CN102492092B - Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization - Google Patents
Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization Download PDFInfo
- Publication number
- CN102492092B CN102492092B CN201110432108.4A CN201110432108A CN102492092B CN 102492092 B CN102492092 B CN 102492092B CN 201110432108 A CN201110432108 A CN 201110432108A CN 102492092 B CN102492092 B CN 102492092B
- Authority
- CN
- China
- Prior art keywords
- acid
- monomer
- ionic
- phase
- follow
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 150000001408 amides Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title abstract description 14
- 238000012688 inverse emulsion polymerization Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001993 dienes Chemical class 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- -1 vinyl compound Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 30
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 150000003926 acrylamides Chemical class 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 10
- 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
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002148 esters 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
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- 229950007687 macrogol ester Drugs 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical class SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 3
- 229940068968 polysorbate 80 Drugs 0.000 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- 210000002268 wool Anatomy 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
- 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 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
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 2
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- TUXPQPLAXQYORY-UHFFFAOYSA-N 3-methyldioxane Chemical compound CC1CCCOO1 TUXPQPLAXQYORY-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
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 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
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 241000233803 Nypa Species 0.000 claims description 2
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 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
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- IDSLKCIQOSQROT-UHFFFAOYSA-N dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;prop-2-enoate Chemical compound OC(=O)C=C.CN(C)CCOC(=O)C(C)=C IDSLKCIQOSQROT-UHFFFAOYSA-N 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
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 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
- 239000003350 kerosene Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([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
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 6
- 150000001412 amines Chemical class 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920002401 polyacrylamide Polymers 0.000 description 10
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 230000003311 flocculating effect Effects 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 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 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbon oxide sulfide Natural products O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PSXRWZBTVAZNSF-UHFFFAOYSA-N hydron;quinoline;chloride Chemical compound Cl.N1=CC=CC2=CC=CC=C21 PSXRWZBTVAZNSF-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 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
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种反相乳液聚合制备超支化离子型酰胺类聚合物的方法。在表面活性剂的作用下，通过可逆加成-断裂链转移（RAFT）的反相乳液聚合，采用加入后续相的操作工艺，将离子型单体先进行聚合或者离子型单体和部分酰胺类单体先进行共聚，其后加入剩余的酰胺类单体扩链，结合使用二烯类单体及RAFT链转移剂，制备了支化链外末端为离子型单体嵌段或高离子度共聚嵌段的超支化离子型酰胺类聚合物。本发明得到的超支化离子型酰胺类聚合物具有很好的絮凝效果和优良的水溶解性。The invention discloses a method for preparing a hyperbranched ionic amide polymer by inverse emulsion polymerization. Under the action of surfactants, ionic monomers are first polymerized or ionic monomers and some amides are polymerized by reversible addition-fragmentation chain transfer (RAFT) inverse emulsion polymerization and the operation process of adding subsequent phases The monomer is firstly copolymerized, and then the remaining amide monomer is added to extend the chain, and the diene monomer and RAFT chain transfer agent are used in combination to prepare a branched chain with an ionic monomer block or a high ionic degree copolymerization Block hyperbranched ionic amide polymers. The hyperbranched ionic amide polymer obtained by the invention has good flocculation effect and excellent water solubility.
Description
Technical field
The present invention relates to a kind of inverse emulsion polymerization synthetic technology of water-soluble ionic-type acylamide polymer, relate in particular to be a kind ofly applicable to disperse, stick, flocculation and rheology control and there is the preparation method of the ionic acylamide polymer of the dissaving structure that the outer end of branched chain is ionic comonomer block or macroion degree copolymerization block.
Background technology
Ionic acylamide polymer is widely used in the fields such as sewage disposal, mine, iron and steel, petrochemical industry, papermaking, printing and dyeing, sugaring, building materials.
Water-soluble ionic-type acylamide polymer can be by solution polymerization or inverse emulsion polymerization.During solution polymerization, when in system, monomer surpasses 8% as acrylamide content, viscosity is just very high, makes polymerization process wayward, and molecular weight is on the low side.And that inverse emulsion polymerization has polymerization efficiency is high, solid content is high, polymericular weight advantages of higher.CN101298488A discloses adding under the condition that sodium formiate is reagent and additive in polymerization, by conversed phase micro emulsion copolymerization, has prepared the cationic-type polyacrylamide of good stability, and polymericular weight is about 10
6.J.R.Ochoa etc. have reported that take acrylamide (AM) and 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) is reaction monomers, adopt the method for reverse micro emulsion to synthesize the cationic high-molecular flocculant of solid content 30%.
Now widely used ionic acylamide polymer, take linear structure as main as cationic acrylamide flocculating agent, and the ionic acylamide polymer of branched structure is very rarely seen in the application of the aspects such as water treatment.CN1834127c discloses employing composite initiation system, with AM and cationic monomer DMC, carries out aqueous solution adiabatic polymerisation, prepares relative molecular weight and is greater than 10
7cationic-type polyacrylamide.CN1865299 discloses under adiabatic condition and has introduced function monomer, synthesizes the super high molecular weight polyacrylamide of different molecular weight ranges by the synergistic effect of three sections of composite initiation series initiators.But, poorly soluble in water of the linear amides base polymer of ultra-high molecular weight, dissolution rate is lower, and the viscosity of the linear polymer of high molecular is also larger, affects processing characteristics, improves production cost.And compare with linear polymer with the hyperbranched polymer of equimolecular quantity, there is lower viscosity, high rheological variation and good solubility, easy to use.
Hyperbranched polymer is the hyperbranched macromole with triaxial ellipsoid shape D structure of a class, containing a large amount of end and main chain functional groups, conventionally uses the special direct one-step polycondensation of ABx type monomer to make.Sherrington etc. (J.Mater.Chem, 2003,2701-2710) to take the mercaptan of suitable proportion be chain-transfer agent to report, obtains the polymethacrylate of branching by the copolymerization with Ethylene glycol dimethacrylate.(the Macromolecules such as Wang, 2010,4062-4069) reported and adopted semi-continuous operating procedure, by reversible addition-fracture chain, shift (RAFT) polymerization, take dienes monomer as branching agent, under the RAFT of low proportioning chain-transfer agent condition, by the method for solution polymerization, prepare hyperbranched polyacrylamide.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method of preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization is provided.
The object of the invention is to be achieved through the following technical solutions: a kind of inverse emulsion polymerization method of preparing hyperbranched ionic acylamide polymer, comprises the following steps:
(1) preparation external phase: at ambient temperature, by oil-soluble emulsifier, polymeric surface active agent, be dissolved in solvent oil, mix; The mass ratio of described oil-soluble emulsifier, polymeric surface active agent, solvent oil is controlled at 0.4-15:0.01-12:8-68;
(2) preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent, initiator are dissolved in water, are mixed with disperse phase; The mass ratio that wherein water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent, initiator, water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:0.00009-0.45:3-65;
(3) prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
(4) 0.5-25:0.5-25:0.01-10 gets external phase, disperse phase and the follow-up phase that step 1-3 prepares in mass ratio, then under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mixes pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer.
The invention has the beneficial effects as follows: the inventive method is by RAFT polymerization process, employing adds the operating procedure of follow-up phase, ion monomer is first carried out to homopolymerization or first carries out copolymerization with part amides monomer, add residue amides monomer chain extension thereafter, be combined with dienes monomer and RAFT chain-transfer agent, prepared the outer end of branched chain and be ionic comonomer block or macroion degree copolymerization block hyperbranched ionic acylamide polymer.The hyperbranched ionic acylamide polymer that the present invention obtains has good flocculating effect and good water-soluble.
Embodiment
The method of preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization of the present invention shifts (RAFT) inverse emulsion polymerization method by semicontinuous reversible addition-fracture, because used the special chain transfer agent that chain transfer constant is high in RAFT polymerization process, the regeneration of reversible addition-fracture occurs for this chain-transfer agent and Propagating Radical shifts, keep free radical activity, realize controlled and radical polymerization " activity ", and can regulate and control the structure of polymkeric substance.Simultaneously, employing adds the operating procedure of follow-up phase, can obtain the outer end of branched chain and be ionic comonomer block or macroion degree copolymerization block hyperbranched ionic acylamide polymer, use in conjunction with low proportioning chain-transfer agent, polyreaction is easily controlled, and can highly transform the stabilized latex that ground forms high solids content.
Specifically, the method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization of the present invention, comprises the following steps:
One, preparation external phase: at ambient temperature, oil-soluble emulsifier, polymeric surface active agent are dissolved in to solvent oil, mix;
Solvent oil comprises the liquefied hydrocarbon of aromatic series, cycloalkane, aliphatic category and containing substituent compound, comprises isoparaffin, 120# solvent oil, 200# solvent oil, kerosene, whiteruss, white oil a kind of and composition thereof of tetrachloroethylene, tetracol phenixin, toluene, benzene, dimethylbenzene, octane, dodecane, the tetradecane, different carbon chain.The mass ratio of controlling water in solvent oil and disperse phase is 0.5-2:2-0.5.
The mass ratio of oil-soluble emulsifier, polymeric surface active agent, solvent oil is controlled at 0.4-15:0.01-12:8-68; Wherein oil-soluble emulsifier comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol etc. and composition thereof.Polymeric surface active agent is a kind of amphipathic nature polyalcohol, in polymkeric substance, there is hydrophilic, lipophilic group simultaneously, comprise oxyethylene-propylene oxide block copolymer, ten dihydroxystearic acids-epoxyethane block copolymer, acrylate-acrylamide copolymer, acrylate-acrylic copolymer, acrylate-Sipacril 2739OF, acrylate-dimethyl diene ammonium chloride copolymer, acrylate-dimethylaminoethyl methacrylate quaternized copolymer and composition thereof.
Two, preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent, initiator are dissolved in water, are mixed with disperse phase; The mass ratio that wherein water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent, initiator, water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:0.00009-0.45:3-65;
Water soluble emulsifier is nonionic surface active agent, comprise dehydration sorb sugar ester ethylene oxide adduct, alkyl alcohol or alkylphenol ethylene oxide adduct etc., as Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides, polyoxyethylene nonylplenyl ether etc. and composition thereof.
Amides monomer comprises the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, NVP etc.
Ionic comonomer comprises anionic monomer, cationic monomer and amphipathic water-soluble monomer.Described anionic monomer comprises vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, to vinylbenzenesulfonic acid (sodium), to vinyl benzoic acid etc.; Described cationic monomer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine etc.; Described amphipathic water-soluble monomer comprises N-(3-sulfonic acid propyl group) 2-vinyl pyridine, 2-acrylyl oxy-ethyl phosphorylcholine etc.
RAFT chain-transfer agent is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.Described dithioesters class link transfer agent comprises 4-cyanopentanoic acid dithiobenzoic acid ester.The different base dithiobenzoic acid of 2-cyano group third ester, 2-(2-hydroxyethanoic acid 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.Described trithiocarbonate 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 '-thiocarbonyls two (sulfanyl) two (2 Methylpropionic acid) etc., xanthogenic acid 0 ester class is as xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid etc.
Initiator can be the various initiators that are applicable to polar solvent system, as chemical initiator, and photochemical initiators, radiation initiators etc.Chemical initiator when had peroxide initiator, azo-initiator, oxidation-reduction initiator etc.Conventional peroxide initiator comprises ammonium persulphate, Potassium Persulphate etc., and azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl mew quinoline hydrochloride, azo di-isopropyl mew quinoline etc.Described photochemical initiators comprises (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone) etc.
Three, prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
Dienes compound comprises symmetry and asymmetry vinyl compound; Conventional dienes compound comprises N, N '-methylene-bisacrylamide, diacrylate macrogol ester, Ethylene glycol dimethacrylate etc.Described asymmetric dienes compound comprises (methyl) vinylformic acid vinyloxy group macrogol ester etc.
Four, under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mix pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer.
Described emulsifying agent in step 1 and step 2 is nonionic surface active agent.In described step 1, described oil-soluble emulsifier comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol etc.; In described step 2, water soluble emulsifier comprises Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides and polyoxyethylene nonylplenyl ether etc., and the hydrophile-lipophile balance value of composite rear emulsifying agent (HLB) is worth between 2-7.
Polymerization temperature is controlled between 25 ℃ to 80 ℃, react after 0.5-5 hour, 0-3 hour the follow-up of Nei Jiang first part, be added in reaction system, continue reaction after 1-3 hour, in second section follow-up being added to reaction system in 0-3 hour, continue reaction 1-3 hour, total reaction time was controlled between 5-17 hour.The final hyperbranched ionic acylamide polymer obtaining be emulsion total amount 5% to 60% between.
Below by specific examples, further illustrate the present invention program and result, but can not think that the present invention only limits in these examples.In example, except specified otherwise, all marks and percentage ratio are all weight ratios.
Embodiment 1
In 100ml there-necked flask, add 1.2 parts of ten dihydroxystearic acids-epoxyethane block copolymers, 1.56 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 3.175 parts of acrylamides, 3.3 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0348 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.24 part of Tween80 are dissolved in 6.26 parts of water (PH=7), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0292 part of over cure ammonium, is warming up to 50 ℃, adds 0.0137 part of sodium bisulfite to start reaction.React after 3 hours, 1.9 parts of acrylamides are dissolved in 1.5 parts of water, add reaction system, react again after 3 hours, by 1.27 parts of acrylamides and 0.0197 part of N, N '-methylene-bisacrylamide is dissolved in 1 part of water, and the constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched Polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 96.5%, its weight-average molecular weight is 2.80 * 10
5, molecular weight distribution is 1.61, the parameter g ' of polymkeric substance branching degree can characterize the degree of branching of molecule, g '=1 of linear polymer, and the g ' <1 of branching molecule for 0.712(g '; Degree of branching is higher, and g ' is less), the flocculating property of sample represents with relative turbidity, the relative turbidity Tr=T/To of Tr=0.453(, To is initial TiO
2the turbidity of turbid solution, T is the TiO adding after sample flocculation agent for some time
2the turbidity of turbid solution, adds 1mg polymer samples/g TiO
2, flocculation time is 30min).
Embodiment 2
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0145 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 0.5 hour, by 1.37 parts of acrylamides and 0.0082 part of N, N '-methylene-bisacrylamide is dissolved in 1.8 parts of water, add reaction system, react after 1 hour, by 1.37 parts of acrylamides and 0.041 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water again, constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched Polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 86.7%, its weight-average molecular weight is 6.43 * 10
5, molecular weight distribution is 1.5, the parameter g ' of polymkeric substance branching degree is 0.722, the flocculating property of sample represents with relative turbidity, Tr=0.157.
Implementation column 3
The solid content of maintenance system is constant, reduces the content of cationic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, and ion degree is reduced to 15% from 25% of example 2.
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 2.36 parts of acrylamides, 3.88 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0103 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0086 part of over cure ammonium, is warming up to 50 ℃, adds 0.0047 part of sodium bisulfite to start reaction.React after 0.5 hour, by 1.77 parts of acrylamides and 0.0082 part of N, N '-methylene-bisacrylamide is dissolved in 1.8 parts of water, adds reaction system.React again after 3 hours, by 1.77 parts of acrylamides and 0.0246 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 6.7ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.The transformation efficiency of polymerization system is 96%, its weight-average molecular weight is 1.22 * 10
6, molecular weight distribution is 1.18, the parameter g ' of polymkeric substance branching degree is 0.675, the flocculating property of sample represents with relative turbidity, Tr=0.339.
Embodiment 4
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.37 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 1 hour, 1.82 parts of acrylamides are dissolved in 1.8 parts of water, add reaction system, react again after 1.5 hours, by 1.37 parts of acrylamides and 0.0412 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 90.8%, its weight-average molecular weight is 5.93 * 10
5, molecular weight distribution is 1.74, the parameter g ' of polymkeric substance branching degree is 0.628, the flocculating property of sample represents with relative turbidity, Tr=0.325.
Embodiment 5
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 1 hour, 0.46 part of acrylamide is dissolved in 1.8 parts of water, add reaction system, react again after 1.5 hours, by 2.28 parts of acrylamides and 0.0412 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 7.6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 89.7%, its weight-average molecular weight is 4.53 * 10
5, molecular weight distribution is 1.8, the parameter g ' of polymkeric substance branching degree is 0.780, the flocculating property of sample represents with relative turbidity, Tr=0.163.
Embodiment 6
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 0.5 hour, by 2.74 parts of acrylamides and 0.0246 part of N, N '-methylene-bisacrylamide is dissolved in 3.3 parts of water, and the constant rate of speed with 8.5ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 85.9%, its weight-average molecular weight is 5.05 * 10
5, molecular weight distribution is 1.18, the parameter g ' of polymkeric substance branching degree is 0.816, the flocculating property of sample represents with relative turbidity, Tr=0.39.
Above-described embodiment 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 that the present invention is made, all fall into protection scope of the present invention.
Claims (6)
1. a reversed phase emulsion synthesis method of preparing hyperbranched ionic acylamide polymer, is characterized in that, comprises the following steps:
(1) preparation external phase: at ambient temperature, oil-soluble emulsifier, polymeric surface active agent are dissolved in to solvent oil, mix; The mass ratio of described oil-soluble emulsifier, polymeric surface active agent and solvent oil is controlled at 0.4-15:0.01-12:8-68;
(2) preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent are dissolved in water, are mixed with disperse phase; Wherein, the mass ratio that water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent and water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:3-65;
(3) prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
(4) 0.5-25:0.5-25:0.01-10 gets external phase, disperse phase and the follow-up phase that prepare step (1)-(3) in mass ratio, then under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mix pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer;
Described amides monomer comprises: the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, NVP; Described ionic comonomer comprises anionic monomer, cationic monomer and amphipathic water-soluble monomer; Described anionic monomer comprises vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, to vinylbenzenesulfonic acid, to vinyl benzoic acid; Described cationic monomer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-dimethyl ethenylphenyl amine and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine; Described amphipathic water-soluble monomer comprises N-(3-sulfonic acid propyl group) 2-vinyl pyridine and 2-acrylyl oxy-ethyl phosphorylcholine; Described dienes monomer comprises symmetry and asymmetry vinyl compound; Described symmetry dienes compound comprises N, N '-methylene-bisacrylamide, diacrylate macrogol ester and Ethylene glycol dimethacrylate; Described asymmetry dienes compound comprises (methyl) vinylformic acid vinyloxy group macrogol ester.
2. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described oil-soluble emulsifier is nonionic surface active agent, comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol; In described step (2), water soluble emulsifier is nonionic surface active agent, comprises Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides and polyoxyethylene nonylplenyl ether; Polymeric surface active agent in step (1) is a kind of amphipathic nature polyalcohol, in polymkeric substance, there is hydrophilic, lipophilic group simultaneously, comprise oxyethylene-propylene oxide block copolymer, ten dihydroxystearic acids-epoxyethane block copolymer, acrylate-acrylamide copolymer, acrylate-acrylic copolymer, acrylate-Sipacril 2739OF, acrylate-dimethyl diallyl ammonium chloride copolymer and acrylate-dimethylaminoethyl methacrylate quaternized copolymer.
3. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described solvent oil comprises: the liquefied hydrocarbon of aromatic series, cycloalkane, aliphatic category and containing substituent compound.
4. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described solvent oil comprises tetrachloroethylene, tetracol phenixin, toluene, benzene, dimethylbenzene, octane, dodecane, the tetradecane, isoparaffin, 120# solvent oil, 200# solvent oil, kerosene, whiteruss and white oil.
5. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (2), described RAFT chain-transfer agent is dithio or trithio compound, comprises dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class; Described dithiobenzoic acid ester class comprises 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyano group sec.-propyl dithiobenzoic acid ester; Described dithiocarbamate(s) is 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid; Described 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 (sulfanyl) two (2 Methylpropionic acid); Xanthate class is selected from xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
6. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (4), described initiator is chemical initiator, and described chemical initiator comprises peroxide initiator, azo-initiator, oxidation-reduction initiator and photochemical initiators; Described peroxide initiator comprises ammonium persulphate, Potassium Persulphate; Described azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline; 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 |
|---|---|---|---|
| CN201110432108.4A CN102492092B (en) | 2011-12-21 | 2011-12-21 | Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110432108.4A CN102492092B (en) | 2011-12-21 | 2011-12-21 | Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102492092A CN102492092A (en) | 2012-06-13 |
| CN102492092B true CN102492092B (en) | 2014-05-07 |
Family
ID=46183958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110432108.4A Active CN102492092B (en) | 2011-12-21 | 2011-12-21 | Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102492092B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11173112B2 (en) * | 2006-03-07 | 2021-11-16 | Sgn Nanopharma Inc. | Ophthalmic preparations |
| US11311477B2 (en) * | 2006-03-07 | 2022-04-26 | Sgn Nanopharma Inc. | Ophthalmic preparations |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601893B (en) * | 2013-10-23 | 2015-12-09 | 西北工业大学 | Preparation method of long-chain hyperbranched poly(N-isopropylacrylamide) with temperature sensitivity |
| CN103788269B (en) * | 2014-01-24 | 2016-01-20 | 绍兴文理学院 | Polyacrylamide and its preparation method and application |
| CN104327218B (en) * | 2014-10-21 | 2017-03-08 | 山东德仕石油工程集团股份有限公司 | A kind of preparation method of PAMC aqueous emulsion |
| CN105669912B (en) * | 2016-03-03 | 2018-03-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of method for preparing star-like poly carboxylic acid series water reducer |
| CN107383292B (en) * | 2017-07-11 | 2019-11-19 | 四川大学 | A kind of hydrophobic association type tri-block polyacrylamide and its preparation method and application |
| FR3088067B1 (en) * | 2018-11-06 | 2020-11-06 | S N F Sa | PROCESS FOR SYNTHESIS OF POLYMERS BY CONTROLLED RADICAL POLYMERIZATION IN REVERSE EMULSION |
| JP7271962B2 (en) * | 2019-01-22 | 2023-05-12 | 東亞合成株式会社 | Method for producing water-soluble polymer |
| CN111285973A (en) * | 2020-03-18 | 2020-06-16 | 爱森（中国）絮凝剂有限公司 | Star-shaped cationic polymer flocculant and preparation method thereof |
| CN115287021B (en) * | 2022-07-07 | 2024-04-02 | 江苏景宏新材料科技有限公司 | Waterproof Hou Shuixing acrylate pressure-sensitive adhesive and preparation method 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037492A (en) * | 2007-03-28 | 2007-09-19 | 中国石油大学(华东) | Method for preparing propylene amides copolymer with regular branch structure by inverse emulsion method |
| EP2053068A1 (en) * | 2007-10-25 | 2009-04-29 | Societe D'exploitation De Produits Pour Les Industries Chimiques, S.E.P.P.I.C. | New process for the preparation of inverse latex of acrylamide-based polymers and composition comprising said latex |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
| CN102086249A (en) * | 2010-12-27 | 2011-06-08 | 浙江大学 | Method for preparing hyperbranched ethylene or acrylamide polymer by inverse emulsion polymerization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7989401B2 (en) * | 2008-04-21 | 2011-08-02 | Nalco Company | Block copolymers for recovering hydrocarbon fluids from a subterranean reservoir |
-
2011
- 2011-12-21 CN CN201110432108.4A patent/CN102492092B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037492A (en) * | 2007-03-28 | 2007-09-19 | 中国石油大学(华东) | Method for preparing propylene amides copolymer with regular branch structure by inverse emulsion method |
| EP2053068A1 (en) * | 2007-10-25 | 2009-04-29 | Societe D'exploitation De Produits Pour Les Industries Chimiques, S.E.P.P.I.C. | New process for the preparation of inverse latex of acrylamide-based polymers and composition comprising said latex |
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
| CN102086249A (en) * | 2010-12-27 | 2011-06-08 | 浙江大学 | Method for preparing hyperbranched ethylene or acrylamide polymer by inverse emulsion polymerization |
Non-Patent Citations (4)
| Title |
|---|
| Liu Ouyang等.Synthesis and nucleation mechanism of inverse emulsion polymerization of acrylamide by RAFT polymerization: A comparative study.《POLYMER》.2011,第52卷(第1期), |
| Qi Genggeng等.RAFT inverse miniemulsion polymerization of acrylamide.《MACROMOLECULAR RAPID COMMUNICATIONS》.2007,第28卷(第9期), |
| RAFT inverse miniemulsion polymerization of acrylamide;Qi Genggeng等;《MACROMOLECULAR RAPID COMMUNICATIONS》;20070502;第28卷(第9期);第1010-1016页 * |
| Synthesis and nucleation mechanism of inverse emulsion polymerization of acrylamide by RAFT polymerization: A comparative study;Liu Ouyang等;《POLYMER》;20110107;第52卷(第1期);第63-67页 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11173112B2 (en) * | 2006-03-07 | 2021-11-16 | Sgn Nanopharma Inc. | Ophthalmic preparations |
| US11311477B2 (en) * | 2006-03-07 | 2022-04-26 | Sgn Nanopharma Inc. | Ophthalmic preparations |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102492092A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102492092B (en) | Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization | |
| CN101693749B (en) | A method for preparing hyperbranched vinyl or acrylamide polymers | |
| CN102086249A (en) | Method for preparing hyperbranched ethylene or acrylamide polymer by inverse emulsion polymerization | |
| KR101064861B1 (en) | Modified polymer flocculant with improved performance characteristics | |
| RU2632886C2 (en) | Preparation of amphiphilic block copolymers by controlled radial micellar polymerization | |
| CN101037492A (en) | Method for preparing propylene amides copolymer with regular branch structure by inverse emulsion method | |
| CN100500716C (en) | Random copolymer cationic macromolecular emulsifier and preparation method thereof | |
| CN104774289B (en) | Preparation method for 'water-in-water' type hydrophobically associated polyacrylamide emulsion | |
| CA2310719A1 (en) | Inverse emulsion polymer and production thereof | |
| CN105348439A (en) | Preparation method of high-solid-content polyacrylamide emulsion | |
| CN112708013B (en) | Drag reducer and preparation method and application thereof | |
| CN112708012A (en) | Emulsion polymer for fracturing and preparation method and application thereof | |
| JP4847833B2 (en) | Stable emulsion composition and sludge dewatering method | |
| JP6388329B2 (en) | Water-soluble polymer dispersion containing low inorganic salt and process for producing the same | |
| JP4886228B2 (en) | Water-soluble polymer dispersion and paper making method using the same | |
| CN102153714A (en) | Method for preparing cation type hyperbranched ethylene or acrylamide polymer | |
| CN109467641A (en) | A kind of preparation method of high solids content cation polyacrylamide emulsion | |
| JP5866096B2 (en) | Wastewater treatment method | |
| JP2017159193A (en) | Wastewater treatment method by water-soluble polymer dispersion liquid | |
| US5116923A (en) | Hydrophobically associating polymers containing dimethyl acrylamide functionality | |
| JPH0966300A (en) | Agglomeration treatment agent for cement-containing waste mud | |
| JP2022126023A (en) | Anionic water-soluble polymer dispersion and method for producing the same | |
| JP7489058B2 (en) | Water-in-oil emulsion type flocculation treatment agent and its dissolution method | |
| JP5630782B2 (en) | Sludge dewatering agent and sludge dewatering method | |
| WO2025141012A1 (en) | Method for preparing a polymer by radical polymerization in inverse emulsion |
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 |