EP1178955A1 - Polyalcoxyamines obtained from beta-substituted nitroxides - Google Patents
Polyalcoxyamines obtained from beta-substituted nitroxidesInfo
- Publication number
- EP1178955A1 EP1178955A1 EP00929608A EP00929608A EP1178955A1 EP 1178955 A1 EP1178955 A1 EP 1178955A1 EP 00929608 A EP00929608 A EP 00929608A EP 00929608 A EP00929608 A EP 00929608A EP 1178955 A1 EP1178955 A1 EP 1178955A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- formula
- ranging
- polyalkoxyamines
- carbon atoms
- 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- Withdrawn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
- -1 nitroxides Chemical class 0.000 title claims abstract description 57
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 150000003254 radicals Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003446 ligand Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000003480 eluent Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 7
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000005262 alkoxyamine group Chemical class 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- VGUWFGWZSVLROP-UHFFFAOYSA-N 1-pyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CC1=CC=CC=N1 VGUWFGWZSVLROP-UHFFFAOYSA-N 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 235000012907 honey Nutrition 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- CMBILWTXEXMRBX-UHFFFAOYSA-N 1,2-bis(2-bromoethyl)benzene Chemical compound BrCCC1=CC=CC=C1CCBr CMBILWTXEXMRBX-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-M 2-bromopropanoate Chemical compound CC(Br)C([O-])=O MONMFXREYOKQTI-UHFFFAOYSA-M 0.000 description 1
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- BHQGXUAZDCYQMG-UHFFFAOYSA-N 6-(2-bromopropanoyloxy)hexyl 2-bromopropanoate Chemical compound CC(Br)C(=O)OCCCCCCOC(=O)C(C)Br BHQGXUAZDCYQMG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 150000005691 triesters Chemical class 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
- C08F4/00—Polymerisation catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Definitions
- the present invention relates to polyalkoxyamines obtained from ⁇ -substituted nitroxides, which can be used in particular as initiators of radical polymerizations.
- M representing a polymerizable olefin
- P representing the growing polymer chain
- the control key is linked to the constants k deact , k act and k p (T. Fukuda and A. Goto, Macromolecules 1 999, 32, pages 61 8 to 623). If the ratio k inact / k act is too high, the polymerization is blocked, while when the ratio k p / k inact is too high, or when the ratio k inact / k act is too low, the polymerization is not controlled.
- A represents a polyfunctional core and R L a radical having a molar mass greater than 1 5, A and R L will be more fully defined later, it could synthesize polymers and copolymers with well defined architectures.
- the subject of the invention is therefore polyalkoxyamines of formula
- - A represents a di- or multipurpose structure which can be chosen from the structures given below without implied limitation:
- R 1 and R 2 represent an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 10, phenyl or thienyl radicals optionally substituted by a halogen atom such as F, Cl, Br, or alternatively by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 4, or alternatively by nitro, alkoxy, aryloxy, carbonyl, carboxy radicals; a benzyl radical, a cycloalkyl radical having a number of carbon atoms ranging from 3 to 1 2, a radical comprising one or more unsaturations;
- B represents a linear or branched alkylene radical, having a number of carbon atoms ranging from 1 to 20;
- m is an integer ranging from 1 to 10;
- R 3 and R 4 identical or different, represent aryl, pyridyl, furyl, thienyl radicals optionally substituted by a halogen atom such as F, Cl, Br, or else by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 4, or alternatively by nitro, alkoxy, aryloxy, carbonyl, carboxy radicals;
- D represents an alkylene radical, linear or branched, having a number of carbon atoms ranging from 1 to 6, a phenylene radical, a cycloalkylene radical; p ranging from 0 to 10;
- R 5 , R 6 and R 7 identical or different, have the same meanings as R 1 and R 2 of the formula (II), q, r and s are whole numbers ranging from 1 to 5;
- R 8 has the same meaning as R 3 and R 4 of formula (III), t is an integer ranging from 1 to 4, u is> 2 and ⁇ 6;
- R 9 has the same meaning as the radical R 8 of the formula (V) and v is> 2 and ⁇ 6;
- R 10 , R 1 1 and R 12 identical or different, represent a phenyl radical, optionally substituted by a halogen atom such as Cl, Br, or else by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10,; W represents an oxygen, sulfur, selenium atom, w is zero or 1;
- R has the same meaning as R 1 of formula (II), R 14 has the same meaning as R 3 or R 4 of formula (III);
- R 15 and R 16 which are identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, having a number carbon atoms ranging from 1 to 1 0, an aryl radical, optionally substituted by a halogen atom or a hetero atom,
- R L has a molar mass greater than 1 5;
- the radical R L monovalent is said to be in position ⁇ relative to the nitrogen atom, the remaining valences of the carbon atom and of the nitrogen atom in formula (1) may be linked to radicals various such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aralkyl radical, comprising from 1 to 10 carbon atoms, the carbon atom and the nitrogen atom in formula (1) can also be linked together via a bivalent radical, so as to form a ring; preferably, however, the remaining valences of the carbon atom and the nitrogen atom of formula (I) are linked to monovalent radicals; preferably, the radical R L has a molar mass greater than 30, the radical R L can for example have a molar mass of between 40 and 450, for example, the radical R L can be a radical comprising a phosphoryl group , said radical R L can be represented by the formula:
- R 17 and R 18 which may be identical or different, can be chosen from the alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl, aralkyl radicals and can comprise from 1 to 20 carbon atoms; R 17 and / or R 18 may also be a halogen atom such as a chlorine or bromine or fluorine or iodine atom; the radical R L may also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, the latter possibly being substituted, for example by an alkyl radical comprising from 1 to 10 carbon atoms.
- the monovalent radicals linked to the carbon atom carrying the radical R L may be a hydrogen atom, an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 1 2, a phenyl radical, an aralkyl radical comprising for example from 1 to 1 0 carbon atoms.
- a hydrogen atom an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 1 2
- a phenyl radical an aralkyl radical comprising for example from 1 to 1 0 carbon atoms.
- the two remaining valences of the carbon atom can also be linked to a divalent radical so as to form a ring including the carbon atom carrying the radical R L , said cycle possibly having a carbon number ranging from 3 to 10 and which may contain a heteroatom such as N, O, S.
- This method consists in transferring an atom or a group of atoms onto another molecule in the presence of an organometallic CuX / ligand system in solvent medium according to the scheme:
- a generally used procedure consists in dissolving the organometallic system such as CuBr / Iigand in an organic solvent preferably aromatic such as benzene or toluene, then in introducing into the solution the compound A (X) n and the nitroxide ⁇ -substituted
- ligands used include bipyridine, 4- 4'-di (5nonyl) 2,2'-bipyridine, tris (2-pyridylmethyl) amine (TPA).
- TPA 2,2'-bipyridine
- the reaction mixture is then stirred at a temperature between 20 ° C and 90 ° C for a period which can reach 48 hours, or even more.
- the precipitate is filtered, rinsed with a solvent such as ether then the filtrate is washed with an aqueous solution at 5% by weight of CuSO 4 then finally with water. It is dried over magnesium sulfate, then the solvents are evaporated under reduced pressure.
- a metal salt MX such as CuX, a ligand, the compound A (X) n and the ⁇ -substituted nitroxide are mixed with stirring in an organic solvent:
- the reaction medium is kept under stirring at a temperature between 20 ° C and 90 ° C until disappearance of the ⁇ -nitroxide substituted, the organic phase is recovered which is washed with water and then the polyalkoxyamine (I) is isolated by evaporation of the organic solvent under reduced pressure.
- ligands used according to this procedure include:
- HMTETA 10-hexamethyltriethylenetetramine
- cyclic polyamines such as:
- PMDETA should preferably be used.
- the degree of oxidation of the active species of the metal M of the metal salt is equal to 1 (M 1 ).
- This active species can be added as such to the reaction medium, preferably in the form of a metal halide such as
- the active species can also be generated in situ according to the REDOX reaction:
- the ligand is used according to a ligand / M 'molar ratio ranging from 1 to 5 and, preferably, ranging from 1 to 2.
- the molar ratio ⁇ -substituted nitroxide / A (X) n ranges from n to 1.4n and preferably is close to 1.
- R 5 , R 6 and R 7 identical or different, represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10, a phenyl radical, a benzyl radical, a radical cycloalkyl having a number of carbon atoms ranging from 3 to 1 2, q, r and s are whole numbers ranging from 1 to 5.
- the compounds obtained are identified by mass spectrometry and by 1 H and 13 C NMR.
- the polyalkoxyamines of formula (I) according to the present invention can be used for the polymerization and the copolymerization of any monomer having a carbon-carbon double bond capable of polymerizing by radical route.
- the polymerization or copolymerization is carried out under the usual conditions known to those skilled in the art, taking into account the monomer (s) considered.
- the polymerization or copolymerization can be carried out in bulk, in solution, in emulsion, in suspension, at temperatures ranging from 50 ° C to 250 ° C and, preferably, ranging from 70 ° C to 150 ° C.
- vinyl aromatic monomers such as styrene, substituted styrenes, dienes, acrylic monomers such as alkyl or aryl acrylates and methacrylates, optionally fluorinated such as methyl acrylate, butyl acrylate, methyl methacrylate, acrylamides such as N, N-dimethylacrylamide.
- the monomer can also be vinyl chloride, vinylidene difluoride or acrylonitrile.
- a nitroxide can be added to the polymerization medium - optionally corresponding to the polyalkoxyamine (I) used - in a nitroxide / polyalkoxyamine (I) molar ratio ranging from
- n% 0.01 n% to 20n% and preferably ranging from n% to 10n%.
- the polyalkoxyamines (I) according to the present invention can also be used for the synthesis of so-called block block copolymers according to an operating protocol which consists in carrying out in a first step the polymerization in mass, in solution, in suspension or in emulsion of a monomer M 1 or a mixture of monomers having a carbon-carbon double bond capable of polymerizing by the radical route in the presence of a polyalkoxyamine (I) at a temperature ranging from 50 ° C to 250 ° C and, preferably, ranging from
- block block copolymers such as polystyrene - polybutylacrylate - polystyrene (PS-ABU-PS) can be prepared in this way.
- PS-ABU-PS polystyrene - polybutylacrylate - polystyrene
- H was obtained by oxidation of diethyl 2,2-dimethyl-1 - (1, 1 - dimethylethylamino) propylphosphonate using acid metachloroperbenzoic agent according to a protocol described in international application WO 96/24620.
- the polyazotated ligands used are:
- A- (X) n denotes a polyfunctional core comprising n halogenated functions.
- Example 8 where we used the paradi (bromo1 -ethyl) benzene obtained according to a conventional method by reaction of diethylbenzene with two equivalents of N-bromosuccinimide.
- the triestertribrominated used in Example 5 is obtained by reaction of 1,3,5-tris (2-hydroxyethyl) cyanuric acid with 2-bromopropionyl bromide and is described in Example 5.
- alkoxyamines A1, A2 are those having acrylate-DEPN type sequences. Those designated by a type name S1, S2, S3, S4 have phenylethyl-DEPN type sequences. EXAMPLE 1
- the product is purified by chromatography on a silica column using an eluent ether / heptane 4/1, then ether / methanol 1/1. Out of 0.96 g used, 0.73 g of colorless oil is recovered.
- the overall yield of isolated product is 75%.
- 1 H, 13 C and 31 P NMR the product has four asymmetric carbon atoms and a center of symmetry.
- the NMR signals are complex and reveal two families of distinct isomers in relative proportions 50/50.
- the different atoms are identified by an index indicated on the formula A1 developed above. When the signals are distinct, the two families of isomers are separated by a ";".
- the procedure is the same as in Example 1.
- the PMDETA ligand makes it possible to reduce the reaction time to 3 h.
- the product is purified by chromatography on a silica column using an el . uant ether / ethanol to 1% ethanol. On 1 g committed, 0.86 g of colorless honey is recovered.
- the product was characterized by mass spectrometry and by 1 H, 13 C and 31 P NMR.
- the NMR spectra show that there are two distinct families of isomers in a relative 50/50 proportion.
- the different atoms are identified by an index on the formula developed below. When the signals are distinct, the two families of isomers are separated by a ";"
- DEPN / triester-tribromé 3
- CuBr / triester-tribromé 3
- PMDETA / CuBr 2
- Cu (0) / CuBr 1
- solvent toluene
- T 20 ° C
- t 7 h .
- the product is purified by washing with water (5x500 ml)
- the material balance is given in table 5.
- the percentages of trialkoxyamine and of mono- and di-alkoxyamines were determined by 1 H and 31 P NMR.
- the content of residual DEPN was determined by HPLC.
- the residual solvent content was determined by 1 H NMR
- the reaction is carried out in a Schlenk tube under an argon atmosphere.
- Para di (bromo 1 -ethyl) benzene and DEPN are degassed beforehand.
- Toluene is distilled under argon on sodium-benzophenone.
- 1.02 g of CuBr are introduced into the 1000 ml Schlenk tube.
- the 31 P NMR shows two families of peaks corresponding to two types of diastereoisomers.
- the reaction is carried out in a Schlenk tube under an atmosphere
- the styrene or butyl acrylate are distilled and stored under an inert atmosphere at 5 ° C.
- the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
- the curve Mn as a function of the conversion - FIG. 2 - clearly indicates that the polymerization with trialkoxyamine A2 is well controlled. In this figure 2:
- the polydispersity index at the end of polymerization is equal to: 1.27.
- the curve Mn as a function of the conversion -figure 3 - clearly indicates that the polymerization with trialkoxyamine S4 is well controlled. In this figure 3:
- the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
- the curve Mn as a function of the conversion - FIG. 4 - clearly indicates that the polymerization with alkoxyamine A1 is well controlled.
- - -O- - represents MnTh
- the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
- the curve Mn as a function of the conversion - FIG. 5 - clearly indicates that the polymerization with trialkoxyamine A2 is well controlled. In this figure 5:
- the polymer obtained is diluted in styrene (260 g).
- the temperature of the reactor is raised to 123 °.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR9906329 | 1999-05-19 | ||
FR9906329A FR2794459B1 (en) | 1999-05-19 | 1999-05-19 | POLYALCOXYAMINES FROM BETA-SUBSTITUTED NITROXIDES |
PCT/FR2000/001287 WO2000071501A1 (en) | 1999-05-19 | 2000-05-12 | POLYALCOXYAMINES OBTAINED FROM β-SUBSTITUTED NITROXIDES |
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EP1178955A1 true EP1178955A1 (en) | 2002-02-13 |
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EP00929608A Withdrawn EP1178955A1 (en) | 1999-05-19 | 2000-05-12 | Polyalcoxyamines obtained from beta-substituted nitroxides |
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US (1) | US6657043B1 (en) |
EP (1) | EP1178955A1 (en) |
JP (1) | JP2003500378A (en) |
AU (1) | AU4763100A (en) |
FR (1) | FR2794459B1 (en) |
MX (1) | MXPA01011916A (en) |
WO (1) | WO2000071501A1 (en) |
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FR2807439B1 (en) | 2000-04-07 | 2003-06-13 | Atofina | MULTIMODAL POLYMERS BY CONTROLLED RADICAL POLYMERIZATION IN THE PRESENCE OF ALCOXYAMINES |
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FR2843393B1 (en) * | 2002-08-07 | 2005-12-30 | Atofina | ALCOXYAMINES FROM NITROXIDES B-PHOSPHORUS, THEIR USE IN RADICAL POLYMERIZATION |
FR2843394B1 (en) * | 2002-08-07 | 2005-12-30 | Atofina | ALCOXYAMINES FROM NITROXIDES B-PHOSPHORUS, THEIR USE IN RADICAL POLYMERIZATION |
KR101100626B1 (en) * | 2002-09-23 | 2012-01-03 | 시바 홀딩 인크 | Polymeric alkoxyamines prepared by atom transfer radical additionATRA |
US20040185017A1 (en) * | 2002-12-13 | 2004-09-23 | Nathalie Mougin | Nail varnish composition comprising at least one film-forming gradient copolymer and cosmetic process for making up and/or caring for the nails |
US20040202688A1 (en) * | 2002-12-13 | 2004-10-14 | Nathalie Mougin | Nail varnish composition comprising at least one film-forming gradient copolymer and cosmetic process for making up or caring for the nails |
FR2852961B1 (en) * | 2003-03-26 | 2006-07-07 | Atofina | NEW PROCESS FOR THE SYNTHESIS / MANUFACTURE OF ACRYLIC FILMS |
FR2852963A1 (en) * | 2003-03-26 | 2004-10-01 | Atofina | Acrylic film for use e.g. for in-mould decoration, comprises a methacrylic/acrylic block copolymer made by radical polymerisation in presence of an alkoxyamine derived from a sterically-hindered nitroxide |
FR2853317B1 (en) * | 2003-04-01 | 2006-07-07 | Atofina | ALCOXYAMINES FROM NITROXIDES B-PHOSPHORES, THEIR USE FOR THE PREPARATION OF MONO OR POLYALCOXYAMINES, POLYMERIZED OR NOT |
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US7632905B2 (en) * | 2004-04-09 | 2009-12-15 | L'oreal S.A. | Block copolymer, composition comprising it and cosmetic treatment process |
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CN103068922B (en) | 2010-08-10 | 2017-02-15 | 株式会社钟化 | Curable composition |
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MY200976A (en) | 2012-05-31 | 2024-01-27 | Kaneka Corp | Polymer Having Terminal Structure Including Plurality of Reactive Silicon Groups, Method for Manufacturing Same, and use for Same |
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JP6475615B2 (en) | 2013-05-30 | 2019-02-27 | 株式会社カネカ | Curable composition and cured product thereof |
FR3010081B1 (en) * | 2013-09-05 | 2017-11-17 | Centre Nat Rech Scient | PROCESS FOR THE SEQUENTIAL SYNTHESIS OF POLY (ALCOXYAMINE AMIDE) S, COPOLYMERS OBTAINED AND USES THEREOF |
WO2015035342A2 (en) | 2013-09-08 | 2015-03-12 | Oligasis Llc | Factor viii zwitterionic polymer conjugates |
JP6527589B2 (en) | 2015-10-02 | 2019-06-05 | 株式会社カネカ | Curable composition |
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EP4011978A4 (en) | 2019-08-06 | 2023-07-19 | Kaneka Corporation | Curable composition |
JP2022553640A (en) | 2019-10-10 | 2022-12-26 | コディアック サイエンシーズ インコーポレイテッド | Methods of treating eye disorders |
JPWO2023282298A1 (en) | 2021-07-07 | 2023-01-12 | ||
FR3130824A1 (en) | 2021-12-22 | 2023-06-23 | Arkema France | Adhesive light-curing composition for encapsulating electronic or optoelectronic devices |
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FR2730240A1 (en) * | 1995-02-07 | 1996-08-09 | Atochem Elf Sa | STABILIZATION OF A POLYMER BY A STABLE FREE RADICAL |
JP2001510208A (en) * | 1997-07-15 | 2001-07-31 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Polymerizable composition containing an alkoxyamine compound derived from a nitroso compound or a nitrone compound |
-
1999
- 1999-05-19 FR FR9906329A patent/FR2794459B1/en not_active Expired - Fee Related
-
2000
- 2000-05-12 JP JP2000619758A patent/JP2003500378A/en not_active Abandoned
- 2000-05-12 WO PCT/FR2000/001287 patent/WO2000071501A1/en active Application Filing
- 2000-05-12 US US09/979,124 patent/US6657043B1/en not_active Expired - Fee Related
- 2000-05-12 MX MXPA01011916A patent/MXPA01011916A/en active IP Right Grant
- 2000-05-12 AU AU47631/00A patent/AU4763100A/en not_active Abandoned
- 2000-05-12 EP EP00929608A patent/EP1178955A1/en not_active Withdrawn
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AU4763100A (en) | 2000-12-12 |
JP2003500378A (en) | 2003-01-07 |
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WO2000071501A1 (en) | 2000-11-30 |
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