EP2470548A2 - Method for preparing silica particles containing a phthalocyanine derivative, said particles, and uses thereof - Google Patents
Method for preparing silica particles containing a phthalocyanine derivative, said particles, and uses thereofInfo
- Publication number
- EP2470548A2 EP2470548A2 EP10747212A EP10747212A EP2470548A2 EP 2470548 A2 EP2470548 A2 EP 2470548A2 EP 10747212 A EP10747212 A EP 10747212A EP 10747212 A EP10747212 A EP 10747212A EP 2470548 A2 EP2470548 A2 EP 2470548A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- microemulsion
- phthalocyanine
- silicone
- 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- Withdrawn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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 title claims abstract description 21
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims description 53
- 229920001296 polysiloxane Polymers 0.000 claims description 48
- 239000002798 polar solvent Substances 0.000 claims description 41
- -1 hydroxypropyl Chemical group 0.000 claims description 35
- 229910000077 silane Inorganic materials 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- 150000003573 thiols Chemical class 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000004064 cosurfactant Substances 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 4
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 3
- IYAYDWLKTPIEDC-UHFFFAOYSA-N 2-[2-hydroxyethyl(3-triethoxysilylpropyl)amino]ethanol Chemical compound CCO[Si](OCC)(OCC)CCCN(CCO)CCO IYAYDWLKTPIEDC-UHFFFAOYSA-N 0.000 claims description 2
- WBWAUFJXONIXBV-UHFFFAOYSA-N 2-triethoxysilylethyl acetate Chemical compound CCO[Si](OCC)(OCC)CCOC(C)=O WBWAUFJXONIXBV-UHFFFAOYSA-N 0.000 claims description 2
- IQYKGYBHXJYZSS-UHFFFAOYSA-N 3-(triethoxysilylmethyl)pentan-3-ylphosphonic acid Chemical compound CCO[Si](OCC)(OCC)CC(CC)(CC)P(O)(O)=O IQYKGYBHXJYZSS-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- WYTQXLFLAMZNNZ-UHFFFAOYSA-N 3-trihydroxysilylpropane-1-sulfonic acid Chemical compound O[Si](O)(O)CCCS(O)(=O)=O WYTQXLFLAMZNNZ-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- HYFWOBSAALCFRS-UHFFFAOYSA-N 3-trimethoxysilylpropyl benzoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C1=CC=CC=C1 HYFWOBSAALCFRS-UHFFFAOYSA-N 0.000 claims description 2
- CCGWVKHKHWKOIQ-UHFFFAOYSA-N [2-hydroxy-4-(3-triethoxysilylpropoxy)phenyl]-phenylmethanone Chemical compound OC1=CC(OCCC[Si](OCC)(OCC)OCC)=CC=C1C(=O)C1=CC=CC=C1 CCGWVKHKHWKOIQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 230000000368 destabilizing effect Effects 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- MKAWPVONNWUREJ-UHFFFAOYSA-M sodium;methyl(3-trihydroxysilylpropoxy)phosphinate Chemical compound [Na+].CP([O-])(=O)OCCC[Si](O)(O)O MKAWPVONNWUREJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000005649 substituted arylene group Chemical group 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- JACPFCQFVIAGDN-UHFFFAOYSA-M sipc iv Chemical class [OH-].[Si+4].CN(C)CCC[Si](C)(C)[O-].C=1C=CC=C(C(N=C2[N-]C(C3=CC=CC=C32)=N2)=N3)C=1C3=CC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 JACPFCQFVIAGDN-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000002105 nanoparticle Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 5
- 239000002563 ionic surfactant Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 150000002678 macrocyclic compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- CEQGXFSRENZDFH-UHFFFAOYSA-N triethoxy(sulfanyl)silane Chemical compound CCO[Si](S)(OCC)OCC CEQGXFSRENZDFH-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WIHIUFRJMOAJFO-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 WIHIUFRJMOAJFO-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RFFGWGJUTJJDGK-UHFFFAOYSA-N O.O.[SiH4] Chemical compound O.O.[SiH4] RFFGWGJUTJJDGK-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WPMWEFXCIYCJSA-UHFFFAOYSA-N Tetraethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCO WPMWEFXCIYCJSA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002592 cumenyl group Chemical class C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- LGAILEFNHXWAJP-BMEPFDOTSA-N macrocycle Chemical group N([C@H]1[C@@H](C)CC)C(=O)C(N=2)=CSC=2CNC(=O)C(=C(O2)C)N=C2[C@H]([C@@H](C)CC)NC(=O)C2=CSC1=N2 LGAILEFNHXWAJP-BMEPFDOTSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011234 nano-particulate material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DQXAGPTUVYYCHJ-UHFFFAOYSA-J tetrasodium;2-(2-ethylhexyl)-2-sulfobutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].CCCCC(CC)CC(S(O)(=O)=O)(C([O-])=O)CC([O-])=O.CCCCC(CC)CC(S(O)(=O)=O)(C([O-])=O)CC([O-])=O DQXAGPTUVYYCHJ-UHFFFAOYSA-J 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/108—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a phthalocyanine dye
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/09—Colouring agents for toner particles
- G03G9/0906—Organic dyes
- G03G9/0918—Phthalocyanine dyes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to the field of silica particles and in particular silica nanoparticles containing silica phthalocyanine dyes.
- the present invention relates to a process for preparing silica particles incorporating phthalocyanine and naphthalocyanine derivatives. It also relates to silica particles incorporating phthalocyanine and naphthalocyanine derivatives, capable of being prepared by this process and their various uses and applications.
- phthalocyanines and other macrocyclic analogues have attracted considerable attention as molecular materials with exceptional electronic and optical properties. These properties come from the delocalization of the electronic cloud, and make these products interesting for different areas of research in materials science and especially in nanotechnology. Thus, phthalocyanines have been successfully incorporated into semiconductor components, electrochromic devices, information storage systems.
- a crucial problem to consider in incorporating phthalocyanines into technological devices is the control of the spatial arrangement of these macrocycles. This makes it possible to extend and improve the chemical and physical properties of phthalocyanines at the macromolecular or molecular scale.
- the co-facial superposition of the phthalocyanines is necessary in order to obtain supramolecular properties.
- the increase in conductivity can be along the main axis of the phthalocyanine stacking system by delocalization of electrons through the co-planar macrocycles.
- Conductivity in phthalocyanine-based systems generally depends on the intrinsic properties of particular phthalocyanines.
- silicone phthalocyanines have been used for the preparation of devices such as field effect transistors.
- phthalocyanine-based polymers Good conductivity is also obtained in phthalocyanine-based polymers.
- phthalocyanine-based semiconductor polymers the most important family is that of phthalocyanine siloxanes [PcSiC ⁇ ] n -
- nano-objects and other siloxane phthalocyanine polymers are well known in the art. These structures are made in various ways in the literature. Several methods have been validated for the polymerization of silica phthalocyanine.
- phthalocyanine polysiloxanes The preparation of phthalocyanine polysiloxanes has been described in the literature. Thus polymers were synthesized using silicone phthalocyanines as precursors. These compounds are used in the Langmuir-Blodgett film preparation, one-dimensional films of very rigid polymer type [11]. The polymerization is carried out under vacuum at 350-400 0 C for 2 h, very extreme conditions. Another synthesis of polymers is carried out with the same silicone phthalocyanine precursor in dimethylsulfoxide at 135 ° C. for 24 hours [12].
- silicone phthalocyanines have also been the subject of some studies. In view of the pronounced and recognized hydrophobicity of phthalocyanine-based materials, it is very difficult to encapsulate them in silica nano-objects using a conventional wet process.
- CdSe cadmium selenide nanoparticles conjugated to silicone phthalocyanines.
- the surface of the CdSe nanoparticles is thus functionalized by condensation of the active group (amino group) located in the axial position of the macrocycle of the silicone phthalocyanine and connected thereto via an alkyl group [18].
- a similar study published in 2006 presents the introduction of tetrasulphonate Copper phthalocyanine on the surface of silica nanoparticles modified by functionalization with amino groups [19].
- the present invention overcomes the disadvantages and technical problems listed above. Indeed, the latter proposes a process for the preparation of spherical silica-based particulate materials and in particular nanoparticulate materials whose size is advantageously less than 100 nm incorporating phthalocyanine derivatives, said process being applicable at the industrial level, not requiring processes or heavy steps and using easily accessible, non-hazardous and low-toxicity products.
- silicone phthalocyanine derivatives as silica precursors makes it possible to fabricate silica particles such as silica nanoparticles incorporating phthalocyanine derivatives.
- the availability of axial ligands combined with the presence of the silica atom introduced into the cavity of the phthalocyanine macrocycle makes it possible to use it as a precursor necessary for the proper synthesis of silica nanoparticles in the reverse micelle pathway.
- the surface of the silica particles obtained by the process according to the invention can be functionalized thus making it possible to influence the polarity of the particles, and thus the affinity with the solvent to be used in the process. case of the application, that is to say, polar, apolar, etc. and therefore the desired dispersion.
- the present invention relates to a method for preparing a silica particle incorporating at least one phthalocyanine derivative, said particle being prepared from at least one derivative silicone phthalocyanine via an inverse microemulsion.
- reverse microemulsion also called “water-in-oil” microemulsion
- water-in-oil microemulsion a clear, thermodynamically stable suspension of fine droplets of a first polar liquid in a second non-polar liquid and therefore immiscible with the first liquid.
- reverse micellar pathway is equivalent to the expression “via an inverse microemulsion”.
- sicone phthalocyanine derivative is meant a compound of formula (I)
- R 1, R 2, R 3 and R 4 which are identical or different, represent an optionally substituted arylene group and
- R 5 and R 6 which are identical or different, are chosen from the group consisting of -Cl, -F, -OH and
- R' representing a linear or branched alkyl of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted.
- optionally substituted is meant, in the context of alkyl groups, compounds of formula (I), substituted by a halogen, an amino group, a diamine group, an amide group, an acyl group, a vinyl group, a group hydroxyl, an epoxy group, a phosphonate group, a sulfonic acid group, an isocyanate group, a carboxyl group, a thiol (or mercapto) group, a glycidoxy group or an acryloxy group and in particular a methacryloxy group.
- R ' represents a methyl or an ethyl.
- arylene group means an aromatic or heteroaromatic carbon structure, optionally mono- or polysubstituted, consisting of one or more aromatic or heteroaromatic rings each comprising from 3 to 8 atoms, and the heteroatom (s). can be N, 0, P or S.
- arylene group which may be mono- or polysubstituted by a group selected from the group consisting of a carboxylate; an aldehyde; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
- the groups R 1, R 2, R 3 and R 4 are identical or different, each representing a phenylene, a naphthylene or a anthracene. More particularly, the groups R 1, R 2, R 3 and R 4 are identical and represent a phenylene, a naphthylene or an anthracene.
- silicone phthalocyanine derivative used in the context of the present invention is a compound of formula (II):
- the groups R 7 to R 22, which are identical or different, are chosen from the group consisting of hydrogen; a carboxylate; an aldehyde; a ketone; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
- the groups R 5 and Re are as previously defined.
- a compound of formula (II) that is preferred in the context of the present invention is the compound in which the groups R 7 to R 22 represent a hydrogen and the groups R 5 and Re are as previously defined.
- the silicone phthalocyanine derivative used in the context of the present invention is a compound of formula (III) of the naphthalocyanine type:
- R 23 to R 4 6 are selected from the group consisting of a hydrogen; a carboxylate; an aldehyde; a ketone; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
- a compound of formula (III) which is preferred in the context of the present invention is the compound in which the groups R 23 to R 46 represent a hydrogen and the groups R 5 and Re are as previously defined.
- the groups R 5 and Re in the compounds of formula (I), (II) or (III) are identical and are chosen from the group consisting of -Cl, -F, -OH and -OR 'with R' representing an alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted and in particular selected from the group consisting of -Cl, -F, -OH, -OCH 3 and -OC 2 H 5 . More particularly, the groups R 5 and Re in the compounds of formula (I), (II) or (III) are identical and represent -OH or -Cl.
- the compounds of formula (II) and (III) especially used in the context of the The present invention is a phthalocyanine dodichlorosilane complex, a phthalocyanine dihydroxysilane complex, a naphthalocyanine dodichlorosilane complex and a naphthalocyanine dihydroxysilane complex.
- These complexes can be represented with R representing -OH or -Cl as follows:
- the process according to the invention comprises, more particularly, the following successive steps:
- M a a microemulsion of the water-in-oil type containing at least one silicone phthalocyanine derivative
- step (b) optionally adding, to the microemulsion (M a ) obtained in step (a), at least one silane-based compound, c) adding, to the microemulsion (M b ) obtained in step (b), at least one compound for the hydrolysis of silane compounds,
- step (c) adding to the microemulsion (M c ) obtained in step (c) a solvent for destabilizing said microemulsion,
- step (d) recovering the silica particles incorporating at least one silicone phthalocyanine derivative, precipitated during step (d).
- Step (a) of the process according to the invention therefore consists in preparing a microemulsion (M a ) of the water-in-oil type containing at least one silicone phthalocyanine derivative.
- a microemulsion M a
- Any technique making it possible to prepare such a microemulsion can be used in the context of the present invention.
- microemulsion (M a ) directly by mixing together the various components and therefore a (or) silicone derivative (s) phthalocyanine.
- step (a) of the process according to the invention consists in preparing a first solution (Mi) in which is (are) subsequently incorporated (s) silicone derivative (s) phthalocyanine.
- This solution (Mi) is obtained by mixing together
- At least one surfactant at least one surfactant, - optionally at least one co-surfactant and
- the surfactant, the optional cosurfactant and the non-polar or weakly polar solvent are added one after the other and, in the following order, surfactant then optionally cosurfactant and then non-polar or weakly polar solvent.
- Mixing is carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, and can be implemented at a temperature of between 10 and 40 ° C., advantageously between 15 and 30 ° C. and more particularly at ambient temperature (ie 23 ° C. ⁇ 5 ° C.) for a period of between 1 and 45 minutes, in particular between 5 and 30 minutes and, in particular, for 15 minutes.
- the surfactant (s) that may be used in the context of the present invention aims to introduce hydrophilic species in a hydrophobic environment and may be chosen from ionic surfactants, nonionic surfactants and mixtures thereof
- mixtures is meant, in the context of the present invention, a mixture of at least two different ionic surfactants, a mixture of at least two different nonionic surfactants or a mixture of at least one nonionic surfactant.
- ionic agent and at least one ionic surfactant may in particular be in the form of a hydrocarbon chain, charged whose charge is counterbalanced by a counter-ion.
- ionic surfactants mention may be made of sodium bis (2-ethylhexyl sulphosuccinate) (AOT), cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and mixtures thereof.
- a nonionic surfactant that may be used in the context of the present invention may be chosen from the group consisting of polyethoxylated alcohols, polyethoxylated phenols, oleates, laurates and their mixtures.
- Triton X such as Triton X-100
- Brij such as Brij -30
- Igepal COs such as Igepal CO-720
- Tween such as Tween 20
- Spans such as the Span 85.
- the surfactant used in the context of the present invention is Triton X-100.
- a co-surfactant may optionally be added to the solution (Mi).
- co-surfactant in the context of the present invention an agent capable of facilitating the formation of microemulsions and stabilize them.
- said co-surfactant is an amphiphilic compound chosen from the group consisting of a sodium alkyl sulphate of 8 to 20 carbon atoms, such as SDS (for "sodium dodecyl sulphate”); an alcohol such as an isomer of propanol, butanol, pentanol and hexanol; a glycol and their mixtures.
- the co-surfactant used in the context of the present invention is n-hexanol.
- non-polar or weakly polar solvent is usable in the context of the present invention.
- said non-polar or weakly polar solvent is a nonpolar or slightly polar organic solvent and, in particular, selected from the group consisting of n-butanol, hexanol, cyclopentane, pentane, cyclohexane, n hexane, cycloheptane, n-heptane, n-octane, iso-octane, hexadecane, petroleum ether, benzene, isobutylbenzene, toluene, xylene, cumenes, diethyl ether, n-butyl acetate, isopropyl myristate and mixtures thereof.
- non-polar or weakly polar solvent used in the context of the present invention is cyclohexane.
- the surfactant is present in a proportion of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20% by volume relative to the total volume of said solution.
- the co-surfactant is optionally present in the solution (Mi) in a proportion of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20% by volume relative to the total volume of said solution.
- the non-polar or weakly polar solvent is present in the solution (Mi) in a proportion of between 40 and 98%, especially between 50 and 90% and, in particular, between 60 and 80% by volume relative to the total volume of said solution.
- the phthalocyanine silicone derivative (s) as previously defined is (are) incorporated to form the microemulsion (M a ). water-in-oil type.
- the silicone derivative (s) phthalocyanine can be added in solid form, in liquid form or in solution in a polar solvent. When several different silicone phthalocyanine derivatives are used, they may be mixed at one time or added one after the other or in groups.
- a polar solvent is added to the microemulsion (M a ) after the incorporation of said silicone derivative (s) in the solution (Mi).
- the silicone derivative (s) of phthalocyanine is (are) added to the solution (Mi) in solution in a polar solvent and then the polar solvent, which is identical to or different from the first, is still added.
- the two polar solvents used are identical.
- the two polar solvents used are different but at least partially miscible: for example THF and water.
- the addition of the silicone derivative of phthalocyanine and optionally the polar solvent may be carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer.
- polar solvent in the context of the present invention a solvent selected from the group consisting of water, deionized water, distilled water, acidified or basic, hydroxylated solvents such as methanol and sodium hydroxide. ethanol, low molecular weight liquid glycols such as ethylene glycol, dimethyl sulfoxide (DMSO), acetonitrile, acetone, tetrahydrofuran (THF) and mixtures thereof.
- DMSO dimethyl sulfoxide
- THF tetrahydrofuran
- the polar solvent or the mixture of polar solvents (polar solvent in which the phthalocyanine silicone derivative (s) is (are) in solution and / or other polar solvent subsequently added) is present in the microemulsion (M a ), in a proportion of between 0.5 and 20%, especially between 1 and 15% and, in particular, between 2 and 10% by volume relative to the total volume of said microemulsion.
- the silicone derivative (s) phthalocyanine (s) is (are) present in this polar solvent or this mixture of polar solvents in an amount between 0.05 and 10%, especially between 0.1 and 5% and, in particular, between 0.2 and 1% by volume relative to the total volume of polar solvent.
- Step (b) is optional.
- microemulsion (M a ) When it is used, it consists in incorporating in the microemulsion (M a ) thus obtained a silane compound or several silane compounds, identical or different, which will give (have), just like the (or the silicone derivative (s) of phthalocyanine by sol-gel reaction the silica of the silica particles according to the invention.
- the incorporation into the microemulsion (M a ) of the silane-based compound (s) to obtain the microemulsion (M b ) of the water-in-oil type is carried out by injection, advantageously followed by stirring using a stirrer.
- a magnetic bar an ultrasonic bath or a homogenizer
- a temperature of between 10 and 40 ° C. advantageously between 15 and 30 ° C. and, more particularly, at room temperature (ie 23 ° C. ⁇ 5 ° C) for a period of between 5 min and 2 h, in particular between 15 min and 1 h and, in particular, for 30 min.
- said silane-based compound (s) is (are) an alkylsilane or an alkoxysilane. More particularly, said silane-based compound (s) is (are) of the general formula SiR a R b R c Rd in which R a , R b , R c and R d are, independently of one another selected from the group consisting of hydrogen; a halogen; an amino group; a diamine group; an amide group; an acyl group; a vinyl group; a hydroxyl group; an epoxy group; a phosphonate group; a sulfonic acid group; an isocyanate group; a carboxyl group; a thiol group (or mercapto); a glycidoxy group; an acryloxy group such as a methacryloxy group; an alkyl group, linear or branched, optionally substituted, of 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; an aryl group, linear or
- the silane-based compound is, more particularly, selected from the group consisting of dimethylsilane (DMSi), phenyltriethoxysilane (PTES), tetraethoxysilane (TEOS), n-octyltriethoxysilane, n-octadecyltriethoxysilane, dimethyldimethoxysilane (DMDMOS) (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (mercapto) triethoxysilane, (3-aminopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- [bis (2- hydroxyethyl) amino] propyltriethoxysilane,
- silane compound is tetraethoxysilane (TEOS, Si (OC 2 H 5 ) 4 ).
- the silane compound used may be a mixture containing less than 20% and in particular 5 to 15% of a prefunctionalized silane relative to to the total amount of silane compounds.
- a mixture containing TEOS and 5 to 15% of mercaptotriethoxysilane may be used for the preparation of silica particles according to the invention and functionalized with thiol groups.
- the silane-based compound (s) is (are) present in a proportion of between 0.05 and 20%, especially between 0.1 and 10%, and in particular between 0.5 and 5% by volume relative to the total volume of said microemulsion.
- Step (c) of the process according to the invention aims to provide for the hydrolysis of a silane-based compound by adding to the microemulsion (M b ) a compound allowing this hydrolysis, the microemulsion (M c ) thus obtained being a microemulsion water in oil.
- compound allowing the hydrolysis of silane-based compounds means a compound which allows not only the hydrolysis of a silane-based compound but also the hydrolysis of a silicone phthalocyanine derivative. .
- the compound for hydrolyzing the silane compound is preferably selected from the group consisting of ammonia, sodium hydroxide (KOH), lithium hydroxide (LiOH) and sodium hydroxide (NaOH) and, advantageously, a solution of such a compound in a polar solvent, identical or different, to the polar solvent used during step (b).
- the compound for hydrolyzing the silane-based compound is, more particularly, ammonia or a solution of ammonia in a polar solvent as defined above. Indeed, ammonia acts as reagent (H 2 O) and as catalyst (NH 4 OH) of the hydrolysis of the silane-based compound or silicone phthalocyanine derivative.
- the compound allowing the hydrolysis of the silane-based compound, when in solution in the polar solvent, is present in a proportion of between 5 and 50%, in particular between 10 and 40% and, in particular, between 20 and 50%. 30% by volume relative to the total volume of said solution.
- said solution is present in a proportion of between 0.05 and 20%, especially between 0.1 and 10% and, in particular, between 0.5 and 5% by volume relative to the total volume of the microemulsion ( M c ).
- Step (c) may be carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, and at a temperature of between 10 and 40 ° C., advantageously between 15 and 30 ° C., and more particularly at ambient temperature (ie 23 ° C. ⁇ 5 ° C.) for a period of between 6 and 48 hours, especially between 12 and 36 h and, in particular, for 24 h.
- a stirrer a magnetic bar, an ultrasonic bath or a homogenizer
- Step (d) of the process according to the invention aims at precipitating the silica particles by adding a solvent which does not denature the structure of the particles but which destabilizes or denatures the microemulsion (M c ) obtained in step ( vs) .
- the solvent used is a polar solvent as defined above.
- a particular polar solvent to be used in step (d) is selected from the group consisting of ethanol, acetone and methanol.
- the solvent used in step (d) of the process according to the invention is ethanol. So, is added, at the microemulsion (M c ), a volume of solvent greater than the volume of said microemulsion, in particular greater by a factor of 1.5; in particular, greater by a factor of 2; and even a factor of 3.
- step (e) implements one or more steps, identical or different, chosen from the centrifugation, sedimentation and washing steps.
- the washing step (s) is (are) carried out in a polar solvent as defined above.
- centrifugation stage it (they) can be implemented by centrifuging the silica particles, in particular in a washing solvent at ambient temperature, at a speed between 4000 and 8000 rpm and, in particular, of the order of 6000 rpm (ie 6000 ⁇ 500 rpm) and this, for a period of between 5 min and 2 h, in particular between 10 min and 1 h and, in particular, during 15 min.
- the method according to the present invention may comprise, after step (e), a step further comprising purifying the silica particles obtained hereinafter referred to as "step (f)".
- this step (f) consists in putting the recovered silica particles after step (e) of the process according to the invention in contact with a very large volume of water.
- very large volume is meant a volume greater by a factor of 50, in particular by a factor of 500 and, in particular, by a factor of 1000 to the volume of silica particles, recovered after step (e) of process according to the invention.
- Step (f) may be a dialysis step, the silica particles being separated from the volume by a cellulose membrane, of the Zellu trans type (Roth company).
- an ultrafiltration step may be provided instead of the dialysis step, via a polyethersulfone membrane. step
- (f) may, in addition, be carried out under agitation using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, at a temperature of between 0 and 30 ° C., advantageously between 2 and 20 ° C., and more particularly, cold (ie 6 ° C ⁇ 2 ° C) and this, for a period of between 30 h and 15 d, especially between 3 and 10 days and, in particular, for 1 week.
- a stirrer a magnetic bar, an ultrasonic bath or a homogenizer
- the present invention also relates to the microemulsion (M c ) that can be implemented in the context of the process according to the invention.
- This microemulsion of water-in-oil type comprises:
- At least one surfactant especially as defined above, optionally at least one cosurfactant, especially as defined above,
- At least one compound capable of hydrolyzing a compound based on silane in particular as previously defined.
- the water-in-oil microemulsion which is the subject of the present invention comprises:
- At least one surfactant in an amount of between 1 and 30%, in particular between 5 and 25% and, in particular, between 10 and 20%;
- co-surfactant in an amount of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20%;
- At least one non-polar or weakly polar solvent in an amount of between 40 and 95%, especially between 50 and 90% and, in particular, between 60 and 80%;
- At least one polar solvent in an amount of between 0.5 and 20%, especially between 1 and 15% and, in particular, between 2 and 10%; at least one silicone phthalocyanine derivative in an amount of between 0.001 and 1%, in particular between 0.005 and 0.1% and, in particular, between 0.001 and 0.05%;
- silane compound in an amount of between 0.05 and 20%, especially between 0.1 and 10% and, in particular, between 0.5 and 5%;
- At least one compound capable of hydrolyzing said silane-based compound in an amount of between 0.01 and 5%, especially between 0.05 and 1% and, in particular, between 0.1 and 0.5%,
- the present invention further relates to a silica particle capable of being prepared by the process of the present invention.
- This particle is a silica particle comprising at least one phthalocyanine derivative, as previously defined. It differs from the silica particles of the state of the art by the two covalent bonds which bind the Si atom to the phthalocyanine derivative, the phthalocyanine derivative not being a moiety which functionalizes the silica particle. Indeed, the covalent bonds which bind the Si atom with the phthalocyanine derivative are retained in the silica particle formed at the end of the process according to the invention. Thus, there is a strong interaction between the network structure of the silica particle and the derivative (s) of phthalocyanine by the presence of covalent bonds. Therefore, the phthalocyanine derivative is covalently bonded to the silica network of the particle according to the invention.
- the silica particles according to the invention are nanoparticles having a mean size less than or equal to 100 nm, in particular between 10 and 80 nm, in particular between 20 and 60 nm and, even, of the order of 40. nm (ie 40 ⁇ 10 nm).
- the silica particles according to the invention may be optionally functionalized.
- the silica particles according to the invention may be optionally porous.
- the present invention finally relates to the use of a silica particle according to the invention in fields selected from the group consisting of catalysis, printing, painting, filtration, polymerization, heat exchange, stability. thermal, materials chemistry, hydrocarbon refining, hydrogen production, sorbents, food industry, active agent transport, biomolecules, pharmaceuticals, heat-insulating coatings, bioelectronic compounds and electronic, optical, semiconductor and sensor devices.
- FIG. 1 shows a view obtained by transmission electron microscopy (TEM) of the agglomerates with silica nanoparticles prepared by the process according to the invention.
- TEM transmission electron microscopy
- FIG. 2 shows a view obtained by transmission electron microscopy (TEM) of silica nanoparticles prepared by the process according to the invention without agglomerate.
- TEM transmission electron microscopy
- a solution (Mi solution according to the invention) was generated by adding, in this order, the following chemicals, Triton X100 surfactant (2.1 mL), co-surfactant n-hexanol (2.05 mL), the organic cyclohexane solvent (9.38 mL). The solution was then stirred at room temperature for 15 minutes.
- silica phthalocyanine derivative, 2,3-naphthalocyanine dihydroxide silane or in English "silicon 2,3-naphthalocyanine dihydroxide” in a solution of THF was added (100 ⁇ l at 0.1 M in THF).
- the resulting emulsion was stirred at room temperature for 30 minutes.
- the hydrolysis of TEOS was initiated by the addition of 25% aqueous ammonia (125 ⁇ l) and the reaction mixture was stirred for 24 h at room temperature.
- the emulsion was destabilized by the addition of ethanol (50 mL) and the silica beads were washed three times with ethanol and once with water, each wash being followed by centrifuge sedimentation (15 min. at 6000 rpm).
- the purification of the nanoparticles obtained was completed by dialysis in water (1 L) with magnetic stirring for one week.
- silica nanoparticles dispersed in water (40 mL) prepared according to the method of Part I were then characterized by transmission electron microscopy (TEM) analysis which allows to appreciate the nanostructure of these nanoparticles.
- TEM transmission electron microscopy
- FIG. 1 shows agglomerates with spherical nanoparticles without agglomerate.
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Abstract
The present invention relates to a method for preparing a silica particle including at least one phthalocyanine derivative, said particle being prepared from at least one silicon phthalocyanine derivative via reverse microemulsion, to said silica particles, and to the uses thereof.
Description
PROCEDE DE PREPARATION DE PARTICULES DE SILICE PROCESS FOR PREPARING SILICA PARTICLES
CONTENANT UN DÉRIVÉ DE PHTALOCYANINE , LESDITES CONTAINING A PHTHALOCYANINE DERIVATIVE, THE SAME
PARTICULES ET LEURS UTILISATIONS DESCRIPTION PARTICLES AND THEIR USES DESCRIPTION
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention se rapporte au domaine des particules de silice et notamment des nanoparticules de silice contenant des colorants de type phtalocyanine de silice. The present invention relates to the field of silica particles and in particular silica nanoparticles containing silica phthalocyanine dyes.
En effet, la présente invention a pour objet un procédé de préparation de particules de silice incorporant des dérivés de phtalocyanine et de naphthalocyanine . Elle concerne également les particules de silice incorporant des dérivés de phtalocyanine et de naphthalocyanine, susceptibles d'être préparées par ce procédé et leurs différentes utilisations et applications. Indeed, the present invention relates to a process for preparing silica particles incorporating phthalocyanine and naphthalocyanine derivatives. It also relates to silica particles incorporating phthalocyanine and naphthalocyanine derivatives, capable of being prepared by this process and their various uses and applications.
ÉTAT DE LA TECHNIQUE ANTÉRIEURE STATE OF THE PRIOR ART
La synthèse et les propriétés des colorants dérivés des complexes de phtalocyanines ou de naphtalocyanines de silicone possédant des ligands axiaux ont été décrites dans la littérature par Kenney [1], Joyner [2], et Esposito [3]. Un intérêt considérable s'est développé ces dernières années pour les propriétés physiques et chimiques des phtalocyanines. Cet intérêt provient en partie de leurs possibles applications dans divers domaines tels que 1' électrophotographie [4], les cristaux liquides [5],
les polymères conducteurs [6], l'affichage électrochromique [7] , la conversion photoélectrochimique d'énergie [8], les agents absorbants d' infrarouge pour les thermoplastiques transparents et les polymères réticulés [9] , et la photoconductivité [10] . The synthesis and properties of dyes derived from phthalocyanine or silicone naphthalocyanine complexes with axial ligands have been described in the literature by Kenney [1], Joyner [2], and Esposito [3]. Considerable interest has developed in recent years for the physical and chemical properties of phthalocyanines. This interest comes partly from their possible applications in various fields such as electrophotography [4], liquid crystals [5], conducting polymers [6], electrochromic display [7], photoelectrochemical energy conversion [8], infrared absorbing agents for transparent thermoplastics and crosslinked polymers [9], and photoconductivity [10].
En effet, les phtalocyanines et autres analogues macrocycliques ont considérablement attiré l'attention en tant que matériaux moléculaires aux propriétés électroniques et optiques exceptionnelles. Ces propriétés proviennent de la délocalisation du nuage électronique, et rendent ces produits intéressants pour différents domaines de recherche en science des matériaux et tout particulièrement en nanotechnologie . Ainsi, des phtalocyanines ont été incorporées avec succès dans des composants de semiconducteurs, de dispositifs électrochromiques, de systèmes de stockage d'information. Indeed, phthalocyanines and other macrocyclic analogues have attracted considerable attention as molecular materials with exceptional electronic and optical properties. These properties come from the delocalization of the electronic cloud, and make these products interesting for different areas of research in materials science and especially in nanotechnology. Thus, phthalocyanines have been successfully incorporated into semiconductor components, electrochromic devices, information storage systems.
Un problème crucial à prendre en compte afin d'incorporer des phtalocyanines dans des dispositifs technologiques est le contrôle de l'arrangement spatial de ces macrocycles. Ceci permet d'étendre et d'améliorer les propriétés chimiques et physiques des phtalocyanines à l'échelle macromoléculaire ou moléculaire. La superposition co- faciale des phtalocyanines est nécessaire afin d'obtenir des propriétés supramoléculaires . Par exemple, l'augmentation de la conductivité peut se faire le long de l'axe principal du système d'empilage des phtalocyanines par une délocalisation d'électrons à travers les macrocycles co-planaires . La conductivité
dans des systèmes à base de phtalocyanines dépend généralement des propriétés intrinsèques de phtalocyanines bien particulières. Ainsi, des phtalocyanines de silicone ont été utilisées pour la préparation de dispositifs comme les transistors à effet de champs. Une bonne conductivité est également obtenue dans des polymères à base de phtalocyanines. Parmi une importante variété de polymères semiconducteurs basés sur des phtalocyanines, la famille la plus importante est celle des siloxanes de phtalocyanines [PcSiC^]n-A crucial problem to consider in incorporating phthalocyanines into technological devices is the control of the spatial arrangement of these macrocycles. This makes it possible to extend and improve the chemical and physical properties of phthalocyanines at the macromolecular or molecular scale. The co-facial superposition of the phthalocyanines is necessary in order to obtain supramolecular properties. For example, the increase in conductivity can be along the main axis of the phthalocyanine stacking system by delocalization of electrons through the co-planar macrocycles. Conductivity in phthalocyanine-based systems generally depends on the intrinsic properties of particular phthalocyanines. Thus, silicone phthalocyanines have been used for the preparation of devices such as field effect transistors. Good conductivity is also obtained in phthalocyanine-based polymers. Among a large variety of phthalocyanine-based semiconductor polymers, the most important family is that of phthalocyanine siloxanes [PcSiC ^] n -
Ainsi, les nano-objets et autres polymères de phtalocyanines siloxanes sont bien connus de l'art antérieur. Ces structures sont fabriquées de diverses façons dans la littérature. Plusieurs méthodes ont été validées pour la polymérisation de phtalocyanine de silice . Thus, nano-objects and other siloxane phthalocyanine polymers are well known in the art. These structures are made in various ways in the literature. Several methods have been validated for the polymerization of silica phthalocyanine.
La préparation de polysiloxanes de phtalocyanines a été décrite dans la littérature. Ainsi des polymères ont été synthétisés en utilisant les phtalocyanines de silicone comme précurseurs. Ces composés entrent dans la préparation de film Langmuir- Blodgett, films unidimensionnels de type polymères très rigides [11] . La polymérisation est effectuée sous vide à 350-4000C pendant 2 h, conditions très extrêmes. Une autre synthèse de polymères est conduite avec le même précurseur de phtalocyanine de silicone dans la diméthylsulfoxide à 1350C pendant 24 h [12] . Plus récemment, un protocole nouveau et plus opportun a été rapporté afin de préparer des oligomères de 3 à 4 unités de monomères (phtalocyanine de silicone) [13] ,
ledit protocole comprenant la condensation des monomères en présence de quinoléine suivie par une silylation avec du chlorure de tert-butyldiméthylsilyle (TBDMSCl) . The preparation of phthalocyanine polysiloxanes has been described in the literature. Thus polymers were synthesized using silicone phthalocyanines as precursors. These compounds are used in the Langmuir-Blodgett film preparation, one-dimensional films of very rigid polymer type [11]. The polymerization is carried out under vacuum at 350-400 0 C for 2 h, very extreme conditions. Another synthesis of polymers is carried out with the same silicone phthalocyanine precursor in dimethylsulfoxide at 135 ° C. for 24 hours [12]. More recently, a new and more timely protocol has been reported to prepare oligomers of 3 to 4 monomer units (silicone phthalocyanine) [13], said protocol comprising condensation of the monomers in the presence of quinoline followed by silylation with tert-butyldimethylsilyl chloride (TBDMSCl).
Une autre approche a été développée afin d' obtenir un polymère réticulé axialement au plan du macrocycle aromatique de la phtalocyanine . Ainsi, une fonctionnalisation axiale a conduit à l'obtention de phtalocyanine de silicone conjuguée axialement avec un poly (anhydride d'acide polysébacique) . Le produit ainsi obtenu a ensuite été utilisé pour former des nanoparticules hydrophiles via une méthode d' inversion de microphase [14] . Another approach has been developed to obtain a polymer crosslinked axially in terms of the aromatic macrocycle of phthalocyanine. Thus, axial functionalization has led to the production of silicone phthalocyanine conjugated axially with a poly (polyshepic acid anhydride). The product thus obtained was then used to form hydrophilic nanoparticles via a microphase inversion method [14].
Il convient de souligner qu'en général, ces polymères produisent des conductivités électriques élevées. Cependant, ces matériaux sont aussi bien insolubles dans l'eau que dans les solvants organiques communs, ce qui rend difficile leur préparation industrielle. En effet, le caractère organique des macrocycles aromatiques de type phtalocyanine rend ces derniers très insolubles. L'insolubilité est plus manifeste lors de l'utilisation des naphtalocyanines ou des analogues anthracènes. Ce phénomène est en partie dû aux agrégats formés par interactions π-π. Ainsi, il est parfois nécessaire de substituer le macrocycle aromatique en positions périphérique et/ou non- périphérique afin de conférer à cette famille de colorants une bonne solubilité dans les solvants organiques. Malheureusement, cette fonctionnalisation peut entraîner des changements des propriétés intrinsèques. Ainsi, dans certains cas, il est
préférable de garder le réseau aromatique du macrocycle non-substitué . It should be emphasized that, in general, these polymers produce high electrical conductivities. However, these materials are both insoluble in water and in common organic solvents, which makes their industrial preparation difficult. Indeed, the organic nature of phthalocyanine aromatic macrocycles makes them very insoluble. Insolubility is more evident when using naphthalocyanines or anthracene analogues. This phenomenon is partly due to the aggregates formed by π-π interactions. Thus, it is sometimes necessary to substitute the aromatic macrocycle in peripheral and / or non-peripheral positions in order to confer on this family of dyes a good solubility in organic solvents. Unfortunately, this functionalization can lead to changes in the intrinsic properties. So in some cases it is better to keep the aromatic network of the unsubstituted macrocycle.
L' encapsulation de phtalocyanines de silicone a également fait l'objet de quelques études. Compte-tenu de 1 ' hydrophobie prononcée et reconnue des matériaux à base de phtalocyanines, il est très difficile de les encapsuler dans des nano-objets de silice en utilisant un procédé classique par voie humide . The encapsulation of silicone phthalocyanines has also been the subject of some studies. In view of the pronounced and recognized hydrophobicity of phthalocyanine-based materials, it is very difficult to encapsulate them in silica nano-objects using a conventional wet process.
Ainsi un dérivé du bis-oléate de phtalocyanine de silicone a été introduit dans des nanoparticules de lipoprotéine, afin d'utiliser ces produits comme des nanoplateformes à base lipoprotéine. Ces composés sont par la suite utilisés comme dispositifs de diagnostic multifonctionnels et thérapeutiques [15] . Une demande de brevet relate également l' encapsulation de cristaux de phtalocyanines de cuivre (aucune présence de silicone mentionnée) [16]. L'étude des nanoparticules ainsi préparées pour les encres contenant des dispersions, pour les filtres de couleurs et la composition de résine photosensible et colorée est également rapportée [17] . Thus, a derivative of silicone phthalocyanine bis-oleate has been introduced into lipoprotein nanoparticles, in order to use these products as lipoprotein-based nanoplateforms. These compounds are subsequently used as multifunctional and therapeutic diagnostic devices [15]. A patent application also relates to the encapsulation of copper phthalocyanine crystals (no silicone presence mentioned) [16]. The study of the nanoparticles thus prepared for the inks containing dispersions, for the color filters and the photosensitive and colored resin composition is also reported [17].
Enfin, une étude décrit la formation de nanoparticules de séléniure de cadmium (CdSe) conjuguées à des phtalocyanines de silicone. La surface des nanoparticules de CdSe est ainsi fonctionnalisée par condensation du groupement actif (groupement aminé) , situé en position axiale du macrocycle de la phtalocyanine de silicone et relié à celui-ci via un groupement alkyle [18] . Une étude similaire publiée en 2006 présente l'introduction de tétrasulphonate de
phtalocyanine de cuivre sur la surface de nanoparticules de silice modifiée par fonctionnalisation avec des groupements aminé [19] . Finally, a study describes the formation of cadmium selenide nanoparticles (CdSe) conjugated to silicone phthalocyanines. The surface of the CdSe nanoparticles is thus functionalized by condensation of the active group (amino group) located in the axial position of the macrocycle of the silicone phthalocyanine and connected thereto via an alkyl group [18]. A similar study published in 2006 presents the introduction of tetrasulphonate Copper phthalocyanine on the surface of silica nanoparticles modified by functionalization with amino groups [19].
La demande internationale WO 2008/138727 rapporte la préparation de nanoparticules de silice fonctionnalisées par du phtalocyanine de cuivre. La fonction siloxane portée par le phtalocyanine de cuivre et nécessaire à la formation de nanoparticules de silice, est en position périphérique et nécessite une étape de fonctionnalisation du phtalocyanine de cuivre International application WO 2008/138727 reports the preparation of silica nanoparticles functionalized with copper phthalocyanine. The siloxane function carried by the copper phthalocyanine and necessary for the formation of silica nanoparticles, is in the peripheral position and requires a step of functionalization of the copper phthalocyanine
[20] . [20].
Il existe un réel besoin d'un procédé simple, pratique et applicable au niveau industriel pour préparer des matériaux à base de phtalocyanines tels que des particules de silice. There is a real need for a simple, practical and industrially applicable process for preparing phthalocyanine materials such as silica particles.
EXPOSÉ DE L'INVENTION STATEMENT OF THE INVENTION
La présente invention permet de remédier aux inconvénients et problèmes techniques listés ci- dessus. En effet, cette dernière propose un procédé de préparation de matériaux particulaires, sphériques à base de silice et notamment des matériaux nanoparticulaires dont la taille est avantageusement inférieure à 100 nm incorporant des dérivés de phtalocyanine, ledit procédé étant applicable au niveau industriel, ne nécessitant pas de procédés ou d'étapes lourd (e) s et utilisant des produits facilement accessibles, non dangereux et peu toxiques. The present invention overcomes the disadvantages and technical problems listed above. Indeed, the latter proposes a process for the preparation of spherical silica-based particulate materials and in particular nanoparticulate materials whose size is advantageously less than 100 nm incorporating phthalocyanine derivatives, said process being applicable at the industrial level, not requiring processes or heavy steps and using easily accessible, non-hazardous and low-toxicity products.
Les travaux des inventeurs ont mis en évidence que l'utilisation de dérivés de phtalocyanines de silicone comme précurseurs de silice permet de
fabriquer des particules de silice telles que des nanoparticules de silice incorporant des dérivés de phtalocyanine . La disponibilité des ligands axiaux combinée avec la présence de l'atome de silice introduit dans la cavité du macrocycle de phtalocyanine permet de l'utiliser comme précurseur nécessaire à une synthèse correcte de nanoparticules de silice en voie micellaire inverse. The work of the inventors has shown that the use of silicone phthalocyanine derivatives as silica precursors makes it possible to fabricate silica particles such as silica nanoparticles incorporating phthalocyanine derivatives. The availability of axial ligands combined with the presence of the silica atom introduced into the cavity of the phthalocyanine macrocycle makes it possible to use it as a precursor necessary for the proper synthesis of silica nanoparticles in the reverse micelle pathway.
Ces travaux ont également permis de surmonter le préjugé technique lié au caractère hydrophobe prononcé des matériaux à base de phtalocyanines . En effet, l'homme du métier n'aurait pas utilisé un système micellaire inverse pour préparer des particules de silice incorporant des dérivés de phtalocyanine puisque les micelles formées contiennent de l'eau ce qui est considéré comme incompatible avec le caractère hydrophobe de ces dérivés. This work also overcame the technical prejudice related to the pronounced hydrophobicity of phthalocyanine-based materials. Indeed, those skilled in the art would not have used a reverse micellar system to prepare silica particles incorporating phthalocyanine derivatives since the micelles formed contain water which is considered incompatible with the hydrophobic character of these derivatives. .
De plus, dans le cadre de la présente invention, la surface des particules de silice obtenues par le procédé selon l'invention peut être fonctionnalisée permettant ainsi d'influencer la polarité des particules, et ainsi l'affinité avec le solvant à utiliser dans le cas de l'application, c'est- à-dire, polaire, apolaire, etc. et donc de la dispersion désirée. In addition, in the context of the present invention, the surface of the silica particles obtained by the process according to the invention can be functionalized thus making it possible to influence the polarity of the particles, and thus the affinity with the solvent to be used in the process. case of the application, that is to say, polar, apolar, etc. and therefore the desired dispersion.
Ainsi, la présente invention concerne un procédé de préparation d'une particule de silice incorporant au moins un dérivé de phtalocyanine, ladite particule étant préparée à partir d'au moins un dérivé
siliconé de phtalocyanine via une microémulsion inverse . Thus, the present invention relates to a method for preparing a silica particle incorporating at least one phthalocyanine derivative, said particle being prepared from at least one derivative silicone phthalocyanine via an inverse microemulsion.
Par « microémulsion inverse », également appelée microémulsion « eau dans huile », on entend une suspension limpide, thermodynamiquement stable, de fines goutelettes d'un premier liquide polaire dans un second liquide non-polaire et donc non miscible avec le premier liquide. L'expression « par voie micellaire inverse » est équivalente à l'expression « via une microémulsion inverse ». By "reverse microemulsion", also called "water-in-oil" microemulsion, is meant a clear, thermodynamically stable suspension of fine droplets of a first polar liquid in a second non-polar liquid and therefore immiscible with the first liquid. The expression "reverse micellar pathway" is equivalent to the expression "via an inverse microemulsion".
Par « dérivé siliconé de phtalocyanine », on entend un composé de formule (I) By "silicone phthalocyanine derivative" is meant a compound of formula (I)
(I) (I)
dans laquelle in which
- Ri, R2, R3 et R4, identiques ou différents, représentent un groupement arylène éventuellement substitué et R 1, R 2, R 3 and R 4 , which are identical or different, represent an optionally substituted arylene group and
- R5 et Rε, identiques ou différents, sont choisis dans le groupe constitué par -Cl, -F, -OH etR 5 and R 6 , which are identical or different, are chosen from the group consisting of -Cl, -F, -OH and
-OR' avec R' représentant un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué.
Par « éventuellement substitué », on entend, dans le cadre des groupes alkyle des composés de formule (I), substitué par un halogène, un groupe aminé, un groupe diamine, un groupe amide, un groupe acyle, un groupe vinyle, un groupe hydroxyle, un groupe epoxy, un groupe phosphonate, un groupe acide sulfonique, un groupe isocyanate, un groupe carboxyle, un groupe thiol (ou mercapto) , un groupe glycidoxy ou un groupe acryloxy et notamment un groupe méthacryloxy . Avantageusement, R' représente un méthyle ou un éthyle. -OR 'with R' representing a linear or branched alkyl of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted. By "optionally substituted" is meant, in the context of alkyl groups, compounds of formula (I), substituted by a halogen, an amino group, a diamine group, an amide group, an acyl group, a vinyl group, a group hydroxyl, an epoxy group, a phosphonate group, a sulfonic acid group, an isocyanate group, a carboxyl group, a thiol (or mercapto) group, a glycidoxy group or an acryloxy group and in particular a methacryloxy group. Advantageously, R 'represents a methyl or an ethyl.
Par « groupement arylène », on entend dans le cadre de la présente invention une structure carbonée aromatique ou hétéroaromatique, éventuellement mono- ou polysubstituée, constituée d'un ou plusieurs cycles aromatiques ou hétéroaromatiques comportant chacun de 3 à 8 atomes, le ou les hétéroatomes pouvant être N, 0, P ou S . For the purposes of the present invention, the term "arylene group" means an aromatic or heteroaromatic carbon structure, optionally mono- or polysubstituted, consisting of one or more aromatic or heteroaromatic rings each comprising from 3 to 8 atoms, and the heteroatom (s). can be N, 0, P or S.
Par « éventuellement substitué », on entend un groupement arylène qui peut être mono- ou polysubstitué par un groupement choisi dans le groupe constitué par un carboxylate ; un aldéhyde ; un ester ; un éther ; un hydroxyle ; un halogène ; un aryle tel qu'un phényle, un benzyle ou un naphthyle ; un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué tel qu'un méthyle, un éthyle, un propyle ou un hydroxypropyle ; une aminé ; un amide ; un sulfonyle ; un suifoxyde et un thiol. By "optionally substituted" is meant an arylene group which may be mono- or polysubstituted by a group selected from the group consisting of a carboxylate; an aldehyde; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
Avantageusement, les groupements Ri, R2, R3 et R4 sont, identiques ou différents, chacun représentant un phénylène, un naphthylène ou un
anthracène . Plus particulièrement, les groupements Ri, R2, R3 et R4 sont identiques et représentent un phénylène, un naphthylène ou un anthracène. Advantageously, the groups R 1, R 2, R 3 and R 4 are identical or different, each representing a phenylene, a naphthylene or a anthracene. More particularly, the groups R 1, R 2, R 3 and R 4 are identical and represent a phenylene, a naphthylene or an anthracene.
En particulier, le dérivé siliconé de phtalocyanine mis en œuvre dans le cadre de la présente invention est un composé de formule (II) : In particular, the silicone phthalocyanine derivative used in the context of the present invention is a compound of formula (II):
(H) (H)
dans laquelle in which
- les groupements R7 à R22, identiques ou différents, sont choisis dans le groupe constitué par un hydrogène ; un carboxylate ; un aldéhyde ; une cétone ; un ester ; un éther ; un hydroxyle ; un halogène ; un aryle tel qu'un phényle, un benzyle ou un naphthyle ; un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué tel qu'un méthyle, un éthyle, un propyle ou un hydroxypropyle ; une aminé ; un amide ; un sulfonyle ; un suifoxyde et un thiol.
les groupements R5 et Re sont tels que précédemment définis. the groups R 7 to R 22, which are identical or different, are chosen from the group consisting of hydrogen; a carboxylate; an aldehyde; a ketone; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol. the groups R 5 and Re are as previously defined.
Un composé de formule (II) préféré dans le cadre de la présente invention est le composé dans lequel les groupements R7 à R22 représentent un hydrogène et les groupements R5 et Re sont tels que précédemment définis. A compound of formula (II) that is preferred in the context of the present invention is the compound in which the groups R 7 to R 22 represent a hydrogen and the groups R 5 and Re are as previously defined.
En variante, le dérivé siliconé de phtalocyanine mis en œuvre dans le cadre de la présente invention est un composé de formule (III) du type naphtalocyanine : As a variant, the silicone phthalocyanine derivative used in the context of the present invention is a compound of formula (III) of the naphthalocyanine type:
(III) (III)
dans laquelle in which
- les groupements R23 à R46, identiques ou différents, sont choisis dans le groupe constitué par
un hydrogène ; un carboxylate ; un aldéhyde ; une cétone ; un ester ; un éther ; un hydroxyle ; un halogène ; un aryle tel qu'un phényle, un benzyle ou un naphthyle ; un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué tel qu'un méthyle, un éthyle, un propyle ou un hydroxypropyle ; une aminé ; un amide ; un sulfonyle ; un suifoxyde et un thiol. - the groups R 23 to R 4 6, identical or different, are selected from the group consisting of a hydrogen; a carboxylate; an aldehyde; a ketone; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
les groupements R5 et Re sont tels que précédemment définis. the groups R 5 and Re are as previously defined.
Un composé de formule (III) préféré dans le cadre de la présente invention est le composé dans lequel les groupements R23 à R46 représentent un hydrogène et les groupements R5 et Re sont tels que précédemment définis. A compound of formula (III) which is preferred in the context of the present invention is the compound in which the groups R 23 to R 46 represent a hydrogen and the groups R 5 and Re are as previously defined.
Dans les formules (I), (II) et (III), les liaisons en pointillé représentent des liaisons de coordination ou des liaisons datives. In the formulas (I), (II) and (III), the dotted bonds represent coordination bonds or dative bonds.
Avantageusement, les groupements R5 et Re dans les composés de formule (I), (II) ou (III) sont identiques et sont choisis dans le groupe constitué par -Cl, -F, -OH et -OR' avec R' représentant un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué et notamment choisis dans le groupe constitué par -Cl, -F, -OH, -OCH3 et -OC2H5. Plus particulièrement, les groupements R5 et Re dans les composés de formule (I), (II) ou (III) sont identiques et représentent -OH ou -Cl. Advantageously, the groups R 5 and Re in the compounds of formula (I), (II) or (III) are identical and are chosen from the group consisting of -Cl, -F, -OH and -OR 'with R' representing an alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted and in particular selected from the group consisting of -Cl, -F, -OH, -OCH 3 and -OC 2 H 5 . More particularly, the groups R 5 and Re in the compounds of formula (I), (II) or (III) are identical and represent -OH or -Cl.
Les composés de formule (II) et (III) tout particulièrement mis en œuvre dans le cadre de la
présente invention sont un complexe phtalocyaninatodichlorosilane, un complexe phtalocyaninadihydroxysilane, un complexe naphtalocyaninatodichlorosilane et un complexe naphtalocyaninatodihydroxysilane . Ces complexes peuvent être représentés avec R représentant -OH ou -Cl de la façon suivante : The compounds of formula (II) and (III) especially used in the context of the The present invention is a phthalocyanine dodichlorosilane complex, a phthalocyanine dihydroxysilane complex, a naphthalocyanine dodichlorosilane complex and a naphthalocyanine dihydroxysilane complex. These complexes can be represented with R representing -OH or -Cl as follows:
Le procédé selon l'invention comprend, plus particulièrement, les étapes successives suivantes : The process according to the invention comprises, more particularly, the following successive steps:
a) préparer une microémulsion (Ma) du type eau dans huile contenant au moins un dérivé siliconé de phtalocyanine, a) preparing a microemulsion (M a ) of the water-in-oil type containing at least one silicone phthalocyanine derivative,
b) éventuellement ajouter, à la microémulsion (Ma) obtenue à l'étape (a), au moins un composé à base de silane,
c) ajouter, à la microémulsion (Mb) obtenue à l'étape (b) , au moins un composé permettant l'hydrolyse de composés à base de silane, b) optionally adding, to the microemulsion (M a ) obtained in step (a), at least one silane-based compound, c) adding, to the microemulsion (M b ) obtained in step (b), at least one compound for the hydrolysis of silane compounds,
d) ajouter à la microémulsion (Mc) obtenue à l'étape (c) un solvant permettant de déstabiliser ladite microémulsion, d) adding to the microemulsion (M c ) obtained in step (c) a solvent for destabilizing said microemulsion,
e) récupérer les particules de silice incorporant au moins un dérivé siliconé de phtalocyanine, précipitées lors de l'étape (d) . e) recovering the silica particles incorporating at least one silicone phthalocyanine derivative, precipitated during step (d).
L'étape (a) du procédé selon l'invention consiste donc à préparer une microémulsion (Ma) du type eau dans huile contenant au moins un dérivé siliconé de phtalocyanine. Toute technique permettant de préparer une telle microémulsion est utilisable dans le cadre de la présente invention. Ainsi, il est possible de : Step (a) of the process according to the invention therefore consists in preparing a microemulsion (M a ) of the water-in-oil type containing at least one silicone phthalocyanine derivative. Any technique making it possible to prepare such a microemulsion can be used in the context of the present invention. Thus, it is possible to:
- soit préparer une première solution (Mi) et d'y incorporer ultérieurement un (ou des) dérivé (s) siliconé (s) de phtalocyanine pour obtenir la microémulsion (Ma) ; - Either prepare a first solution (Mi) and subsequently incorporate a (or) silicone derivative (s) phthalocyanine to obtain the microemulsion (M a );
soit préparer la microémulsion (Ma) directement en mélangeant ensemble les différents composants et donc un (ou des) dérivé (s) siliconé (s) de phtalocyanine . or prepare the microemulsion (M a ) directly by mixing together the various components and therefore a (or) silicone derivative (s) phthalocyanine.
Avantageusement, l'étape (a) du procédé selon l'invention consiste à préparer une première solution (Mi) dans laquelle est (sont) ultérieurement incorporé (s) un (ou des) dérivé (s) siliconé (s) de phtalocyanine. Cette solution (Mi) est obtenue en mélangeant ensemble Advantageously, step (a) of the process according to the invention consists in preparing a first solution (Mi) in which is (are) subsequently incorporated (s) silicone derivative (s) phthalocyanine. This solution (Mi) is obtained by mixing together
- au moins un tensioactif,
- éventuellement au moins un co-tensioactif et at least one surfactant, - optionally at least one co-surfactant and
au moins un solvant non-polaire ou faiblement polaire. at least one non-polar or weakly polar solvent.
Avantageusement, le tensioactif, l'éventuel co-tensioactif et le solvant non-polaire ou faiblement polaire sont ajoutés les uns après les autres et, dans l'ordre suivant, tensioactif puis éventuellement co- tensioactif puis solvant non-polaire ou faiblement polaire. Advantageously, the surfactant, the optional cosurfactant and the non-polar or weakly polar solvent are added one after the other and, in the following order, surfactant then optionally cosurfactant and then non-polar or weakly polar solvent.
Le mélange est effectué sous agitation en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur, et peut être mis en œuvre à une température comprise entre 10 et 400C, avantageusement entre 15 et 300C et, plus particulièrement, à température ambiante (i.e. 23°C ± 5°C) pendant une durée comprise entre 1 et 45 min, notamment entre 5 et 30 min et, en particulier, pendant 15 min. Mixing is carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, and can be implemented at a temperature of between 10 and 40 ° C., advantageously between 15 and 30 ° C. and more particularly at ambient temperature (ie 23 ° C. ± 5 ° C.) for a period of between 1 and 45 minutes, in particular between 5 and 30 minutes and, in particular, for 15 minutes.
Le (ou les) tensioactif (s) utilisable (s) dans le cadre de la présente invention vise (nt) à introduire des espèces hydrophiles dans un environnement hydrophobe et peu (ven) t être choisi (s) parmi les tensioactifs ioniques, les tensioactifs non- ioniques et leurs mélanges. Par « mélanges », on entend, dans le cadre de la présente invention, un mélange d'au moins deux tensioactifs ioniques différents, un mélange d'au moins deux tensioactifs non-ioniques différents ou un mélange d'au moins un tensioactif non-ionique et d'au moins un tensioactif ionique .
Un tensioactif ionique peut notamment se présenter sous forme d'une chaîne hydrocarbonée, chargée dont la charge est contre-balancée par un contre-ion. A titre d'exemples non limitatifs de tensioactifs ioniques, on peut citer le bis (2- éthylhexyl suifosuccinate) de sodium (AOT) , le bromure de cétyltriméthylammonium (CTAB) , le bromure de cétylpyridinium (CPB) et leurs mélanges. The surfactant (s) that may be used in the context of the present invention aims to introduce hydrophilic species in a hydrophobic environment and may be chosen from ionic surfactants, nonionic surfactants and mixtures thereof By "mixtures" is meant, in the context of the present invention, a mixture of at least two different ionic surfactants, a mixture of at least two different nonionic surfactants or a mixture of at least one nonionic surfactant. ionic agent and at least one ionic surfactant. An ionic surfactant may in particular be in the form of a hydrocarbon chain, charged whose charge is counterbalanced by a counter-ion. As non-limiting examples of ionic surfactants, mention may be made of sodium bis (2-ethylhexyl sulphosuccinate) (AOT), cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and mixtures thereof.
Un tensioactif non-ionique utilisable dans le cadre de la présente invention peut être choisi dans le groupe constitué par les alcools polyéthoxylés, les phénols polyéthoxylés, les oléates, les laurates et leurs mélanges. A titre d'exemples non limitatifs de tensioactifs non-ioniques commerciaux, on peut citer les Triton X tels que le Triton X-IOO ; les Brij tels que Brij -30 ; les Igepal CO tels que le Igepal CO-720 ; les Tween tels que le Tween 20 ; les Span tels que le Span 85. A nonionic surfactant that may be used in the context of the present invention may be chosen from the group consisting of polyethoxylated alcohols, polyethoxylated phenols, oleates, laurates and their mixtures. As non-limiting examples of commercial nonionic surfactants, mention may be made of Triton X such as Triton X-100; Brij such as Brij -30; Igepal COs such as Igepal CO-720; Tween such as Tween 20; Spans such as the Span 85.
Avantageusement, le tensioactif utilisé dans le cadre de la présente invention est du Triton X-IOO. Advantageously, the surfactant used in the context of the present invention is Triton X-100.
Un co-tensioactif peut éventuellement être ajouté dans la solution (Mi) . A co-surfactant may optionally be added to the solution (Mi).
Par « co-tensioactif », on entend dans le cadre de la présente invention un agent capable de faciliter la formation des microémulsions et de les stabiliser. Avantageusement, ledit co-tensioactif est un composé amphiphile choisi dans le groupe constitué par un sulfate d'alkyle sodique à 8 à 20 atomes de carbone tel que le SDS (pour « Sodium Dodecyl Sulfate ») ; un alcool tel qu'un isomère de propanol,
de butanol, de pentanol et d'hexanol ; un glycol et leurs mélanges. By "co-surfactant" is meant in the context of the present invention an agent capable of facilitating the formation of microemulsions and stabilize them. Advantageously, said co-surfactant is an amphiphilic compound chosen from the group consisting of a sodium alkyl sulphate of 8 to 20 carbon atoms, such as SDS (for "sodium dodecyl sulphate"); an alcohol such as an isomer of propanol, butanol, pentanol and hexanol; a glycol and their mixtures.
Avantageusement, le co-tensioactif utilisé dans le cadre de la présente invention est du n-hexanol. Advantageously, the co-surfactant used in the context of the present invention is n-hexanol.
Tout solvant non-polaire ou faiblement polaire est utilisable dans le cadre de la présente invention. Avantageusement, ledit solvant non-polaire ou faiblement polaire est un solvant organique non- polaire ou faiblement polaire et, notamment, choisi dans le groupe constitué par le n-butanol, l'hexanol, le cyclopentane, le pentane, le cyclohexane, le n-hexane, le cycloheptane, le n-heptane, le n-octane, 1' iso-octane, l' hexadécane, l'éther de pétrole, le benzène, l' isobutyl-benzène, le toluène, le xylène, les cumènes, le diéthyl éther, le n-butyl acétate, l'isopropyl myristate et leurs mélanges. Any non-polar or weakly polar solvent is usable in the context of the present invention. Advantageously, said non-polar or weakly polar solvent is a nonpolar or slightly polar organic solvent and, in particular, selected from the group consisting of n-butanol, hexanol, cyclopentane, pentane, cyclohexane, n hexane, cycloheptane, n-heptane, n-octane, iso-octane, hexadecane, petroleum ether, benzene, isobutylbenzene, toluene, xylene, cumenes, diethyl ether, n-butyl acetate, isopropyl myristate and mixtures thereof.
Avantageusement, le solvant non-polaire ou faiblement polaire utilisé dans le cadre de la présente invention est du cyclohexane. Advantageously, the non-polar or weakly polar solvent used in the context of the present invention is cyclohexane.
Dans la solution (Mi) , le tensioactif est présent dans une proportion comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % en volume par rapport au volume total de ladite solution. Le co-tensioactif est éventuellement présent, dans la solution (Mi) , dans une proportion comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % en volume par rapport au volume total de ladite solution. Ainsi, le solvant non- polaire ou faiblement polaire est présent, dans la solution (Mi) , dans une proportion comprise entre 40 et
98 %, notamment entre 50 et 90 % et, en particulier, entre 60 et 80 % en volume par rapport au volume total de ladite solution. In the solution (Mi), the surfactant is present in a proportion of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20% by volume relative to the total volume of said solution. The co-surfactant is optionally present in the solution (Mi) in a proportion of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20% by volume relative to the total volume of said solution. Thus, the non-polar or weakly polar solvent is present in the solution (Mi) in a proportion of between 40 and 98%, especially between 50 and 90% and, in particular, between 60 and 80% by volume relative to the total volume of said solution.
Une fois la solution (Mi) préparée, le (ou les) dérivé (s) siliconé(s) de phtalocyanine tel (s) que précédemment défini (s) est (sont) incorporé (s) pour former la microémulsion (Ma) du type eau dans huile. Once the solution (Mi) has been prepared, the phthalocyanine silicone derivative (s) as previously defined is (are) incorporated to form the microemulsion (M a ). water-in-oil type.
Le (ou les) dérivé (s) siliconé(s) de phtalocyanine peu (ven) t être ajouté (s) sous forme solide, sous forme liquide ou en solution dans un solvant polaire. Lorsque plusieurs dérivés siliconés de phtalocyanine différents sont utilisés, ils peuvent être mélangés en une fois ou être ajoutés les uns après les autres ou par groupe. The silicone derivative (s) phthalocyanine can be added in solid form, in liquid form or in solution in a polar solvent. When several different silicone phthalocyanine derivatives are used, they may be mixed at one time or added one after the other or in groups.
Quelle que soit la variante mise en œuvre, un solvant polaire est rajouté à la microémulsion (Ma) après l'incorporation dudit (ou desdits) dérivé (s) siliconé(s) de phtalocyanine dans la solution (Mi). Avantageusement, le (ou les) dérivé (s) siliconé(s) de phtalocyanine est (sont) ajouté (s) à la solution (Mi) en solution dans un solvant polaire puis du solvant polaire, identique ou différent du premier, est encore ajouté. Plus particulièrement, les deux solvants polaires utilisés sont identiques. En variante, les deux solvants polaires utilisés sont différents mais au moins partiellement miscibles : par exemple du THF et de l'eau. L'ajout du dérivé siliconé de phtalocyanine et éventuellement du solvant polaire peut être effectué sous agitation en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur .
Par « solvant polaire », on entend dans le cadre de la présente invention un solvant choisi dans le groupe constitué par l'eau, l'eau désionisée, l'eau distillée, acidifiées ou basiques, les solvants hydroxylés comme le méthanol et l'éthanol, les glycols liquides de faible poids moléculaire tels que 1 ' éthylèneglycol, le diméthylsulfoxyde (DMSO), 1' acétonitrile, l'acétone, le tétrahydrofurane (THF) et leurs mélanges. Whatever the variant used, a polar solvent is added to the microemulsion (M a ) after the incorporation of said silicone derivative (s) in the solution (Mi). Advantageously, the silicone derivative (s) of phthalocyanine is (are) added to the solution (Mi) in solution in a polar solvent and then the polar solvent, which is identical to or different from the first, is still added. More particularly, the two polar solvents used are identical. Alternatively, the two polar solvents used are different but at least partially miscible: for example THF and water. The addition of the silicone derivative of phthalocyanine and optionally the polar solvent may be carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer. By "polar solvent" is meant in the context of the present invention a solvent selected from the group consisting of water, deionized water, distilled water, acidified or basic, hydroxylated solvents such as methanol and sodium hydroxide. ethanol, low molecular weight liquid glycols such as ethylene glycol, dimethyl sulfoxide (DMSO), acetonitrile, acetone, tetrahydrofuran (THF) and mixtures thereof.
Le solvant polaire ou le mélange de solvants polaires (solvant polaire dans lequel le (ou les) dérivé (s) siliconé(s) de phtalocyanine est (sont) en solution et/ou autre solvant polaire ultérieurement ajouté) est présent, dans la microémulsion (Ma) , dans une proportion comprise entre 0,5 et 20 %, notamment entre 1 et 15 % et, en particulier, entre 2 et 10 % en volume par rapport au volume total de ladite microémulsion. Le (ou les) dérivé (s) siliconé(s) de phtalocyanine est (sont) présent (s) dans ce solvant polaire ou ce mélange de solvants polaires en une quantité comprise entre 0,05 et 10 %, notamment entre 0,1 et 5 % et, en particulier, entre 0,2 et 1 % en volume par rapport au volume total de solvant polaire. L'étape (b) est optionnelle. Lorsqu'elle est mise en œuvre, elle consiste à incorporer dans la microémulsion (Ma) ainsi obtenue un composé à base de silane ou plusieurs composés à base de silane, identiques ou différents, qui donnera (ont) , tout comme le (ou les) dérivé (s) siliconé(s) de phtalocyanine par réaction sol-gel la silice des particules de silice
selon l'invention. L'incorporation dans la microémulsion (Ma) du (ou des) composé (s) à base de silane pour obtenir la microémulsion (Mb) du type eau dans huile est effectuée par injection, avantageusement suivie par une agitation en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur, et peut être mise en œuvre à une température comprise entre 10 et 400C, avantageusement entre 15 et 300C et, plus particulièrement, à température ambiante (i.e. 23°C ± 5°C) pendant une durée comprise entre 5 min et 2 h, notamment entre 15 min et 1 h et, en particulier, pendant 30 min. The polar solvent or the mixture of polar solvents (polar solvent in which the phthalocyanine silicone derivative (s) is (are) in solution and / or other polar solvent subsequently added) is present in the microemulsion (M a ), in a proportion of between 0.5 and 20%, especially between 1 and 15% and, in particular, between 2 and 10% by volume relative to the total volume of said microemulsion. The silicone derivative (s) phthalocyanine (s) is (are) present in this polar solvent or this mixture of polar solvents in an amount between 0.05 and 10%, especially between 0.1 and 5% and, in particular, between 0.2 and 1% by volume relative to the total volume of polar solvent. Step (b) is optional. When it is used, it consists in incorporating in the microemulsion (M a ) thus obtained a silane compound or several silane compounds, identical or different, which will give (have), just like the (or the silicone derivative (s) of phthalocyanine by sol-gel reaction the silica of the silica particles according to the invention. The incorporation into the microemulsion (M a ) of the silane-based compound (s) to obtain the microemulsion (M b ) of the water-in-oil type is carried out by injection, advantageously followed by stirring using a stirrer. , a magnetic bar, an ultrasonic bath or a homogenizer, and may be implemented at a temperature of between 10 and 40 ° C., advantageously between 15 and 30 ° C. and, more particularly, at room temperature (ie 23 ° C. ± 5 ° C) for a period of between 5 min and 2 h, in particular between 15 min and 1 h and, in particular, for 30 min.
Avantageusement, ledit (ou lesdits) composé (s) à base de silane est (sont) un alkylsilane ou un alcoxysilane . Plus particulièrement, ledit (ou lesdits) composé (s) à base de silane est (sont) de formule générale SiRaRbRcRd dans laquelle Ra, Rb, Rc et Rd sont, indépendamment les uns des autres, choisis dans le groupe constitué par un hydrogène ; un halogène ; un groupe aminé ; un groupe diamine ; un groupe amide ; un groupe acyle ; un groupe vinyle ; un groupe hydroxyle ; un groupe époxy ; un groupe phosphonate ; un groupe acide sulfonique ; un groupe isocyanate ; un groupe carboxyle ; un groupe thiol (ou mercapto) ; un groupe glycidoxy ; un groupe acryloxy tel qu'un groupe méthacryloxy ; un groupe alkyle, linéaire ou ramifié, éventuellement substitué, de 1 à 12 atomes de carbone, notamment de 1 à 6 atomes de carbone ; un groupe aryle, linéaire ou ramifié, éventuellement substitué, de 4 à 15 atomes de carbone, notamment de 4 à 10 atomes de carbone ; un groupe alcoxyle de formule -ORe avec Re
représentant un groupe alkyle tel que précédemment défini et leurs sels. Advantageously, said silane-based compound (s) is (are) an alkylsilane or an alkoxysilane. More particularly, said silane-based compound (s) is (are) of the general formula SiR a R b R c Rd in which R a , R b , R c and R d are, independently of one another selected from the group consisting of hydrogen; a halogen; an amino group; a diamine group; an amide group; an acyl group; a vinyl group; a hydroxyl group; an epoxy group; a phosphonate group; a sulfonic acid group; an isocyanate group; a carboxyl group; a thiol group (or mercapto); a glycidoxy group; an acryloxy group such as a methacryloxy group; an alkyl group, linear or branched, optionally substituted, of 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; an aryl group, linear or branched, optionally substituted, of 4 to 15 carbon atoms, in particular of 4 to 10 carbon atoms; an alkoxyl group of formula -OR e with R e representing an alkyl group as defined above and their salts.
Par « éventuellement substitué », on entend, dans le cadre des groupes alkyle et aryle des composés à base de silane, substitué par un halogène, un groupe aminé, un groupe diamine, un groupe amide, un groupe acyle, un groupe vinyle, un groupe hydroxyle, un groupe epoxy, un groupe phosphonate, un groupe acide sulfonique, un groupe isocyanate, un groupe carboxyle, un groupe thiol (ou mercapto) , un groupe glycidoxy ou un groupe acryloxy et notamment un groupe méthacryloxy . By "optionally substituted" is meant, in the context of alkyl and aryl groups, silane compounds substituted with halogen, amino group, diamine group, amide group, acyl group, vinyl group, hydroxyl group, an epoxy group, a phosphonate group, a sulfonic acid group, an isocyanate group, a carboxyl group, a thiol (or mercapto) group, a glycidoxy group or an acryloxy group and especially a methacryloxy group.
Le composé à base de silane est, plus particulièrement, choisi dans le groupe constitué par le diméthylsilane (DMSi), le phényltriéthoxysilane (PTES), le tétraéthoxysilane (TEOS), le n-octyltriéthoxysilane, le n-octadécyltriéthoxysilane, le diméthyldiméthoxysilane (DMDMOS), le (3- mercaptopropyl) triméthoxysilane, le (3- mercaptopropyl) triéthoxysilane, le (mercapto) - triéthoxysilane, le (3-aminopropyl) triéthoxysilane, le 3- (2-aminoéthylamino) propyltriméthoxysilane, le 3- [bis (2-hydroxyéthyl) amino] propyltriéthoxysilane, The silane-based compound is, more particularly, selected from the group consisting of dimethylsilane (DMSi), phenyltriethoxysilane (PTES), tetraethoxysilane (TEOS), n-octyltriethoxysilane, n-octadecyltriethoxysilane, dimethyldimethoxysilane (DMDMOS) (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (mercapto) triethoxysilane, (3-aminopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- [bis (2- hydroxyethyl) amino] propyltriethoxysilane,
1' hexadécyltriméthoxysilane, le phényltriméthoxysilane, le N- [ 3- (triméthoxysilyl) propyl ] -1 , 2-ethanediamine et 1' acétoxyéthyltriéthoxysilane, le 2-hydroxy-4- (3- triéthoxysilylpropoxy) diphénylkétone, le méthyl- triéthoxysilane, le vinyltriméthoxysilane, le (3- glycidoxypropyl) triméthoxysilane, leHexadecyltrimethoxysilane, phenyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine and acetoxyethyltriethoxysilane, 2-hydroxy-4- (3-triethoxysilylpropoxy) diphenyl ketone, methyltriethoxysilane, vinyltrimethoxysilane; , (3-glycidoxypropyl) trimethoxysilane,
(benzoyloxypropyl) triméthoxysilane, le 3- trihydroxysilylpropylméthylphosphonate de sodium, l'acide (3-trihydroxysilyl) -1-propanesulphonique, le
(diéthylphosphonatoéthyl) triéthoxysilane, et leurs mélanges. De façon plus particulière, le composé à base de silane est le tétraéthoxysilane (TEOS, Si(OC2H5)4). (benzoyloxypropyl) trimethoxysilane, sodium 3-trihydroxysilylpropylmethylphosphonate, (3-trihydroxysilyl) -1-propanesulphonic acid, (diethylphosphonatoethyl) triethoxysilane, and mixtures thereof. More particularly, the silane compound is tetraethoxysilane (TEOS, Si (OC 2 H 5 ) 4 ).
En vue de la fonctionnalisation de la surface des particules de silice obtenues selon l'invention, le composé à base de silane mis en œuvre peut être un mélange contenant moins de 20% et notamment de 5 à 15% d'un silane préfonctionnalisé par rapport à la quantité totale de composés à base de silane. A titre d'exemple, un mélange contenant du TEOS et de 5 à 15% de mercaptotriéthoxysilane peut être utilisé pour la préparation de particules de silice selon l'invention et fonctionnalisées par des groupements thiol. In order to functionalize the surface of the silica particles obtained according to the invention, the silane compound used may be a mixture containing less than 20% and in particular 5 to 15% of a prefunctionalized silane relative to to the total amount of silane compounds. By way of example, a mixture containing TEOS and 5 to 15% of mercaptotriethoxysilane may be used for the preparation of silica particles according to the invention and functionalized with thiol groups.
Dans la microémulsion (Mb) , le (ou les) composé (s) à base de silane est (sont) présent (s) dans une proportion comprise entre 0,05 et 20 %, notamment entre 0,1 et 10 % et, en particulier, entre 0,5 et 5 % en volume par rapport au volume total de ladite microémulsion. In the microemulsion (M b ), the silane-based compound (s) is (are) present in a proportion of between 0.05 and 20%, especially between 0.1 and 10%, and in particular between 0.5 and 5% by volume relative to the total volume of said microemulsion.
L'étape (c) du procédé selon l'invention vise à prévoir l'hydrolyse d'un composé à base de silane en ajoutant à la microémulsion (Mb) un composé permettant cette hydrolyse, la microémulsion (Mc) ainsi obtenue étant une microémulsion eau dans huile. Il convient de remarquer que par « composé permettant l'hydrolyse de composés à base de silane », on entend un composé permettant non seulement l'hydrolyse d'un composé à base de silane mais aussi l'hydrolyse d'un dérivé siliconé de phtalocyanine .
Le composé permettant l'hydrolyse du composé à base de silane est avantageusement choisi dans le groupe constitué par l'ammoniaque, l'hydroxyde de sodium (KOH), l'hydroxyde de lithium (LiOH) et l'hydroxyde de sodium (NaOH) et, avantageusement, une solution d'un tel composé dans un solvant polaire, identique ou différent, au solvant polaire mis en œuvre lors de l'étape (b) . Le composé permettant l'hydrolyse du composé à base de silane est, plus particulièrement, de l'ammoniaque ou une solution d'ammoniaque dans un solvant polaire tel que précédemment défini. En effet, l'ammoniaque agit comme réactif (H2O) et comme catalyseur (NH4OH) de l'hydrolyse du composé à base de silane ou du dérivé siliconé de phtalocyanine . Step (c) of the process according to the invention aims to provide for the hydrolysis of a silane-based compound by adding to the microemulsion (M b ) a compound allowing this hydrolysis, the microemulsion (M c ) thus obtained being a microemulsion water in oil. It should be noted that the term "compound allowing the hydrolysis of silane-based compounds" means a compound which allows not only the hydrolysis of a silane-based compound but also the hydrolysis of a silicone phthalocyanine derivative. . The compound for hydrolyzing the silane compound is preferably selected from the group consisting of ammonia, sodium hydroxide (KOH), lithium hydroxide (LiOH) and sodium hydroxide (NaOH) and, advantageously, a solution of such a compound in a polar solvent, identical or different, to the polar solvent used during step (b). The compound for hydrolyzing the silane-based compound is, more particularly, ammonia or a solution of ammonia in a polar solvent as defined above. Indeed, ammonia acts as reagent (H 2 O) and as catalyst (NH 4 OH) of the hydrolysis of the silane-based compound or silicone phthalocyanine derivative.
Le composé permettant l'hydrolyse du composé à base de silane, lorsqu'il est en solution dans le solvant polaire, est présent dans une proportion comprise entre 5 et 50 %, notamment entre 10 et 40 % et, en particulier, entre 20 et 30 % en volume par rapport au volume total de ladite solution. De plus, ladite solution est présente dans une proportion comprise entre 0,05 et 20 %, notamment entre 0,1 et 10 % et, en particulier, entre 0,5 et 5 % en volume par rapport au volume total de la microémulsion (Mc) . The compound allowing the hydrolysis of the silane-based compound, when in solution in the polar solvent, is present in a proportion of between 5 and 50%, in particular between 10 and 40% and, in particular, between 20 and 50%. 30% by volume relative to the total volume of said solution. In addition, said solution is present in a proportion of between 0.05 and 20%, especially between 0.1 and 10% and, in particular, between 0.5 and 5% by volume relative to the total volume of the microemulsion ( M c ).
L'étape (c) peut être mise en œuvre sous agitation en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur, et à une température comprise entre 10 et 400C, avantageusement entre 15 et 300C et, plus particulièrement, à température ambiante (i.e. 23°C ± 5°C) pendant une durée comprise entre 6 et 48 h,
notamment entre 12 et 36 h et, en particulier, pendant 24 h. Step (c) may be carried out with stirring using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, and at a temperature of between 10 and 40 ° C., advantageously between 15 and 30 ° C., and more particularly at ambient temperature (ie 23 ° C. ± 5 ° C.) for a period of between 6 and 48 hours, especially between 12 and 36 h and, in particular, for 24 h.
Lorsque le composé à base de silane utilisé est du TEOS, la réaction qui intervient lors de l'étape When the silane compound used is TEOS, the reaction that occurs during the step
(c) du procédé i.e. la condensation du dérivé siliconé de phtalocyanine avec du TEOS en présence d' ammoniaque peut être schématisée de la façon suivante : (c) the process i.e. the condensation of the silicone phthalocyanine derivative with TEOS in the presence of ammonia can be schematized as follows:
OH OH
L'étape (d) du procédé selon l'invention vise à précipiter les particules de silice par addition d'un solvant qui ne dénature pas la structure des particules mais qui déstabilise ou dénature la microémulsion (Mc) obtenue à l'étape (c) . Step (d) of the process according to the invention aims at precipitating the silica particles by adding a solvent which does not denature the structure of the particles but which destabilizes or denatures the microemulsion (M c ) obtained in step ( vs) .
Avantageusement, le solvant mis en œuvre est un solvant polaire tel que précédemment défini. Un solvant polaire particulier à mettre en œuvre lors de l'étape (d) est choisi dans le groupe constitué par l'éthanol, l'acétone et le méthanol. Avantageusement, le solvant utilisé lors de l'étape (d) du procédé selon l'invention est de l'éthanol. Ainsi, est ajouté, à la
microémulsion (Mc) , un volume de solvant supérieur au volume de ladite microémulsion, notamment supérieur d'un facteur 1,5 ; en particulier, supérieur d'un facteur 2 ; et voire supérieur d'un facteur 3. Advantageously, the solvent used is a polar solvent as defined above. A particular polar solvent to be used in step (d) is selected from the group consisting of ethanol, acetone and methanol. Advantageously, the solvent used in step (d) of the process according to the invention is ethanol. So, is added, at the microemulsion (M c ), a volume of solvent greater than the volume of said microemulsion, in particular greater by a factor of 1.5; in particular, greater by a factor of 2; and even a factor of 3.
Toute technique permettant de récupérer les particules de silice incorporant au moins un dérivé de phtalocyanine, précipitées lors de l'étape (d) peut être mise en œuvre lors de l'étape (e) du procédé selon l'invention. Avantageusement, cette étape (e) met en œuvre une ou plusieurs étapes, identiques ou différentes, choisies parmi les étapes de centrifugation, de sédimentation et de lavages. La (ou les) étape (s) de lavage est (sont) effectuée (s) dans un solvant polaire tel que précédemment défini. Lorsque l'étape de récupération met en œuvre plusieurs lavages, un même solvant polaire est utilisé pour plusieurs voire pour tous les lavages ou plusieurs solvants polaires différents sont utilisés à chaque lavage. Concernant une (ou plusieurs) étape (s) de centrifugation, elle (s) peu (ven) t être mise (s) en œuvre en centrifugeant les particules de silice notamment dans un solvant de lavage à température ambiante, à une vitesse comprise entre 4000 et 8000 rpm et, en particulier, de l'ordre de 6000 rpm (i.e. 6000 ± 500 rpm) et ce, pendant une durée comprise entre 5 min et 2 h, notamment entre 10 min et 1 h et, en particulier, pendant 15 min. Le procédé selon la présente invention peut comprendre, suite à l'étape (e) , une étape
supplémentaire consistant à purifier les particules de silice obtenues ci-après désignée « étape (f) ». Any technique making it possible to recover the silica particles incorporating at least one phthalocyanine derivative, precipitated during step (d) may be implemented during step (e) of the process according to the invention. Advantageously, this step (e) implements one or more steps, identical or different, chosen from the centrifugation, sedimentation and washing steps. The washing step (s) is (are) carried out in a polar solvent as defined above. When the recovery step uses several washes, the same polar solvent is used for several or even all washes or several different polar solvents are used at each wash. Regarding one (or more) centrifugation stage (s), it (they) can be implemented by centrifuging the silica particles, in particular in a washing solvent at ambient temperature, at a speed between 4000 and 8000 rpm and, in particular, of the order of 6000 rpm (ie 6000 ± 500 rpm) and this, for a period of between 5 min and 2 h, in particular between 10 min and 1 h and, in particular, during 15 min. The method according to the present invention may comprise, after step (e), a step further comprising purifying the silica particles obtained hereinafter referred to as "step (f)".
Avantageusement, cette étape (f) consiste à mettre les particules de silice récupérées après l'étape (e) du procédé selon l'invention au contact d'un très large volume d'eau. Par « très large volume », on entend un volume supérieur d'un facteur 50, notamment d'un facteur 500 et, en particulier, d'un facteur 1000 au volume de particules de silice, récupérées après l'étape (e) du procédé selon l'invention. L'étape (f) peut être une étape de dialyse, les particules de silice étant séparées du volume par une membrane de cellulose, du type Zellu trans (société Roth) . Alternativement, on peut prévoir une étape d' ultrafiltration à la place de l'étape de dialyse, via une membrane en polyéthersulfone . L'étape Advantageously, this step (f) consists in putting the recovered silica particles after step (e) of the process according to the invention in contact with a very large volume of water. By "very large volume" is meant a volume greater by a factor of 50, in particular by a factor of 500 and, in particular, by a factor of 1000 to the volume of silica particles, recovered after step (e) of process according to the invention. Step (f) may be a dialysis step, the silica particles being separated from the volume by a cellulose membrane, of the Zellu trans type (Roth company). Alternatively, an ultrafiltration step may be provided instead of the dialysis step, via a polyethersulfone membrane. step
(f) peut, de plus, être mise en œuvre sous agitation en utilisant un agitateur, un barreau magnétique, un bain à ultrasons ou un homogénéisateur, à une température comprise entre 0 et 300C, avantageusement entre 2 et 200C et, plus particulièrement, à froid (i.e. 6°C ± 2°C) et ce, pendant une durée comprise entre 30 h et 15 j, notamment entre 3 j et 10 j et, en particulier, pendant 1 semaine. (f) may, in addition, be carried out under agitation using a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, at a temperature of between 0 and 30 ° C., advantageously between 2 and 20 ° C., and more particularly, cold (ie 6 ° C ± 2 ° C) and this, for a period of between 30 h and 15 d, especially between 3 and 10 days and, in particular, for 1 week.
La présente invention concerne également la microémulsion (Mc) susceptible d'être mise en œuvre dans le cadre du procédé selon l'invention. Cette microémulsion de type eau dans huile comprend : The present invention also relates to the microemulsion (M c ) that can be implemented in the context of the process according to the invention. This microemulsion of water-in-oil type comprises:
- au moins un tensioactif, notamment tel que précédemment défini,
éventuellement au moins un co- tensioactif, notamment tel que précédemment défini, at least one surfactant, especially as defined above, optionally at least one cosurfactant, especially as defined above,
au moins un solvant non-polaire ou faiblement polaire, notamment tel que précédemment défini, at least one non-polar or weakly polar solvent, especially as defined above,
au moins un solvant polaire, notamment tel que précédemment défini, at least one polar solvent, especially as defined above,
au moins un dérivé siliconé de phtalocyanine notamment tel que précédemment défini, at least one silicone phthalocyanine derivative, especially as defined above,
- éventuellement au moins un composé à base de silane, notamment tel que précédemment défini, et - optionally at least one silane-based compound, especially as defined above, and
- au moins un composé capable d'hydrolyser un composé à base de silane, notamment tel que précédemment défini. at least one compound capable of hydrolyzing a compound based on silane, in particular as previously defined.
Avantageusement, la microémulsion de type eau dans huile objet de la présente invention comprend : Advantageously, the water-in-oil microemulsion which is the subject of the present invention comprises:
- au moins un tensioactif en une quantité comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % ; at least one surfactant in an amount of between 1 and 30%, in particular between 5 and 25% and, in particular, between 10 and 20%;
- éventuellement au moins un co-tensioactif en une quantité comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % ; - optionally at least one co-surfactant in an amount of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20%;
au moins un solvant non-polaire ou faiblement polaire en une quantité comprise entre 40 et 95 %, notamment entre 50 et 90 % et, en particulier, entre 60 et 80 % ; at least one non-polar or weakly polar solvent in an amount of between 40 and 95%, especially between 50 and 90% and, in particular, between 60 and 80%;
au moins un solvant polaire en une quantité comprise entre 0,5 et 20 %, notamment entre 1 et 15 % et, en particulier, entre 2 et 10 % ;
au moins un dérivé siliconé de phtalocyanine en une quantité comprise entre 0,001 et 1 %, notamment entre 0,005 et 0,1 % et, en particulier, entre 0,001 et 0,05 % ; at least one polar solvent in an amount of between 0.5 and 20%, especially between 1 and 15% and, in particular, between 2 and 10%; at least one silicone phthalocyanine derivative in an amount of between 0.001 and 1%, in particular between 0.005 and 0.1% and, in particular, between 0.001 and 0.05%;
- éventuellement au moins un composé à base de silane en une quantité comprise entre 0,05 et 20 %, notamment entre 0,1 et 10 % et, en particulier, entre 0,5 et 5 % ; et - optionally at least one silane compound in an amount of between 0.05 and 20%, especially between 0.1 and 10% and, in particular, between 0.5 and 5%; and
- au moins un composé capable d'hydrolyser ledit composé à base de silane en une quantité comprise entre 0,01 et 5 %, notamment entre 0,05 et 1 % et, en particulier, entre 0,1 et 0,5 %, at least one compound capable of hydrolyzing said silane-based compound in an amount of between 0.01 and 5%, especially between 0.05 and 1% and, in particular, between 0.1 and 0.5%,
les quantités étant exprimées en volume par rapport au volume de ladite microémulsion . the quantities being expressed in volume relative to the volume of said microemulsion.
La présente invention concerne, de plus, une particule de silice susceptible d'être préparée par le procédé de la présente invention. Cette particule est une particule de silice comprenant au moins un dérivé de phtalocyanine, telle que précédemment définie. Elle se distingue des particules de silice de l'état de la technique de par les deux liaisons covalentes qui lient l'atome Si au dérivé de phtalocyanine, le dérivé de phtalocyanine n'étant pas un groupement qui fonctionnalise la particule de silice. En effet, les liaisons covalentes qui lient l'atome Si avec le dérivé de phtalocyanine sont conservées dans la particule de silice formée à l'issue du procédé selon l'invention. Ainsi, il existe une interaction forte entre la structure en réseau de la particule de silice et le (ou les) dérivé (s) de
phtalocyanine par la présence des liaisons covalentes. Par conséquent, le dérivé de phtalocyanine est lié de façon covalente au réseau de silice de la particule selon l'invention. The present invention further relates to a silica particle capable of being prepared by the process of the present invention. This particle is a silica particle comprising at least one phthalocyanine derivative, as previously defined. It differs from the silica particles of the state of the art by the two covalent bonds which bind the Si atom to the phthalocyanine derivative, the phthalocyanine derivative not being a moiety which functionalizes the silica particle. Indeed, the covalent bonds which bind the Si atom with the phthalocyanine derivative are retained in the silica particle formed at the end of the process according to the invention. Thus, there is a strong interaction between the network structure of the silica particle and the derivative (s) of phthalocyanine by the presence of covalent bonds. Therefore, the phthalocyanine derivative is covalently bonded to the silica network of the particle according to the invention.
Avantageusement, les particules de silice selon l'invention sont des nanoparticules présentant une taille moyenne inférieure ou égale à 100 nm, notamment comprise entre 10 et 80 nm, en particulier comprise entre 20 et 60 nm et, voire, de l'ordre de 40 nm (i.e. 40 ± 10 nm) . Les particules de silice selon l'invention peuvent être éventuellement fonctionnalisées. De plus, les particules de silice selon l'invention peuvent être éventuellement poreuses. La présente invention concerne enfin l'utilisation d'une particule de silice selon l'invention dans des domaines choisis dans le groupe constitué par la catalyse, l'imprimerie, les peintures, la filtration, la polymérisation, l'échange thermique, la stabilité thermique, la chimie des matériaux, le raffinage d'hydrocarbures, la production d'hydrogène, les absorbants, l'industrie alimentaire, le transport d'agents actifs, les biomolécules, les produits pharmaceutiques, les revêtements calorifuges, les composés bioélectroniques et les dispositifs électroniques, optiques, de semi-conducteurs et de capteurs . Advantageously, the silica particles according to the invention are nanoparticles having a mean size less than or equal to 100 nm, in particular between 10 and 80 nm, in particular between 20 and 60 nm and, even, of the order of 40. nm (ie 40 ± 10 nm). The silica particles according to the invention may be optionally functionalized. In addition, the silica particles according to the invention may be optionally porous. The present invention finally relates to the use of a silica particle according to the invention in fields selected from the group consisting of catalysis, printing, painting, filtration, polymerization, heat exchange, stability. thermal, materials chemistry, hydrocarbon refining, hydrogen production, sorbents, food industry, active agent transport, biomolecules, pharmaceuticals, heat-insulating coatings, bioelectronic compounds and electronic, optical, semiconductor and sensor devices.
D'autres caractéristiques et avantages de la présente invention apparaîtront encore à l'homme du métier à la lecture des exemples ci-dessous donnés à
titre illustratif et non limitatif, et faisant référence aux figures annexées. Other features and advantages of the present invention will become apparent to those skilled in the art upon reading the examples below given to illustrative and non-limiting, and with reference to the appended figures.
BRÈVE DESCRIPTION DES DESSINS BRIEF DESCRIPTION OF THE DRAWINGS
La Figure 1 présente une vue obtenue par microscopie électronique en transmission (MET) des agglomérats avec des nanoparticules de silice préparées par le procédé selon l'invention. FIG. 1 shows a view obtained by transmission electron microscopy (TEM) of the agglomerates with silica nanoparticles prepared by the process according to the invention.
La Figure 2 présente une vue obtenue par microscopie électronique en transmission (MET) de nanoparticules de silice préparées par le procédé selon l'invention sans agglomérat. FIG. 2 shows a view obtained by transmission electron microscopy (TEM) of silica nanoparticles prepared by the process according to the invention without agglomerate.
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERS I. Procédé de préparation de nanoparticules de silice selon l'invention. DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS I. Process for the Preparation of Silica Nanoparticles According to the Invention
Une solution (solution Mi selon l'invention) a été générée en ajoutant, dans cet ordre, les produits chimiques suivants, le tensioactif Triton XlOO (2,1 mL) , le co-tensioactif n-hexanol (2,05 mL) , le solvant organique cyclohexane (9,38 mL) . La solution était alors agitée à température ambiante pendant 15 min. A solution (Mi solution according to the invention) was generated by adding, in this order, the following chemicals, Triton X100 surfactant (2.1 mL), co-surfactant n-hexanol (2.05 mL), the organic cyclohexane solvent (9.38 mL). The solution was then stirred at room temperature for 15 minutes.
Ensuite, le dérivé de phtalocyanine de silice qu'est le dihydroxyde de 2, 3-naphtalocyanine silane ou en anglais « silicon 2, 3-naphtalocyanine dihydroxide » dans une solution de THF était ajouté (100 μL à 0,1 M dans le THF, M = 774,88 g. mol"1, n = 10~5 mol) suivi par de l'eau (0,5 mL) .
Le dérivé silicone TEOS (tétraéthoxysilane, 125 μL, 5,6 x 10"4 mol, d = 0,934, M = 208,33 gmol"1) était injecté dans cette émulsion. L'émulsion résultante était agitée à température ambiante pendant 30 min. L'hydrolyse du TEOS était initiée par l'addition de l'ammoniaque aqueuse à 25% (125 μL) et le mélange réactionnel était agité pendant 24 h à température ambiante. Then, the silica phthalocyanine derivative, 2,3-naphthalocyanine dihydroxide silane or in English "silicon 2,3-naphthalocyanine dihydroxide" in a solution of THF was added (100 μl at 0.1 M in THF). , M = 774.88 g. mol "1, n = 10 ~ 5 mol) followed by water (0.5 mL). The TEOS silicone derivative (tetraethoxysilane, 125 μl, 5.6 × 10 -4 mol, d = 0.934, M = 208.33 gmol -1 ) was injected into this emulsion. The resulting emulsion was stirred at room temperature for 30 minutes. The hydrolysis of TEOS was initiated by the addition of 25% aqueous ammonia (125 μl) and the reaction mixture was stirred for 24 h at room temperature.
L'émulsion était déstabilisée par l'addition d'éthanol (50 mL) et les billes de silice étaient lavées trois fois à l'éthanol et une fois à l'eau, chaque lavage étant suivi par une sédimentation à la centrifugeuse (15 min à 6000 rpm) . The emulsion was destabilized by the addition of ethanol (50 mL) and the silica beads were washed three times with ethanol and once with water, each wash being followed by centrifuge sedimentation (15 min. at 6000 rpm).
Après l'étape de lavage, la purification des nanoparticules obtenues était achevée par dialyse dans l'eau (1 L) sous agitation magnétique pendant une semaine . After the washing step, the purification of the nanoparticles obtained was completed by dialysis in water (1 L) with magnetic stirring for one week.
II. Caractérisation des nanoparticules de silice selon l'invention. II. Characterization of silica nanoparticles according to the invention.
Les nanoparticules de silice dispersées dans l'eau (40 mL) préparées selon le procédé de la partie I étaient alors caractérisées par analyse en microscope électronique en transmission (MET) qui permet d'apprécier la nanostructure de ces nanoparticules . The silica nanoparticles dispersed in water (40 mL) prepared according to the method of Part I were then characterized by transmission electron microscopy (TEM) analysis which allows to appreciate the nanostructure of these nanoparticles.
Ainsi, sont observés des agglomérats avec des nanoparticules sphériques (Figure 1). La taille de ces nanoparticules varie entre 40 et 50 nm. La Figure 2 montre des nanoparticules sphériques sans agglomérat.
RÉFÉRENCES Thus, agglomerates with spherical nanoparticles are observed (FIG. 1). The size of these nanoparticles varies between 40 and 50 nm. Figure 2 shows spherical nanoparticles without agglomerate. REFERENCES
[I] Brevet US 3,094,536 (Kenney) publié le 18 juin 1963 ; [I] US Patent 3,094,536 (Kenney) published June 18, 1963;
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[20] Demande internationale WO 2008/138727 (CIBA HOLDING Inc) publiée le 20 novembre 2008.
[20] International Application WO 2008/138727 (CIBA HOLDING Inc) published November 20, 2008.
Claims
REVENDICATIONS
1) Procédé de préparation d'une particule de silice incorporant au moins un dérivé de phtalocyanine, ladite particule étant préparée à partir d'au moins un dérivé siliconé de phtalocyanine via une microémulsion inverse. 1) Process for preparing a silica particle incorporating at least one phthalocyanine derivative, said particle being prepared from at least one silicone phthalocyanine derivative via an inverse microemulsion.
2) Procédé selon la revendication 1, caractérisé en ce que ledit dérivé siliconé de phtalocyanine est un composé de formule (I) 2) Process according to claim 1, characterized in that said silicone phthalocyanine derivative is a compound of formula (I)
(I) (I)
dans laquelle in which
- Ri, R2, R3 et R4, identiques ou différents, représentent un groupement arylène éventuellement substitué et R 1, R 2 , R 3 and R 4 , which may be identical or different, represent an optionally substituted arylene group and
- R5 et Rε, identiques ou différents, sont choisis dans le groupe constitué par -Cl, -F, -OH et -OR' avec R' représentant un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué.
3) Procédé selon la revendication 1 ou 2, caractérisé en ce que ledit dérivé siliconé de phtalocyanine est un composé de formule (II) : R 5 and R 6 , which are identical or different, are chosen from the group consisting of -Cl, -F, -OH and -OR 'with R' representing a linear or branched alkyl of 1 to 12 carbon atoms, and especially of 1 to 6 carbon atoms, optionally substituted. 3) Process according to claim 1 or 2, characterized in that said silicone phthalocyanine derivative is a compound of formula (II):
(H) (H)
dans laquelle in which
- les groupements R7 à R22, identiques ou différents, sont choisis dans le groupe constitué par un hydrogène ; un carboxylate ; un aldéhyde ; un ester ; un éther ; un hydroxyle ; un halogène ; un aryle tel qu'un phényle, un benzyle ou un naphthyle ; un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué tel qu'un méthyle, un éthyle, un propyle ou un hydroxypropyle ; une aminé ; un amide ; un sulfonyle ; un suifoxyde et un thiol. the groups R 7 to R 22, which are identical or different, are chosen from the group consisting of hydrogen; a carboxylate; an aldehyde; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol.
les groupements R5 et Re sont tels que définis à la revendication 2.
4) Procédé selon la revendication 1 ou 2, caractérisé en ce que ledit dérivé siliconé de phtalocyanine est un composé de formule (III) du type naphtalocyanine : the groups R 5 and Re are as defined in claim 2. 4) Process according to claim 1 or 2, characterized in that said silicone phthalocyanine derivative is a compound of formula (III) of the naphthalocyanine type:
(III) (III)
dans laquelle in which
- les groupements R23 à R46, identiques ou différents, sont choisis dans le groupe constitué par un hydrogène ; un carboxylate ; un aldéhyde ; un ester ; un éther ; un hydroxyle ; un halogène ; un aryle tel qu'un phényle, un benzyle ou un naphthyle ; un alkyle, linéaire ou ramifié, de 1 à 12 atomes de carbone et notamment de 1 à 6 atomes de carbone, éventuellement substitué tel qu'un méthyle, un éthyle, un propyle ou un hydroxypropyle ; une aminé ; un amide ; un sulfonyle ; un suifoxyde et un thiol.
les groupements R5 et Re sont tels que définis à la revendication 2. the groups R 23 to R 46, which are identical or different, are chosen from the group consisting of hydrogen; a carboxylate; an aldehyde; an ester; an ether; a hydroxyl; a halogen; aryl such as phenyl, benzyl or naphthyl; alkyl, linear or branched, of 1 to 12 carbon atoms and in particular of 1 to 6 carbon atoms, optionally substituted such as methyl, ethyl, propyl or hydroxypropyl; an amine; a friend of ; a sulfonyl; a sulphoxide and a thiol. the groups R 5 and Re are as defined in claim 2.
5) Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ledit procédé comprend les étapes successives suivantes : 5) Method according to any one of claims 1 to 4, characterized in that said method comprises the following successive steps:
a) préparer une microémulsion (Ma) du type eau dans huile contenant au moins un dérivé siliconé de phtalocyanine, a) preparing a microemulsion (M a ) of the water-in-oil type containing at least one silicone phthalocyanine derivative,
b) éventuellement ajouter, à la microémulsion (Ma) obtenue à l'étape (a), au moins un composé à base de silane, b) optionally adding, to the microemulsion (M a ) obtained in step (a), at least one silane-based compound,
c) ajouter, à la microémulsion (Mb) obtenue à l'étape (b) , au moins un composé permettant l'hydrolyse de composés à base de silane, c) adding, to the microemulsion (M b ) obtained in step (b), at least one compound for the hydrolysis of silane compounds,
d) ajouter à la microémulsion (Mc) obtenue à l'étape (c) un solvant permettant de déstabiliser ladite microémulsion, d) adding to the microemulsion (M c ) obtained in step (c) a solvent for destabilizing said microemulsion,
e) récupérer les particules de silice incorporant au moins un dérivé siliconé de phtalocyanine, précipitées lors de l'étape (d) . e) recovering the silica particles incorporating at least one silicone phthalocyanine derivative, precipitated during step (d).
6) Procédé selon la revendication 5, caractérisé en ce que ladite étape (a) consiste à préparer une première solution (Mi) dans laquelle est ultérieurement incorporé un (ou des) dérivé (s) siliconé (s) de phtalocyanine. 6) Process according to claim 5, characterized in that said step (a) comprises preparing a first solution (Mi) in which is subsequently incorporated a (or) silicone derivative (s) phthalocyanine.
7) Procédé selon la revendication 5 ou 6, caractérisé en ce que ladite microémulsion (Mi) du type eau dans huile est obtenue en mélangeant ensemble
- au moins un tensioactif, 7) Process according to claim 5 or 6, characterized in that said microemulsion (Mi) of the water-in-oil type is obtained by mixing together at least one surfactant,
- éventuellement au moins un co-tensioactif et - optionally at least one co-surfactant and
au moins un solvant non-polaire ou faiblement polaire. at least one non-polar or weakly polar solvent.
8) Procédé selon l'une quelconque des revendications 5 à 7, caractérisé en ce qu'un solvant polaire est rajouté à la microémulsion (Ma) après l'incorporation dudit (ou desdits) dérivé (s) siliconé(s) de phtalocyanine dans la solution (Mi). 8) Process according to any one of claims 5 to 7, characterized in that a polar solvent is added to the microemulsion (M a ) after incorporation of (or said) derivative (s) silicone (s) phthalocyanine in the solution (Mi).
9) Procédé selon l'une quelconque des revendications 5 à 8, caractérisé en ce que ledit (ou lesdits) composé (s) à base de silane est (sont) de formule générale : 9) Process according to any one of claims 5 to 8, characterized in that said (or said) compound (s) based on silane is (are) of general formula:
SiRaRbRcRd SiR a R b R c R d
dans laquelle Ra, Rb, Rc et Rd sont, indépendamment les uns des autres, choisis dans le groupe constitué par un hydrogène ; un halogène ; un groupe aminé ; un groupe diamine ; un groupe amide ; un groupe acyle ; un groupe vinyle ; un groupe hydroxyle ; un groupe époxy ; un groupe phosphonate ; un groupe acide sulfonique ; un groupe isocyanate ; un groupe carboxyle ; un groupe thiol (ou mercapto) ; un groupe glycidoxy ; un groupe acryloxy tel qu'un groupe méthacryloxy ; un groupe alkyle, linéaire ou ramifié, éventuellement substitué, de 1 à 12 atomes de carbone, notamment de 1 à 6 atomes de carbone ; un groupe aryle, linéaire ou ramifié, éventuellement substitué, de 4 à 15 atomes de carbone, notamment de 4 à 10 atomes de
carbone ; un groupe alcoxyle de formule -0Re avec Re représentant un groupe alkyle tel que précédemment défini et leurs sels. 10) Procédé selon l'une quelconque des revendications 5 à 9, caractérisé en ce que ledit (ou lesdits) composé (s) à base de silane est (sont) choisi (s) dans le groupe constitué par le diméthylsilane (DMSi), le phényltriéthoxysilane (PTES), le tétraéthoxysilane (TEOS), le n-octyltriéthoxysilane, le n-octadécyltriéthoxysilane, le diméthyldiméthoxysilane (DMDMOS) , le (3- mercaptopropyl) triméthoxysilane, le (3- mercaptopropyl) triéthoxysilane, le (mercapto) - triéthoxysilane, le (3-aminopropyl) triéthoxysilane, le 3- (2-aminoéthylamino) propyltriméthoxysilane, le 3- [bis (2-hydroxyéthyl) amino] propyltriéthoxysilane, wherein R a , R b , R c and R d are, independently of one another, selected from the group consisting of hydrogen; a halogen; an amino group; a diamine group; an amide group; an acyl group; a vinyl group; a hydroxyl group; an epoxy group; a phosphonate group; a sulfonic acid group; an isocyanate group; a carboxyl group; a thiol group (or mercapto); a glycidoxy group; an acryloxy group such as a methacryloxy group; an alkyl group, linear or branched, optionally substituted, of 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; an aryl group, linear or branched, optionally substituted, of 4 to 15 carbon atoms, in particular of 4 to 10 carbon atoms, carbon; an alkoxyl group of formula -OR e with R e representing an alkyl group as defined above and their salts. 10) Process according to any one of claims 5 to 9, characterized in that said (or said) compound (s) based on silane is (are) chosen from the group consisting of dimethylsilane (DMSi), phenyltriethoxysilane (PTES), tetraethoxysilane (TEOS), n-octyltriethoxysilane, n-octadecyltriethoxysilane, dimethyldimethoxysilane (DMDMOS), (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (mercapto) triethoxysilane (3-aminopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- [bis (2-hydroxyethyl) amino] propyltriethoxysilane,
1' hexadécyltriméthoxysilane, le phényltriméthoxysilane, le N- [3- (triméthoxysilyl) propyl] -1, 2-ethanediamine et 1' acétoxyéthyltriéthoxysilane, le 2-hydroxy-4- (3- triéthoxysilylpropoxy) diphénylkétone, le méthyl- triéthoxysilane, le vinyltriméthoxysilane, le (3- glycidoxypropyl) triméthoxysilane, leHexadecyltrimethoxysilane, phenyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine and acetoxyethyltriethoxysilane, 2-hydroxy-4- (3-triethoxysilylpropoxy) diphenyl ketone, methyltriethoxysilane, vinyltrimethoxysilane; , (3-glycidoxypropyl) trimethoxysilane,
(benzoyloxypropyl) triméthoxysilane, le 3- trihydroxysilylpropylméthylphosphonate de sodium, l'acide (3-trihydroxysilyl) -1-propanesulphonique, le (diéthylphosphonatoéthyl) triéthoxysilane, et leurs mélanges . 11) Procédé selon l'une quelconque des revendications 5 à 10, caractérisé en ce que ledit
composé permettant l'hydrolyse du composé à base de silane est choisi dans le groupe constitué par l'ammoniaque, l'hydroxyde de sodium (KOH), l'hydroxyde de lithium (LiOH) et l'hydroxyde de sodium (NaOH) . (benzoyloxypropyl) trimethoxysilane, sodium 3-trihydroxysilylpropylmethylphosphonate, (3-trihydroxysilyl) -1-propanesulphonic acid, (diethylphosphonatoethyl) triethoxysilane, and mixtures thereof. 11) Method according to any one of claims 5 to 10, characterized in that said The compound that hydrolyzes the silane compound is selected from the group consisting of ammonia, sodium hydroxide (KOH), lithium hydroxide (LiOH), and sodium hydroxide (NaOH).
12) Microémulsion (Mc) de type eau dans huile susceptible d'être mise en œuvre dans le cadre d'un procédé tel que défini à l'une quelconque des revendications précédentes, comprenant : 12) Microemulsion (M c ) of water-in-oil type capable of being implemented in the context of a process as defined in any one of the preceding claims, comprising:
- au moins un tensioactif, at least one surfactant,
- éventuellement au moins un co- tensioactif, optionally at least one cosurfactant,
- au moins un solvant non-polaire ou faiblement polaire, at least one non-polar or slightly polar solvent,
- au moins un solvant polaire, at least one polar solvent,
- au moins un dérivé siliconé de phtalocyanine, at least one silicone derivative of phthalocyanine,
- éventuellement au moins un composé à base de silane, et - optionally at least one silane-based compound, and
- au moins un composé capable d'hydrolyser un composé à base de silane. at least one compound capable of hydrolyzing a silane-based compound.
13) Microémulsion selon la revendication 12, caractérisée en ce qu'elle comprend : 13) Microemulsion according to claim 12, characterized in that it comprises:
- au moins un tensioactif en une quantité comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % ; at least one surfactant in an amount of between 1 and 30%, in particular between 5 and 25% and, in particular, between 10 and 20%;
- éventuellement au moins un co-tensioactif en une quantité comprise entre 1 et 30 %, notamment entre 5 et 25 % et, en particulier, entre 10 et 20 % ;
au moins un solvant non-polaire ou faiblement polaire en une quantité comprise entre 40 et 95 %, notamment entre 50 et 90 % et, en particulier, entre 60 et 80 % ; - optionally at least one co-surfactant in an amount of between 1 and 30%, especially between 5 and 25% and, in particular, between 10 and 20%; at least one non-polar or weakly polar solvent in an amount of between 40 and 95%, especially between 50 and 90% and, in particular, between 60 and 80%;
- au moins un solvant polaire en une quantité comprise entre 0,5 et 20 %, notamment entre 1 et 15 % et, en particulier, entre 2 et 10 % ; at least one polar solvent in an amount of between 0.5 and 20%, especially between 1 and 15% and, in particular, between 2 and 10%;
au moins un dérivé siliconé de phtalocyanine en une quantité comprise entre 0,001 et 1 %, notamment entre 0,005 et 0,1 % et, en particulier, entre 0,001 et 0,05 % ; at least one silicone phthalocyanine derivative in an amount of between 0.001 and 1%, in particular between 0.005 and 0.1% and, in particular, between 0.001 and 0.05%;
- éventuellement au moins un composé à base de silane en une quantité comprise entre 0,05 et 20 %, notamment entre 0,1 et 10 % et, en particulier, entre 0,5 et 5 % ; et - optionally at least one silane compound in an amount of between 0.05 and 20%, especially between 0.1 and 10% and, in particular, between 0.5 and 5%; and
- au moins un composé capable d'hydrolyser ledit composé à base de silane en une quantité comprise entre 0,01 et 5 %, notamment entre 0,05 et 1 % et, en particulier, entre 0,1 et 0,5 %, at least one compound capable of hydrolyzing said silane-based compound in an amount of between 0.01 and 5%, especially between 0.05 and 1% and, in particular, between 0.1 and 0.5%,
les quantités étant exprimées en volume par rapport au volume de ladite microémulsion . the quantities being expressed in volume relative to the volume of said microemulsion.
14) Particule de silice comprenant au moins un dérivé de phtalocyanine, susceptible d'être préparée par un procédé tel que défini à l'une quelconque des revendications 1 à 11, ledit dérivé de phtalocyanine étant lié de façon covalente au réseau de silice de ladite particule. 15) Particule de silice selon la revendication 14, caractérisée en ce qu'elle présente
une taille moyenne inférieure ou égale à 100 nm, notamment comprise entre 10 et 80 nm, en particulier comprise entre 20 et 60 nm et, voire, de l'ordre de 40 nm.
14) silica particle comprising at least one phthalocyanine derivative, capable of being prepared by a process as defined in any one of claims 1 to 11, said phthalocyanine derivative being covalently bonded to the silica network of said particle. 15) silica particle according to claim 14, characterized in that it has an average size less than or equal to 100 nm, in particular between 10 and 80 nm, in particular between 20 and 60 nm and, even, of the order of 40 nm.
Applications Claiming Priority (2)
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FR0955843A FR2949471B1 (en) | 2009-08-27 | 2009-08-27 | PROCESS FOR THE PREPARATION OF SILICA PARTICLES CONTAINING A PHTHALOCYANINE DERIVATIVE, THE SAID PARTICLES AND USES THEREOF |
PCT/EP2010/062516 WO2011023783A2 (en) | 2009-08-27 | 2010-08-26 | Method for preparing silica particles containing a phthalocyanine derivative, said particles, and uses thereof |
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EP10747212A Withdrawn EP2470548A2 (en) | 2009-08-27 | 2010-08-26 | Method for preparing silica particles containing a phthalocyanine derivative, said particles, and uses thereof |
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US (1) | US20120156495A1 (en) |
EP (1) | EP2470548A2 (en) |
JP (1) | JP2013503097A (en) |
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FR2971508A1 (en) * | 2011-02-16 | 2012-08-17 | Commissariat Energie Atomique | MICROWAVE IRRADIATION PREPARATION PROCESS OF SILICA PARTICLES CONTAINING PHTALOCYANINE DERIVATIVE, THE SAID PARTICLES AND USES THEREOF |
JP2014129317A (en) * | 2012-02-23 | 2014-07-10 | Canon Inc | Photoacoustic contrast pigment containing nano particle |
EP2859053B1 (en) | 2012-06-08 | 2019-12-25 | University Of Houston | Self-cleaning coatings and methods for making same |
US9694388B2 (en) | 2013-05-14 | 2017-07-04 | University Of Houston System | Waterproof coating with nanoscopic/microscopic features and methods of making same |
CN103880021B (en) * | 2014-04-02 | 2016-03-30 | 北京化工大学 | A kind of method preparing white carbon black in anti-microemulsion system |
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US3094536A (en) | 1961-01-03 | 1963-06-18 | Malcolm E Kenney | Silicon phthalocyanines |
US5209998A (en) * | 1991-11-25 | 1993-05-11 | Xerox Corporation | Colored silica particles |
US6251687B1 (en) * | 1993-09-24 | 2001-06-26 | Biosite Diagnostics, Inc. | Fluorescence energy transfer and intramolecular energy transfer in particles using novel compounds |
JP2005272760A (en) | 2004-03-26 | 2005-10-06 | Toyo Ink Mfg Co Ltd | epsilon-TYPE CRYSTAL FORM COPPER PHTHALOCYANINE AND METHOD FOR PRODUCING THE SAME |
WO2008083918A1 (en) | 2007-01-11 | 2008-07-17 | Ciba Holding Inc. | Near infrared absorbing phthalocyanines and their use |
ATE488521T1 (en) | 2007-05-11 | 2010-12-15 | Basf Se | FUNCTIONALIZED NANOPARTICLES |
JP2009180980A (en) * | 2008-01-31 | 2009-08-13 | Konica Minolta Business Technologies Inc | Toner for developing electrostatic charge image, and developer using the same |
-
2009
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- 2010-08-26 JP JP2012526069A patent/JP2013503097A/en active Pending
- 2010-08-26 WO PCT/EP2010/062516 patent/WO2011023783A2/en active Application Filing
- 2010-08-26 CN CN2010800376664A patent/CN102639541A/en active Pending
- 2010-08-26 US US13/392,865 patent/US20120156495A1/en not_active Abandoned
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