CN101643527A - Amphoteric or cationic polymer flocculant - Google Patents
Amphoteric or cationic polymer flocculant Download PDFInfo
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- CN101643527A CN101643527A CN200810117712A CN200810117712A CN101643527A CN 101643527 A CN101643527 A CN 101643527A CN 200810117712 A CN200810117712 A CN 200810117712A CN 200810117712 A CN200810117712 A CN 200810117712A CN 101643527 A CN101643527 A CN 101643527A
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- monomer
- cationic
- amphoteric
- initiator
- flocculant
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- 229920006317 cationic polymer Polymers 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 82
- 125000002091 cationic group Chemical group 0.000 claims abstract description 65
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000008394 flocculating agent Substances 0.000 claims abstract 4
- 239000000084 colloidal system Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000005457 ice water Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000033116 oxidation-reduction process Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000004160 Ammonium persulphate Substances 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- TUDGMESWIBQVBE-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])CCCCCCCCCC Chemical compound C(C=C)(=O)NC(C[Na])CCCCCCCCCC TUDGMESWIBQVBE-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- CGRRTNMGLUWMLJ-UHFFFAOYSA-N 2-phenyl-2-(prop-2-enoylamino)ethanesulfonic acid Chemical compound C=CC(=O)NC(CS(=O)(=O)O)C1=CC=CC=C1 CGRRTNMGLUWMLJ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 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
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 16
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- -1 morpholine alkyl methacrylates Chemical class 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000010865 sewage Substances 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 38
- 238000012360 testing method Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 230000000694 effects Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000012545 processing Methods 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 14
- 238000005469 granulation Methods 0.000 description 14
- 230000003179 granulation Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000007639 printing Methods 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 14
- 238000007873 sieving Methods 0.000 description 14
- 239000002699 waste material Substances 0.000 description 13
- 125000004494 ethyl ester group Chemical group 0.000 description 10
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 description 10
- 238000005189 flocculation Methods 0.000 description 8
- 230000016615 flocculation Effects 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- QJGQUHMNIGDVPM-OUBTZVSYSA-N nitrogen-15 Chemical compound [15N] QJGQUHMNIGDVPM-OUBTZVSYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003311 flocculating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
本发明属于环保材料领域，涉及一类具有高效相转变能力的两性型或阳离子型高分子絮凝剂，具体的涉及到含有丙烯酸吗啉烷基酯类或甲基丙烯酸吗啉烷基酯类的高分子絮凝剂。本发明是采用水溶液聚合制备：将一定量的中性单体、阳离子单体(丙烯酸吗啉烷基酯类单体或甲基丙烯酸吗啉烷基酯类单体)、阴离子单体配成溶液，调节pH值，通惰性气体以除去氧气，再加入其它试剂如引发剂等，停止通惰性气体并保持反应器密闭，在0℃～60℃下调节反应温度使聚合得以进行，就可制得两性或阳离子型高分子絮凝剂。The invention belongs to the field of environmental protection materials, and relates to a class of amphoteric or cationic polymer flocculants with high-efficiency phase transition capabilities, in particular to high-molecular flocculants containing morpholine alkyl acrylates or morpholine alkyl methacrylates. Molecular flocculants. The present invention is prepared by aqueous solution polymerization: a certain amount of neutral monomers, cationic monomers (morpholine alkyl acrylate monomers or morpholine alkyl methacrylate monomers) and anionic monomers are formulated into a solution , adjust the pH value, pass an inert gas to remove oxygen, then add other reagents such as initiators, stop passing the inert gas and keep the reactor closed, adjust the reaction temperature at 0°C to 60°C to allow the polymerization to proceed, and then it can be obtained Amphoteric or cationic polymer flocculant.
Description
Technical field
The invention belongs to the environment-friendly materials field, relate to a class and have amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually, be specifically related to contain the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Background technology
Amphoteric and cationic high-molecular flocculant are family macromolecule polyelectrolyte, and it can play neutralization and bridging action with electronegative colloidal particle in the water, makes the particulate in the system take off surely, flocculate, thereby helps particulate sedimentation and filter dehydration.It is widely used in paper industry and helps filter, retention, enhancing, the sludge dewatering in the urban sewage treatment process, field waste water flocculatings such as textile printing and dyeing, leather processing, processing of aquatic products, food-processing.20th century six the seventies, Merck company and Halliborton company take the lead in succeeding in developing cationic polyacrylamide---dimethyl diallyl ammonium chloride homopolymer (PDMDAAC) and dimethyl diallyl ammonium chloride and acrylamide copolymer [P (DMDAAC/AM)], and very fast input suitability for industrialized production and obtain U.S. FDA authentication and be used for water treatment.The nineties is comparatively active to research, the exploitation of amphiprotic polyacrylamide abroad, and existing procucts come out.In American-European countries, the development of amphoteric and cationic-type polyacrylamide is more and more faster, has accounted for 60% of flocculation agent total amount, and with annual about 6% speed increment.But the output at present amphoteric of China and cationic-type polyacrylamide flocculation agent only accounts for about 10% of synthetic flocculant total amount, and exists the monomer kind few, and cationic degree is not high, the price height, relative molecular mass is lower, and efficient is the deficiency of high aspect inadequately, with the big gap of external existence.And the Application and Development gap of amphoteric and cationic-type polyacrylamide is bigger.
The cationic monomer of widespread use at present mainly contains methylacryoyloxyethyl trimethyl ammonium chloride (being called for short DMC), dimethylaminoethyl methacrylate (being called for short DMAEMA), dimethyl diallyl ammonium chloride (being called for short DADAAC), acrylyl oxy-ethyl-trimethyl salmiac (being called for short DAC), dimethylaminoethyl acrylate (being called for short DMAEA) etc.Use these cationic monomer institute synthetic flocculation agents to have better effects, but effect is relatively poor when flocculation is dissolved in organic waste such as dyestuff in the water at the suspended particulates of flocculation in the sewage.In order to overcome these shortcomings, usually adding hydrophobic monomer when preparing polymeric flocculant with these monomers with acrylamide makes polymkeric substance have the ability that changes mutually, hydrophobic grouping can combine with organism in the water body simultaneously, and this has all improved the bridge formation adsorptive power of flocculation agent, strengthens throwing out.The adding of hydrophobic monomer also helps improving the forms consumption of flocculation agent.General hydrophobic monomer is poorly soluble in the aqueous solution, need use surface active agent solubilization during interpolation, and it is dispersed in the solution.Tensio-active agent may contain impurity, letting nitrogen in and deoxidizing can produce a large amount of foams during polymerization, the hydrophobic monomer reactive behavior also with system in other monomer have than big difference, this all can cause institute's synthetic polymeric flocculant molecular weight low, poorly soluble, directly influence flocculating effect.Also make simultaneously polymerizing condition relatively harsher, polymerization is difficult to control.Seek new itself having suitable hydrophobic cationic monomer and be used for synthetic both sexes and the cationic high-molecular flocculant tool bright prospects that efficiently change ability mutually that have.Vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer are a kind of potential cationic monomers, once have bibliographical information to cross its synthetic method and polyreaction [C.E.Rehberg, W. A.Faucette; J.Am.Chem.Soc.; 1949; 71 (9); 3164～3165.], but use it for preparation amphoteric and cationic high-molecular flocculant clearly and yet there are no report.
Summary of the invention
One of purpose of the present invention provides has amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually, particularly contains the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Two of purpose of the present invention provides to have efficiently and changes the amphoteric of ability or the preparation method of cationic high-molecular flocculant mutually, particularly contains the preparation method of the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Institute of the present invention synthetic amphoteric or the required monomer of cationic high-molecular flocculant comprise neutral monomer, cationic monomer, anionic monomer.It is to adopt the aqueous solution polymerization preparation: with certain amount of neutral monomer, cationic monomer, anionic monomer wiring solution-forming, regulate the pH value, logical rare gas element is to remove oxygen, add other reagent such as initiator etc. again, stop logical rare gas element and keep reactor airtight, regulate temperature of reaction down at 0 ℃～60 ℃ polymerization is carried out, just can make amphoteric or cationic high-molecular flocculant.
Of the present invention have the amphoteric or the cationic high-molecular flocculant that efficiently change ability mutually and prepare by the following method:
In closed reactor, adding neutral monomer, cationic monomer in proportion---vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, anionic monomer, deionized water are mixed with the polymerization reaction system aqueous solution; Telo merization system pH value of aqueous solution is 2～9, the ice-water bath cooling; Logical rare gas element (being generally 15～40 minutes) is to remove oxygen in reactor, add initiator, stop logical rare gas element, under 0 ℃～60 ℃, carry out polyreaction (being generally 2～24 hours), translucent colloid, be and have amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually; Obtain having amphoteric or the cationic high-molecular flocculant powder that efficiently changes ability mutually with this colloid granulation, oven dry, after pulverizing, sieving.
Wherein: neutral monomer, cationic monomer, the total concn of anionic monomer in the polymerization reaction system aqueous solution are 5wt%～40wt%; Described neutral monomer accounts for the 20wt%～95wt% of above-mentioned total monomer; Cationic monomer---vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer account for the 5wt%～80wt% of above-mentioned total monomer; Anionic monomer accounts for the 0wt%～75wt% of above-mentioned total monomer.
The synthetic product is a cationic high-molecular flocculant when no anionic monomer polymerization time institute; As cationic monomer and anionic monomer polymerization time institute synthetic product is the amphoteric polymeric flocculant.
The concentration of described initiator in the polymerization reaction system aqueous solution is 0.005wt%～1wt%, and used initiator is selected from azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, more than one in the oxidation-reduction class initiator etc.
Described azo-initiator is (being called for short ABVN) or their mixtures such as Diisopropyl azodicarboxylate (being called for short AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxy class initiator is selected from more than one in dibenzoyl peroxide (being called for short BPO), peroxy dicarbonate ethylhexyl (being called for short EHP), dicumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid etc.; Described inorganic peroxy class initiator is selected from more than one in Potassium Persulphate, ammonium persulphate, the hydrogen peroxide etc.; Oxygenant in the described oxidation-reduction class initiator (mol ratio of oxygenant and reductive agent is 1: 5 to 5: 1) is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or potassium permanganate etc., and reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, amine or oxalic acid etc.
Described neutral monomer is selected from more than one in acrylamide, Methacrylamide, the N,N-DMAA (being called for short DMAA) etc.
Described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, has following structure:
R
1For-H or-CH
3R
2For containing the alkyl of 1 to 6 carbon; R
3For-H ,-CH
3,-CH
2-CH
3Or-CH
2-C
6H
5Deng; X is negatively charged ion such as halogen (fluorine, chlorine, bromine or iodine) ion or sulfate ion.
But the vinylformic acid morpholine ethyl ester hydrochloride reference literature [Chem.Abstr. of one of above-mentioned cationic monomer wherein; 77; 88822t; 1972.] method synthesize and obtain:
3.67ml morpholine ethanol and 20ml acetone are added 50ml single port flask, abundant cooling and stirring under the ice-water bath condition.Slowly in morpholine ethanol solution, splash into the 2.44ml acrylate chloride with constant pressure funnel, after acrylate chloride dropwises, remove ice-water bath, be warming up to room temperature naturally and continued stirring reaction 4 hours, stopped reaction.Filter to isolate vinylformic acid morpholine ethyl ester hydrochloride solid, normal temperature vacuum-drying gets vinylformic acid morpholine ethyl ester hydrochloride 5.0g.Meet other cationic monomer of said structure, all can synthesize with reference to aforesaid method.
Described anionic monomer is selected from more than one in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS), 2-acrylamido-2-phenyl ethyl sulfonic acid (being called for short AMSS), the 2-acrylamido dodecyl sodium sulfonate (being called for short ADS) etc.
Described rare gas element comprises nitrogen or argon gas etc.
Described telo merization system pH value of aqueous solution is to regulate with sodium hydroxide, potassium hydroxide, hydrochloric acid or sulfuric acid etc.
Employed cationic monomer reactive behavior height was easy to polymerization and obtains high-molecular weight amphoteric or cationic high-molecular flocculant when the present invention prepared amphoteric or cationic high-molecular flocculant; Gained amphoteric or cationic high-molecular flocculant have surfactivity, can in the aqueous solution, form micella, when polyreaction, the free radical that initiator was decomposed to form enters in the micella that cationic monomer forms and makes cationic monomer homopolymerization in the micella microcell, free radical entered other monomer reaction in the aqueous phase continuation and the aqueous solution after cationic monomer in the micella exhausted, and multipolymer just has micro-block structure like this.Simultaneously this type of cationic monomer has hydrophobicity, and hydrophobic grouping can combine with organism in the water body, and these characteristics make prepared polymeric flocculant bridge formation high adsorption capacity, it is high and have efficient flocculating ability and a wide application field to change ability mutually.
The present invention compared with prior art has following characteristics:
The present invention has introduced cationic monomer---synthetic amphoteric of vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer or cationic high-molecular flocculant.Because the cationic monomer that adopts has the effect of tensio-active agent, can in the aqueous solution, form micella and make multipolymer have micro-block structure; Have hydrophobicity, make the polymeric flocculant of preparation have hydrophobicity, make polymkeric substance have the ability that changes mutually, hydrophobic grouping can combine with organism in the water body simultaneously.These characteristics make prepared polymeric flocculant bridge formation high adsorption capacity, change the ability height mutually.Prepared amphoteric polymkeric substance has the zwitterion synergy when being used as flocculation agent, the floc sedimentation of generation is big and tight, and dehydrating effect is good.
Embodiment
Embodiment 1
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1.875 * 10
-4The Potassium Persulphate of g and 0.855 * 10
-4The oxidation-reduction initiator system that the S-WAT of g is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 2
At capacity is to add 22.5g deionized water, 2.125g acrylamide, 0.225g vinylformic acid morpholine ethyl ester methyl quaternary ammonium and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 7.4, the ice-water bath cooling, and logical nitrogen 20 minutes is to remove oxygen.Add 0.208 * 10
-4The ammonium persulphate of g and 0.095 * 10
-4The oxidation-reduction initiator system that the S-WAT of g is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 25 ℃ were reacted 6 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 3
At capacity is to add 20g deionized water, 2.5g Methacrylamide, 2.25g vinylformic acid morpholine ethyl ester hydrochloride and 0.25g 2-acrylamido-2-methyl propane sulfonic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 7.0, the ice-water bath cooling, and logical nitrogen 25 minutes is to remove oxygen.Add 0.832 * 10
-4G Potassium Persulphate and 0.18 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 12 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 4
At capacity is to add 20g deionized water, 3g N,N-DMAA, 1g vinylformic acid morpholine propyl ester ethyl quaternary ammonium salt and 1g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 9, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1 * 10
-2G 2,2'-Azobis(2,4-dimethylvaleronitrile) initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 15 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 5
At capacity is to add 22.5g deionized water, 2g acrylamide, 0.5g methacrylic acid morpholine ethyl ester benzyl quaternary ammonium salt in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 20 minutes is to remove oxygen.Add 5 * 10
-3G dibenzoyl peroxide initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 45 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 6
At capacity is to add 20g deionized water, 2g acrylamide, 3g methacrylic acid morpholine ethyl ester ethyl quaternary ammonium salt in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 5.4, the ice-water bath cooling, and logical nitrogen 30 minutes is to remove oxygen.Add 0.625 * 10
-4G ammonium persulphate and 0.285 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 25 ℃ were reacted 4 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 7
At capacity is to add 15g deionized water, 2g acrylamide, 8g vinylformic acid morpholine ethyl ester methyl quaternary ammonium in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.4, the ice-water bath cooling, and logical nitrogen 40 minutes is to remove oxygen.Add 0.625 * 10
-4G ammonium persulphate and 0.285 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 0 ℃ was reacted 24 hours, got translucent colloid, was to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 8
At capacity is to add 22.5g deionized water, 0.5g acrylamide, 0.125g vinylformic acid morpholine ethyl ester hydrochloride and 1.875g 2-acrylamido dodecyl sodium sulfonate in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 8.0, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 2.5 * 10
-2G Diisopropyl azodicarboxylate initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 60 ℃ were reacted 2 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 9
At capacity is to add 20g deionized water, 4.75g acrylamide, 0.25g vinylformic acid morpholine ethyl ester hydrochloride in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 4.0, the ice-water bath cooling, and logical nitrogen 35 minutes is to remove oxygen.Add 2.5 * 10
-2G dilauroyl peroxide initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height (can reach more than 1,500 ten thousand), bridge formation high adsorption capacity, molecular weight height, solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 10
At capacity is to add 20g deionized water, 1g acrylamide, 0.25g methacrylic acid morpholine butyl ester methyl quaternary ammonium in the tool plug scale test tube of 25ml, the 3.75g methacrylic acid, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.0, the ice-water bath cooling, and logical nitrogen 25 minutes is to remove oxygen.Add 2.5 * 10
-4G potassium permanganate and 1.425 * 10
-4The initiator system that g oxalic acid is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 0 ℃ was reacted 24 hours, got translucent colloid, was to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 11
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 0.375 * 10
-4G ammonium persulphate and 0.875 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 12
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1.875 * 10
-4G ammonium persulphate and 4.375 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 13
At capacity is to add 20g deionized water, 4.75g acrylamide, 0.25g vinylformic acid morpholine ethyl ester hydrochloride in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 4.0, the ice-water bath cooling, and logical nitrogen 35 minutes is to remove oxygen.Add 2.5 * 10
-4The g ammonium persulfate initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Claims (6)
1. amphoteric or cationic high-molecular flocculant is characterized in that this amphoteric or cationic high-molecular flocculant prepare by the following method:
In closed reactor, add neutral monomer, cationic monomer, anionic monomer, deionized water and be mixed with the polymerization reaction system aqueous solution; Telo merization system pH value of aqueous solution is 2～9, the ice-water bath cooling; Logical rare gas element adds initiator to remove oxygen in reactor, stops logical rare gas element, carries out polyreaction under 0 ℃～60 ℃, gets translucent colloid, is amphoteric or cationic high-molecular flocculant;
Wherein: neutral monomer, cationic monomer, the total concn of anionic monomer in the polymerization reaction system aqueous solution are 5wt%～40wt%; Described neutral monomer accounts for the 20wt%～95wt% of above-mentioned total monomer; Cationic monomer accounts for the 5wt%～80wt% of above-mentioned total monomer; Anionic monomer accounts for the 0wt%～75wt% of above-mentioned total monomer;
Described neutral monomer is selected from more than one in acrylamide, Methacrylamide, the N,N-DMAA;
Described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer;
Described anionic monomer is selected from more than one in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido-2-phenyl ethyl sulfonic acid, the 2-acrylamido dodecyl sodium sulfonate.
2. amphoteric according to claim 1 or cationic high-molecular flocculant is characterized in that: the synthetic product is a cationic high-molecular flocculant when no anionic monomer polymerization time institute; As cationic monomer and anionic monomer polymerization time institute synthetic product is the amphoteric polymeric flocculant.
3. amphoteric according to claim 1 or cationic high-molecular flocculant is characterized in that: the concentration of described initiator in the polymerization reaction system aqueous solution is 0.005wt%～1wt%.
4. according to claim 1 or 3 described amphoteric or cationic high-molecular flocculants, it is characterized in that: described initiator is selected from azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, more than one in the oxidation-reduction class initiator.
5. amphoteric according to claim 4 or cationic high-molecular flocculant is characterized in that: described azo-initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or their mixture; Described organic peroxy class initiator is selected from more than one in dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, dicumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid; Described inorganic peroxy class initiator is selected from more than one in Potassium Persulphate, ammonium persulphate, the hydrogen peroxide; Oxygenant in the described oxidation-reduction class initiator is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or potassium permanganate, and reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, amine or oxalic acid; Wherein: the mol ratio of oxygenant and reductive agent is 1: 5 to 5: 1.
6. amphoteric according to claim 1 and 2 or cationic high-molecular flocculant is characterized in that: described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, has following structure:
R
1For-H or-CH
3R
2For containing the alkyl of 1 to 6 carbon; R
3For-H ,-CH
3,-CH
2-CH
3Or-CH
2-C
6H
5Deng; X is halide-ions or sulfate ion.
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