CA2554335A1 - Use of statistical copolymers - Google Patents
Use of statistical copolymers Download PDFInfo
- Publication number
- CA2554335A1 CA2554335A1 CA002554335A CA2554335A CA2554335A1 CA 2554335 A1 CA2554335 A1 CA 2554335A1 CA 002554335 A CA002554335 A CA 002554335A CA 2554335 A CA2554335 A CA 2554335A CA 2554335 A1 CA2554335 A1 CA 2554335A1
- Authority
- CA
- Canada
- Prior art keywords
- range
- process according
- precursors
- radicals
- reacted
- 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.)
- Abandoned
Links
- 229920006301 statistical copolymer Polymers 0.000 title claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007957 coemulsifier Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 125000001165 hydrophobic group Chemical group 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- 239000004094 surface-active agent Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 preferably Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229940085262 cetyl dimethicone Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000011234 nano-particulate material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940044603 styrene Drugs 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/003—Organic compounds containing only carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/007—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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Abstract
The invention relates to the use of statistical copolymers, comprising at least one structural unit with hydrophobic groups and at least one structural unit with hydrophilic groups, as emulsifiers, in particular, for the synthesis of nanoparticles and a production method for such particles with the steps a) production of an inverse emulsion containing one or several water-soluble precursors for the nanoparticles, or a melt, from a statistical copolymer of one monomer with hydrophobic groups and at least one monomer with hydrophilic groups and b) the generation of particles.
Description
' CA 02554335 2006-07-25 P04004 Ho Use of statistical copolymers The invention relates to the use of statistical copolymers as emulsifiers, in particular in the synthesis of nanoparticles, and to processes for the production of such particles.
The incorporation of inorganic nanoparticles into a polymer matrix can influence not only the mechanical properties, such as, for example, impact strength, of the matrix, but also modifies its optical properties, such as, for example, wavelength-dependent transmission, colour (absorption spectrum) and refractive index. In mixtures for optical appli-cations, the particle size plays an important role since the addition of a substance having a refractive index which differs from the refractive index of the matrix inevitably results in light scattering and ultimately in light opacity. The drop in the intensity of radiation of a defined wave-length on passing through a mixture shows a high dependence on the diameter of the inorganic particles.
The development of suitable nanomaterials for dispersion in polymers requires not only control of the particle size, but also of the surface properties of the particles. Simple mixing (for example by extrusion) of hydrophilic particles with a hydrophobic polymer matrix results in in-homogeneous distribution of the particles throughout the polymer and additionally in aggregation thereof. For homogeneous incorporation of inorganic particles into polymers, their surface must therefore be at least hydrophobically modified. In addition, the nanoparticulate materials, in particular, exhibit a great tendency to form agglomerates, which also survive subsequent surface treatment.
Surprisingly, it has now been found that nanoparticles can be precipi-tated from emulsions directly with a suitable surface modification with P04004 Ho virtually no agglomerates if certain statistical copolymers are employed as emulsifier.
The present invention therefore relates firstly to the use of statistical co-g polymers containing at least one structural unit containing hydrophobic radicals and at least one structural unit containing hydrophilic radicals as emulsifier, in particular in the synthesis of nanoparticles from emul-sions.
The present invention furthermore relates to a process for the produc-tion of polymer-modified nanoparticles which is characterised in that, in a step a), an inverse emulsion comprising one or more water-soluble precursors of the nanoparticles or a melt is prepared with the aid statistical copolymer of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals, and, in a step b), particles are produced.
The emulsion technique for the production of nanoparticles is known in principle. Thus, M. P. Pileni; J. Phys. Chem. 1993, 97, 6961-6973, describes the production of semiconductor particles, such as CdSe, CdTe and ZnS, in inverse emulsions.
However, the syntheses of the inorganic materials frequently require high salt concentrations of precursor materials in the emulsion, while the concentration additionally varies during the reaction. Low-molecular-weight surfactants react to such high salt concentrations, and con-sequently the stability of the emulsions is at risk (Paul Kent and Brian R.
Saunders; Journal of Colloid and Interface Science 242, 437-442 (2001)). In particular, the particle sizes can only be controlled to a lim-ited extent (M.-H. Lee, C. Y. Tai, C. H. Lu, Korean J. Chem. Eng. 16, 1999, 818-822).
P04004 Ho K. Landfester (Adv. Mater. 2001, 13, No. 10, 765-768) proposes the use of high-molecular-weight surfactants (PEO-PS block copolymers) in combination with ultrasound for the production of nanoparticles in the particle size range from about 150 to about 300 nm from metal salts.
The choice of statistical copolymers of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals has now enabled the provision of emulsifiers which facilitate the production of inorganic nanoparticles from inverse emulsions with control of the particle size and particle-size distribution. At the same time, the use of these novel emulsifiers enables the nanoparticles to be isolated from the dispersions with virtually no agglomerates since the individual particles form directly with polymer coatings.
In addition, the nanoparticles obtainable by this method can be dis-persed particularly simply and uniformly in polymers, with, in particular, it being possible substantially to avoid undesired impairment of the transparency of such polymers in visible light.
The statistical copolymers preferably to be employed in accordance with the invention exhibit a weight ratio of structural units containing hydro-phobic radicals to structural units containing hydrophilic radicals in the statistical copolymers which is in the range from 1:2 to 500:1, preferably in the range from 1:1 to 100:1 and particularly preferably in the range from 7:3 to 10:1. The weight average molecular weight of the statistical copolymers is usually in the range from MW = 1000 to 1,000,000 g/mol, preferably in the range from 1500 to 100.000 g/mol and particularly preferably in the range from 2000 to 40.000 g/mol.
It has been found here that, in particular, copolymers which conform to the formula I
P04004 Ho * ran ran I
R~iX R2iY
where X and Y correspond to the radicals of conventional nonionic or ionic monomers, and R' stands for hydrogen or a hydrophobic side group, preferably selected from branched or unbranched alkyl radicals having at least 4 carbon atoms, in which one or more, preferably all, H atoms may have been replaced by fluorine atoms, and R2 stands for a hydrophilic side group, which preferably has a phos-phonate, sulfonate, polyol or polyether radical, and where -X-R' and -Y-R2 may each have a plurality of different meanings within a molecule that satisfy the requirements according to the invention in a particular manner.
Particular preference is given in accordance with the invention to polymers in which -Y-R2 stands for a betaine structure.
Particular preference is in turn given here to polymers of the formula I
in which X and Y, independently of one another, stand for -O-, -C(=O)-O-, -C(=O)-NH-, -(CH2)~-, phenyl, naphthyl or pyridyl. Further-more, polymers in which at least one structural unit contains at least one quaternary nitrogen atom, where R2 preferably stands for a -(CH2)m-(N+(CH3)2)-(Chi2)n-S03- side group or a -(CH2)m-(N+(CHs)2)-(CH2)~-P032- side group, where m stands for an integer from the range from 1 to 30, preferably from the range from 1 to 6, particularly preferably 2, and n stands for an integer from the range from 1 to 30, preferably from the range from 1 to 8, particularly preferably 3, can advantageously be employed.
P04004 Ho Statistical copolymers particularly preferably to be employed can be prepared in accordance with the following scheme:
S
AIBN n 0 -0 O 0 0 toluene, 70oC O 0 0 O THF, reflux /
C H 0lzHzs 0lzHzs -N-~N~ ~N~
O=~=O
O
The desired amounts of lauryl methacrylate (LMA) and dimethyl-aminoethyl methacrylate (DMAEMA) are copolymerised here by known processes, preferably by means of free radicals in toluene through addition of AIBN. A betaine structure is subsequently obtained by known methods by reaction of the amine with 1,3-pro-pane sultone.
Alternative copolymers preferably to be employed can contain sty-rene, vinylpyrrolidone, vinylpyridine, halogenated styrene or meth-oxystyrene, where these examples do not represent a limitation. In another, likewise preferred embodiment of the present invention, use is made of polymers which are characterised in that at least one structural unit is an oligomer or polymer, preferably a macromono mer, where polyethers, polyolefins and polyacrylates are particularly preferred as macromonomers.
Precursors which can be employed for the inorganic nanoparticles are water-soluble metal compounds, preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium compounds, where these precursors are preferably reacted with an acid or lye for the production of corresponding metal-oxide particles.
P04004 Ho Mixed oxides can be obtained in a simple manner here by suitable mixing of the corresponding precursors. The choice of suitable pre-cursors presents the person skilled in the art with no difficulties; suit-able compounds are all those which are suitable for the precipitation of the corresponding target compounds from aqueous solution. An overview of suitable precursors for the preparation of oxides is given, for example, in Table 6 in K. Osseo-Asare "Microemulsion-mediated Synthesis of nanosize Oxide Materials" in: Kumar P., Mittal KL, (edi-tors), Handbook of microemulsion science and technology, New York:
Marcel Dekker, Inc., pp. 559-573, the contents of which expressly belong to the disclosure content of the present application.
Hydrophilic melts can likewise serve as precursors of nanoparticles in the sense of this invention. A chemical reaction for the production of the nanoparticles is not absolutely necessary in this case.
In particular, alkali or alkaline earth metal silicates, preferably sodium silicates, as precursors can also be reacted with acid or lye to give silicon dioxide.
In likewise preferred embodiments of the present invention, at least one soluble compound of a noble metal, preferably silver nitrate, is reacted with a reducing agent, preferably citric acid, to give the metal.
For the preparation of nanoparticulate metal sulfides, which is like-wise preferred in accordance with the invention, a soluble metal compound, preferably a soluble Pb, Cd or Zn compound, is reacted with hydrogen sulfide to give the metal sulfide.
In another embodiment of the present invention, a soluble metal compound, such as, preferably, for example, calcium chloride, is P04004 Ho reacted with carbon dioxide to give a nanoparticulate metal carbon-ate.
Nanoparticles particularly preferably produced are those which essentially consist of oxides or hydroxides of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium.
The particles preferably have a mean particle size, determined by means of dynamic light scattering or a transmission electron micro-scope, of from 3 to 200 nm, in particular from 20 to 80 nm and very particularly preferably from 30 to 50 nm. In specific, likewise preferred embodiments of the present invention, the distribution of the particle sizes is narrow, i.e. the variation latitude is less than 100% of the mean, particularly preferably a maximum of 50% of the mean.
In the context of the use of these nanoparticles for UV protection in polymers, it is particularly preferred if the nanoparticles have an absorption maximum in the range 300 - 500 nm, preferably in the range up to 400 nm, where particularly preferred nanoparticles absorb radiation, in particular, in the UV-A region.
The emulsion process can be carried out here in various ways:
As already stated, particles are usually produced in step b) by reac tion of the precursors or by cooling of the melt. The precursors can be reacted here, depending on the process variant selected, with an acid, a lye, a reducing agent or an oxidant.
For the production of particles in the desired particle-size range, it is particularly advantageous if the droplet size in the emulsion is in the range from 5 to 500 nm, preferably in the range from 10 to 200 nm.
The droplet size in the given system is set here in the manner known P04004 Ho _$_ to the person skilled in the art, where the oil phase is matched indi-vidually to the reaction system by the person skilled in the art. For the production of Zn0 particles, toluene and cyclohexane, for example, have proven successful as the oil phase.
In certain cases, it may be helpful to employ a further coemulsifier, preferably a nonionic surfactant, in addition to the statistical copolymer. Preferred coemulsifiers are optionally ethoxylated or propoxylated, relatively long-chain alkanols or alkylphenols having various degrees of ethoxylation or propoxylation (for example adducts with from 0 to 50 mol of alkylene oxide).
It may also be advantageous to employ dispersion aids, preferably water-soluble, high-molecular-weight, organic compounds containing polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinylpyrrolidone, partially saponified co-polymers of an acrylate and acrylonitrile, polyvinyl alcohols having various residual acetate contents, cellulose ethers, gelatine, block copolymers, modified starch, low-molecular-weight, carboxyl- and/or sulfonyl-containing polymers, or mixtures of these substances.
Particularly preferred protective colloids are polyvinyl alcohols having a residual acetate content of below 40 mol%, in particular from 5 to 39 mol%, and/or vinylpyrrolidone-vinyl propionate copolymers having a vinyl ester content of below 35% by weight, in particular from 5 to 30% by weight.
The desired property combinations of the nanoparticles required can be set in a targeted manner by adjustment of the reaction conditions, such as temperature, pressure and reaction duration. The corre-sponding setting of these parameters presents the person skilled in the art with absolutely no difficulties. For example, work can be car-P04004 Ho _g_ ried out at atmospheric pressure and room temperature for many purposes.
In a preferred process variant, a second emulsion in which a reactant for the precursors is in emulsified form is mixed in step b) with the precursor emulsion from step a). This two-emulsion process allows the production of particles having a particularly narrow particle-size distribution. It may be particularly advantageous here for the two emulsions to be mixed with one another by the action of ultrasound.
In another, likewise preferred process variant, the precursor emulsion is mixed in step b) with a precipitant which is soluble in the continu-ous phase of the emulsion. The precipitation is then carried out by diffusion of the precipitant into the precursor-containing micelles. For example, titanium dioxide particles can be obtained by diffusion of pyridine into titanyl chloride-containing micelles or silver particles can be obtained by diffusion of long-chain aldehydes into silver nitrate-containing micelles.
The nanoparticles according to the invention are used, in particular, in polymers. Polymers into which the nanoparticles according to the invention can be incorporated well are, in particular, polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA) or copolymers comprising at least a fraction of one of the said polymers.
The incorporation can be carried out here by conventional methods for the preparation of polymer compositions. For example, the poly mer material can be mixed with nanoparticles according to the inven tion, preferably in an extruder or compounder.
Depending on the polymer used, it is also possible to employ com-pounders.
P04004 Ho A particular advantage of the particles according to the invention consists in that only a low energy input compared with the prior art is necessary for homogeneous distribution of the particles in the poly-mer.
The polymers here can also be dispersions of polymers, such as, for example, paints. The incorporation can be carried out here by con-ventional mixing operations.
The polymer compositions according to the invention comprising the nanoparticles are furthermore also particularly suitable for the coating of surfaces. This enables the surface or the material lying beneath the coating to be protected, for example, against UV radiation.
The following examples are intended to explain the invention in greater detail without limiting it.
""
P04004 Ho Examples Example 1: Synthesis of the macrosurfactants The first step comprises the synthesis of a statistical copolymer of dode-cyl methacrylate (lauryl methacrylate; LMA) and dimethylaminoethyl methacrylate (DMAEMA). Control of the molecular weight can be achieved by addition of mercaptoethanol. The copolymer obtained in this way is modified by means of 1,3-propane sultone in order to supply saturated groups.
To this end, 7 g of LMA and DMAEMA, in an amount corresponding to Table 1 below, are initially introduced in 12 g of toluene and subjected to free-radical polymerisation under argon at 70°C after initiation of the reaction by addition of 0.033 g of AIBN in 1 ml of toluene. The chain growth can be controlled here by addition of 2-mercaptoethanol (see Table 1 ). The crude polymer is washed, freeze-dried and subsequently reacted with 1,3-propane sultone, as described in V. Butun, C. E. Ben-nett, M. Vamvakaki, A. B. Lowe, N. C. Billingham, S. P. Armes, J. Mater.
Chem., 1997, 7(9), 1693-1695.
The characterisation of the resultant polymers is given in Table 1.
P04004 Ho Table 1: Amounts of monomers employed and characterisation of the resultant polymers DMAEMA DMAEMA in 1-Mercapto-M~ MW Betaine [g] the polymerethanol [g/mol][g/mol] groups [mol%] [g] [mol%]
E 1.08 19 0.033 18000 31000 16 E2 1.08 19 0.011 28000 51000 19 E3 1.08 21 0.066 13000 21000 21 E4 1.09 20 --- 59000 158000 14.6 E5 0.48 10.7 --- 52000 162000 7.5 Example 2: Precipitation of Zn0 particles Zn0 particles are precipitated by the following method:
1. Preparation of in each case an inverse emulsion of an aqueous solution of 0.4 g of Zn(Ac0)2*2H20 in 1.1 g of water (emulsion 1 ) and 0.15 g of NaOH in 1.35 g of water (emulsion 2) by means of ultrasound.
Emulsion 1 and emulsion 2 each comprise 150 mg of a statistical copolymer E1 - E5 from Table 1.
2. Ultrasound treatment of the mixture of emulsion 1 and emulsion 2, followed by drying.
3. Purification of sodium acetate by washing the resultant solid with water.
4. Drying and redispersal of the powder functionalised on the surface by the emulsifier by stirring in toluene.
FT-IR spectroscopy and X-ray diffraction show the formation of ZnO.
Furthermore, no reflections of sodium acetate are visible in the X-ray diagram.
P04004 Ho Thus, Example 2 results in a product which consists of the synthesised macrosurfactant and zinc oxide particles.
Diameter [nm] Variance [nm] Proportion of Copolymer Zn0 (light scattering) (wt-%) E 1 37 30 30.3 E2 66 53 30.5 Comparative Example 2a: Use of the emulsifier ABIL EM 90~
The procedure as described in Example 2 with the commercially avail-able emulsifier ABIL EM 90~ (cetyl dimethicone copolyol, Goldschmidt) instead of the statistical copolymer from Example 1 does not result in a stable emulsion. The particles obtained exhibit diameters of between 500 and 4000 nm.
Example 3: Precipitation of silicon dioxide The precipitation of Si02 particles is carried out by the following method:
1. Preparation of in each case an inverse emulsion of an aqueous solu-tion of Na2Si03 (emulsion 1 ) and H2S04 (emulsion 2) by means of ultra-sound (concentrations corresponding to Table 2).
2. Ultrasound treatment of the mixture of emulsion 1 and emulsion 2 followed by drying.
3. Purification by washing the resultant solid with water.
4. Drying and redispersal of the powder obtained.
FT-IR spectroscopy and X-ray diffraction show the formation of Si02 and the non-presence/absence of sodium silicate.
P04004 Ho The step thus gives a product which consists of the synthesised macro-surfactant and silicon dioxide particles.
Table 2: Composition of the emulsions and characterisation of the products Particle size Standard of the ExperimentEmulsion E1 Emulsion E2 deviation nanoparticles (nm]
[nm]
0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3a 11.7 g of toluene;11.7 g of 59 19 toluene;
1.25 g of water2.2 g of water;
1.25 g of Na2Si030.3 g of HzS04 0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3b 11.7 g of toluene;11.7 g of 40 15 toluene;
1.25 g of water;1.76 g of water;
1.00 g of NazSi030.24 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3c 11.7 g of toluene;11.7 g of 50 20 toluene;
0.75 g of water;1.32 g of water;
0.75 g of Na2Si030.18 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3d 11.7 g of toluene;11.7 g of 43 15 toluene;
0.75 g of water;1.32 g of water;
0.75 g of NaZSi030.18 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3e 11.7 g of toluene;11.7 g of 53 12 toluene;
1.25 g of water;2.2 g of water;
1.25 g of NaZSi030.3 g of HZS04 ,"
P04004 Ho 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3f 11.7 g of toluene;11.7 g of 93 30 toluene;
1.0 g of water;1.76 g of 1.0 g water;
of Na2Si03 0.24 g of Example 4: Polymer composition A dispersion of the particles from Example 2-E1 in PMMA lacquer is prepared by mixing, applied to glass substrates and dried. The Zn0 content after drying is 10% by weight. The films exhibit a virtually im perceptible haze. Measurements using a UV-VIS spectrometer confirm this impression. The sample exhibits the following absorption values, depending on the layer thickness (the percentage of incident light lost in transmission is shown).
Layer thickness UV-A (350 nm) VIS (400 nm) 1.2 Nm 35% 4%
1.6 ~m 40% 5%
2.2 pm 45% 7%
Comparison:
(Zn0 (extra pure, Merck) in PMMA lacquer as above) 2 pm 64% 46%
The incorporation of inorganic nanoparticles into a polymer matrix can influence not only the mechanical properties, such as, for example, impact strength, of the matrix, but also modifies its optical properties, such as, for example, wavelength-dependent transmission, colour (absorption spectrum) and refractive index. In mixtures for optical appli-cations, the particle size plays an important role since the addition of a substance having a refractive index which differs from the refractive index of the matrix inevitably results in light scattering and ultimately in light opacity. The drop in the intensity of radiation of a defined wave-length on passing through a mixture shows a high dependence on the diameter of the inorganic particles.
The development of suitable nanomaterials for dispersion in polymers requires not only control of the particle size, but also of the surface properties of the particles. Simple mixing (for example by extrusion) of hydrophilic particles with a hydrophobic polymer matrix results in in-homogeneous distribution of the particles throughout the polymer and additionally in aggregation thereof. For homogeneous incorporation of inorganic particles into polymers, their surface must therefore be at least hydrophobically modified. In addition, the nanoparticulate materials, in particular, exhibit a great tendency to form agglomerates, which also survive subsequent surface treatment.
Surprisingly, it has now been found that nanoparticles can be precipi-tated from emulsions directly with a suitable surface modification with P04004 Ho virtually no agglomerates if certain statistical copolymers are employed as emulsifier.
The present invention therefore relates firstly to the use of statistical co-g polymers containing at least one structural unit containing hydrophobic radicals and at least one structural unit containing hydrophilic radicals as emulsifier, in particular in the synthesis of nanoparticles from emul-sions.
The present invention furthermore relates to a process for the produc-tion of polymer-modified nanoparticles which is characterised in that, in a step a), an inverse emulsion comprising one or more water-soluble precursors of the nanoparticles or a melt is prepared with the aid statistical copolymer of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals, and, in a step b), particles are produced.
The emulsion technique for the production of nanoparticles is known in principle. Thus, M. P. Pileni; J. Phys. Chem. 1993, 97, 6961-6973, describes the production of semiconductor particles, such as CdSe, CdTe and ZnS, in inverse emulsions.
However, the syntheses of the inorganic materials frequently require high salt concentrations of precursor materials in the emulsion, while the concentration additionally varies during the reaction. Low-molecular-weight surfactants react to such high salt concentrations, and con-sequently the stability of the emulsions is at risk (Paul Kent and Brian R.
Saunders; Journal of Colloid and Interface Science 242, 437-442 (2001)). In particular, the particle sizes can only be controlled to a lim-ited extent (M.-H. Lee, C. Y. Tai, C. H. Lu, Korean J. Chem. Eng. 16, 1999, 818-822).
P04004 Ho K. Landfester (Adv. Mater. 2001, 13, No. 10, 765-768) proposes the use of high-molecular-weight surfactants (PEO-PS block copolymers) in combination with ultrasound for the production of nanoparticles in the particle size range from about 150 to about 300 nm from metal salts.
The choice of statistical copolymers of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals has now enabled the provision of emulsifiers which facilitate the production of inorganic nanoparticles from inverse emulsions with control of the particle size and particle-size distribution. At the same time, the use of these novel emulsifiers enables the nanoparticles to be isolated from the dispersions with virtually no agglomerates since the individual particles form directly with polymer coatings.
In addition, the nanoparticles obtainable by this method can be dis-persed particularly simply and uniformly in polymers, with, in particular, it being possible substantially to avoid undesired impairment of the transparency of such polymers in visible light.
The statistical copolymers preferably to be employed in accordance with the invention exhibit a weight ratio of structural units containing hydro-phobic radicals to structural units containing hydrophilic radicals in the statistical copolymers which is in the range from 1:2 to 500:1, preferably in the range from 1:1 to 100:1 and particularly preferably in the range from 7:3 to 10:1. The weight average molecular weight of the statistical copolymers is usually in the range from MW = 1000 to 1,000,000 g/mol, preferably in the range from 1500 to 100.000 g/mol and particularly preferably in the range from 2000 to 40.000 g/mol.
It has been found here that, in particular, copolymers which conform to the formula I
P04004 Ho * ran ran I
R~iX R2iY
where X and Y correspond to the radicals of conventional nonionic or ionic monomers, and R' stands for hydrogen or a hydrophobic side group, preferably selected from branched or unbranched alkyl radicals having at least 4 carbon atoms, in which one or more, preferably all, H atoms may have been replaced by fluorine atoms, and R2 stands for a hydrophilic side group, which preferably has a phos-phonate, sulfonate, polyol or polyether radical, and where -X-R' and -Y-R2 may each have a plurality of different meanings within a molecule that satisfy the requirements according to the invention in a particular manner.
Particular preference is given in accordance with the invention to polymers in which -Y-R2 stands for a betaine structure.
Particular preference is in turn given here to polymers of the formula I
in which X and Y, independently of one another, stand for -O-, -C(=O)-O-, -C(=O)-NH-, -(CH2)~-, phenyl, naphthyl or pyridyl. Further-more, polymers in which at least one structural unit contains at least one quaternary nitrogen atom, where R2 preferably stands for a -(CH2)m-(N+(CH3)2)-(Chi2)n-S03- side group or a -(CH2)m-(N+(CHs)2)-(CH2)~-P032- side group, where m stands for an integer from the range from 1 to 30, preferably from the range from 1 to 6, particularly preferably 2, and n stands for an integer from the range from 1 to 30, preferably from the range from 1 to 8, particularly preferably 3, can advantageously be employed.
P04004 Ho Statistical copolymers particularly preferably to be employed can be prepared in accordance with the following scheme:
S
AIBN n 0 -0 O 0 0 toluene, 70oC O 0 0 O THF, reflux /
C H 0lzHzs 0lzHzs -N-~N~ ~N~
O=~=O
O
The desired amounts of lauryl methacrylate (LMA) and dimethyl-aminoethyl methacrylate (DMAEMA) are copolymerised here by known processes, preferably by means of free radicals in toluene through addition of AIBN. A betaine structure is subsequently obtained by known methods by reaction of the amine with 1,3-pro-pane sultone.
Alternative copolymers preferably to be employed can contain sty-rene, vinylpyrrolidone, vinylpyridine, halogenated styrene or meth-oxystyrene, where these examples do not represent a limitation. In another, likewise preferred embodiment of the present invention, use is made of polymers which are characterised in that at least one structural unit is an oligomer or polymer, preferably a macromono mer, where polyethers, polyolefins and polyacrylates are particularly preferred as macromonomers.
Precursors which can be employed for the inorganic nanoparticles are water-soluble metal compounds, preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium compounds, where these precursors are preferably reacted with an acid or lye for the production of corresponding metal-oxide particles.
P04004 Ho Mixed oxides can be obtained in a simple manner here by suitable mixing of the corresponding precursors. The choice of suitable pre-cursors presents the person skilled in the art with no difficulties; suit-able compounds are all those which are suitable for the precipitation of the corresponding target compounds from aqueous solution. An overview of suitable precursors for the preparation of oxides is given, for example, in Table 6 in K. Osseo-Asare "Microemulsion-mediated Synthesis of nanosize Oxide Materials" in: Kumar P., Mittal KL, (edi-tors), Handbook of microemulsion science and technology, New York:
Marcel Dekker, Inc., pp. 559-573, the contents of which expressly belong to the disclosure content of the present application.
Hydrophilic melts can likewise serve as precursors of nanoparticles in the sense of this invention. A chemical reaction for the production of the nanoparticles is not absolutely necessary in this case.
In particular, alkali or alkaline earth metal silicates, preferably sodium silicates, as precursors can also be reacted with acid or lye to give silicon dioxide.
In likewise preferred embodiments of the present invention, at least one soluble compound of a noble metal, preferably silver nitrate, is reacted with a reducing agent, preferably citric acid, to give the metal.
For the preparation of nanoparticulate metal sulfides, which is like-wise preferred in accordance with the invention, a soluble metal compound, preferably a soluble Pb, Cd or Zn compound, is reacted with hydrogen sulfide to give the metal sulfide.
In another embodiment of the present invention, a soluble metal compound, such as, preferably, for example, calcium chloride, is P04004 Ho reacted with carbon dioxide to give a nanoparticulate metal carbon-ate.
Nanoparticles particularly preferably produced are those which essentially consist of oxides or hydroxides of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and/or zirconium.
The particles preferably have a mean particle size, determined by means of dynamic light scattering or a transmission electron micro-scope, of from 3 to 200 nm, in particular from 20 to 80 nm and very particularly preferably from 30 to 50 nm. In specific, likewise preferred embodiments of the present invention, the distribution of the particle sizes is narrow, i.e. the variation latitude is less than 100% of the mean, particularly preferably a maximum of 50% of the mean.
In the context of the use of these nanoparticles for UV protection in polymers, it is particularly preferred if the nanoparticles have an absorption maximum in the range 300 - 500 nm, preferably in the range up to 400 nm, where particularly preferred nanoparticles absorb radiation, in particular, in the UV-A region.
The emulsion process can be carried out here in various ways:
As already stated, particles are usually produced in step b) by reac tion of the precursors or by cooling of the melt. The precursors can be reacted here, depending on the process variant selected, with an acid, a lye, a reducing agent or an oxidant.
For the production of particles in the desired particle-size range, it is particularly advantageous if the droplet size in the emulsion is in the range from 5 to 500 nm, preferably in the range from 10 to 200 nm.
The droplet size in the given system is set here in the manner known P04004 Ho _$_ to the person skilled in the art, where the oil phase is matched indi-vidually to the reaction system by the person skilled in the art. For the production of Zn0 particles, toluene and cyclohexane, for example, have proven successful as the oil phase.
In certain cases, it may be helpful to employ a further coemulsifier, preferably a nonionic surfactant, in addition to the statistical copolymer. Preferred coemulsifiers are optionally ethoxylated or propoxylated, relatively long-chain alkanols or alkylphenols having various degrees of ethoxylation or propoxylation (for example adducts with from 0 to 50 mol of alkylene oxide).
It may also be advantageous to employ dispersion aids, preferably water-soluble, high-molecular-weight, organic compounds containing polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinylpyrrolidone, partially saponified co-polymers of an acrylate and acrylonitrile, polyvinyl alcohols having various residual acetate contents, cellulose ethers, gelatine, block copolymers, modified starch, low-molecular-weight, carboxyl- and/or sulfonyl-containing polymers, or mixtures of these substances.
Particularly preferred protective colloids are polyvinyl alcohols having a residual acetate content of below 40 mol%, in particular from 5 to 39 mol%, and/or vinylpyrrolidone-vinyl propionate copolymers having a vinyl ester content of below 35% by weight, in particular from 5 to 30% by weight.
The desired property combinations of the nanoparticles required can be set in a targeted manner by adjustment of the reaction conditions, such as temperature, pressure and reaction duration. The corre-sponding setting of these parameters presents the person skilled in the art with absolutely no difficulties. For example, work can be car-P04004 Ho _g_ ried out at atmospheric pressure and room temperature for many purposes.
In a preferred process variant, a second emulsion in which a reactant for the precursors is in emulsified form is mixed in step b) with the precursor emulsion from step a). This two-emulsion process allows the production of particles having a particularly narrow particle-size distribution. It may be particularly advantageous here for the two emulsions to be mixed with one another by the action of ultrasound.
In another, likewise preferred process variant, the precursor emulsion is mixed in step b) with a precipitant which is soluble in the continu-ous phase of the emulsion. The precipitation is then carried out by diffusion of the precipitant into the precursor-containing micelles. For example, titanium dioxide particles can be obtained by diffusion of pyridine into titanyl chloride-containing micelles or silver particles can be obtained by diffusion of long-chain aldehydes into silver nitrate-containing micelles.
The nanoparticles according to the invention are used, in particular, in polymers. Polymers into which the nanoparticles according to the invention can be incorporated well are, in particular, polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA) or copolymers comprising at least a fraction of one of the said polymers.
The incorporation can be carried out here by conventional methods for the preparation of polymer compositions. For example, the poly mer material can be mixed with nanoparticles according to the inven tion, preferably in an extruder or compounder.
Depending on the polymer used, it is also possible to employ com-pounders.
P04004 Ho A particular advantage of the particles according to the invention consists in that only a low energy input compared with the prior art is necessary for homogeneous distribution of the particles in the poly-mer.
The polymers here can also be dispersions of polymers, such as, for example, paints. The incorporation can be carried out here by con-ventional mixing operations.
The polymer compositions according to the invention comprising the nanoparticles are furthermore also particularly suitable for the coating of surfaces. This enables the surface or the material lying beneath the coating to be protected, for example, against UV radiation.
The following examples are intended to explain the invention in greater detail without limiting it.
""
P04004 Ho Examples Example 1: Synthesis of the macrosurfactants The first step comprises the synthesis of a statistical copolymer of dode-cyl methacrylate (lauryl methacrylate; LMA) and dimethylaminoethyl methacrylate (DMAEMA). Control of the molecular weight can be achieved by addition of mercaptoethanol. The copolymer obtained in this way is modified by means of 1,3-propane sultone in order to supply saturated groups.
To this end, 7 g of LMA and DMAEMA, in an amount corresponding to Table 1 below, are initially introduced in 12 g of toluene and subjected to free-radical polymerisation under argon at 70°C after initiation of the reaction by addition of 0.033 g of AIBN in 1 ml of toluene. The chain growth can be controlled here by addition of 2-mercaptoethanol (see Table 1 ). The crude polymer is washed, freeze-dried and subsequently reacted with 1,3-propane sultone, as described in V. Butun, C. E. Ben-nett, M. Vamvakaki, A. B. Lowe, N. C. Billingham, S. P. Armes, J. Mater.
Chem., 1997, 7(9), 1693-1695.
The characterisation of the resultant polymers is given in Table 1.
P04004 Ho Table 1: Amounts of monomers employed and characterisation of the resultant polymers DMAEMA DMAEMA in 1-Mercapto-M~ MW Betaine [g] the polymerethanol [g/mol][g/mol] groups [mol%] [g] [mol%]
E 1.08 19 0.033 18000 31000 16 E2 1.08 19 0.011 28000 51000 19 E3 1.08 21 0.066 13000 21000 21 E4 1.09 20 --- 59000 158000 14.6 E5 0.48 10.7 --- 52000 162000 7.5 Example 2: Precipitation of Zn0 particles Zn0 particles are precipitated by the following method:
1. Preparation of in each case an inverse emulsion of an aqueous solution of 0.4 g of Zn(Ac0)2*2H20 in 1.1 g of water (emulsion 1 ) and 0.15 g of NaOH in 1.35 g of water (emulsion 2) by means of ultrasound.
Emulsion 1 and emulsion 2 each comprise 150 mg of a statistical copolymer E1 - E5 from Table 1.
2. Ultrasound treatment of the mixture of emulsion 1 and emulsion 2, followed by drying.
3. Purification of sodium acetate by washing the resultant solid with water.
4. Drying and redispersal of the powder functionalised on the surface by the emulsifier by stirring in toluene.
FT-IR spectroscopy and X-ray diffraction show the formation of ZnO.
Furthermore, no reflections of sodium acetate are visible in the X-ray diagram.
P04004 Ho Thus, Example 2 results in a product which consists of the synthesised macrosurfactant and zinc oxide particles.
Diameter [nm] Variance [nm] Proportion of Copolymer Zn0 (light scattering) (wt-%) E 1 37 30 30.3 E2 66 53 30.5 Comparative Example 2a: Use of the emulsifier ABIL EM 90~
The procedure as described in Example 2 with the commercially avail-able emulsifier ABIL EM 90~ (cetyl dimethicone copolyol, Goldschmidt) instead of the statistical copolymer from Example 1 does not result in a stable emulsion. The particles obtained exhibit diameters of between 500 and 4000 nm.
Example 3: Precipitation of silicon dioxide The precipitation of Si02 particles is carried out by the following method:
1. Preparation of in each case an inverse emulsion of an aqueous solu-tion of Na2Si03 (emulsion 1 ) and H2S04 (emulsion 2) by means of ultra-sound (concentrations corresponding to Table 2).
2. Ultrasound treatment of the mixture of emulsion 1 and emulsion 2 followed by drying.
3. Purification by washing the resultant solid with water.
4. Drying and redispersal of the powder obtained.
FT-IR spectroscopy and X-ray diffraction show the formation of Si02 and the non-presence/absence of sodium silicate.
P04004 Ho The step thus gives a product which consists of the synthesised macro-surfactant and silicon dioxide particles.
Table 2: Composition of the emulsions and characterisation of the products Particle size Standard of the ExperimentEmulsion E1 Emulsion E2 deviation nanoparticles (nm]
[nm]
0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3a 11.7 g of toluene;11.7 g of 59 19 toluene;
1.25 g of water2.2 g of water;
1.25 g of Na2Si030.3 g of HzS04 0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3b 11.7 g of toluene;11.7 g of 40 15 toluene;
1.25 g of water;1.76 g of water;
1.00 g of NazSi030.24 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E4); (E4);
3c 11.7 g of toluene;11.7 g of 50 20 toluene;
0.75 g of water;1.32 g of water;
0.75 g of Na2Si030.18 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3d 11.7 g of toluene;11.7 g of 43 15 toluene;
0.75 g of water;1.32 g of water;
0.75 g of NaZSi030.18 g of 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3e 11.7 g of toluene;11.7 g of 53 12 toluene;
1.25 g of water;2.2 g of water;
1.25 g of NaZSi030.3 g of HZS04 ,"
P04004 Ho 0.15 g of polymer0.15 g of polymer surfactant surfactant (E5); (E5);
3f 11.7 g of toluene;11.7 g of 93 30 toluene;
1.0 g of water;1.76 g of 1.0 g water;
of Na2Si03 0.24 g of Example 4: Polymer composition A dispersion of the particles from Example 2-E1 in PMMA lacquer is prepared by mixing, applied to glass substrates and dried. The Zn0 content after drying is 10% by weight. The films exhibit a virtually im perceptible haze. Measurements using a UV-VIS spectrometer confirm this impression. The sample exhibits the following absorption values, depending on the layer thickness (the percentage of incident light lost in transmission is shown).
Layer thickness UV-A (350 nm) VIS (400 nm) 1.2 Nm 35% 4%
1.6 ~m 40% 5%
2.2 pm 45% 7%
Comparison:
(Zn0 (extra pure, Merck) in PMMA lacquer as above) 2 pm 64% 46%
Claims (20)
1. Use of statistical copolymers containing at least one structural unit containing hydrophobic radicals and at least one structural unit con-taining hydrophilic radicals as emulsifier.
2. Use according to Claim 1, characterised in that the copolymers are used as emulsifier in the synthesis of nanoparticles from emulsions.
3. Use according to at least one of the preceding claims, characterised in that the weight ratio of structural units containing hydrophobic radicals to structural units containing hydrophilic radicals in the statistical, copolymers is in the range from 1:2 to 500:1, preferably in the range from 1:1 to 100:1 and particularly preferably in the range from 7:3 to 10:1.
4. Use according to at least one of the preceding claims, characterised in that the weight average molecular weight of the statistical copoly-mers is in the range from M w= 1000 to 1,000,000 g/mol, preferably in the range from 1500 to 100,000 g/mol and particularly preferably in the range from 2000 to 40,000 g/mol.
5. Use according to at least one of the preceding claims, characterised in that the copolymers conform to the formula I
where X and Y correspond to the radicals of conventional nonionic or ionic monomers, and R1 stands for hydrogen or a hydrophobic side group, preferably selected from branched or unbranched alkyl radicals having at least 4 carbon atoms, in which one or more, preferably all, H atoms may have been replaced by fluorine atoms, and R2 stands for a hydrophilic side group, which preferably has a phos-phonate, sulfonate, polyol or polyether radical, and where -X-R1 and -Y-R2 may each have a plurality of different meanings within a molecule.
where X and Y correspond to the radicals of conventional nonionic or ionic monomers, and R1 stands for hydrogen or a hydrophobic side group, preferably selected from branched or unbranched alkyl radicals having at least 4 carbon atoms, in which one or more, preferably all, H atoms may have been replaced by fluorine atoms, and R2 stands for a hydrophilic side group, which preferably has a phos-phonate, sulfonate, polyol or polyether radical, and where -X-R1 and -Y-R2 may each have a plurality of different meanings within a molecule.
6. Use according to Claim 5, characterised in that X and Y, independ-ently of one another, stand for -O-, -C(=O)-O-, -C(=O)-NH-, -(CH2)n-, phenylene or pyridyl.
7. Use according to at least one of the preceding claims, characterised in that at least one structural unit contains at least one quaternary nitrogen atom, where R2 preferably stands for a -(CH2)m-(N+(CH3)2)-(CH2)n-SO3- side group or a -(CH2)m-(N+(CH3)2)-(CH2)n-PO3 2- side group, where m stands for an integer from the range from 1 to 30, preferably from the range from 1 to 6, particularly preferably 2, and n stands for an integer from the range from 1 to 30, preferably from the range from 1 to 8, particularly preferably 3.
8. Use according to at least one of the preceding claims, characterised in that at least one structural unit is an oligomer or polymer, prefera-bly a macromonomer, where polyethers, polyolefins and polyacry-lates are particularly preferred as macromonomers.
9. Process for the production of polymer-modified nanoparticles, characterised in that, in a step a) an inverse emulsion comprising one or more water-soluble precursors of the nanoparticles or a melt is prepared with the aid of a statistical copolymer of at least one monomer containing hydrophobic radicals and at least one monomer containing hydrophilic radicals, and, in a step b), particles are pro-duced.
10. Process according to Claim 9, characterised in that particles are pro-duced in step b) by reaction of the precursors or by cooling of the melt.
11. Process according to Claim 10, characterised in that the precursors are reacted with an acid, a lye, a reducing agent or an oxidant.
12. Process according to Claim 11, characterised in that a sodium silicate as precursor is reacted with an acid or lye to give silicon dioxide.
13. Process according to Claim 11, characterised in that a soluble com-pound of a noble metal, preferably silver nitrate, is reacted with a reducing agent, preferably citric acid, to give the metal.
14. Process according to Claim 11, characterised in that a soluble metal compound, preferably a soluble Pb, Cd or Zn compound, is reacted with hydrogen sulfide to give the metal sulfide.
15. Process according to Claim 11, characterised in that a soluble metal compound, preferably calcium chloride, is reacted with carbon diox-ide to give a metal carbonate.
16. Process according to at least one of the preceding claims, character-ised in that the droplet size in the emulsion is in the range from 5 to 500 nm, preferably in the range from 10 to 200 nm.
17. Process according to at least one of the preceding claims, character-ised in that a second emulsion in which a reactant for the precursors is in emulsified form is mixed in step b) with the precursor emulsion from step a).
18. Process according to Claim 17, characterised in that the two emul-sions are mixed with one another by the action of ultrasound.
19. Process according to at least one of the preceding claims, character-ised in that the one or more precursors are selected from water-solu-ble metal compounds, preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium or zirconium compounds, and the precursors are preferably reacted with an acid or lye.
20. Process according to at least one of the preceding claims, character-ised in that a coemulsifier, preferably a nonionic surfactant, is em-ployed.
Applications Claiming Priority (5)
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DE102004004209A DE102004004209A1 (en) | 2004-01-27 | 2004-01-27 | Use of random copolymer with hydrophobic and hydrophilic groups in different structural units as emulsifier is useful for producing polymer-modified nanoparticles, e.g. of silica, silver or metal sulfide or carbonate for use in polymer |
DE102004004209.8 | 2004-01-27 | ||
EP04023002 | 2004-09-28 | ||
EP04023002.1 | 2004-09-28 | ||
PCT/EP2004/014389 WO2005070979A1 (en) | 2004-01-27 | 2004-12-17 | Use of statistical copolymers |
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JP (1) | JP2007519786A (en) |
KR (1) | KR20070004599A (en) |
CA (1) | CA2554335A1 (en) |
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Cited By (6)
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US8633136B2 (en) | 2006-10-16 | 2014-01-21 | Rhodia Operations | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
US8637622B2 (en) | 2007-04-05 | 2014-01-28 | Rhodia Operations | Copolymer including betaine units and hydrophobic and/or amphiphilic units, method for preparing same and uses thereof |
US8653001B2 (en) | 2005-11-14 | 2014-02-18 | Rhodia Operations | Agricultural adjuvant compostions, pesticide compositions, and methods for using such compositions |
US8748344B2 (en) | 2009-07-14 | 2014-06-10 | Rhodia Operations | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
US8841235B2 (en) | 2010-08-10 | 2014-09-23 | Rhodia Operations | Agricultural pesticide compositions |
US9045720B2 (en) | 2004-12-30 | 2015-06-02 | Rhodia Chimie | Herbicidal composition comprising an aminophosphate or aminophosphonate salt, a betaine and an amine oxide |
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DE102005019391A1 (en) * | 2005-04-25 | 2006-10-26 | Merck Patent Gmbh | Method for fabricating metal polymer-modified nano-particles, requires inverse emulsion containing one or more water-soluble precursors |
DE102005056621A1 (en) * | 2005-11-25 | 2007-05-31 | Merck Patent Gmbh | Modified zinc oxide nano-particles with a specific average particle size, obtained by converting nano-particle precursor to nano-particles and terminating the growth of nano-particles, useful for UV-stabilization of polymer |
DE102007032189A1 (en) | 2007-06-22 | 2008-12-24 | Merck Patent Gmbh | curing |
DE102007029283A1 (en) | 2007-06-22 | 2008-12-24 | Merck Patent Gmbh | hardening accelerator |
US9399075B2 (en) | 2008-12-29 | 2016-07-26 | General Electric Company | Nanoparticle contrast agents for diagnostic imaging |
DE102010018073A1 (en) | 2010-04-20 | 2011-10-20 | Aesculap Ag | Copolymer-modified nanoparticles, in particular for use in medical articles |
CN103282388B (en) | 2010-10-19 | 2017-02-15 | 马克斯·普朗克科学促进学会 | Ultra fast process for the preparation of polymer nanoparticles |
US8921444B2 (en) | 2010-10-19 | 2014-12-30 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. | Process for the modification of polymers, in particular polymer nanoparticles |
ITPA20110012A1 (en) * | 2011-08-30 | 2013-03-01 | Salvo Santina Di | INNOVATIVE SONOCHIMIC PROCESS THAT EMPLOYS THE ULTRASONIC CAVITATION FOR THE SYNTHESIS OF NANOPARTICELLE MONODISPERSE AMORPHES OF SILICON DIOXIDE AND METHOD FOR PREPARING A LOTION OF HYDRO-SOLUBLE LITHIUM COMPOUND FOR HIGH PERFORMANCE, TO BE APPLIED IN SIT |
WO2019092036A1 (en) | 2017-11-07 | 2019-05-16 | Clariant Plastics & Coatings Ltd | Dispersion agent for pigments in non-aqueous colourant preparations |
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DE1817309A1 (en) * | 1968-12-28 | 1970-07-02 | Hoechst Ag | Basic and cationic ethylene copolymers |
DE2612886A1 (en) * | 1976-03-26 | 1977-10-06 | Henkel & Cie Gmbh | WATER-IN-OIL TYPE COSMETIC EMULSIONS AND THEIR PRODUCTION |
JPH11140133A (en) * | 1997-11-04 | 1999-05-25 | Asahi Denka Kogyo Kk | Styrene oligomer and its production |
FR2774096B1 (en) * | 1998-01-29 | 2000-04-07 | Virsol | NOVEL SURFACTANT COPOLYMERS BASED ON METHYLIDENE MALONATE |
DE69832422T2 (en) * | 1998-11-23 | 2006-08-10 | M-I L.L.C., Houston | AMPHIPHILE POLYMERS STABILIZED INVERT EMULSIONS AND USE TO DRILLING LIQUIDS |
DE10003297C2 (en) * | 2000-01-27 | 2003-08-21 | Clariant Gmbh | Explosives containing modified copolymers of polyisobutylene, vinyl esters and maleic anhydride as emulsifiers |
-
2004
- 2004-12-17 KR KR1020067015218A patent/KR20070004599A/en not_active Application Discontinuation
- 2004-12-17 JP JP2006549912A patent/JP2007519786A/en active Pending
- 2004-12-17 WO PCT/EP2004/014389 patent/WO2005070979A1/en active Application Filing
- 2004-12-17 EP EP04803997A patent/EP1709092A1/en not_active Withdrawn
- 2004-12-17 CA CA002554335A patent/CA2554335A1/en not_active Abandoned
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Cited By (7)
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US9045720B2 (en) | 2004-12-30 | 2015-06-02 | Rhodia Chimie | Herbicidal composition comprising an aminophosphate or aminophosphonate salt, a betaine and an amine oxide |
US8653001B2 (en) | 2005-11-14 | 2014-02-18 | Rhodia Operations | Agricultural adjuvant compostions, pesticide compositions, and methods for using such compositions |
US9107405B2 (en) | 2005-11-14 | 2015-08-18 | Rhodia Operations | Agricultural adjuvant compostions, pesticide compositions, and methods for using such compositions |
US8633136B2 (en) | 2006-10-16 | 2014-01-21 | Rhodia Operations | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
US8637622B2 (en) | 2007-04-05 | 2014-01-28 | Rhodia Operations | Copolymer including betaine units and hydrophobic and/or amphiphilic units, method for preparing same and uses thereof |
US8748344B2 (en) | 2009-07-14 | 2014-06-10 | Rhodia Operations | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
US8841235B2 (en) | 2010-08-10 | 2014-09-23 | Rhodia Operations | Agricultural pesticide compositions |
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KR20070004599A (en) | 2007-01-09 |
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