CN102229690A - Method for preparing starch grafted hyperbranched amide polymer - Google Patents
Method for preparing starch grafted hyperbranched amide polymer Download PDFInfo
- Publication number
- CN102229690A CN102229690A CN 201110126696 CN201110126696A CN102229690A CN 102229690 A CN102229690 A CN 102229690A CN 201110126696 CN201110126696 CN 201110126696 CN 201110126696 A CN201110126696 A CN 201110126696A CN 102229690 A CN102229690 A CN 102229690A
- Authority
- CN
- China
- Prior art keywords
- starch
- acid
- initiator
- hyperbranched
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 86
- 235000019698 starch Nutrition 0.000 title claims abstract description 84
- 239000008107 starch Substances 0.000 title claims abstract description 82
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001408 amides Chemical class 0.000 title claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- 239000002798 polar solvent Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- -1 and wherein Substances 0.000 claims description 27
- 229920000578 graft copolymer Polymers 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 239000000126 substance Substances 0.000 claims description 10
- 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
- 239000003795 chemical substances by application Substances 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
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000000872 buffer Substances 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
- 239000002904 solvent Substances 0.000 claims description 6
- 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
- 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
- 125000002091 cationic group Chemical group 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
- 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
- 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 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
- 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
- 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
- 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 6
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 5
- 238000012711 chain transfer polymerization Methods 0.000 abstract 1
- 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 12
- 239000000243 solution Substances 0.000 description 11
- 238000000520 microinjection Methods 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 8
- 230000003311 flocculating effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000005303 weighing Methods 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
- 239000007864 aqueous solution Substances 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
- 238000010792 warming Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920000587 hyperbranched polymer Polymers 0.000 description 3
- 238000012546 transfer Methods 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
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 238000007334 copolymerization reaction Methods 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
- 238000004043 dyeing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 150000003242 quaternary ammonium salts Chemical group 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
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a starch grafted hyperbranched amide polymer. The method is characterized by: preparing a mixed phase and a branching reagent phase, gelatinizing the mixed phase for 0.1-1 hour at a temperature of 25-95 DEG C, then adjusting the temperature to 40-80 DEG C, adding a RAFT chain transfer agent to the gelatinized mixed phase, then adding a initiator to initiate a polymerization; during the polymerization, adding the branching reagent phase to the mixed phase in a dropwise manner within 1-10 hours, and sequentially carrying out the reaction for 0.5-4 hours after completing the adding, finally, carrying out a high-conversion preparation to prepare the starch grafted hyperbranched amide polymer. With the present invention, diene monomers and the chain transfer agent with low ratio are provided for high-polymerization rate and high- conversion preparation of the starch grafted hyperbranched amide polymer in a polar solvent system by using a semi-continuous polymerization process through a reversible addition and fragmentation chain transfer polymerization; the polymerization is easy to be controlled and turbidity removal effect of the product is significant.
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 vinyl of the starch-grafted dissaving structure of flocculation and rheology control or the preparation method of propenyl amide polymer.
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.
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 the hyperbranched acylamide polymer of starch graft copolymer type is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of method for preparing the hyperbranched acylamide polymer of starch graft copolymer type, 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; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; Branching reagent accounts for 0.1 ~ 5% of polar solvent quality;
(3) 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 ℃;
(4) 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 0.5 ~ 4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; 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 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, the high starch-grafted 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.
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 the amides monomer system gradually, polymerization temperature is controlled between 40 ~ 80 ℃, the dienes compound joining day was controlled at 1 ~ 10 hour, obtained the high starch graft copolymer hyperbranched polymer of final transformation efficiency.
The present invention prepares the method for the hyperbranched acylamide polymer of starch graft copolymer type, 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 starch graft copolymer dissaving vinyl or propenyl amide polymer 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 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.
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; Branching reagent accounts for 0.1 ~ 5% of 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, 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 ℃.
4, 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 0.5 ~ 4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; 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 the hyperbranched acylamide polymer of starch graft copolymer is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.Dithiobenzoic acid ester 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).
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 0.5 hour;
(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, continued reaction afterwards and obtained the hyperbranched poly acrylamide in 0.5 hour.
The result shows that transformation efficiency is 98.6%, and the limiting viscosity number of polymerisate is 86.8 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 30.1 %.
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.
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, continued reaction afterwards and obtained the hyperbranched poly acrylamide in 1 hour;
The result shows that transformation efficiency is 99.2%, and the limiting viscosity number of polymerisate is 93.8 ml/g, and the turbidity removal rate of flocculating experiment 4ppm is 26.4 %; 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, continued reaction afterwards and obtained the hyperbranched poly acrylamide in 1 hour;
The result shows that transformation efficiency is 98.7%, and the limiting viscosity number of polymerisate is 63.6 ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 12.7 %; 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, continued reaction afterwards and obtained the hyperbranched poly acrylamide in 0.5 hour;
The result shows that transformation efficiency is 98.0%, and limiting viscosity number is 90.8ml/g, and the turbidity removal rate of flocculating experiment 3ppm is 28.4 %; 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, high starch-grafted 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.
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 (8)
1. a method for preparing the hyperbranched acylamide polymer of starch graft copolymer type 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; Wherein, branching reagent is dienes compound or Polyenes; Polar solvent is water or acidic buffer solvent; Branching reagent accounts for 0.1 ~ 5% of polar solvent quality;
(3) 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 ℃;
(4) 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 0.5 ~ 4 hour, the final high hyperbranched acylamide polymer of preparation starch graft copolymer that transforms; 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.
2. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type 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 and wheat starch etc.; Potato starch comprises tapioca (flour), sweet potato starch, yam starch, yam bean starch, arrowroot starch, Rhizoma Dioscoreae starch and banana lily starch etc.; Legume starch comprises green starch, broad bean starch, pea starch and cowpea starch etc.; Treated starch comprises cationic starch, carboxymethyl starch, methyl starch, hydroxyalkyl starch and Sumstar 190 etc.; Described 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 and 2-acrylyl oxy-ethyl phosphorylcholine etc.
3. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type 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 and (methyl) vinylformic acid vinyloxy group macrogol ester etc.
4. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1, it is characterized in that, in the described step (4), described RAFT chain-transfer agent is dithio or trithio compound, comprises dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s) and xanthate class etc.; Dithio trityl ester 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 and 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc., trithiocarbonic acid salt chain-transfer agent comprises (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 and 2 thio-carbonyl sulfide), 2 '-thiocarbonyl two (sulfane base), two (2 Methylpropionic acids) etc., xanthate class comprise xanthogenic acid guanidine-acetic acid and (2-(acetoxyl group) methyl) the xanthogen phenylformic acid etc.
5. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 1, it is characterized in that, in the described step (4), described initiator comprises chemical initiator, photochemical initiators and radiation initiators etc., and chemical initiator comprised peroxide initiator, azo-initiator and oxidation-reduction initiator.
6. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5, it is characterized in that, described 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.
7. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5, it is characterized in that described oxidation-reduction initiator comprises the compound system of superoxide and reductive agent; Superoxide can be Potassium Persulphate or ammonium persulphate, and reductive agent can be S-WAT, sodium bisulfite or sodium formaldehyde sulphoxylate.
8. according to the described method for preparing the hyperbranched acylamide polymer of starch graft copolymer type of claim 5, it is characterized in that described photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126696 CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126696 CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229690A true CN102229690A (en) | 2011-11-02 |
| CN102229690B CN102229690B (en) | 2012-12-19 |
Family
ID=44842302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110126696 Active CN102229690B (en) | 2011-05-17 | 2011-05-17 | Method for preparing starch grafted hyperbranched amide polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229690B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936318A (en) * | 2012-11-20 | 2013-02-20 | 孙安顺 | Multi-functional efficient oil scavenge polymer and preparation method of raw material graft modification starch thereof |
| CN104250381A (en) * | 2013-06-26 | 2014-12-31 | 通用电气公司 | Polymer used for water treatment |
| CN106006903A (en) * | 2016-05-27 | 2016-10-12 | 浙江理工大学 | Preparation method of bamboo-pulp cellulose and poly(N-vinylformamide) composite flocculating and decolorizing material |
| WO2020127568A1 (en) * | 2018-12-20 | 2020-06-25 | S.P.C.M. Sa | Method for treating suspensions of solid particles in water using amphoteric polymers |
| CN113072215A (en) * | 2021-04-15 | 2021-07-06 | 浙江德正建设有限公司 | Energy-saving emission-reducing town sewage treatment system |
| CN116162290A (en) * | 2023-03-09 | 2023-05-26 | 深圳丹伦基因科技有限公司 | Porous microcarrier, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
-
2011
- 2011-05-17 CN CN 201110126696 patent/CN102229690B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936318A (en) * | 2012-11-20 | 2013-02-20 | 孙安顺 | Multi-functional efficient oil scavenge polymer and preparation method of raw material graft modification starch thereof |
| CN102936318B (en) * | 2012-11-20 | 2014-11-26 | 孙安顺 | Multi-functional efficient oil scavenge polymer and preparation method of raw material graft modification starch thereof |
| CN104250381A (en) * | 2013-06-26 | 2014-12-31 | 通用电气公司 | Polymer used for water treatment |
| CN104250381B (en) * | 2013-06-26 | 2017-09-12 | 通用电气公司 | Polymer available for water process |
| CN106006903A (en) * | 2016-05-27 | 2016-10-12 | 浙江理工大学 | Preparation method of bamboo-pulp cellulose and poly(N-vinylformamide) composite flocculating and decolorizing material |
| CN106006903B (en) * | 2016-05-27 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of bamboo pulp fiber element & polyvinylformamide composite flocculation decoloring material |
| WO2020127568A1 (en) * | 2018-12-20 | 2020-06-25 | S.P.C.M. Sa | Method for treating suspensions of solid particles in water using amphoteric polymers |
| FR3090617A1 (en) * | 2018-12-20 | 2020-06-26 | S.N.F. Sa | process for the treatment of suspensions of solid particles in water using amphoteric polymers |
| CN113260442A (en) * | 2018-12-20 | 2021-08-13 | S.P.C.M.股份公司 | Method for treating suspensions of solid particles in water by means of amphoteric polymers |
| CN113072215A (en) * | 2021-04-15 | 2021-07-06 | 浙江德正建设有限公司 | Energy-saving emission-reducing town sewage treatment system |
| CN113072215B (en) * | 2021-04-15 | 2022-06-14 | 浙江德正建设有限公司 | Energy-saving emission-reducing town sewage treatment system |
| CN116162290A (en) * | 2023-03-09 | 2023-05-26 | 深圳丹伦基因科技有限公司 | Porous microcarrier, preparation method and application thereof |
| CN116162290B (en) * | 2023-03-09 | 2024-05-28 | 深圳丹伦基因科技有限公司 | Porous microcarrier, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229690B (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102286132B (en) | Method for preparing starch graft cationic type hyperbranched amide polymer | |
| CN101693749B (en) | Method for preparing dissaving vinyl or propenyl amide polymer | |
| CN102229690B (en) | Method for preparing starch grafted hyperbranched amide polymer | |
| CN103059828B (en) | For viscosifying agent and the synthetic method thereof of aqueous fracturing fluid | |
| CN102050926B (en) | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof | |
| CN102050913B (en) | Temperature and salt resistant grafted polyacrylamide and preparation method thereof | |
| CN105062455B (en) | A kind of water-based fracturing fluid gelatinizer and its synthetic method | |
| JP2011252163A (en) | High molecular weight cationic polymer obtained by post-polymerization crosslinking reaction | |
| CN103987746A (en) | Preparation of polyvinylamide cellulose reactive adducts | |
| WO2017209105A1 (en) | Polymer, method for producing polymer and polymer flocculant | |
| JP2013543066A5 (en) | ||
| CN112279963B (en) | Temperature-resistant salt-resistant multi-copolymerization pre-crosslinked gel particles and preparation method and application thereof | |
| CN102153714A (en) | Method for preparing cation type hyperbranched ethylene or acrylamide polymer | |
| CN105037644A (en) | Polymer cationic surfactant, preparation method and applications thereof | |
| US20210253770A1 (en) | High melt index thermoplastic elastomer and preparation method therefor | |
| CN101220263A (en) | Water-based fracturing fluid gelatinizer and producing method thereof | |
| CN103408701B (en) | The method that uv-light polymerization prepares drying strengthening agent | |
| CN103408702B (en) | Preparation method of graft-polymer cationic dry strength agent | |
| CN103304465B (en) | A kind of N-alkylsulphonic acid base maleimide monomer and its preparation method and application | |
| CN105385433A (en) | Quick-dissolving thickening agent used for water-based fracture and synthesizing method thereof | |
| CN108084297A (en) | There is the composition of initiated polymerization and the method for preparing acrylamide copolymer | |
| CN106608976B (en) | A kind of starch-containing tackifier copolymerization associated matter and preparation method thereof | |
| CN103435752B (en) | The method for synthesizing graft-polymer both sexes drying strengthening agent | |
| CN106608946A (en) | Tackifier copolymerization associate used for drilling fluid and preparation method of tackifier copolymerization associate | |
| CN108084298A (en) | There is the composition of initiated polymerization and the method for preparing acrylamide copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |