EP2049573A2 - Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren - Google Patents
Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymerenInfo
- Publication number
- EP2049573A2 EP2049573A2 EP07787075A EP07787075A EP2049573A2 EP 2049573 A2 EP2049573 A2 EP 2049573A2 EP 07787075 A EP07787075 A EP 07787075A EP 07787075 A EP07787075 A EP 07787075A EP 2049573 A2 EP2049573 A2 EP 2049573A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- soluble
- derivatives
- vinyl
- reactor
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 90
- 239000006185 dispersion Substances 0.000 title claims abstract description 64
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007800 oxidant agent Substances 0.000 claims abstract description 109
- 239000000178 monomer Substances 0.000 claims abstract description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 74
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 37
- 150000002978 peroxides Chemical class 0.000 claims abstract description 32
- 150000008049 diazo compounds Chemical class 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001400 block copolymer Polymers 0.000 claims abstract description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims abstract description 19
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 81
- 230000001590 oxidative effect Effects 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 56
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- -1 vinylic pyridine derivatives Chemical class 0.000 abstract description 27
- 239000003999 initiator Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 124
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 91
- 238000006116 polymerization reaction Methods 0.000 description 80
- 229910052786 argon Inorganic materials 0.000 description 62
- 239000000243 solution Substances 0.000 description 58
- 239000012429 reaction media Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 239000002245 particle Substances 0.000 description 24
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 22
- 239000011521 glass Substances 0.000 description 18
- 239000003995 emulsifying agent Substances 0.000 description 15
- 241000605112 Scapanulus oweni Species 0.000 description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 13
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 13
- 239000012300 argon atmosphere Substances 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000009518 sodium iodide Nutrition 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- FNLAIMLJECXVQU-UHFFFAOYSA-N diazanium;4-[(4-carboxylato-2-cyanobutan-2-yl)diazenyl]-4-cyanopentanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC(C)(C#N)N=NC(C)(CCC([O-])=O)C#N FNLAIMLJECXVQU-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- ICCKYZGDUAOTHD-UHFFFAOYSA-L disodium;4-[(4-carboxylato-2-cyanobutan-2-yl)diazenyl]-4-cyanopentanoate Chemical compound [Na+].[Na+].[O-]C(=O)CCC(C)(C#N)N=NC(C)(CCC([O-])=O)C#N ICCKYZGDUAOTHD-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- 101001090860 Homo sapiens Myeloblastin Proteins 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 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 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 102100034681 Myeloblastin Human genes 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- GLGAUBPACOBAMV-DOFZRALJSA-N arachidonylcyclopropylamide Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)NC1CC1 GLGAUBPACOBAMV-DOFZRALJSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000002270 exclusion chromatography Methods 0.000 description 2
- 229960002413 ferric citrate Drugs 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000002777 nucleoside Substances 0.000 description 2
- 125000003835 nucleoside group Chemical group 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- GYTOJALPPLZKKP-UHFFFAOYSA-N 1-(2-chloroethoxy)prop-1-ene Chemical compound CC=COCCCl GYTOJALPPLZKKP-UHFFFAOYSA-N 0.000 description 1
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 1
- JNMJJTLOYAEWAV-UHFFFAOYSA-N 1-bromo-3-ethenoxypropane Chemical compound BrCCCOC=C JNMJJTLOYAEWAV-UHFFFAOYSA-N 0.000 description 1
- PNEWSCXZLUPKET-UHFFFAOYSA-N 1-chloro-4-ethenoxybutane Chemical compound ClCCCCOC=C PNEWSCXZLUPKET-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
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- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- PEOHLVWFSVQRLK-UHFFFAOYSA-N ethenylcarbamic acid Chemical compound OC(=O)NC=C PEOHLVWFSVQRLK-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- IZKUWTDESDNCCG-UHFFFAOYSA-N n'-acetylprop-2-enehydrazide Chemical compound CC(=O)NNC(=O)C=C IZKUWTDESDNCCG-UHFFFAOYSA-N 0.000 description 1
- HQHSMYARHRXIDS-UHFFFAOYSA-N n,n-dimethyl-1-phenylprop-2-en-1-amine Chemical compound CN(C)C(C=C)C1=CC=CC=C1 HQHSMYARHRXIDS-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- VXRNYQMFDGOGSI-UHFFFAOYSA-N n-(1,3-dihydroxy-2-methylpropan-2-yl)-2-[[1-[(1,3-dihydroxy-2-methylpropan-2-yl)amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(C)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(C)(CO)CO VXRNYQMFDGOGSI-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- OKPYIWASQZGASP-UHFFFAOYSA-N n-(2-hydroxypropyl)-2-methylprop-2-enamide Chemical compound CC(O)CNC(=O)C(C)=C OKPYIWASQZGASP-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- QHGUPRQTQITEPO-UHFFFAOYSA-N oxan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCO1 QHGUPRQTQITEPO-UHFFFAOYSA-N 0.000 description 1
- FGWRVVZMNXRWDQ-UHFFFAOYSA-N oxan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCO1 FGWRVVZMNXRWDQ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- INRGAWUQFOBNKL-UHFFFAOYSA-N {4-[(Vinyloxy)methyl]cyclohexyl}methanol Chemical compound OCC1CCC(COC=C)CC1 INRGAWUQFOBNKL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- the present invention relates to a radical polymerization process in aqueous dispersion for the preparation of polymers and a radical polymerization process in aqueous dispersion for the preparation of block copolymers.
- radical polymerization is the chain polymerization mechanism that accommodates the least demanding experimental conditions and the widest range of monomers, giving it the characteristics of a living polymerization has remained a major challenge for a very long time.
- the main limitation of conventional free-radical polymerization stems from the crucial importance of irreversible termination reactions, by combination and / or disproportionation of the radicals responsible for chain growth.
- the growing chains are primed, grow and then end randomly and irreversibly, along with the priming of new chains.
- the polymerization ends when all the polymer chains are inactive, which are of variable length and unpredictable. This technique therefore offers little opportunity to act on the molar mass, the distribution of molar masses, the nature of the chain ends and, more generally, the molecular structure of the polymer.
- nitroxide-controlled radical polymerization Nonroxide-Mediated Polymerization or NMP
- Atom Transfer Radical Polymerization ATRP
- addition-fragmentation chain transfer Reversible Addition- Fragmentation Chain Transfer Polymerization or RAFT / MADIX
- ITP iodine Transfer Polymerization
- Iodine Transfer Polymerization or RITP using iodine as a control agent has also been developed.
- the application WO 03/097704 discloses such a controlled radical polymerization process according to which at least one ethylenically unsaturated monomer is polymerized in the presence of at least one radical-generating agent and molecular iodine.
- the target average molar mass (M n ) of the polymer is controlled by the ratio between the mass of monomer and twice the number of initial moles of iodine (n 12; mit1 ai) according to equation 1 below, in which MA-I is the molar mass of the chain ends:
- M n (mass of monomer) / (2x ni2, mitiai) + MA-I (equation 1) If the text of the application WO 03/097704 describes the polymerization of vinyl chloride in aqueous suspension, the process in question does not allow, however, not to obtain a polymer whose experimental average molar mass (20 000) is very close to the theoretical average molar mass (target molecular weight taking into account the conversion rate) (8700).
- the present invention therefore relates to a radical polymerization process in aqueous dispersion for the preparation of polymers which allows a better control of the polymerization and therefore the average molar mass of the polymers obtained compared to the processes of the prior art while preserving their benefits.
- the invention relates to a radical polymerization process in aqueous dispersion for the preparation of polymers using
- At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- polymerization in aqueous dispersion is meant the polymerization processes taking place in water in the presence of at least one surfactant.
- At least one surfactant it is meant that the polymerization process can take place in the presence of one or more surfactants.
- surfactant any compound having in its structure one or more hydrophilic parts and one or more hydrophobic parts. This hydrophilic / hydrophobic balance allows the surfactant to have an interfacial activity which makes it possible to ensure dispersion and stabilization of the aqueous and organic phases in the presence.
- Some polymerizations in aqueous dispersion can be carried out in the absence of surfactant but with the consequence of the formation of aqueous dispersions unstable and characterized by a very low solids content.
- the present invention does not relate to such polymerizations but to polymerizations in aqueous dispersion carried out in the presence of at least one surfactant.
- dispersing agents also called protective colloids or suspending agents (hereinafter referred to as dispersing agents), but also emulsifiers.
- aqueous dispersion polymerization is intended to denote radical polymerization in aqueous suspension, radical polymerization in aqueous microsuspension, radical polymerization in aqueous emulsion and radical polymerization in aqueous miniemulsion.
- radical polymerization in aqueous suspension is meant any radical polymerization process being carried out in an aqueous medium in the presence of dispersing agents as surfactants and oil-soluble radical generating agents.
- aqueous microsuspension also called homogenized aqueous dispersion
- any radical polymerization process in which is implemented oil-soluble radical generating agents and is carried out an emulsion of monomer droplets through a powerful mechanical agitation and which is characterized by the presence of emulsifying agents as surfactants.
- radical polymerization in aqueous emulsion is meant any radical polymerization process being carried out in an aqueous medium in the presence of emulsifiers as surfactants and agents for generating water-soluble radicals.
- the aqueous emulsion polymerization is sometimes also called ab initio emulsion polymerization.
- aqueous mini-emulsion polymerization is intended to denote any radical polymerization process in which oil-soluble radical generating agents and / or water-soluble radical-generating agents and a hydrophobic agent are used and an emulsion of droplets is produced. of monomers thanks to a powerful mechanical agitation and which is characterized by the presence of emulsifiers and optionally dispersing agents as surfactants.
- dispersing agents By way of examples of dispersing agents, mention may be made of partially hydrolysed polyvinylacetates, gelatin, starch, polyvinylpyrrolidinone, copolymers of vinyl acetate and of maleic anhydride, cellulose-soluble ethers derivatives which are soluble in water. water such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose.
- the dispersing agents are water-soluble cellulosic ether derivatives.
- hydroxypropyl methylcellulose is particularly preferred.
- the emulsifiers may be anionic emulsifiers, nonionic emulsifiers or cationic emulsifiers.
- alkyl sulphates such as sodium lauryl sulphate, alkyl sulphonates such as sodium dodecylbenzene sulphonate and pure sodium 1-hexadecanesulphonate or in the form of a mixture of C 12 -C 20 alkyl sulphonates sometimes called paraffins sulfonates, alkylaryl mono or disulfonates and dialkyl sulfosuccinates such as sodium diethylhexylsulfosuccinate and sodium dihexylsulfosuccinate.
- nonionic emulsifiers mention may be made in a nonlimiting manner, alkyl- or alkylarylethoxylated derivatives, alkyl- or alkylarylpropoxylated derivatives and sugar esters or ethers.
- cationic emulsifiers mention may be made of ethoxylated alkylamines and propoxylated alkylamines.
- the emulsifiers are preferably anionic emulsifiers, optionally in admixture with one or more nonionic emulsifiers.
- Anionic emulsifiers are particularly preferred.
- the hydrophobic agents may be alkanes such as hexadecane, silanes, siloxanes, perfluorinated alkanes or compounds usually used as pigments, comonomers, transfer agents, initiators or plasticizers as long as they are hydrophobic.
- the process for the preparation of polymers according to the invention uses at least one ethylenically unsaturated monomer, one of which is used as the main monomer and is chosen from styrene and its derivatives, the acid acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N monomers -vinyliques.
- ethylenically unsaturated monomer By at least one ethylenically unsaturated monomer, one of them being used as the main monomer, it is meant that the polymerization process may employ one or more ethylenically unsaturated monomers and that in the case where several monomers are, one of them is the main monomer.
- main monomer is intended to denote the monomer present in a proportion of at least 100% by weight of the monomer mixture and which will generate at least 100% by weight of the monomeric units of the polymer obtained, where n is the number of monomers in the monomer unit. the monomeric mixture.
- the ethylenically unsaturated monomer used as the main monomer is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, derivatives vinyls of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers.
- styrene derivatives mention may be made of para-tert-butylstyrene, para-methylstyrene, meta-methylstyrene, alpha-methylstyrene, para-bromostyrene, para-chlorostyrene and meta- (1-chloroethyl) styrene, para-fluorostyrene, para-trifluoromethylstyrene, meta-trifluoromethylstyrene, pentafluorostyrene, para-acetoxystyrene, para-methoxystyrene, para-tertbutoxystyrene, para-epoxystyrene, para-aminostyrene, alkali metal salts styrene para-sulfonic acid, vinylbenzoic acid, alkali metal salts of vinylbenzoic acid, para-chloromethylstyrene, perfluorooctyleth
- esters of acrylic acid is meant salts of acrylic acid such as alkali metal salts, acrylic acid protected with a trimethylsilyl group, tert-butyl, tetrahydropyranyl, 1-ethoxyethyl or benzyl, the acrylates alkyl, acrylonitrile, acrylamide and its derivatives.
- alkyl acrylates mention may be made of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate and the like.
- s-butyl isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, stearyl acrylate, acrylate glycidyl, benzyl acrylate, isobornyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-dimethylaminoethyl acrylate, acrylate chloride 2-trimethylaminoethyl, the potassium salt of 3-sulfopropyl acrylate, fluoroalkyl acrylates such as 1,1,2,2-tetrahydroperfluorodecyl acrylate, allyl acrylate, vinyl acrylate, sugars and nucleosides protected or not such as 2-beta-D-glucopyranosyloxyethyl acrylate, n-buty
- AMPS 2-acrylamido-2-methylpropane sulfonic acid
- salts of methacrylic acid such as alkali metal salts, methacrylic acid protected with a trimethylsilyl group, tert-butyl, tetrahydropyranyl, 1-ethoxyethyl or benzyl, methacrylates of alkyl, methacrylonitrile, methacrylamide and its derivatives.
- alkyl methacrylates mention may be made of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, s-butyl methacrylate and methacrylate.
- methacrylamide derivatives there may be mentioned N, N- (2-hydroxypropyl) methacrylamide, [3- (methacryloylamino) propyl] trimethyl ammonium chloride, methacryloylaminopropyldimethylammonium sulfobetaine.
- diene monomers mention may be made of butadiene, isoprene, chloroprene and isobutene. Particularly preferred are butadiene and chloroprene.
- vinyl esters mention may be made of vinyl acetate, vinyl trifluoroacetate, vinyl versatate, the ethylenic ester of tert-decanoic acid (VeoValO), the ethylenic ester of neononanoic acid (VeoVa9 ) and vinyl pivalate. Vinyl acetate is particularly preferred.
- vinyl ethers there may be mentioned methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, 2-methoxyethyl vinyl ether, 2-chloroethyl vinyl ether, 2-chloroethyl propenyl ether, 3-bromo-n-propyl vinyl ether, 4-chloro-n-butyl vinyl ether, 2-hydroxy ethyl vinyl ether A-hydroxy butyl vinyl ether, 6-hydroxyhexyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, n-butyldiethoxy vinyl ether, n-hexyl ethoxy vinyl ether, methyl dipropylene glycol vinyl ether, cyclohe
- vinyl derivatives of pyridine there may be mentioned 4-vinyl pyridine, 3-vinyl pyridine, 2-vinyl pyridine and 1 - (3-sulfopropyl) -2-vinylpyridinium betaine.
- N-vinyl monomers include N-vinylcarbazole, N-vinylcarbamate, N-vinylcaprolactam, N-vinylpyrrolidinone and N-vinylimidazole.
- the process according to the invention is therefore advantageously a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives, N-vinyl monomers.
- polymers is meant homopolymers and copolymers of these monomers as the main monomer.
- copolymers is meant the copolymers of one of the aforementioned monomers, which is the main monomer, with one or more monomers copolymerizable therewith.
- the copolymerizable monomers mention may be made, in a non-limiting manner, of the monomers listed above as main monomer but also the monomers of the maleimide, maleate, fumarate and allylic type as well as itaconic acid, cro tonic acid and maleic anhydride.
- the process according to the invention is preferably a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters and vinyl ethers.
- the process according to the invention is particularly preferably a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives and methacrylic acid and its derivatives .
- the mode of introduction of the ethylenically unsaturated monomer (s) (A) in the process according to the invention may be variable.
- step (1) in the case where (A) consists of a single ethylenically unsaturated monomer, all the monomer can be introduced in step (1) or a fraction thereof can be introduced in step (1). and the balance in step (2).
- the introduction to step (2) preferably takes place continuously.
- step (1) In the case where (A) consists of at least two ethylenically unsaturated monomers, one part of the monomers can be introduced in step (1) and the other part in step (2), preferably in a continuous manner. . In the particular case where (A) consists of a mixture of at least two ethylenically unsaturated monomers, the entire mixture can be introduced in step (1) or a fraction of the mixture can be introduced in step ( 1) and the balance of the same mixture introduced in step (2), preferably in a continuous manner.
- the process for the preparation of polymers according to the invention uses at least one agent generating radicals chosen from diazocompounds, peroxides and dialkyldiphenylalkanes.
- At least one radical-generating agent chosen from diazocompounds, peroxides and dialkyldiphenylalkanes it is meant that the polymerization process may use one or more radical-generating agents chosen from diazocompounds, peroxides and dialkyldiphenylalkanes.
- radical generating agent used in the singular or the plural must be understood as designating one or more radical-generating agents unless it is designated otherwise.
- the process according to the invention preferably employs at least one agent generating radicals chosen from diazocompounds and peroxides.
- the process according to the invention uses a single radical-generating agent.
- the radical-generating agents may be oil-soluble or water-soluble.
- oil-soluble radical generating agents is meant the soluble radical generating agents in the monomer or monomers, as used for the polymerization in aqueous suspension, microsuspension or aqueous mini-emulsion.
- water-soluble radical-generating agents is intended to mean the water-soluble radical generating agents as used for the aqueous emulsion or mini-emulsion polymerization.
- the agent that generates water-soluble radicals may be an oxidizer as defined below.
- Diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide and didecanoyl peroxide,
- Organic hydroperoxides such as cumyl hydroperoxide and tert-amyl hydroperoxide,
- Dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate, dimyristyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di [2-ethylhexyl] peroxydicarbonate, di [4-tert-butyl] cyclohexyl peroxydicarbonate and dicetyl peroxydicarbonate,
- Peresters such as t-amylperpivalate, t-butylperpivalate, t-amylperoxneodecanoate, t-butylperoxneodecanoate and cumylperoxineodecanoate.
- water-soluble peroxides mention may be made of
- Inorganic peroxides such as sodium, potassium and ammonium persulfates,
- Persulfates of sodium, potassium and ammonium as well as hydrogen peroxide are preferred.
- the mode of introduction of the radical generating agent (s) (B) in the process according to the invention may be variable.
- step (1) all of the radical generating agent can be introduced in step (1) or a fraction thereof can be introduced to step (1) and the balance in step (2).
- the introduction to step (2) preferably takes place continuously.
- (B) consists of at least two radical generators
- a part of the radical-generating agents can be introduced in step (1) and the other part in step (2), preferably continuously.
- step (1) the entire mixture can be introduced in step (1) or a fraction of the mixture can be introduced in step ( 1) and the balance of the same mixture in step (2), preferably continuously.
- the process according to the invention uses (C) molecular iodine.
- Molecular iodine can be used as such or in the form of a precursor thereof.
- precursor a compound capable of forming molecular iodine in the polymerization medium.
- precursors include iodides of alkali metals, such as sodium iodide or potassium iodide.
- the conversion of the precursor to molecular iodine can be obtained by adding an oxidant (D ') in the polymerization medium.
- the oxidant (D ') that can be used for this purpose meets the definition of oxidant (D) as detailed below.
- the number of moles of molecular iodine (C) relative to the number of moles of (A) is advantageously at least 2.5 ⁇ 10 -5 , preferably at least 5 ⁇ 10 -5 and particularly preferably at least 10 -4 .
- the number of moles of molecular iodine (C) relative to the number of moles of (A) is advantageously at most 10 -1 and preferably at most 10 -2 .
- At least 50 mol% of the molecular iodine (C) or its precursor and the oxidant (D ') are introduced into the reactor in step (1).
- the 100% of the molecular iodine (C) or its precursor and the oxidant (D ') are introduced into the reactor in step (1). They may be introduced in step (1) at one time or in a continuous injection before step (2) begins.
- the oxidant (D ') may be introduced into the reactor from the beginning of step (1) or delayed, all at once or in a continuous injection.
- the method according to the invention implements (D) at least one oxidant whose solubility in water is at least 10 g / 1, at least one of which may be one of (B).
- At least one oxidant (D) is meant that the polymerization process can implement one or more oxidants (D).
- oxidant (D) is meant any compound which is able to oxidize iodide ions to molecular iodine; in other words, which is capable of generating an oxidation-reduction reaction with the iodide ions so that the iodide ions are oxidized to molecular iodine and the oxidant is reduced in its reduced form and therefore has a potential redox higher than that of the pair I 2 ZI " (0.53).
- the oxidant (D) according to the invention has a solubility in water of at least
- oxidants (D) having a solubility in water of at least 10 g / l there may be mentioned in particular sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, the compounds generating MnO 4 " , ClO “ , ClO 2 " , ClO 3 " ions, manganese (III) salts and iron (III) salts such as ferric citrate, ammonic / ferric citrate, ammonic / ferric sulfate, ferric acetylacetonate, ferric bromide, ferric phosphate and ferric pyrophosphate.
- At least one oxidant at least one of which may be one of (B)
- at least one of the oxidants (D) is one of the radical-generating agents (B), in particular the one of the water-soluble radical generating agents (B), or that none of the oxidants is one of the radical-generating agents (B), in particular one of the water-soluble radical generating agents (B).
- the mode of introduction of the oxidant (s) (D) in the process according to the invention may be variable.
- the whole of (D) can be introduced in step (1) or a fraction of it can be introduced in step (1) and the balance in step (2).
- the introduction is preferably continuous.
- the introduction to step (2) preferably takes place continuously.
- all of (D) is introduced into the reactor between the beginning of step (1) and the moment of step (2) where the conversion rate reaches 70%.
- the process according to the invention is either an aqueous suspension polymerization process or an aqueous suspension microsuspension polymerization process, preferably in aqueous suspension, for the preparation of polymers employing
- At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the process implements (D) at least one oxidant whose solubility in water is from minus 10 g / 1.
- none of the oxidants is one of the radical-generating agents (B).
- a single oil-soluble radical generating agent (B) is preferably used.
- a single oxidant is preferably used as oxidant (D).
- the preferred oxidant (D) is hydrogen peroxide.
- the molecular iodine (C) in the form of a precursor and it is then necessary to add an oxidant (D ') in the medium.
- the added oxidant (D ') is preferably hydrogen peroxide.
- the total number of moles of oxidant (oxidizing agent (D) and optionally oxidizing agent (D ') relative to the number of moles of molecular iodine is preferably at least 0.5, particularly preferably at least 1.5, of very particularly preferably at least 2 and most preferably at least 3. A ratio of at least 4 is particularly advantageous.
- the total number of moles of oxidant (oxidant (D) and optionally oxidizing agent (D ') relative to the number of moles of molecular iodine is preferably at most 10, particularly preferably at most 9.
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers which implements
- At least one of the oxidants (D) may be one of the water-soluble radical generating agents (B), preferably at least one of the oxidizing agents (D). ) is one of the water-soluble radical generating agents (B).
- the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical-generating agents (B) relative to the number of moles of molecular iodine is preferably at least 1.5, from particularly preferably at least 2, most preferably at least 2.5 and most preferably at least 3. A ratio of at least 4 is particularly preferred.
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing (A) at least one ethylenically unsaturated monomer, one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing
- At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the radical-generating and oxidizing agent is chosen from sodium persulfate, ammonium persulfate and potassium persulfate.
- the oxidant (D ') may be the radical generating agent (B) and oxidizing agent (D) or an oxidizing agent (D') different from (B), such as, for example, the peroxide of 'hydrogen.
- the oxidant (D ') is the radical generating agent (B) and oxidizing agent (D).
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers using
- At least one ethylenically unsaturated monomer one of which is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of the pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- one of the radical-generating agents is chosen from ammonium 4,4'-azobis (4-cyanovalerate), sodium 4,4'-azobis (4-cyanovalerate) and 4,4-azobis (4-cyanovalerate). potassium azobis (4-cyanovalerate) and the other which is also the oxidant (D) is hydrogen peroxide.
- the oxidant (D ') is preferably the oxidant (D), thus particularly preferably hydrogen peroxide.
- the first subvariant is preferred to the second subvariant.
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers implementing
- At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the process uses a persulfate chosen from sodium persulfate, ammonium persulfate and potassium persulfate, and hydrogen peroxide.
- the oxidant (D ') may be one of the two oxidants (D) or an oxidant different from the two oxidants (D).
- the oxidant (D ') is one of the two oxidants (D), thus particularly preferably one of the above-mentioned persulfates or hydrogen peroxide.
- the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing
- At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of the pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers, (B) at least one oil-soluble radical generating agent selected from oil-soluble diazocompounds and oil-soluble peroxides and / or at least one water-soluble radical generating agent selected from water-soluble diazocomposites and water-soluble peroxides, (C) molecular iodine, and
- the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which between them is implemented as the main monomer and is selected from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers, (B) at least one oil-soluble radical generating agent chosen from oil-soluble diazocompounds and oil-soluble peroxides,
- the process uses (D) at least one oxidant whose solubility in water is at least 10 g / l.
- none of the oxidants is one of the radical-generating agents (B).
- a single oil-soluble radical generating agent (B) is preferably used.
- a single oxidant is also preferably used as oxidant (D).
- the preferred oxidant (D) is hydrogen peroxide.
- the molecular iodine (C) in the form of a precursor and it is then necessary to add an oxidizing agent (D ' ) in the polymerization medium to generate iodine, the added oxidant (D ') is preferably hydrogen peroxide.
- the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) relative to the number of moles of molecular iodine is preferably at least 0.5, particularly preferably at least 1.5, of very particularly preferably at least 2 and most preferably at least 3. A ratio of at least 4 is particularly advantageous.
- the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) relative to the number of moles of molecular iodine is preferably at most 10, particularly preferably at most 9.
- the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which between them is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, derivatives vinyl pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
- the process uses (D) at least one oxidant whose solubility in water is at least 10 g / l, of which at least one is one of (B).
- a single water-soluble radical generating agent (B) is preferably used.
- a single oxidant is also preferably used as oxidant (D).
- the generating agent of water-soluble radicals and the oxidant (D) are particularly preferably the same compound.
- the particularly preferred oxidant (D) and radical generating agent (B) is selected from sodium persulfate, potassium persulfate and ammonium persulfate.
- the added oxidant (D ') is preferably the radical generating agent (B) and oxidizing agent (D).
- the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical-generating agents (B) relative to the number of moles of molecular iodine is preferably at least 1.5, from particularly preferably at least 2, most preferably at least 2.5 and most preferably at least 3. A ratio of at least 4 is particularly preferred.
- the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical generating agents (B) relative to the number of moles of molecular iodine is preferably at most 11, from in a particularly preferred manner of at most 10.
- means are used by which radicals are generated within it. For this purpose, it can especially heat it or expose it to intense light radiation.
- the temperature at which the reactor contents is reacted is advantageously at least 30 ° C. and preferably at least 40 ° C. In addition, it is advantageously at most 200 ° C. and preferably at most 120 ° C.
- step (2) is carried out until the ethylenically unsaturated monomer or monomers have reacted within certain limits.
- the step (2) is carried out until the conversion rate of the ethylenically unsaturated monomer (s) is preferably at least 82%.
- Step (2) will be carried out until the conversion rate of the ethylenically unsaturated monomer (s) is preferably at most 100%.
- the radical polymerization process for the preparation of polymers according to the invention may optionally also comprise a step (3) during which the reaction is terminated by introducing a chemical agent capable of decomposing the excess radical generating agent. and / or extracting the fraction of (A) which has not reacted, these operations being performed simultaneously or successively, in the reactor or outside thereof.
- the radical polymerization process for the preparation of polymers according to the invention may optionally further comprise a step, subsequent to the preceding steps, in which the polymer is isolated from the reactor contents (step (4)).
- step (4) all the separation techniques known to those skilled in the art, in particular dewatering and drying in a fluidized bed, may be carried out in addition to the demonomerization treatment already discussed above (especially when the polymer has been produced by a slurry process) and spray drying or coagulation drying (particularly when the polymer has been produced by an emulsion or mini-emulsion process). These operations are advantageously carried out outside the reactor.
- the present invention relates to a radical polymerization process in aqueous dispersion for the preparation of block copolymers.
- the invention relates to a radical polymerization process in aqueous dispersion for the preparation of block copolymers using (A ') at least one ethylenically unsaturated monomer chosen from styrene and its derivatives, acrylic acid and its derivatives.
- (1 ') is introduced into a reactor at least a fraction of (A') and at least a fraction of (E '), then
- the process for the preparation of block copolymers according to the invention advantageously makes it possible to prepare copolymers comprising two blocks by polymerizing (A ') in the presence of a polymer prepared by the process according to the invention.
- invention as described above but also copolymers of more than two blocks for example three blocks by polymerizing (A ') in the presence of a precursor block copolymer already comprising two blocks and so on.
- the radical polymerization process for the preparation of block copolymers according to the invention has the same characteristics and preferences as those described above concerning the radical polymerization process for the preparation of polymers according to the invention, unless contraindicated or unless it is stated otherwise.
- the number of ethylenically unsaturated monomers constituting (A ') can be any.
- (E ') can be introduced into the reactor in any form whatsoever, especially in the form of an aqueous powder or dispersion, and after being isolated or not from the reactor contents in which it was previously prepared .
- (E ') is introduced into the reactor preferably in the form of an aqueous dispersion containing the polymer prepared by the process according to the invention; this being then used as it is for the process of synthesis of block copolymers according to the invention without having undergone prior treatment.
- the number of polymers constituting (E ') may be any but preferably 1.
- all of (E ') is introduced into the reactor in step (1').
- the weight of (E ') with respect to the weight of (A') is advantageously at least 0.05, preferably at least 0.1 and particularly preferably at least 0.5. In addition, it is advantageously at most 19, preferably at most 10 and particularly preferably at most 4.
- (B ' ) at least one radical generating agent selected from peroxides, diazocompounds and dialkyldiphenylalkanes.
- (B ') has the same characteristics and preferences as (B), and to whatever degree of preference it is.
- (B ') may be introduced entirely in step (1'), partly in step (1 ') and partly in step (2') or completely in step (2 ').
- step (3 ') it is possible, for example, to cool the contents of the reactor and / or introduce therein a chemical agent capable of decomposing the excess radical generating agent and / or extracting the fraction thereof.
- (A ') which has not reacted (demonomerization) these operations can be performed simultaneously or successively, in the reactor or outside thereof.
- the demonomerization operation can be carried out as described above for step (3).
- the radical polymerization process for the preparation of block copolymers according to the invention may optionally further comprise a step (4 '), subsequent to the preceding steps, wherein the copolymer is isolated from the reactor contents.
- Step (4 ') can be performed as previously described for step (4).
- the radical polymerization method in aqueous dispersion for the preparation of polymers according to the invention has multiple advantages.
- the process according to the invention makes it possible to improve the control of the number-average molecular weight (or weight) of the polymers prepared in dispersion. aqueous as well as their polydispersity.
- the difference between the theoretical molecular mass and the experimental molecular mass is significantly smaller than in the case of the previous process.
- radical polymerization process for the preparation of polymers and the radical polymerization process for the preparation of block copolymers according to the invention is that the growth of the polymer chains prepared in aqueous dispersion can be restarted by reacting the polymers with ethylenically unsaturated monomers, identical or different from those which had been polymerized beforehand. In this way, block copolymers can be prepared.
- radical polymerization process it is not usually possible to synthesize such copolymers.
- radical polymerization processes according to the invention do not require the use of usually expensive raw materials such as iodinated organic transfer agents.
- a last specific advantage to the first sub-variant of the first particularly preferred variant of the second embodiment is that it is entirely appropriate for industrial operation in terms of saving industrial hygiene costs.
- the degree of conversion to monomers was determined by gravimetric analysis in an aluminum cup. For this, a known amount of aqueous dispersion was weighed. A grain of inhibitor was then added to stop the polymerization and the water and residual monomer were evaporated. The dry polymer extract was recovered after drying under vacuum at 40 ° C. and the degree of conversion calculated according to the equation: (Esf-Eso) / (Esth-Eso) in which Esf is the final dry extract, Eso is the initial extract and Esth is the theoretical final dry extract at 100% conversion. Determination of molecular weights
- the target molecular weight (M njVls e e ), for a 100% conversion, was determined by applying the formula according to equation (1) namely M njVls ee (monomer mass) / (2x ni2, mitiai) + MA-I (equation 1) according to which nomai is the number of initial moles of molecular iodine and M A - I is the molar mass of the chain ends (A being the end of chain from the radical generating agent and I being the iodine atom).
- the experimental molecular weight (M njexp ) was determined by steric exclusion chromatography on dry samples dissolved in tetrahydrofuran using a Spectra Physics Instruments SP8810 pump equipped with a Shodex RIse-61 refractometric detector, a spectrometric detector Milton Roy Ultra-Violet and two columns thermostated at 30 ° C.
- Tetrahydrofuran was used as eluent at a flow rate of 1 ml.min -1 . Calibration was performed using polystyrene standards from Polymer Laboratories.
- the polydispersity index PDI M w / M n is the ratio of the weight-average molecular weight to the number-average molecular mass determined by steric exclusion chromatography. Determination of the average diameter
- the average particle diameter of the aqueous dispersion (d p ) was determined using a Nanotrac Particle Size Analyzer 250 particle analyzer (Microtrac Inc.) based on the retro-scattering of light and the Doppler effect.
- a polyBuA-b- [poly (BuA-co-styrene)] block copolymer was prepared by seeded polymerization of styrene.
- 40.45 g (0.64 mmol) of the aqueous dispersion obtained in Example 1 (80% conversion) was introduced into a 100 ml glass reactor and purged by bubbling argon for 20 minutes.
- the reaction medium was stirred for 1 hour and the polymerization continued under argon in the absence of light and for 14 hours at 75 ° C.
- the intended molecular weight (M njVls é e), the polymerization time, the conversion rate, the theoretical molecular weight (M n> th), the experimental molecular weight (M njeX p), the polydispersity index (PDI ) measured on the obtained block copolymer are shown in Table 2 as well as the average particle diameter of the aqueous dispersion (d p ).
- Example 8 was reproduced in the absence of iodine, hydrochloric acid and hydrogen peroxide, all other conditions being equal.
- the pH measured at the end of the experiment after recovery of the aqueous dispersion was 4.74.
- the polymerization time, the conversion rate, the experimental molecular mass (M n> exp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are shown in Table 3.
- Example 10 comparativative
- Example 8 was repeated in the absence of hydrochloric acid and hydrogen peroxide and with a Perkadox / iodine ratio of 2 instead of 2.5, all other conditions being equal.
- the pH of the aqueous phase measured at the end of the experiment after recovery of the aqueous dispersion was 2.36.
- the polymerization time, the conversion rate, the experimental molecular weight (M n> exp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are given in Table 3.
- the target molecular weight (M njVls e e ), the polymerization time, the conversion rate, the experimental molecular weight (M njexp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are shown in Table 3.
- Example 11 (according to the invention)
- Example 8 was reproduced in the absence of hydrochloric acid, all other conditions being equal.
- the pH of the aqueous phase measured at the end of the experiment after recovery of the aqueous dispersion was 6.75 and the polymerization time was 18 hours.
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 3.
- Example 9 In the absence of iodine (Example 9), the PDI is much higher and the polymer obtained does not allow to restart the chains to make a block copolymer.
- Example 13 (according to the invention)
- the target molecular weight (M njVls e e ), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular weight (M njexp ) and the polydispersity index (PDI) measured on the block copolymer obtained are shown in Table 4 as well as the average particle diameter of the aqueous dispersion (d p ).
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 5.
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 6.
- the intended molecular weight (M njVls é e), the polymerization time, conversion rate, the theoretical molecular weight (M n> th), the experimental molecular weight (M njeX p) and the polydispersity index (PDI ) measured on the block copolymer obtained are shown in Table 7 as well as the average particle diameter of the aqueous dispersion (d p ).
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 8.
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are given in Table 9.
- the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (M njVls ee), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M njeX p), the polydispersity index (PDI) are shown in Table 10.
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Applications Claiming Priority (3)
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FR0606079A FR2903409A1 (fr) | 2006-07-04 | 2006-07-04 | Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres |
US81827606P | 2006-07-05 | 2006-07-05 | |
PCT/EP2007/056779 WO2008003729A2 (fr) | 2006-07-04 | 2007-07-04 | Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres |
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EP2049573A2 true EP2049573A2 (de) | 2009-04-22 |
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EP07787074.9A Active EP2041185B1 (de) | 2006-07-04 | 2007-07-04 | Polymerisierungsverfahren mit freien radikalen in wässriger dispersion zur herstellung eines blockcopolymers mit mindestens einem halogenierten polymerblock |
EP07787075A Withdrawn EP2049573A2 (de) | 2006-07-04 | 2007-07-04 | Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren |
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EP07787074.9A Active EP2041185B1 (de) | 2006-07-04 | 2007-07-04 | Polymerisierungsverfahren mit freien radikalen in wässriger dispersion zur herstellung eines blockcopolymers mit mindestens einem halogenierten polymerblock |
Country Status (6)
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US (2) | US8541524B2 (de) |
EP (2) | EP2041185B1 (de) |
JP (1) | JP5201419B2 (de) |
FR (1) | FR2903409A1 (de) |
MX (1) | MX2008016485A (de) |
WO (2) | WO2008003728A1 (de) |
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US7741524B2 (en) | 2003-04-22 | 2010-06-22 | Solvay (Societe Anonyme) | Iodinated organic substances of low molecular mass and process for preparing them |
FR2903409A1 (fr) * | 2006-07-04 | 2008-01-11 | Solvay | Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres |
DE102008054482A1 (de) * | 2008-12-10 | 2010-06-17 | Wacker Chemie Ag | Pfropfcopolymere und deren Verwendung als Low-Profile-Additive |
JP2013018953A (ja) * | 2011-06-15 | 2013-01-31 | Canon Inc | 高分子粒子の製造方法 |
KR101507999B1 (ko) | 2011-08-03 | 2015-04-07 | 인하대학교 산학협력단 | Ritp 중합법과 용액 재결정법을 이용한 안정화된 단분산 구형 고분자 입자의 제조 방법 |
JP6312599B2 (ja) * | 2011-12-21 | 2018-04-18 | ソルヴェイ(ソシエテ アノニム) | 塩化ビニリデン重合体の製造方法 |
US9394394B2 (en) * | 2013-09-30 | 2016-07-19 | Honeywell International Inc. | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization |
FR3053970A1 (fr) | 2016-07-13 | 2018-01-19 | Centre National De La Recherche Scientifique (Cnrs) | Procede de synthese d'une polyolefine par romp en presence d'un catalyseur a base de ruthenium |
EP4107229A4 (de) | 2020-02-21 | 2024-03-06 | Swimc LLC | Fleckenblockierende polymere, primer, kits und verfahren |
CN117715885A (zh) | 2021-07-30 | 2024-03-15 | 巴斯夫欧洲公司 | 组合物及其在受控活性水基乳液聚合中的应用 |
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WO2003097704A1 (fr) * | 2002-05-17 | 2003-11-27 | Solvay (Société Anonyme) | Procedes de polymerisation radicalaire et polymeres halogenes |
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---|---|---|---|---|
US3467636A (en) | 1967-02-24 | 1969-09-16 | Du Pont | Redox catalyst system for preparing vinylidene fluoride interpolymers |
LU73211A1 (de) | 1975-08-18 | 1977-04-15 | ||
JPS5386787A (en) * | 1977-09-30 | 1978-07-31 | Daikin Ind Ltd | Polymer having fluorine-containing segment and its production |
JPS63260914A (ja) * | 1987-04-17 | 1988-10-27 | Nippon Mektron Ltd | ブロツク共重合体の製造方法 |
BE1007648A3 (fr) | 1993-10-21 | 1995-09-05 | Solvay | Procede pour la polymerisation radicalaire du chlorure de vinyle a ph acide en dispersion aqueuse. |
EP1026152B1 (de) * | 1997-03-31 | 2006-07-26 | Daikin Industries, Limited | Verfahren zur herstellung von perfluorvinylethersulfonsäure-derivaten |
EP0947527A1 (de) | 1998-04-03 | 1999-10-06 | The B.F. Goodrich Company | Wässrige Blockcopolymere und ein Verfahren zu deren Herstellung |
US6911515B2 (en) | 2001-03-23 | 2005-06-28 | University Of Pennsylvania | Aqueous room temperature living radical polymerization of vinyl halides |
FR2826658B1 (fr) * | 2001-06-29 | 2003-09-05 | Rhodia Chimie Sa | Synthese de polymeres par voie radicalaire controlee en miniemulsion |
FR2839725A1 (fr) * | 2002-05-17 | 2003-11-21 | Solvay | Polymeres alpha-fluoroacryliques a faible indice de polydispersite, procede pour les synthetiser et procede de fabrication d'articles les mettant en oeuvre |
US7034085B2 (en) | 2002-07-23 | 2006-04-25 | Nuplex Resins, B.V. | Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer |
WO2004094356A1 (en) | 2003-04-22 | 2004-11-04 | Solvay (Societe Anonyme) | Iodinated organic substances of low molecular mass and process for preparing them |
FR2858319B1 (fr) | 2003-08-01 | 2005-09-23 | Solvay | Procede de preparation de substances organiques iodees de faible masse moleculaire et substances organiques iodees de faible masse moleculaire |
US7741524B2 (en) | 2003-04-22 | 2010-06-22 | Solvay (Societe Anonyme) | Iodinated organic substances of low molecular mass and process for preparing them |
FR2896505B1 (fr) | 2006-01-26 | 2008-03-07 | Rhodia Recherches & Tech | Procede de preparation par polymerisation par transfert d'iode d'un copolymere a architecture controlee de type telomere ou de copolymere a bloc issu de monomeres vinyl phosphonate |
FR2903409A1 (fr) * | 2006-07-04 | 2008-01-11 | Solvay | Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres |
EP2158237B1 (de) * | 2007-06-21 | 2012-10-24 | DSM IP Assets B.V. | Verfahren zum erhalt von niedrigen niveaus freier monomere in einer mittels (inverser) iodtransferpolymerisation hergestellten blockcopolymeremulsion |
-
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- 2006-07-04 FR FR0606079A patent/FR2903409A1/fr not_active Withdrawn
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- 2007-07-04 JP JP2009517266A patent/JP5201419B2/ja active Active
- 2007-07-04 US US12/305,255 patent/US8541524B2/en active Active
- 2007-07-04 EP EP07787074.9A patent/EP2041185B1/de active Active
- 2007-07-04 EP EP07787075A patent/EP2049573A2/de not_active Withdrawn
- 2007-07-04 MX MX2008016485A patent/MX2008016485A/es active IP Right Grant
- 2007-07-04 US US12/308,977 patent/US20090306302A1/en not_active Abandoned
- 2007-07-04 WO PCT/EP2007/056778 patent/WO2008003728A1/en active Application Filing
- 2007-07-04 WO PCT/EP2007/056779 patent/WO2008003729A2/fr active Application Filing
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---|---|---|---|---|
WO2003097704A1 (fr) * | 2002-05-17 | 2003-11-27 | Solvay (Société Anonyme) | Procedes de polymerisation radicalaire et polymeres halogenes |
Non-Patent Citations (2)
Title |
---|
J. TONNAR, P. LACROIX-DESMAZES, B. BOUTEVIN: "Controlled radical polymerization of styrene by reverse iodine transfer polymerization (RITP) in miniemulsion: Use of hydrogen peroxide as oxidant", MACROMOLECULES, vol. 40, 22 December 2006 (2006-12-22), pages 186 - 190 * |
See also references of WO2008003729A2 * |
Also Published As
Publication number | Publication date |
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US8541524B2 (en) | 2013-09-24 |
US20090292071A1 (en) | 2009-11-26 |
US20090306302A1 (en) | 2009-12-10 |
JP5201419B2 (ja) | 2013-06-05 |
JP2009541567A (ja) | 2009-11-26 |
FR2903409A1 (fr) | 2008-01-11 |
WO2008003729A3 (fr) | 2008-05-08 |
WO2008003728A1 (en) | 2008-01-10 |
EP2041185A1 (de) | 2009-04-01 |
MX2008016485A (es) | 2009-02-25 |
EP2041185B1 (de) | 2019-01-09 |
WO2008003729A2 (fr) | 2008-01-10 |
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