CN102286132A - Method for preparing starch graft cationic type hyperbranched amide polymer - Google Patents
Method for preparing starch graft cationic type hyperbranched amide polymer Download PDFInfo
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- CN102286132A CN102286132A CN 201110126689 CN201110126689A CN102286132A CN 102286132 A CN102286132 A CN 102286132A CN 201110126689 CN201110126689 CN 201110126689 CN 201110126689 A CN201110126689 A CN 201110126689A CN 102286132 A CN102286132 A CN 102286132A
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- Prior art keywords
- starch
- acid
- initiator
- vinyl
- mixed phase
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Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 89
- 235000019698 starch Nutrition 0.000 title claims abstract description 87
- 239000008107 starch Substances 0.000 title claims abstract description 85
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001408 amides Chemical class 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 239000002798 polar solvent Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 7
- -1 and wherein Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229920000578 graft copolymer Polymers 0.000 claims description 22
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000004160 Ammonium persulphate Substances 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 14
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000000872 buffer Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 150000003926 acrylamides Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 7
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 6
- 229950007687 macrogol ester Drugs 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 229940100486 rice starch Drugs 0.000 claims description 6
- 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 claims description 5
- 150000004291 polyenes Chemical class 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical class SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 4
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 claims description 4
- 235000021374 legumes Nutrition 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- 150000002978 peroxides Chemical class 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
- 230000001131 transforming effect Effects 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- SEHANOMIAIWILJ-UHFFFAOYSA-N 2-ethenyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1C=C SEHANOMIAIWILJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 2
- XYNOUFAWYQMLKS-UHFFFAOYSA-N CC(=O)C.OC1(C(C(=O)O)(C=CC=C1C(=O)O)C1=CC=C(C=C1)O)C Chemical compound CC(=O)C.OC1(C(C(=O)O)(C=CC=C1C(=O)O)C1=CC=C(C=C1)O)C XYNOUFAWYQMLKS-UHFFFAOYSA-N 0.000 claims description 2
- LWLHCZLCSDUDEL-UHFFFAOYSA-O C[N+](C)(C)CC(O)=P(=O)CCOC(=O)C=C Chemical compound C[N+](C)(C)CC(O)=P(=O)CCOC(=O)C=C LWLHCZLCSDUDEL-UHFFFAOYSA-O 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 241000234435 Lilium Species 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 244000151018 Maranta arundinacea Species 0.000 claims description 2
- 235000010804 Maranta arundinacea Nutrition 0.000 claims description 2
- 240000008790 Musa x paradisiaca Species 0.000 claims description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 244000215747 Pachyrhizus erosus Species 0.000 claims description 2
- 235000001591 Pachyrhizus erosus Nutrition 0.000 claims description 2
- 235000018669 Pachyrhizus tuberosus Nutrition 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000012419 Thalia geniculata Nutrition 0.000 claims description 2
- 240000006677 Vicia faba Species 0.000 claims description 2
- 235000010749 Vicia faba Nutrition 0.000 claims description 2
- 235000002098 Vicia faba var. major Nutrition 0.000 claims description 2
- 235000010726 Vigna sinensis Nutrition 0.000 claims description 2
- 244000042314 Vigna unguiculata Species 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
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbon oxide sulfide Natural products O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims 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 claims description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- IPGRTXQKFZCLJS-UHFFFAOYSA-N n-(2-hydroxypropyl)prop-2-enamide Chemical compound CC(O)CNC(=O)C=C IPGRTXQKFZCLJS-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 abstract description 2
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 abstract 3
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920002401 polyacrylamide Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000000520 microinjection Methods 0.000 description 8
- 230000003311 flocculating effect Effects 0.000 description 6
- GHWDJXKWJOXXSF-UHFFFAOYSA-N 2-methyl-3-sulfanylideneprop-2-enoic acid Chemical compound S=C=C(C)C(O)=O GHWDJXKWJOXXSF-UHFFFAOYSA-N 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007974 sodium acetate buffer Substances 0.000 description 5
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- JCRDPEHHTDKTGB-UHFFFAOYSA-N dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound Cl.CN(C)CCOC(=O)C(C)=C JCRDPEHHTDKTGB-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- LOXMJHHMCYVQJE-UHFFFAOYSA-N C(=S)=S.C(CC)(=O)O Chemical compound C(=S)=S.C(CC)(=O)O LOXMJHHMCYVQJE-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Paper (AREA)
Abstract
The invention discloses a method for preparing a starch graft cationic type hyperbranched vinyl or allyl amide polymer. The method comprises the following steps: preparing a mixed phase and a branching reagent phase, preparing a cationic monomer phase, gelatinizing the mixed phase at 25-95 DEG C for 0.1-1 hour, and adjusting the temperature to 40-80 DEG C; then adding a reversible addition-fragmentation chain transfer (RAFT) agent in the gelatinized mixed phase, adding an initiator to initiate a polymerization reaction; and finally adding the cationic monomer phase in a hyperbranched polymer system prepared from the mixed phase, and continuously reacting for 1-24 hours to obtain the starch graft copolymerization cationic type hyperbranched vinyl or allyl amide polymer. The method adopts the RAFT polymerization method and the semi-continuous polymerization technology and uses the diene monomer and the chain transfer agent with a low molar ratio to prepare the starch graft cationic type hyperbranched vinyl or allyl amide polymer in a polar solvent system with high polymerization rate and conversion rate, the polymerization reaction is easy to control and the turbidity removal effect of the product is remarkable.
Description
Technical field
The present invention relates to a kind of preparation method of flocculation agent, relate in particular to and a kind ofly be applicable to dispersion, stick, the preparation method of the acylamide polymer of the cationic starch graft copolymer type dissaving structure of flocculation and rheology control.
Background technology
Vinyl or propenyl amide polymer are widely used in great fields such as water treatment, papermaking, printing and dyeing, mining, oil recovery, building materials.Present widely used vinyl or propenyl amide polymer such as polyacrylamide and multipolymer thereof are based on linear structure, and still, the vinyl of branched structure or propenyl amide polymer are very rarely seen in the application of aspects such as water treatment.Starch all is widely used in various fields as a kind of aboundresources, low-cost natural high moleculer eompound, and water treatment also is one of them.CN1196334A discloses and has a kind ofly caused starch or Microcrystalline Cellulose skeleton grafted polyacrylamide and through the preparation method of hydrolysis and alkylamino methyl alcohol prepared in reaction cationically ampholytic graft polyacrylamide flocculating agent with potassium permanganate; CN101700922A discloses a kind of compound prepared in reaction that contains quaternary ammonium salt group by starch and 2-4 kind and has obtained the cationic starch flocculation agent; CN1990392 discloses a kind of with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or N-(2,3-epoxy chloropropionate base) trimethyl ammonium chloride is made positively charged ion as etherifying agent, under sodium hydroxide/catalyst promoter composite catalytic system katalysis, adopt the method for the synthetic high degree of substitution quaternary ammonium cationic starch flocculating agent of dry method; CN1792854 disclose a kind of with W-Gum respectively with dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate hydrochloride generation graft reaction, obtain starch-grafted dimethylaminoethyl methacrylate and starch-grafted dimethylaminoethyl methacrylate hydrochloride, carry out compositely then according to mass ratio at 1: 2, obtain the method for combined type modified starch flocculant.
But from angle of practical application, on the one hand, the polymkeric substance of branched structure effect aspect utilizations such as flocculation is better; On the other hand, the viscosity of branched polymer is lower than the linear polymer with molecular weight, can dissolve fast, and is easy to use.In addition, cationic-type polyacrylamide promptly has bridging action, positively charged ion again can with suspended particle generation charge neutrality effect, reduce the Coulomb repulsion between the particle, more help flocculation.
Hyperbranched polymer is dendroid, and there is distribution in functional group in polymkeric substance, and part functional group is positioned at the end of polymer chain, and part functional group then is connected on the main body of polymer chain, uses the special direct one-step polycondensation of ABx type monomer to make usually.Yet WO 99/46301 discloses the mercaptan that uses polyenoid class monomer and suitable proportion and has been chain-transfer agent, obtain the branching polymethylmethacrylate by traditional radical polymerization preparation, but the polymkeric substance generation is crosslinked under the high-conversion rate, can not get branched polymer.(Chemical Communication such as Sherrington, 2004:1138-1139) report adopts controlled active atom transfer radical polymerization method, by with the copolymerization of Ethylene glycol dimethacrylate, under low-conversion, prepare the methyl methacrylate of branching.(Macromolecules such as Perrier, 2005,38:2131-2136) report adopts reversible addition-fracture to shift (RAFT) polymerization process, by using Ethylene glycol dimethacrylate to prepare the hyperbranched poly methyl methacrylate, but need to use a large amount of chain-transfer agents in the polymerization process and reach tens hours reaction to obtain hyperbranched polymers.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer, and this method may further comprise the steps:
(1) preparation mixed phase: mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25 ~ 5% and 2 ~ 20% of polar solvent quality respectively;
(2) preparation branching reagent phase: branching reagent comprises polar solvent and branching reagent mutually, and wherein, branching reagent is dienes compound or Polyenes, and polar solvent is water or acidic buffer solvent, and the branching reagent quality is 0.1 ~ 5% of a polar solvent quality;
(3) preparation cationic monomer phase: cationic monomer comprises polar solvent and cationic monomer mutually, and wherein, polar solvent is water or acidic buffer solvent, and the cationic monomer mass concentration is 10 ~ 100%;
(4) with mixed phase 25 ~ 95 ℃ of gelatinizations 0.1 ~ 1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40 ~ 80 ℃;
(5) the RAFT chain-transfer agent is joined in the mixed phase that gelatinization finishes, add the initiator initiated polymerization then; In the polymerization process, branching reagent was joined in the mixed phase in 1 ~ 10 hour, dropwise the back and continue reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000 ~ 1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10 ~ 1/1, and the quality of branching reagent phase is 10 ~ 50% of a mixed phase quality;
(6) cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction 1 ~ 24 hour, obtain the hyperbranched acylamide polymer of cationic starch graft copolymer type; Wherein, cationic monomer phase quality is 10 ~ 50% of a mixed phase quality.
The invention has the beneficial effects as follows, the inventive method shifts (RAFT) polymerization process by reversible addition-fracture, adopt semi-continuous polymerzation technology, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, high starch-grafted cationic hyperbranched vinyl of preparation or the propenyl amide polymer polymkeric substance of transforming in the polar solvent system, polyreaction is controlled easily, and the product turbidity removal effect is remarkable.
Embodiment
The present invention prepares the method for the hyperbranched acylamide polymer of starch graft copolymer type by reversible addition-fracture chain transfer (RAFT) polymerization process, because of in the RAFT polymerization process, having used the high special chain transfer agent of chain transfer constant, this chain-transfer agent shifts with the regeneration that reversible addition-fracture takes place the growth free radical, keep free radical activity, realize controlled and radical polymerization " activity ", and can regulate and control the structure of polymkeric substance, simultaneously, adopt semi continuous operation technology, use the chain-transfer agent of low proportioning, the dienes compound is joined in vinyl or the propenyl amide monomer system gradually, polymerization temperature is controlled between 40 ~ 80 ℃, the dienes compound joining day was controlled at 1 ~ 10 hour, and second monomer adds the back and continues reaction 1 ~ 24 hour, obtains the high starch graft copolymer hyperbranched polymer of final transformation efficiency.
The present invention prepares the method for starch graft copolymer type dissaving vinyl or propenyl amide polymer, may further comprise the steps:
1, preparation mixed phase, mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25 ~ 5% and 2 ~ 20% of polar solvent quality respectively.
The starch that is used to prepare the hyperbranched acylamide polymer of starch graft copolymer can be various cereal starchs, potato starch, legume starch and various treated starch.Cereal starch comprises glutinous rice starch, polished rice starch, long-grained nonglutinous rice starch, W-Gum, wheat starch; Potato starch tapioca (flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch, banana lily starch etc.; Legume starch comprises green starch, broad bean starch, pea starch, cowpea starch; Treated starch comprises cationic starch, carboxymethyl starch, methyl starch, hydroxyalkyl starch, Sumstar 190; The amides monomer comprises the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, N-N-isopropylacrylamide, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, N-vinyl pyrrolidone, N-(3-sulfonic acid propyl group) 2-vinyl pyridine, 2-acrylyl oxy-ethyl phosphorylcholine.
2, preparation branching reagent phase, branching reagent comprises polar solvent and branching reagent mutually; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; The branching reagent quality is 0.1 ~ 5% of a polar solvent quality.
Dienes compound or Polyenes comprise N, N '-methylene-bisacrylamide, diacrylate macrogol ester, dimethacrylate macrogol ester, (methyl) vinylformic acid vinyloxy group macrogol ester etc.
3, preparation cationic monomer phase, cationic monomer comprises polar solvent and cationic monomer mutually; Wherein, polar solvent is water or acidic buffer solvent; The cationic monomer mass concentration is 10 ~ 100%.
The cationic monomer that is used to prepare starch graft copolymer dissaving vinyl or propenyl amide polymer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, methylacryoyloxyethyl trimethyl ammonium chloride, diethylaminoethyl methacrylate, ethyl propenoate base trimethyl ammonium chloride, dimethylaminoethyl acrylate, N, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine.
4, with mixed phase 25 ~ 95 ℃ of gelatinizations 0.1 ~ 1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40 ~ 80 ℃.
5, the RAFT chain-transfer agent is joined in the mixed phase that gelatinization finishes, add the initiator initiated polymerization then.In the polymerization process, branching reagent was joined in the mixed phase in 1 ~ 10 hour, dropwise the back and continue reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000 ~ 1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10 ~ 1/1, and the quality of branching reagent phase is 10 ~ 50% of a mixed phase quality.
The RAFT chain-transfer agent that is used to prepare starch graft copolymer dissaving vinyl or propenyl amide polymer is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.Dithioesters class chain-transfer agent such as 4-cyanopentanoic acid dithiobenzoic acid ester commonly used, 2-cyano group sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid, 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc., the trithiocarbonic acid salt is as (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) propionic acid thio-carbonyl sulfide), 2,2 '-thiocarbonyl two (sulfane base), two (2 Methylpropionic acids) etc., xanthate class such as xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
The initiator that is used to prepare the hyperbranched acylamide polymer of starch graft copolymer can be the various initiators that are applicable to the polar solvent system, as chemical initiator, photochemical initiators, radiation initiators, suitable chemical initiator had peroxide initiator, azo-initiator, oxidation-reduction initiator.Peroxide initiator commonly used comprises ammonium persulphate, Potassium Persulphate, azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline, oxidation-reduction initiator comprises the compound system of superoxide (for example Potassium Persulphate, ammonium persulphate) and a kind of reductive agent (as S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate).Photochemical initiators is as (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone).
6, cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction and obtained the hyperbranched acylamide polymer of cationic starch graft copolymer type in 1 ~ 24 hour; Wherein, cationic monomer phase quality is 10 ~ 50% of a mixed phase quality.
Further specify the present invention program and result below by specific embodiment, but can not think that the present invention only limits among these embodiment.In an embodiment, remove specified otherwise, all marks and percentage ratio all are weight ratios.
Embodiment 1
(1) in the 250ml there-necked flask, adds 1.0 parts of carboxymethyl starch (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA), mechanical stirring, be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in the above-mentioned amidin;
(3) with 0.59 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes by weighing 8.66 parts of methylacryoyloxyethyl trimethyl ammonium chlorides is dissolved in 15 parts of water, adds after the letting nitrogen in and deoxidizing to continue reaction 180 minutes in the above-mentioned hyperbranched poly acrylamide soln.
The result shows that transformation efficiency is 96.7%, and the limiting viscosity number of polymerisate is 110.8 ml/g, adds the dienes monomer and increases as branching reagent post polymerization product viscosity, and molecular weight increases, and the turbidity removal rate of flocculating experiment 3ppm is 74.5 %.
Comparative Examples: do not add dienes branching reagent
(1) in the 250ml there-necked flask, adds 1.0 parts of carboxymethyl starch (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA), mechanical stirring, be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in the above-mentioned amidin;
(3) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in the less water;
(4) take by weighing the aqueous solution (80wt.%) of 8.66 parts of methylacryoyloxyethyl trimethyl ammonium chlorides, add after the letting nitrogen in and deoxidizing and continue reaction 240 minutes in the above-mentioned hyperbranched poly acrylamide soln.
The result shows that transformation efficiency is 97.7%, and the limiting viscosity number of polymerisate is 55.29 ml/g, does not have obvious turbidity removal effect.
Embodiment 2
(1) in the 250ml there-necked flask, adds 0.6 part of carboxymethyl starch (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0272 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA), mechanical stirring, be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in the above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes by weighing 8.66 parts of methylacryoyloxyethyl trimethyl ammonium chlorides is dissolved in 40 parts of water, adds after the letting nitrogen in and deoxidizing to continue reaction 180 minutes in the above-mentioned hyperbranched poly acrylamide soln.
The result shows that transformation efficiency is 97.2%, and the limiting viscosity number of polymerisate is 153.0 ml/g, and the turbidity removal rate of flocculating experiment 4ppm is 67.5 %; Improve first monomer concentration, can effectively improve molecular weight product.
Embodiment 3
(1) in the 250ml there-necked flask, adds 1.0 parts of W-Gums (Maize), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA), mechanical stirring, be warming up to 95 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in the above-mentioned amidin;
(3) with 0.45 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) aqueous solution (80wt.%) that takes by weighing 8.66 parts of methylacryoyloxyethyl trimethyl ammonium chlorides is dissolved in 15 parts of water, adds after the letting nitrogen in and deoxidizing to continue reaction 240 minutes in the above-mentioned hyperbranched poly acrylamide soln.
The result shows that transformation efficiency is 98.7%, and the limiting viscosity number of polymerisate is 90.3 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 44.9 %; Changing the total class of starch can influence the molecular weight and the flocculating effect of product.
Embodiment 4
(1) in the 250ml there-necked flask, adds 1.0 parts of carboxymethyl starch (CMS), 100 parts of acetic acid-sodium acetate buffer solution (pH=5), 0.0453 part of 3-benzene first sulfydryl thiocarbonyl propionic acid (BCPA), mechanical stirring, be warming up to 60 ℃ behind the letting nitrogen in and deoxidizing, gelatinization 30 minutes;
(2) 7.1 parts of acrylamides are joined in the above-mentioned amidin;
(3) with 0.55 part of N, N '-methylene-bisacrylamide is dissolved in 50 parts of water, is contained on the micro-injection pump;
(4) take by weighing 0.020 part of ammonium persulphate (APS), be dissolved in initiated polymerization in the mixing solutions that adds starch and acrylamide in the less water;
(5) start micro-injection pump, set drop rate, with N, N '-methylene-bisacrylamide aqueous solution dropwised in 3 hours and obtains the hyperbranched poly acrylamide;
(6) take by weighing the aqueous solution (80wt.%) of 13 parts of acrylyl oxy-ethyl-trimethyl salmiacs, add after the letting nitrogen in and deoxidizing and continue reaction 240 minutes in the above-mentioned hyperbranched poly acrylamide soln.
Change the result and show that the change rate is 95.2%, the limiting viscosity number of polymerisate is 113.2 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 70.6 %; Use different cationic monomers little to the molecular weight and the flocculating effect influence of product.
As fully visible, the inventive method shifts (RAFT) polymerization process by reversible addition-fracture, adopt semi-continuous polymerzation technology, use the chain-transfer agent of dienes monomer and low proportioning, high rate of polymerization, the high starch-grafted cationic hyperbranched acylamide polymer polymkeric substance of preparation that transforms in the polar solvent system, polyreaction is controlled easily, and the product turbidity removal effect is remarkable.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (6)
1. a method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer is characterized in that, this method may further comprise the steps:
(1) preparation mixed phase: mixed phase comprises polar solvent, starch and amides monomer, and wherein, polar solvent is water or acidic buffer solvent, and starch and amides monomer account for 0.25 ~ 5% and 2 ~ 20% of polar solvent quality respectively;
(2) preparation branching reagent phase: branching reagent comprises polar solvent and branching reagent mutually, and wherein, branching reagent is dienes compound or Polyenes, and polar solvent is water or acidic buffer solvent, and the branching reagent quality is 0.1 ~ 5% of a polar solvent quality;
(3) preparation cationic monomer phase: cationic monomer comprises polar solvent and cationic monomer mutually, and wherein, polar solvent is water or acidic buffer solvent, and the cationic monomer mass concentration is 10 ~ 100%;
(4) with mixed phase 25 ~ 95 ℃ of gelatinizations 0.1 ~ 1 hour, subsequently with temperature regulation to temperature of reaction, temperature of reaction is at 40 ~ 80 ℃;
(5) the RAFT chain-transfer agent is joined in the mixed phase that gelatinization finishes, add the initiator initiated polymerization then; In the polymerization process, branching reagent was joined in the mixed phase in 1 ~ 10 hour, dropwise the back and continue reaction 0 ~ 4 hour, final high preparation starch graft copolymer dissaving vinyl or the propenyl amide polymer of transforming; Wherein, RAFT chain-transfer agent and amides monomer mole ratio are 1/1000 ~ 1/100, and the mol ratio of initiator and RAFT chain-transfer agent is 1/10 ~ 1/1, and the quality of branching reagent phase is 10 ~ 50% of a mixed phase quality;
(6) cationic monomer is added in the hyperbranched polymer system that mixed phase prepares, continues reaction 1 ~ 24 hour, obtain the hyperbranched acylamide polymer of cationic starch graft copolymer type; Wherein, cationic monomer phase quality is 10 ~ 50% of a mixed phase quality.
2. according to the described method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer of claim 1, it is characterized in that, in the described step (1), described starch can be various cereal starchs, potato starch, legume starch and various treated starch; Wherein, described cereal starch comprises glutinous rice starch, polished rice starch, long-grained nonglutinous rice starch, W-Gum, wheat starch; Potato starch comprises tapioca (flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch, banana lily starch etc.; Legume starch comprises green starch, broad bean starch, pea starch, cowpea starch; Treated starch comprises cationic starch, carboxymethyl starch, methyl starch, hydroxyalkyl starch, Sumstar 190; The amides monomer comprises the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, N-N-isopropylacrylamide, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, N-vinyl pyrrolidone, N-(3-sulfonic acid propyl group) 2-vinyl pyridine, 2-acrylyl oxy-ethyl phosphorylcholine.
3. according to the described method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer of claim 1, it is characterized in that, in the described step (2), described dienes compound or Polyenes comprise N, N '-methylene-bisacrylamide, diacrylate macrogol ester, dimethacrylate macrogol ester, (methyl) vinylformic acid vinyloxy group macrogol ester etc.
4. according to the described method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer of claim 1, it is characterized in that, in the described step (3), described cationic monomer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, methylacryoyloxyethyl trimethyl ammonium chloride, diethylaminoethyl methacrylate, ethyl propenoate base trimethyl ammonium chloride, dimethylaminoethyl acrylate, N, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine.
5. according to the described method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer of claim 1, it is characterized in that, in the described step (5), described RAFT chain-transfer agent is dithio or trithio compound, comprises dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.; Dithiobenzoic acid ester class chain-transfer agent comprises 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyano group sec.-propyl dithiobenzoic acid ester, 2-(2-propyloic dithio carbonylsulfide) propionic acid, 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid, 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc.; The trithiocarbonic acid salt comprises (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) thio-carbonyl sulfide) propionic acid, 2,2 '-thiocarbonyl two (sulfane base), two (2 Methylpropionic acids) etc.; The xanthate class comprises xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) the xanthogen phenylformic acid.
6. according to the described method for preparing starch graft copolymer type dissaving vinyl or propenyl amide polymer of claim 1, it is characterized in that in the described step (5), described initiator comprises chemical initiator, photochemical initiators and radiation initiators; Wherein, chemical initiator comprised peroxide initiator, azo-initiator and oxidation-reduction initiator; The peroxide initiator comprises ammonium persulphate, Potassium Persulphate, azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate and azo di-isopropyl tetrahydroglyoxaline, oxidation-reduction initiator is the compound system of superoxide and reductive agent, superoxide comprises Potassium Persulphate, ammonium persulphate, and reductive agent comprises S-WAT, sodium bisulfite, sodium formaldehyde sulphoxylate; Photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
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| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
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