JP6585190B2 - 単官能性単位の占有率が低い疎水性エーロゲル - Google Patents
単官能性単位の占有率が低い疎水性エーロゲル Download PDFInfo
- Publication number
- JP6585190B2 JP6585190B2 JP2017556613A JP2017556613A JP6585190B2 JP 6585190 B2 JP6585190 B2 JP 6585190B2 JP 2017556613 A JP2017556613 A JP 2017556613A JP 2017556613 A JP2017556613 A JP 2017556613A JP 6585190 B2 JP6585190 B2 JP 6585190B2
- Authority
- JP
- Japan
- Prior art keywords
- sio
- gel
- units
- primary particles
- less
- 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.)
- Expired - Fee Related
Links
- 230000002209 hydrophobic effect Effects 0.000 title description 7
- 239000000499 gel Substances 0.000 claims description 151
- 239000011164 primary particle Substances 0.000 claims description 74
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 41
- 238000012986 modification Methods 0.000 claims description 39
- 230000004048 modification Effects 0.000 claims description 38
- 239000007858 starting material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000004964 aerogel Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000002537 cosmetic Substances 0.000 claims description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- 230000015572 biosynthetic process Effects 0.000 description 34
- 239000000203 mixture Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 229910052700 potassium Inorganic materials 0.000 description 20
- 238000006884 silylation reaction Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 239000011591 potassium Substances 0.000 description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 17
- 235000019353 potassium silicate Nutrition 0.000 description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000005051 trimethylchlorosilane Substances 0.000 description 7
- -1 trimethylsiloxy unit Chemical group 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000000017 hydrogel Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 238000010908 decantation Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000011240 wet gel Substances 0.000 description 5
- 229910020175 SiOH Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 125000005625 siliconate group Chemical group 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000010415 colloidal nanoparticle Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 2
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000109 continuous material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- GBPOWOIWSYUZMH-UHFFFAOYSA-N sodium;trihydroxy(methyl)silane Chemical compound [Na+].C[Si](O)(O)O GBPOWOIWSYUZMH-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
-
- 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
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/152—Preparation of hydrogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/152—Preparation of hydrogels
- C01B33/154—Preparation of hydrogels by acidic treatment of aqueous silicate solutions
- C01B33/1546—Preparation of hydrogels by acidic treatment of aqueous silicate solutions the first formed hydrosol being converted to a hydrogel by introduction into an organic medium immiscible or only partly miscible with water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/155—Preparation of hydroorganogels or organogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/159—Coating or hydrophobisation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
- Cosmetics (AREA)
- Silicon Polymers (AREA)
- Medicinal Preparation (AREA)
Description
− アルコール、特に化学式R−OH(式中、Rは基Rについて上記で定義したとおりである)(例えば、メタノール、エタノール、イソプロパノール)
− ケトン、特に化学式R1R2C=O(式中、R1およびR2は同一でも異なっていてもよく、基Rについて上記で定義された通りである)(例えば,アセトン(CH3)2C=O)− エーテル、特に化学式R1OR2(式中、R1およびR2は同一でも異なっていてもよく、基Rについて上記で定義された通りである)(例えば、ジエチルエーテル、テトラヒドロフラン、ジメトキシエタン)
− エステル、特に化学式R1COOR2(式中、R1およびR2は同一でも異なっていてもよく、基Rについて上記で定義された通りである)(例えば、酢酸エチル)
− 界面活性剤のような界面活性物質である。
密度の決定
エーロゲル片の密度は、比重瓶法によって決定した。この目的のために、エーロゲル片を分析天秤(m1)上で秤量し、体積を測定するために、室温で、25mlの比重瓶(ブラウブランド(Blaubrand)製のDIN ISO 3507に従うGay−Lussacガラス比重瓶)中で水の変位を測定した。この目的のために、以下の質量を分析天秤で決定した:
m2:蒸留水で満たされた比重瓶の質量
m3:エーロゲル片と蒸留水で満たされた比重瓶の質量
V1=V2=ρw *(m2−(m3−m1))
ρエーロゲル=m1/V1
ここでρwは室温での水の密度(0.998g/cm3)である。
エーロゲルの比表面積を、DIN 9277/66131および9277/66132に従ってBET法により決定した。
試料の炭素含有率(C含有率)は、Leco CS230分析装置で決定した。分析は、酸素流中の試料の高周波燃焼によって行った。検出は、非分散赤外線検出器を用いて行った。
メトラー・トレド(Mettler Toledo)、Seven MultiのpHメーターを用いてpHを決定した。電極:In Lab Science。
表面改質後のTMS基による被覆度は、EP0948395B1に類似の方法を用いて、以下の式を用いて計算した:
被覆度=([CTMSあり]−[CTMSなし])/BET)*K;単位:[nm−2]
K=6.022*1023/100*12*3*1018=167.28;単位:[g−1]
[CTMSあり]:重量%で表される表面改質後のC含有率
[CTMSなし]:重量%で表される表面改質前のC含有率
[BET]:BET比表面積;単位:[m2/g]
ΔC[重量%]=CTMSあり[重量%]−CTMSなし[重量%]
供給源:
水ガラス(シグマ(Sigma)−アルドリッチ(Aldrich):SiO2含有率:26.5重量%、Na2O含有率:10.6重量%)
カリウムメチルシリコネート(ワッカー・ケミー社のSILRES(登録商標)BS 16:34重量%の活性化合物および20重量%のK2Oを含有する水溶液)
SiO2ナノゾル(アクゾ(Akzo) ノーベル(Nobel)のBindzil 17/750:SiO2含有率:15重量%、製造社に従った平均粒径4nm、pH 10.5)
ヘキサメチルジシロキサン(ワッカー・ケミー社のAK 0.65)
トリメチルクロロシラン(ワッカー・ケミー社のSILAN M3)
メチルトリメトキシシラン(シグマ−アルドリッチ、グレード:98%)
セチルトリメチルアンモニウムブロマイド(シグマ−アルドリッチ)
さらなる実験室用化学物質は、別途指示がない限り、シグマ−アルドリッチから調達した。
ガラスビーカー内で、55.5gの水および55.5gの水ガラスを混合し、氷浴中で10℃に冷却した。第2のガラスビーカー内で、55.5gの水および55.5gのカリウムメチルシロコネートを混合し、氷浴中で10℃に冷却した。
密度:0.10g/cm3
BET:587m2/g
表面改質前のC含有率:9.2重量%
表面改質後のC含有率:11.7重量%
TMS基による被覆:0.71nm−2
閉鎖可能なガラス瓶中で、4.8gのHCl溶液(32重量%)および34gの水から構成され、0℃に冷却した溶液に攪拌しながら56.6gのSiO2ナノゾルを加えた。続いて、7.6gのカリウムメチルシリコネートを、0℃に冷却しながら10分間かけて添加し、pH8を確立した。続いて試料を室温まで温め、その結果、ゲル形成が開始し、これは45分以内に終了した。得られたリオゲル(この場合これはヒドロゲルであった)を60℃で48時間インキュベートして熟成させ、その後実施例1に記載したように5mmより小さい片に分割し、ゲル片全体を2つの部分に分けた。
密度:0.11g/cm3
BET:300m2/g
表面改質前のC含有率:3.6重量%
表面改質後のC含有率:3.8重量%
TMS基による被覆:0.11nm−2
(EP0948395B1に基づく方法)
ガラスビーカー内で、150gの水および150gの水ガラスを混合し、氷浴中で10℃まで冷却した。
密度:0.20g/cm3
BET:521m2/g
表面改質前のC含有率:<0.1重量%
表面改質後のC含有率:8.4重量%
TMS基による被覆:2.70nm−2
ガラスビーカー内で、150.0gの水、75.0gの水ガラスおよび75.0gのカリウムメチルシリコネートを混合し、氷浴中で10℃まで冷却した。
密度:0.11g/cm3
BET:644m2/g
表面改質前のC含有率:8.7重量%
表面改質後のC含有率:14.8重量%
TMS基による被覆:1.57nm−2
(Shan Yunら、RSC Adv.、2014、4、4535−4542の方法に基づく)
315gの水および3.0gのセチルトリメチルアンモニウムブロマイド(シグマ−アルドリッチ)をスクリューキャップ瓶に入れ、攪拌しながら(マグネチックスターラー、500rpm)、81.8gのメチルトリメトキシシランと混合し、室温で20分間攪拌した。続いて3.0mlのアンモニア溶液(1.0M)を撹拌しながら添加し、混合物をさらに1分間撹拌し、スターラを取り除くとゲル形成が始まる。熟成を行うために、得られたゲルを、乾燥オーブン中の密閉容器中、60℃で16時間インキュベートした。
密度:0.25g/cm3
BET:615m2/g
表面改質前のC含有率:18.0重量%
表面改質後のC含有率:18.8重量%
TMS基による被覆:0.22nm−2
密閉可能なガラス瓶内で、120gのSiO2ナノゾルを、3.2gのHCl溶液(32重量%)および22.6gの水から構成され、0℃に冷却した溶液に撹拌しながら加え、pH2.5を確立した。その後、15.2gのメチルトリエトキシシランおよび6.3gのジメチルジエトキシシランの混合物を0℃に冷却しながら10分間かけて添加し、混合物を約30分間攪拌した。続いてアンモニア溶液(1M)を用いてpH8を設定した。続いて試料を室温に温め、その結果、ゲル形成が開始し、これは45分以内に終了した。得られたリオゲルを60℃で48時間インキュベートして熟成させた後、実施例1に記載したように5mmより小さい片に分割し、ゲル片全体を2つの部分に分けた。
密度:0.16g/cm3
BET:360m2/g
表面改質前のC含有率:7.7重量%
表面改質後のC含有率:9.2重量%
TMS基による被覆:0.69nm−2
Claims (14)
- 酸化物単位および[RxSiO(4−x)/2]単位から構成されるリオゲルまたはエーロゲル含有一次粒子の中から選択されるゲルであって、一次粒子は内側から外側に向かって勾配の形態で[RxSiO(4−x)/2]単位の濃度の増加を有し、添字xは同一でも異なっていてもよく、いずれの場合も1または2であり、基Rは同一でも異なっていてもよく、それぞれ水素または有機の置換もしくは非置換の基であり、酸化物単位は[SiO4/2]単位を含有する、ゲル。
- 一次粒子は、コア−シェルモデルの形態で形成され、コアは20モル%未満の[RxSiO(4−x)/2]単位の濃度を含み、シェルは80モル%超の[RxSiO(4−x)/2]単位の濃度を含むことを特徴とする請求項1に記載のゲル。
- 基Rがメチル基であることを特徴とする請求項1または2に記載のゲル。
- 表面における単官能性単位による被覆度が1nm2当たり1.5基未満であることを特徴とする請求項1から3のいずれか一項に記載のゲル。
- 0.25g/cm3未満の密度を有するエーロゲルであることを特徴とする請求項1から4のいずれか一項に記載のゲル。
- 15重量%未満の炭素含有率を有するエーロゲルであることを特徴とする請求項1から5のいずれか一項に記載のゲル。
- 0.15g/cm3未満の密度、1nm2当たり1以下という単官能性単位による被覆度、8重量%以下の炭素含有率、および300m2/gを超えるBET比表面積を有するエーロゲルであることを特徴とする請求項1から6のいずれか一項に記載のゲル。
- [SiO4/2]単位のみが酸化物単位として存在することを特徴とする請求項1から7のいずれか一項に記載のゲル。
- i) 酸化物単位を含むコロイド粒子を含有するゾルを反応容器に入れ、ここで、酸化物単位は、[SiO4/2]単位を含み、ゾルは、強塩基性アルカリ金属ケイ酸塩の中和またはアルコキシシランの加水分解によって製造され、
ii) ゾル中の粒子を[RxSiO(4−x)/2]単位と反応させ、式中、添字xは同一でも異なっていてもよく、いずれの場合も1または2であり、基Rは同一でも異なっていてもよく、それぞれ水素または有機の置換もしくは非置換の基であり、
iii) ゾルからゲルを形成することによる、請求項1から8のいずれか一項に対応するゲルを製造する方法。 - [SiO4/2]単位を含有するコロイド粒子の溶液が出発物質として使用され、この粒子は1から8nmの範囲の平均直径を有することを特徴とする請求項9に記載の方法。
- ゲルは、表面改質によって単官能性単位で覆われていることを特徴とする請求項9または10に記載の方法。
- ゲルは乾燥されることを特徴とする請求項9から11のいずれか一項に記載の方法。
- ゲルがエーロゲルである、請求項1から8のいずれか一項に記載のゲルまたは請求項9から12のいずれか一項に記載の方法によって製造されたゲルの、断熱および/または防音の用途における使用。
- 請求項1から8のいずれか一項に記載のゲルまたは請求項9から12のいずれか一項に対応する方法によって製造されたゲルの、化粧品、医療またはクロマトグラフィー用途における、または触媒もしくは触媒担体としての使用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102015207945.7 | 2015-04-29 | ||
DE102015207945.7A DE102015207945A1 (de) | 2015-04-29 | 2015-04-29 | Hydrophobe Aerogele mit einer geringen Belegung an monofunktionellen Einheiten |
PCT/EP2016/058834 WO2016173912A1 (de) | 2015-04-29 | 2016-04-21 | Hydrophobe aerogele mit einer geringen belegung an monofunktionellen einheiten |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2018521937A JP2018521937A (ja) | 2018-08-09 |
JP6585190B2 true JP6585190B2 (ja) | 2019-10-02 |
Family
ID=55809101
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017556613A Expired - Fee Related JP6585190B2 (ja) | 2015-04-29 | 2016-04-21 | 単官能性単位の占有率が低い疎水性エーロゲル |
Country Status (7)
Country | Link |
---|---|
US (1) | US10759666B2 (ja) |
EP (1) | EP3288896B1 (ja) |
JP (1) | JP6585190B2 (ja) |
KR (1) | KR102071966B1 (ja) |
CN (1) | CN107531493B (ja) |
DE (1) | DE102015207945A1 (ja) |
WO (1) | WO2016173912A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015207945A1 (de) * | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Hydrophobe Aerogele mit einer geringen Belegung an monofunktionellen Einheiten |
TWI692493B (zh) * | 2018-11-12 | 2020-05-01 | 台灣氣凝膠科技材料開發股份有限公司 | 連續性製備核殼親疏雙極複合氣凝膠粉末的方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4954327A (en) * | 1988-08-12 | 1990-09-04 | Blount David H | Production of silica aerogels |
DE19525021A1 (de) * | 1995-07-10 | 1997-01-16 | Hoechst Ag | Verfahren zur Herstellung von organisch modifizierten Aerogelen und deren Verwendung |
DE19541992A1 (de) * | 1995-11-10 | 1997-05-15 | Hoechst Ag | Verfahren zur Herstellung von organisch modifizierten Aerogelen unter Verwendung von Alkoholen, bei dem gebildeten Salze ausgefällt werden |
DE19648798C2 (de) * | 1996-11-26 | 1998-11-19 | Hoechst Ag | Verfahren zur Herstellung von organisch modifizierten Aerogelen durch Oberflächenmodifikation des wäßrigen Gels (ohne vorherigen Lösungsmitteltausch) und anschließender Trocknung |
US5789495A (en) * | 1997-02-24 | 1998-08-04 | Dow Corning Corporation | Method for making hydrophobic organosilicate-modified silica gels under neutral conditions |
DE19756633A1 (de) * | 1997-12-19 | 1999-06-24 | Hoechst Ag | Verfahren zur unterkritischen Trocknung von Lyogelen zu Aerogelen |
JP4128363B2 (ja) * | 2002-01-22 | 2008-07-30 | 松下電器産業株式会社 | 多孔質ゲルの製造方法 |
KR101147494B1 (ko) * | 2010-05-14 | 2012-05-21 | 주식회사 화인텍 | 소수성 실리카 에어로젤의 제조방법 및 그 제조방법에 의해 제조된 소수성 실리카 에어로젤 |
US9073759B2 (en) * | 2010-08-10 | 2015-07-07 | Massachusetts Institute Of Technology | Silica aerogels and their preparation |
EP2930147B1 (en) * | 2014-02-06 | 2020-05-27 | LG Chem, Ltd. | Production method for hydrophobic silica aerogel |
DE102015207939A1 (de) * | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Verfahren zur Herstellung organisch modifizierter Aerogele |
DE102015207945A1 (de) * | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Hydrophobe Aerogele mit einer geringen Belegung an monofunktionellen Einheiten |
KR101955307B1 (ko) * | 2015-11-27 | 2019-05-30 | 주식회사 엘지화학 | 소수성의 실리카 에어로겔의 제조방법 및 이로부터 제조된 소수성의 실리카 에어로겔 |
-
2015
- 2015-04-29 DE DE102015207945.7A patent/DE102015207945A1/de not_active Withdrawn
-
2016
- 2016-04-21 US US15/564,334 patent/US10759666B2/en active Active
- 2016-04-21 CN CN201680023938.2A patent/CN107531493B/zh not_active Expired - Fee Related
- 2016-04-21 WO PCT/EP2016/058834 patent/WO2016173912A1/de active Application Filing
- 2016-04-21 JP JP2017556613A patent/JP6585190B2/ja not_active Expired - Fee Related
- 2016-04-21 EP EP16718644.4A patent/EP3288896B1/de not_active Not-in-force
- 2016-04-21 KR KR1020177031178A patent/KR102071966B1/ko active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JP2018521937A (ja) | 2018-08-09 |
WO2016173912A1 (de) | 2016-11-03 |
CN107531493B (zh) | 2020-02-28 |
EP3288896A1 (de) | 2018-03-07 |
US20180141821A1 (en) | 2018-05-24 |
KR20170132829A (ko) | 2017-12-04 |
CN107531493A (zh) | 2018-01-02 |
KR102071966B1 (ko) | 2020-01-31 |
EP3288896B1 (de) | 2018-09-19 |
DE102015207945A1 (de) | 2016-11-03 |
US10759666B2 (en) | 2020-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6545821B2 (ja) | 有機修飾エアロゲルの製造方法 | |
US9199853B2 (en) | Metal oxide powder and method for manufacture thereof | |
CN107073430B (zh) | 用于制备有机改性的液凝胶或气凝胶的经济可行的方法 | |
JPWO2012057086A1 (ja) | エアロゲル及びその製造方法 | |
Ambrożewicz et al. | Fluoroalkylsilane versus alkylsilane as hydrophobic agents for silica and silicates | |
WO2010110852A1 (en) | A particle containing a hydrophobic region and a hydrophilic region and methods to make same | |
JP6585190B2 (ja) | 単官能性単位の占有率が低い疎水性エーロゲル | |
EP4143134A1 (en) | Silica aerogel with increased alkaline stability | |
US5789495A (en) | Method for making hydrophobic organosilicate-modified silica gels under neutral conditions | |
Daneshfar et al. | Preparation and characterization of modified SiO2 nanospheres with dichlorodimethylsilane and phenyltrimethoxysilane | |
JP6518343B2 (ja) | 有機修飾エアロゲルの製造方法 | |
JP4536162B2 (ja) | 有機官能化エーロゲルの製造法 | |
JP2021187692A (ja) | 多孔質金属酸化物粉末及びその製造方法 | |
Shajesh et al. | Effect of 3-glycidoxypropyltrimethoxysilane precursor on the properties of ambient pressure dried silica aerogels | |
WO2023127481A1 (ja) | 球状表面処理シリカエアロゲル及びその製造方法 | |
Ambrohewicz et al. | Research Article Fluoroalkylsilane versus Alkylsilane as Hydrophobic Agents for Silica and Silicates | |
Harrison et al. | bChemistry Department, Brunel University, Uxbridge, Middlesex UB8 3PH |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A529 | Written submission of copy of amendment under article 34 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A529 Effective date: 20171222 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171222 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181122 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181211 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20190307 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190423 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190806 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190904 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6585190 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |