. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- (amino-ethyls-phosphoric acid
Ester)-maleic acid, zwitterionic monomer B is N, N- dimethyl-N-acryloyloxyethyl-N- (methylphosphonic acid)-ammonium beet
Alkali, unsaturated carboxylic acid monomer C are acrylic acid.
5. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- aminoethyl phosphonic acids-horse
Carry out sour acid amides, zwitterionic monomer B be N, N- dimethyl-N-acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, unsaturation
Carboxylic acid monomer C is acrylic acid.
6. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- (2- amino ethoxy second
Base-phosphate)-maleic acid, zwitterionic monomer B is N, N- dimethyl-N-acrylamide propyls-N- (2- carboxymethyls)-
Ammonium glycine betaine, unsaturated carboxylic acid monomer C are acrylic acid.
7. the preparation method of phosphorous terpolymer described in a kind of claim 1, it is characterised in that the polymer is by phosphorous list
Body A, zwitterionic monomer B, unsaturated carboxylic acid monomer C and deionized water are added sequentially in reaction vessel, after stirring heating, are added
Enter initiator and chain-transferring agent, when insulation reaction 1-12 is small；The NaOH for adding 30% after reaction adjusts pH value to 6-8, uses
Water, which adjusts to contain admittedly, both obtains high molecular weight water soluble polymer；The percentage that each monomer accounts for monomer gross mass is respectively：Phosphorous-containing monomers A：
10-60%；Zwitterionic monomer B：10-60%；Unsaturated carboxylic acid monomer C：10-80%；
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In general formula (1), X O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom of expression contains the miscellaneous of O or N atoms substitution
Alkylidene, it is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M、-PHO3M2；M for H, Na, K,
NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4Taken for the alkyl of 1-6 carbon atom or containing O or N atoms
The miscellaneous alkylidene in generation, it is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or
CH2CH(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, one kind in itaconic acid or two kinds of mixing.
8. the preparation method of phosphorous terpolymer according to claim 7, it is characterised in that the initiator is heat point
Solve initiator or redox initiator；Thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, tertiary fourth
One or more of mixing of base hydrogen peroxide；Redox initiator is collectively constituted using thermal decomposition initiating and reducing agent,
Wherein thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, one kind or more of tert-butyl hydroperoxide
Kind mixing, reducing agent is sodium hydrogensulfite, in potassium bisulfite, ferrous sulfate, sodium pyrosulfite, sodium hypophosphite, sodium formaldehyde sulfoxylate
One or more mixing.
9. the preparation method of phosphorous terpolymer according to claim 8, it is characterised in that be added in reaction system
Thermal decomposition initiating dosage is the 0.1%-10.0% of monomer gross mass, and the reducing agent dosage being added in reaction system is monomer
The 0%-10% of gross mass.
10. the preparation method of phosphorous terpolymer according to claim 7, it is characterised in that chain-transferring agent used is different
Propyl alcohol, mercaptoethanol, thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids and one kind in lauryl mercaptan or two kinds, chain-transferring agent
Dosage accounts for the 0%-6.0% of monomer gross mass.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248097A (en) * | 2005-05-18 | 2008-08-20 | 建筑研究和科技有限公司 | Copolymers base on phosphorous-containing monomers, methods for the production thereof and their use |
| CN101058552B (en) * | 2006-04-18 | 2010-12-08 | 上海师范大学 | A kind of bifunctional grouped ionic liquid and its preparation method |
| CN102585092B (en) * | 2012-01-16 | 2013-10-09 | 西南石油大学 | A kind of betaine type salt-resistant polymer and preparation method thereof |
| CN104334589A (en) * | 2012-04-04 | 2015-02-04 | 罗地亚经营管理公司 | Method for synthesising polymers from acrylic acid, one of the salts of same or the mixture thereof |
| US9068108B2 (en) * | 2013-03-14 | 2015-06-30 | Cesi Chemical, Inc. | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
-
2016
- 2016-11-07 CN CN201610971745.1A patent/CN106496400B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248097A (en) * | 2005-05-18 | 2008-08-20 | 建筑研究和科技有限公司 | Copolymers base on phosphorous-containing monomers, methods for the production thereof and their use |
| CN101058552B (en) * | 2006-04-18 | 2010-12-08 | 上海师范大学 | A kind of bifunctional grouped ionic liquid and its preparation method |
| CN102585092B (en) * | 2012-01-16 | 2013-10-09 | 西南石油大学 | A kind of betaine type salt-resistant polymer and preparation method thereof |
| CN104334589A (en) * | 2012-04-04 | 2015-02-04 | 罗地亚经营管理公司 | Method for synthesising polymers from acrylic acid, one of the salts of same or the mixture thereof |
| US9068108B2 (en) * | 2013-03-14 | 2015-06-30 | Cesi Chemical, Inc. | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021160788A1 (en) * | 2020-02-12 | 2021-08-19 | Solvay Sa | Methods for reducing or preventing colloids adhesion and/or fouling on different substrates, compositions, and copolymers useful therefor |
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