JPH0829952B2 - Porous glass manufacturing method - Google Patents
Porous glass manufacturing methodInfo
- Publication number
- JPH0829952B2 JPH0829952B2 JP1245947A JP24594789A JPH0829952B2 JP H0829952 B2 JPH0829952 B2 JP H0829952B2 JP 1245947 A JP1245947 A JP 1245947A JP 24594789 A JP24594789 A JP 24594789A JP H0829952 B2 JPH0829952 B2 JP H0829952B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- solidified
- porous
- dried
- nitric acid
- 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 - Lifetime
Links
- 239000005373 porous glass Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229920000620 organic polymer Polymers 0.000 claims description 33
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 26
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 150000004703 alkoxides Chemical class 0.000 claims description 19
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 229920002125 Sokalan® Polymers 0.000 claims description 12
- 239000004584 polyacrylic acid Substances 0.000 claims description 12
- 238000005191 phase separation Methods 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229920000083 poly(allylamine) Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 94
- 239000011148 porous material Substances 0.000 description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 49
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 45
- 229910017604 nitric acid Inorganic materials 0.000 description 45
- 238000003756 stirring Methods 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 18
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000000499 gel Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- -1 silicon alkoxide Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は触媒担体、酵素担体、分離膜素材のようにサ
ブミクロンからミクロンオーダーの細孔が要求される広
い範囲に利用することができる多孔質ガラスをゾル−ゲ
ル法により製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is applicable to a wide range of pores such as catalyst carriers, enzyme carriers, and separation membrane materials that require submicron to micron order pores. The present invention relates to a method for producing a high quality glass by a sol-gel method.
［従来の技術］ 従来の多孔質セラミックスのうちサブミクロン以下の
極微細孔径を持つものは主としてホウケイ酸塩ガラスの
熱処理による分相現象を利用して、からみ合い分相構造
をとらせた後、片方の相を酸溶出させることにより作製
されている。[Prior Art] Among conventional porous ceramics, those having an extremely fine pore size of submicron or less are mainly used for the entanglement phase-separation structure after the entanglement phase-separation structure is obtained by utilizing the phase-separation phenomenon by the heat treatment of borosilicate glass. It is made by acid eluting one phase.
これに対し、ミクロン以上の細孔径のものはセラミッ
クス原料粉体を仮焼し熱分解させて粒子又は粒子間に開
気孔を作った後、適切な条件で焼結して作られている。
しかしながらこれらの方法ではサブミクロンから数拾ミ
クロンの範囲の揃った細孔径の多孔質セラミックスを製
造することが困難である。更に、用途により要求される
膜状、繊維状のものを作製しにくい欠点がある。このよ
うなことから最近、バルク状、膜状あるいは繊維状のい
ずれの形状のセラミックスも作製できる金属アルコキシ
ドを原料としたゾル−ゲル法が多孔質セラミックスの作
製にも適用されるようになった。On the other hand, those having a pore size of not less than micron are produced by calcining and thermally decomposing ceramic raw material powder to form particles or open pores between particles, and then sintering them under appropriate conditions.
However, it is difficult to produce porous ceramics having a uniform pore size in the range of submicron to several micron by these methods. Further, there is a drawback that it is difficult to produce a film-shaped or fibrous material required for some purposes. For these reasons, recently, the sol-gel method using a metal alkoxide as a raw material, which is capable of producing bulk-shaped, film-shaped, or fibrous shaped ceramics, has also been applied to the production of porous ceramics.
しかし、珪素アルコキシドをアルコール等の有機溶媒
中で加水分解・重合して反応溶液系のゲル化を行なった
後、生成した多孔質ゲルをその後焼成する上記の方法で
作製される多孔質ゲル体の細孔径は、数拾ナノメーター
以下と極めて小さい。そこで細孔をミクロンオーダーと
するため塩酸を多量に加えて加水分解させることも試み
られているが、細孔径分布が広くなる課題がある。However, after the silicon alkoxide is hydrolyzed and polymerized in an organic solvent such as alcohol to gelate the reaction solution system, the resulting porous gel is then fired to produce a porous gel body prepared by the above method. The pore size is extremely small, less than a few nanometers. Therefore, it has been attempted to add a large amount of hydrochloric acid for hydrolysis in order to make the pores on the micron order, but there is a problem that the pore size distribution becomes wide.
また、特開昭62−123032号公報にはシリコンエトキシ
ドのゾル液にポリ酢酸ビニルエマルジョンを添加し混合
してゲル化し焼成して多孔質ガラスを製造する方法が開
示されている。しかしながら、かかる方法により製造さ
れた多孔質ガラスの細孔径分布は広くなるという課題が
あった。Further, JP-A-62-123032 discloses a method for producing a porous glass by adding a polyvinyl acetate emulsion to a sol solution of silicon ethoxide, mixing and gelling the mixture and firing it. However, there has been a problem that the pore size distribution of the porous glass produced by such a method becomes wide.
［発明が解決しようとする課題］ 本発明は従来技術が有していた上記課題を解消し、細
孔径がミクロンオーダーでありその細孔径分布が狭い多
孔質セラミックの得られる製造法の提供を目的とする。[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems of the prior art and aims to provide a method for producing a porous ceramic having a pore size of the order of microns and a narrow pore size distribution. And
［課題を解決するための手段］ 本発明は、金属アルコキシド又はそのオリゴマーと有
機高分子とを含む反応溶液を準備し、該溶液中で該金属
アルコキシド又はそのオリゴマーを加水分解・重合して
ゲルを作成し、該ゲルを焼成して多孔質ガラスを製造す
る方法であって、該有機高分子は、該金属アルコキシド
又はそのオリゴマーの溶液と相溶性を有し、該加水分解
・重合の工程で、相分離を生じ、かつ実質的に沈殿を生
じないものである多孔質ガラスの製造法を提供するもの
である。[Means for Solving the Problem] The present invention provides a gel by preparing a reaction solution containing a metal alkoxide or an oligomer thereof and an organic polymer, and hydrolyzing / polymerizing the metal alkoxide or the oligomer in the solution. A method for producing a porous glass by making the gel and firing the gel, wherein the organic polymer has compatibility with a solution of the metal alkoxide or an oligomer thereof, and in the hydrolysis / polymerization step, It is intended to provide a method for producing a porous glass which causes phase separation and does not substantially cause precipitation.
本発明は均一に溶解した有機高分子が金属アルコキシ
ド又はのそのオリゴマーの加水分解・重合の過程で相分
離する現象を利用するものである。かかる有機高分子と
しては、金属アルコキシド又はそのオリゴマーの加水分
解により生成する溶液に均一に溶解する相溶性を有し、
該加水分解の過程で相分離を生じ、しかも沈殿を生じな
いものが使用される。The present invention utilizes the phenomenon that a uniformly dissolved organic polymer undergoes phase separation in the process of hydrolysis / polymerization of a metal alkoxide or its oligomer. As such an organic polymer, it has the compatibility of being uniformly dissolved in a solution produced by hydrolysis of a metal alkoxide or an oligomer thereof,
A substance that causes phase separation in the hydrolysis process and does not cause precipitation is used.
かかる特性を有する有機高分子としては適当な濃度の
水溶液となし得る水溶性有機高分子であって、金属アル
コキシド又はそのオリゴマーの加水分解により生成する
アルコキシド又はそのオリゴマーの加水分開により生成
するアルコール含有液に均一に溶解するものであればよ
い。具体的には高分子金属塩であるポリスチレンスルホ
ン酸のナトリウム塩、高分子酸であって解離してポリア
ニオンとなるポリアクリル酸等、高分子塩基であって水
溶液中でポリカオチンを生ずるポリアリルアミン及びポ
リエチレンイミン等あるいは中性高分子であって主鎖に
エーテル結合を持つポリエチレンオキシド等側鎖にγ−
ラクタムを有するポリビニルピロリドン等が好適であ
る。An organic polymer having such characteristics is a water-soluble organic polymer that can be formed into an aqueous solution having an appropriate concentration, and is an alcohol-containing liquid produced by hydrolysis of an alkoxide or an oligomer thereof produced by hydrolysis of a metal alkoxide or an oligomer thereof. Any substance that can be uniformly dissolved in Specifically, it is a sodium salt of polystyrene sulfonic acid, which is a polymeric metal salt, polyacrylic acid, which is a polymeric acid that dissociates into a polyanion, and polyallylamine and polyethylene, which are polymeric bases and produce polykaotine in an aqueous solution. Imines or neutral polymers such as polyethylene oxide with ether bond in the main chain γ- in the side chain
Polyvinylpyrrolidone having a lactam is suitable.
金属アルコキシド又はそのオリゴマーとしてはメトキ
シ基、エトキシ基、プロポキシ基等の炭素数の少ないも
のが好ましい。また、その金属としては、最終的に形成
される酸化物の金属例えば、Si,Ti,Zr,Alが使用され
る。この金属としては１種又は２種以上であっても良
い。一方、オリゴマーとしてはアルコールに均一に溶解
分散できるものであればよく、具体的には10量体程度ま
で使用することができる。有機高分子は、金属アルコキ
シド又はそのオリゴマー１重量部に対し、0.03〜0.40重
量部の割合で混合することが好ましい。As the metal alkoxide or its oligomer, those having a small number of carbon atoms such as methoxy group, ethoxy group and propoxy group are preferable. Further, as the metal, a metal of an oxide finally formed, for example, Si, Ti, Zr, Al is used. The metal may be one kind or two or more kinds. On the other hand, the oligomer may be any oligomer as long as it can be uniformly dissolved and dispersed in alcohol, and specifically, up to about 10-mer can be used. The organic polymer is preferably mixed in a proportion of 0.03 to 0.40 parts by weight with respect to 1 part by weight of the metal alkoxide or its oligomer.
有機高分子の量が上記範囲より多くなると、次の点で
好ましくない。即ち、ゲル化時にSiO2ポリマー相が連続
的な骨格を形成せず粒子状に析出する。一方、有機高分
子の量が上記範囲より少なくなると、有機高分子相とシ
リカポリマー相が、からみあった状態でゲル加しないた
め、均一な細孔径の連続貫通孔を有した多孔体ができな
い。有機高分子と金属アルコキシド又はそのオリゴマー
との混合に当たっては特に限定されるものではないが、
有機高分子を酸性水溶液に溶解し、この溶液と金属アル
コキシド又はそのオリゴマーとを撹拌することにより達
成される。酸性水溶液と金属アルコキシド又はそのオリ
ゴマーとを混合した後、有機高分子を添加してもよく、
金属アルコキシド又はそのオリゴマーが一部加水分解・
重合した後、有機高分子を添加することもできる。この
際使用される酸性水溶液としては、通常塩酸、硝酸等の
鉱酸0.001規定以上のものが好ましい。なお、テトラメ
トキシシラン又はそのオリゴマーを使用する場合には酸
を含有しない水溶液を使用して加水分解すると、強度の
高い多孔質ガラスが得られることがある。加水分解に当
たっては、かかる溶液を密閉容器に入れ、室温40〜80℃
で0.5〜５時間保持することにより達成される。加水分
解は当初透明な溶液が白濁して有機高分子との相分離を
生じついにゲル化する過程を経る。この加水分解過程で
有機高分子又はその重合体は分散状態にありそれらの沈
殿は実質的に生じない。When the amount of the organic polymer exceeds the above range, it is not preferable in the following point. That is, during gelation, the SiO 2 polymer phase does not form a continuous skeleton and precipitates in the form of particles. On the other hand, when the amount of the organic polymer is less than the above range, the organic polymer phase and the silica polymer phase do not add gel in a entangled state, so that a porous body having continuous through holes having a uniform pore diameter cannot be obtained. The mixing of the organic polymer and the metal alkoxide or the oligomer thereof is not particularly limited,
It is achieved by dissolving an organic polymer in an acidic aqueous solution and stirring the solution with a metal alkoxide or an oligomer thereof. After mixing the acidic aqueous solution and the metal alkoxide or the oligomer thereof, an organic polymer may be added,
Partial hydrolysis of metal alkoxide or its oligomer
An organic polymer can be added after the polymerization. The acidic aqueous solution used at this time is usually preferably a mineral acid such as hydrochloric acid or nitric acid of 0.001 N or more. When tetramethoxysilane or its oligomer is used, hydrolysis may be performed using an acid-free aqueous solution to obtain a porous glass having high strength. When hydrolyzing, put the solution in a closed container and store at room temperature 40-80 ℃.
At 0.5 to 5 hours. Hydrolysis goes through a process in which an initially transparent solution becomes cloudy, undergoes phase separation from an organic polymer, and finally gels. During this hydrolysis process, the organic polymer or its polymer is in a dispersed state and their precipitation is substantially not caused.
かくしてゲル化したものは、40〜80℃に数時間〜数十
時間程度放置して熟成した後、水により洗浄して有機高
分子を除去し、800〜1000℃程度で焼成して多孔質ガラ
スを得る。The thus gelled product is aged at 40 to 80 ° C for several hours to several tens of hours and then aged, then washed with water to remove the organic polymer and baked at about 800 to 1000 ° C to obtain a porous glass. To get
本発明の目的物の細孔立体構造は、反応系の温度やpH
値、有機高分子の分子量及び含有量、その他金属アルコ
キシド又はそのオリゴマーの反応性および共存する有機
高分子の溶解度に影響を及ぼす各種条件によって変わ
る。従って、細孔立体構造の制御の手法を一律に述べる
ことは困難であるが、前述した条件が同じであれば孔径
等がほぼ同じの目的物を再現性よく提供できる。The pore three-dimensional structure of the object of the present invention is the temperature and pH of the reaction system.
It depends on the value, the molecular weight and content of the organic polymer, the reactivity of the metal alkoxide or its oligomer, and the various conditions that affect the solubility of the coexisting organic polymer. Therefore, it is difficult to uniformly describe the method of controlling the three-dimensional structure of the pores, but if the conditions described above are the same, it is possible to reproducibly provide the target substance having the same pore diameter and the like.
中間物質として生成する多孔質ゲルは、そのままでこ
れを利用することも考えられるが、水中で膨潤し、また
機械的強度も小さいため、その利用は制限される。The porous gel formed as an intermediate substance may be used as it is, but its use is limited because it swells in water and has low mechanical strength.
上記の多孔質ゲルは、これを焼成すれば機械的強度の
向上したSiO2系多孔質セラミックスとなるが、有機高分
子を除去することなく焼成すると、この有機高分子の種
類によってはその分解に伴って生成する物質がSiO2のガ
ラス化を妨げる等の問題を生ぜしめる。The above-mentioned porous gel becomes a SiO 2 -based porous ceramics with improved mechanical strength if it is fired, but if it is fired without removing the organic polymer, it may decompose depending on the type of this organic polymer. The resulting substance causes problems such as hindering the vitrification of SiO 2 .
中間物質として生成する多孔質ゲルからの有機高分子
の除去は、乾燥前のゲルを水で洗浄することによってあ
る程度なすことができるが、洗浄過程の後に更に有機高
分子が分解あるいは燃焼する程度までゲルを十分長時間
加熱してこれを完全に除去する方が有利である。The removal of the organic polymer from the porous gel produced as an intermediate substance can be performed to some extent by washing the gel before drying with water, but to the extent that the organic polymer is further decomposed or burned after the washing process. It is advantageous to heat the gel for a sufficiently long time to completely remove it.
［実施例］ 以下本発明の実施例を説明する。[Examples] Examples of the present invention will be described below.
実施例1:有機高分子としてポリスチレンスルホン酸を用
いる場合 実施例１−１ まず高分子金属塩であるポリスチレンスルホン酸ナト
リウム（アルドリッチ製商品番号24305−１）を、１規
定硝酸水溶液5.51gに溶解して、20重量％溶液とした。
これにメタノール5mlを加え、均一溶液とした後テトラ
メトキシシラン5mlを約１分間かけて滴下し、加水分解
反応を行なった。数分攪拌した後得られた透明溶液を密
閉容器に移し、40℃の恒温槽中に保持したところ約20時
間後に固化した。固化した試料を更に数日熟成させ、60
℃で乾燥した後100℃/hの昇温速度で500℃まで加熱し
た。蒸留水でポリスチレンスルホン酸ナトリウムの分解
生成物を洗浄し、最後に800℃で２時間熱処理した。得
られた多孔質シリカガラス中には５μｍ程度の揃った細
孔がからみあい構造で存在した。なお、60℃で乾燥した
試料の微細構造および細孔径は、熱処理を終えた多孔質
シリカガラスのそれにほぼ一致していた。Example 1: When polystyrene sulfonic acid is used as an organic polymer Example 1-1 First, sodium polystyrene sulfonate which is a polymer metal salt (product number 24305-1 manufactured by Aldrich) is dissolved in 5.51 g of 1N aqueous nitric acid solution. To give a 20 wt% solution.
To this, 5 ml of methanol was added to form a uniform solution, and 5 ml of tetramethoxysilane was added dropwise over about 1 minute to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 20 hours. Aged the solidified sample for a few more days,
After drying at ℃, it was heated up to 500 ℃ at a heating rate of 100 ℃ / h. The decomposition product of sodium polystyrene sulfonate was washed with distilled water and finally heat-treated at 800 ° C. for 2 hours. In the obtained porous silica glass, uniform pores of about 5 μm were present in an entangled structure. The microstructure and pore size of the sample dried at 60 ° C were almost the same as those of the porous silica glass that had been heat-treated.
実施例１−２ メタノール5mlを加えないこととした外は実施例１と
同様にポリスチレンスルホン酸ナトリウムの硝酸水溶液
中でテトラメトキシシランの加水分解を行なった。その
後保持条件を密閉容器中25℃で10時間以内と変え、固化
した試料を実施例１−１と同じ条件で熟成、乾燥、加
熱、洗浄、熱処理することにより多孔質ガラスの細孔径
を１μｍ程度に制御できた。Example 1-2 Tetramethoxysilane was hydrolyzed in an aqueous nitric acid solution of sodium polystyrene sulfonate in the same manner as in Example 1 except that 5 ml of methanol was not added. Thereafter, the holding condition was changed to 25 ° C. within 10 hours in a closed container, and the solidified sample was aged, dried, heated, washed, and heat-treated under the same conditions as in Example 1-1, so that the pore diameter of the porous glass was about 1 μm. I was able to control it.
実施例１−３ ポリスチレンスルホン酸ナトリウムを、１規定硝酸水
溶液5.51gに溶解して、33重量％溶液とした。これにメ
タノール5mlを加えた後、テトラメトキシシラン5mlを約
１分間かけて滴下し、加水分解反応を行なった。数分攪
拌した後得られた透明溶液を密閉容器に移し、40℃の恒
温槽中に保持したところ約20時間後に固化した。固化し
た試料を実施例１−１と同じ条件で熟成、乾燥、加熱、
洗浄、熱処理することにより３μｍ程度の球状粒子の凝
集構造からなる多孔質シリカガラスが得られた。Example 1-3 Sodium polystyrene sulfonate was dissolved in 5.51 g of a 1N aqueous nitric acid solution to give a 33 wt% solution. After adding 5 ml of methanol thereto, 5 ml of tetramethoxysilane was added dropwise over about 1 minute to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 20 hours. The solidified sample was aged, dried and heated under the same conditions as in Example 1-1.
By washing and heat treatment, a porous silica glass having an agglomerated structure of spherical particles of about 3 μm was obtained.
実施例１−４ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS1;分子量１万〜３万）
を、１規定硝酸水溶液5.51gに溶解して、24.1重量％と
し、この溶液に攪拌下でテトラメトキシシラン5mlを滴
下して加水分解反応を行なった。数分攪拌した後得られ
た透明溶液を密閉容器に移し、40℃の恒温槽中に保持し
たところ約２時間以内に固化した。固化した試料を乾燥
に先立って１規定硝酸水溶液に浸漬し、ポリスチレンス
ルホン酸ナトリウムを固化体から洗い出した。この後60
℃で乾燥させた試料は、100μｍ程度の細孔径の絡み合
った構造からなる多孔質であった。この試料を100℃/h
の昇温速度で更に900℃まで加熱することにより、ほぼ
同様の構造を持った多孔質シリカガラスが得られた。Examples 1-4 Those having a clear molecular weight range of sodium polystyrene sulfonate (PS1 manufactured by Tosoh Corp .; molecular weight 10,000 to 30,000)
Was dissolved in 5.51 g of 1N aqueous nitric acid solution to make it 24.1% by weight, and 5 ml of tetramethoxysilane was added dropwise to this solution under stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified within about 2 hours. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out sodium polystyrene sulfonate from the solidified body. After this 60
The sample dried at 0 ° C. was porous having an intertwined structure with a pore size of about 100 μm. This sample is 100 ℃ / h
By further heating at 900 ° C. at a heating rate of 1, a porous silica glass having almost the same structure was obtained.
実施例１−５ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS1;分子量１万〜３万）
を、１規定硝酸水溶液5.51gに溶解して、25.0重量％と
し、この溶液に攪拌下でテトラメトキシシラン5mlを滴
下して加水分解反応を行なった。数分攪拌した後得られ
た透明溶液を密閉容器に移し、60℃の恒温槽中に保持し
たところ約１時間以内に固化した。固化した試料を乾燥
に先立って１規定硝酸水溶液に浸漬し、ポリスチレンス
ルホン酸ナトリウムを固化体から洗い出した。この後60
℃で乾燥させた試料は、0.3μｍ程度の細孔径の絡み合
った構造からなる多孔質であった。また、ポリスチレン
スルホン酸ナトリウムの濃度を27.5重量％まで増加する
ことにより、細孔径を約20μｍまで連続的に制御するこ
とができた。乾燥した試料に所定の熱処理を行なうこと
により、ほぼ同様の構造を持った多孔質シリカガラスが
得られた。Example 1-5 Those having a clear molecular weight range of sodium polystyrene sulfonate (manufactured by Tosoh Corp., PS1; molecular weight 10,000 to 30,000)
Was dissolved in 5.51 g of 1N aqueous nitric acid solution to 25.0% by weight, and 5 ml of tetramethoxysilane was added dropwise to this solution under stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C., whereupon it solidified within about 1 hour. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out sodium polystyrene sulfonate from the solidified body. After this 60
The sample dried at 0 ° C. was porous having an entangled structure with a pore size of about 0.3 μm. Further, by increasing the concentration of sodium polystyrene sulfonate to 27.5% by weight, the pore diameter could be continuously controlled to about 20 μm. By subjecting the dried sample to a predetermined heat treatment, a porous silica glass having a substantially similar structure was obtained.
実施例１−６ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS5;分子量５万〜10万）
を、１規定硝酸水溶液5.51gに溶解して、19.1重量％と
し、この溶液に攪拌下でテトラメトキシシラン5mlを滴
下して加水分解反応を行なった。数分攪拌した後得られ
た透明溶液を密閉容器に移し、40℃の恒温槽中に保持し
たところ約２時間以内に固化した。固化した試料を乾燥
に先立って１規定硝酸水溶液に浸漬し、ポリスチレンス
ルホン酸ナトリウムの分解生成物を固化体から洗い出し
た。この後60℃で乾燥させた試料は、50μｍ程度の細孔
径の絡み合った構造からなる多孔質であった。Examples 1-6 Those having a clear molecular weight range of sodium polystyrenesulfonate (PS5, manufactured by Tosoh Corp .; molecular weight 50,000 to 100,000)
Was dissolved in 5.51 g of a 1N aqueous nitric acid solution to 19.1% by weight, and 5 ml of tetramethoxysilane was added dropwise to this solution under stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified within about 2 hours. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out the decomposition product of sodium polystyrene sulfonate from the solidified body. After that, the sample dried at 60 ° C. was porous having an intertwined structure with a pore size of about 50 μm.
また、ポリスチレンスルホン酸ナトリウムの濃度を1
6.6重量％まで減少させることにより、細孔径の大きさ
を約0.3μｍまで連続的に制御することができた。同様
に、ポリスチレンスルホン酸ナトリウムの添加量を固定
して、１規定硝酸水溶液の量を6.17gまで増加すること
により、細孔径を約0.1μｍまで、連続的に制御するこ
とができた。乾燥した試料に所定の熱処理を行なうこと
により、こほぼ同様の構造を持った多孔質シリカガラス
が得られた。Also, set the concentration of sodium polystyrene sulfonate to 1
By reducing the amount to 6.6% by weight, the size of the pore diameter could be continuously controlled to about 0.3 μm. Similarly, by fixing the amount of sodium polystyrene sulfonate added and increasing the amount of the 1N nitric acid aqueous solution to 6.17 g, the pore diameter could be continuously controlled to about 0.1 μm. By subjecting the dried sample to a predetermined heat treatment, a porous silica glass having substantially the same structure was obtained.
なお、ポリスチレンスルホン酸ナトリウム1.20g,1規
定硝酸水溶液5.51g,テトラメトキシシラン5mlよりなる
溶液から作成した多孔質ガラスについて水銀圧入法によ
り測定した細孔径の分布を第１図に●印で示す。The pore size distribution measured by mercury porosimetry on a porous glass prepared from a solution consisting of 1.20 g of sodium polystyrene sulfonate, 5.51 g of 1N aqueous nitric acid solution and 5 ml of tetramethoxysilane is shown by a circle in FIG.
実施例１−７ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS5;分子量５万〜10万）
を、１規定硝酸水溶液5.51gに溶解して、19.1重量％と
し、この溶液に攪拌下でテトラメトキシシラン5mlを滴
下して加水分解反応を行なった。数分攪拌した後得られ
た透明溶液を密閉容器に移し、60℃の恒温槽中に保持し
たところ約１時間以内に固化した。固化した試料を乾燥
に先立って１規定硝酸水溶液に浸漬し、ポリスチレンス
ルホン酸ナトリウムを固化体から洗い出した。この後60
℃で乾燥させた試料は、0.5μｍ程度の細孔径の絡み合
った構造からなる多孔質であった。また、ポリスチレン
スルホン酸ナトリウムの濃度を21.4重量％まで増加させ
ることにより、細孔径を約20μｍまで連続的に制御する
ことができた。同様に、ポリスチレンスルホン酸ナトリ
ウムの添加量を固定して、１規定硝酸水溶液の量を5.07
gまで減少することにより、細孔径を約20μｍまで連続
的に制御することができた。乾燥した試料に所定の熱処
理を行なうことにより、ほぼ同様の構造を持った多孔質
シリカガラスが得られた。Examples 1-7 Definite molecular weight range of sodium polystyrene sulfonate (Tosoh Corp., PS5; molecular weight 50,000 to 100,000)
Was dissolved in 5.51 g of a 1N aqueous nitric acid solution to 19.1% by weight, and 5 ml of tetramethoxysilane was added dropwise to this solution under stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C., whereupon it solidified within about 1 hour. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out sodium polystyrene sulfonate from the solidified body. After this 60
The sample dried at 0 ° C. was porous having an intertwined structure with a pore size of about 0.5 μm. Further, by increasing the concentration of sodium polystyrene sulfonate to 21.4% by weight, the pore diameter could be continuously controlled to about 20 μm. Similarly, fix the amount of sodium polystyrene sulfonate added and adjust the amount of 1N nitric acid aqueous solution to 5.07.
By reducing to g, the pore size could be controlled continuously to about 20 μm. By subjecting the dried sample to a predetermined heat treatment, a porous silica glass having a substantially similar structure was obtained.
実施例１−８ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS50;分子量40〜60万）
を、１規定硝酸水溶液5.51gに溶解して、14.0重量％と
し、この溶液に攪拌下でテトラメトキシシラン5mlを滴
下して加水分解反応を行なった。数分攪拌した後得られ
た透明溶液を密閉容器に移し、40℃の恒温槽中に保持し
たところ約２時間以内に固化した。固化した試料を乾燥
に先立って１規定硝酸水溶液に浸漬し、ポリスチレンス
ルホン酸ナトリウムを固化体から洗い出した。この後60
℃で乾燥させた試料は、0.3μｍ程度の細孔径の絡み合
った構造からなる多孔質であった。また、ポリスチレン
スルホン酸ナトリウムの濃度を13.2重量％とし、反応時
にメタノール1mlを共存させると、細孔径の大きさは約
0.5μｍとなった。乾燥した試料に所定の熱処理を行な
うことにより、ほぼ同様の構造を持った多孔質シリカガ
ラスが得られた。Example 1-8 Those having a clear molecular weight range of sodium polystyrene sulfonate (PS50, manufactured by Tosoh Corporation; molecular weight 40,000 to 600,000)
Was dissolved in 5.51 g of a 1N aqueous nitric acid solution to 14.0% by weight, and 5 ml of tetramethoxysilane was added dropwise to this solution under stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified within about 2 hours. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out sodium polystyrene sulfonate from the solidified body. After this 60
The sample dried at 0 ° C. was porous having an entangled structure with a pore size of about 0.3 μm. When the concentration of sodium polystyrene sulfonate is 13.2% by weight and 1 ml of methanol is allowed to coexist during the reaction, the pore size is about
It became 0.5 μm. By subjecting the dried sample to a predetermined heat treatment, a porous silica glass having a substantially similar structure was obtained.
実施例１−９ ポリスチレンスルホン酸ナトリウムの分子量範囲の明
確なもの（（株）東ソー製、PS5;分子量５〜10万）を、
１規定硝酸水溶液9.36gに溶解して、11.4重量％とし、
この溶液に攪拌下でテトラエトキシシラン7mlを滴下し
て加水分解反応を行なった。数分攪拌した後得られた透
明溶液を密閉容器に移し、60℃の恒温槽中に保持したと
ころ約２時間以内に固化した。固化した試料を乾燥に先
立って１規定硝酸水溶液に浸漬し、ポリスチレンスルホ
ン酸ナトリウムを固化体から洗い出した。この後60℃で
乾燥させた試料は、２μｍ程度の細孔径の絡み合った構
造からなる多孔質であった。また、ポリスチレンスルホ
ン酸ナトリウムの濃度を10.5重量％から11.8重量％まで
変化させることにより、細孔径を約0.3μｍ〜約15μｍ
まで連続的に制御することができた。同様に、ポリスチ
レンスルホン酸ナトリウムの添加量を固定して、１規定
硝酸水溶液の量を9.64gから9.09gまで変化させることに
より、細孔径を約0.5μｍから約50μｍまで連続的に制
御することができた。更に反応温度を40℃から80℃まで
変化させることにより、細孔径を１μｍ以下から数拾μ
ｍまで制御することができた。乾燥した試料に所定の熱
処理を行なうことにより、ほぼ同様の構造を持った多孔
質シリカガラスが得られた。Example 1-9 A polystyrene polystyrene sulfonate having a clear molecular weight range (manufactured by Tosoh Corp., PS5; molecular weight of 5 to 100,000) was used.
Dissolved in 9.36 g of 1N nitric acid aqueous solution to make 11.4% by weight,
7 ml of tetraethoxysilane was added dropwise to this solution with stirring to carry out a hydrolysis reaction. After stirring for several minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C., whereupon it solidified within about 2 hours. Prior to drying, the solidified sample was immersed in a 1N aqueous nitric acid solution to wash out sodium polystyrene sulfonate from the solidified body. After that, the sample dried at 60 ° C. was porous having an intertwined structure with a pore size of about 2 μm. In addition, by changing the concentration of sodium polystyrene sulfonate from 10.5% by weight to 11.8% by weight, the pore diameter is about 0.3 μm to about 15 μm.
Could be controlled continuously. Similarly, by fixing the amount of sodium polystyrene sulfonate added and changing the amount of 1N nitric acid aqueous solution from 9.64 g to 9.09 g, it is possible to continuously control the pore size from about 0.5 μm to about 50 μm. did it. Furthermore, by changing the reaction temperature from 40 ℃ to 80 ℃, the pore size can be reduced from 1μm or less to several μ
I was able to control up to m. By subjecting the dried sample to a predetermined heat treatment, a porous silica glass having a substantially similar structure was obtained.
実施例2;有機高分子としてポリアクリル酸を用いる場合 実施例２−１ まず高分子酸であるポリアクリル酸の25重量％水溶液
（アルドリッチ製商品番号19205−８、分子量９万）を
蒸留水で希釈して7.4％水溶液とし、これに濃硝酸を加
えて１規定硝酸酸性とした。この溶液5.19gに攪拌下で
テトラエトキシシラン7mlを加えて加水分解反応を行な
った。数分後得られた透明溶液を密閉容器に移し、60℃
の恒温槽中に保持したところ約２時間後に固化した。固
化した試料を更に数時間熟成し、蒸留水とエタノールで
数回洗浄した後、60℃で乾燥した。乾燥した試料には３
μｍ程度の揃った細孔がからみあい構造で存在してい
た。なお、第２図に水銀圧入法で測定した細孔径分布を
●印で示す。上記反応溶液にはエタノールを最大5mlま
で添加して固化させると、得られる多孔質体の細孔径は
小さくなり、最小0.5μｍ程度までこれを連続的に制御
することができた。また、用いる１規定硝酸水溶液の量
を最小3.3gから最大16.5gまで変化させて、生成する多
孔質体の細孔径を最大約20μｍから最小約0.5μｍの範
囲で制御することができた。更に、ポリアクリル酸の濃
度や、反応温度を変化させても同様に細孔径を制御する
ことができた。これらの乾燥した試料を100℃/hの昇温
速度で900℃まで加熱して、この温度に２時間保持した
ところ、ほぼ同じ構造を持った多孔質シリカガラスが得
られた。Example 2; When polyacrylic acid is used as an organic polymer Example 2-1 First, a 25 wt% aqueous solution of polyacrylic acid which is a polymer acid (Aldrich product number 19205-8, molecular weight 90,000) is distilled water. It was diluted to a 7.4% aqueous solution, and concentrated nitric acid was added to this to make 1N nitric acid acidic. 7 ml of tetraethoxysilane was added to 5.19 g of this solution under stirring to carry out a hydrolysis reaction. After a few minutes, transfer the resulting clear solution to a closed container and hold at 60 ° C.
When it was kept in a constant temperature bath, it solidified after about 2 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. 3 for dried samples
Uniform pores of about μm existed in an entangled structure. The pore size distribution measured by the mercury porosimetry is shown in FIG. When ethanol was added to the above reaction solution at a maximum of 5 ml and solidified, the pore diameter of the obtained porous body became small, and this could be controlled continuously to a minimum of about 0.5 μm. Further, the amount of the 1N nitric acid aqueous solution used was changed from a minimum of 3.3 g to a maximum of 16.5 g, and the pore diameter of the produced porous body could be controlled within the range of about 20 μm to about 0.5 μm. Further, the pore size could be controlled in the same manner even if the concentration of polyacrylic acid or the reaction temperature was changed. When these dried samples were heated to 900 ° C. at a heating rate of 100 ° C./h and held at this temperature for 2 hours, porous silica glass having almost the same structure was obtained.
実施例２−２ まず高分子酸であるポリアクリル酸の25重量％水溶液
（アルドリッチ製商品番号19205−8;分子量９万）を蒸
留水で希釈して7.4％水溶液とした後、濃硝酸を加えて
１規定硝酸酸性とした。ポリアクリル酸0.4gと１規定硝
酸5.51gとからなるこの溶液に攪拌下でテトラメトキシ
シラン5mlを加えて加水分解反応を行なった。数分後得
られた透明溶液を密閉容器に移し、60℃の恒温槽中に保
持したとこ約２時間後に固化した。固化した試料を更に
数時間熟成し、蒸留水とエタノールで数回洗浄した後、
60℃で乾燥した。乾燥した試料には300μｍ程度の骨格
と骨格内に微小な細孔を含む絡み合い構造が存在してい
た。上記反応溶液にメタノールを最大5mlまで添加して
固化させると、得られる多孔質体の細孔径は小さくな
り、最小10μｍ程度までこれを連続的に制御することが
できた。また、メタノールを加えずに１規定硝酸水溶液
の量を最大11gまで増加させると、細孔径を最小30μｍ
程度まで連続的に制御することができた。これらの乾燥
した試料に所定の熱処理を行なうことによほぼ同じ構造
を持った多孔質シリカガラスが得られた。Example 2-2 First, a 25% by weight aqueous solution of polyacrylic acid, which is a polymeric acid, (Aldrich product number 19205-8; molecular weight 90,000) was diluted with distilled water to obtain a 7.4% aqueous solution, and then concentrated nitric acid was added. To 1N nitric acid acidity. To this solution consisting of 0.4 g of polyacrylic acid and 5.51 g of 1N nitric acid, 5 ml of tetramethoxysilane was added with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 60 ° C. and solidified after about 2 hours. After aging the solidified sample for a few more hours and washing it several times with distilled water and ethanol,
It was dried at 60 ° C. The dried sample had a skeleton of about 300 μm and an entangled structure containing fine pores in the skeleton. When methanol was added to the above reaction solution at a maximum of 5 ml and solidified, the pore diameter of the obtained porous body became small, and this could be controlled continuously to a minimum of about 10 μm. When the amount of 1N nitric acid aqueous solution is increased up to 11g without adding methanol, the pore diameter becomes 30μm minimum.
It was possible to control continuously to a degree. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having almost the same structure was obtained.
実施例２−３ まず高分子酸であるポリアクリル酸（アルドリッチ製
商品番号18128−5;分子量25万）を１規定硝酸水溶液5.5
1gに溶解して3.50重量％とした。この溶液に攪拌下でテ
トラエトキシシラン7mlを加えて加水分解反応を行なっ
た。数分後得られた透明溶液を密閉容器に移し、80℃の
恒温槽中に保持したところ約１時間後に固化した。固化
した試料を更に数時間熟成し、蒸留水とエタノールで数
回洗浄した後、60℃で乾燥した。乾燥した試料には30μ
ｍ程度の骨格と、骨格内に微小な細孔を含む絡み合い構
造が存在していた。上記反応溶液にはエタノールを最大
5mlまで添加して固化させると、得られる多孔質体の細
孔径は小さくなり、最小10μｍ程度までこれを連続的に
制御することができた。また、エタノールを加えずに１
規定硝酸水溶液の量を最大11gまで増加させると、細孔
径を最小10μｍ程度まで連続的に制御することができ
た。更に、ポリアクリル酸の濃度や、反応温度を変化さ
せても同様に細孔径を制御することができた。これらの
乾燥した試料に所定の熱処理を行なうことによほぼ同じ
構造を持った多孔質シリカガラスが得られた。Example 2-3 First, polyacrylic acid (product number 18128-5 manufactured by Aldrich; molecular weight 250,000), which is a high molecular weight acid, was added with 1N nitric acid aqueous solution 5.5.
It was dissolved in 1 g to make 3.50% by weight. 7 ml of tetraethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a thermostat at 80 ° C., whereupon it solidified after about 1 hour. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. 30μ for dried samples
There was a skeleton of about m and an entangled structure containing minute pores in the skeleton. Maximum ethanol in the above reaction solution
By adding up to 5 ml and solidifying, the pore diameter of the obtained porous body became small, and this could be controlled continuously to a minimum of about 10 μm. Also, 1 without adding ethanol
When the amount of the normal nitric acid aqueous solution was increased up to 11 g, the pore diameter could be controlled continuously to a minimum of about 10 μm. Further, the pore size could be controlled in the same manner even if the concentration of polyacrylic acid or the reaction temperature was changed. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having almost the same structure was obtained.
実施例２−４ まず高分子酸であるポリアクリル酸（アルドリッチ製
商品番号18128−5;分子量25万）を蒸留水5.0gに溶解し
て7.4重量％とした。この溶液に加水分解触媒の酸を加
えずに、攪拌下でテトラメトキシシラン5mlを加えて加
水分解反応を行なった。数分後得られた透明溶液を密閉
容器に移し、60℃の恒温槽中に保持したところ約１時間
後に固化した。固化した試料を更に数時間熟成し、蒸留
水とエタノールで数回洗浄した後、60℃で乾燥した。乾
燥した試料には0.5μｍ程度の揃った細孔が絡み合い構
造で存在していた。上記反応溶液にメタノールを最大2m
lまで添加して固化させると、得られる多孔質体の細孔
径は小さくなり、最小0.2μｍ程度までこれを連続的に
制御することができた。また、メタノールを加えずに蒸
留水の量を最小4.0gから最大6.0gまで変化させると、細
孔径を最大５μｍから最小0.1μｍ程度まで連続的に制
御することができた。更に、ポリアクリル酸の濃度や、
反応温度を変化させても同様に細孔径を制御することが
できた。これらの乾燥した試料に所定の熱処理を行なう
ことにより、ほぼ同じ構造を持った多孔質シリカガラス
が得られた。Example 2-4 First, polyacrylic acid (product number 18128-5 manufactured by Aldrich; molecular weight 250,000), which is a polymer acid, was dissolved in 5.0 g of distilled water to make 7.4% by weight. Hydrolysis reaction was carried out by adding 5 ml of tetramethoxysilane under stirring without adding an acid as a hydrolysis catalyst to this solution. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 60 ° C., whereupon it solidified after about 1 hour. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the dried sample, uniform pores of about 0.5 μm existed in an entangled structure. Up to 2m of methanol in the above reaction solution
When it was added up to 1 and solidified, the pore size of the obtained porous body became small, and this could be controlled continuously to a minimum of about 0.2 μm. When the amount of distilled water was changed from a minimum of 4.0 g to a maximum of 6.0 g without adding methanol, the pore diameter could be continuously controlled from a maximum of 5 μm to a minimum of 0.1 μm. Furthermore, the concentration of polyacrylic acid,
Even if the reaction temperature was changed, the pore size could be controlled similarly. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having almost the same structure was obtained.
実施例２−５ まず高分子酸であるポリアクリル酸（アルドリッチ製
商品番号18128−5;分子量25万）を１規定硝酸5.51gに溶
解して3.50重量％とした。この溶液にあらかじめ混合・
溶解したテトラメトキシシラン5.15gおよびチタンテト
ラブトキシド（オルトチタン酸ブチル）0.515gを攪拌下
で加えて、加水分解反応を行なった。数分後得られた透
明溶液を密閉容器に移し、40℃の恒温槽中に保持したと
ころ約１時間後に固化した。固化した試料を更に数時間
熟成し、１規定硝酸とエタノールで数回洗浄した後、60
℃で乾燥した。乾燥した試料には１μｍ程度の揃った細
孔が絡み合い構造で存在していた。乾燥した試料をさら
に100℃/hの昇温速度で加熱し、800℃で１時間保持した
ところ、ほぼ同じ構造を持ち、Ｘ線回折法によって微結
晶析出の認められないシリカ−チタニア系多孔質ガラス
が得られた。Example 2-5 First, polyacrylic acid (product number 18128-5 manufactured by Aldrich; molecular weight 250,000), which is a polymer acid, was dissolved in 5.51 g of 1N nitric acid to make 3.50% by weight. Pre-mix with this solution
5.15 g of dissolved tetramethoxysilane and 0.515 g of titanium tetrabutoxide (butyl orthotitanate) were added with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 1 hour. The solidified sample was aged for a few more hours, washed with 1N nitric acid and ethanol several times, and then 60
It was dried at ° C. The dried sample had entangled structures with uniform pores of about 1 μm. When the dried sample was further heated at a heating rate of 100 ° C / h and kept at 800 ° C for 1 hour, it had the same structure and silica-titania-based porous material in which fine crystal precipitation was not observed by X-ray diffraction method. A glass was obtained.
実施例3;有機高分子としてポリエチレンオキシド（ポリ
エチレングリコール）を用いる場合 実施例３−１ まず中性高分子であるポリエチレンオキシド（アルド
リッチ製商品番号18198−6:分子量10万）を、１規定硝
酸水溶液6.61gに溶解して13.1重量％とした。この溶液
に攪拌下でテトラエトキシシラン7mlを加えて加水分解
反応を行なった。数分後得られた透明溶液を密閉容器に
移し、40℃の恒温槽中に保持したとこ約８時間後に固化
した。固化した試料を更に数時間熟成し、蒸留水とエタ
ノールで数回洗浄した後、60℃で乾燥した。乾燥した試
料には３μｍ程度の揃った細孔が絡み合い構造で存在し
ていた。上記反応溶液のポリエチレングリコールの濃度
を最小12.6重量％から14.3重量％まで変化しさせると、
細孔径を最大６μｍから最小0.5μｍ程度まで連続的に
制御することができた。さらに１規定硝酸水溶液及びエ
タノールの濃度や反応温度を変化させても同様に細孔径
を制御することができた。これらの乾燥した試料を100
℃/hの昇温速度で900℃まで加熱して、この温度に２時
間保持したところ、ほぼ同様の構造を持った多孔質シリ
カガラスが得られた。Example 3; When Polyethylene Oxide (Polyethylene Glycol) is Used as Organic Polymer Example 3-1 First, a neutral high molecular weight polyethylene oxide (Aldrich product number 18198-6: molecular weight 100,000) was added to a 1N aqueous nitric acid solution. It was dissolved in 6.61 g to make 13.1% by weight. 7 ml of tetraethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C. and solidified after about 8 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the dried sample, uniform pores of about 3 μm existed in an entangled structure. When the concentration of polyethylene glycol in the above reaction solution is changed from a minimum of 12.6% by weight to 14.3% by weight,
The pore size could be controlled continuously from a maximum of 6 μm to a minimum of about 0.5 μm. Further, even if the concentrations of the 1N aqueous nitric acid solution and ethanol and the reaction temperature were changed, the pore size could be controlled similarly. 100 of these dried samples
When heated to 900 ° C. at a temperature rising rate of ° C./h and kept at this temperature for 2 hours, a porous silica glass having almost the same structure was obtained.
実施例３−２ まず中性高分子であるポリエチレンオキシド（アルド
リッチ製商品番号18199−4:分子量20万）を、１規定硝
酸水溶液6.61gに溶解して13.1重量％とした。この溶液
に攪拌下でテトラエトキシシラン7mlを加えて加水分解
反応を行なった。数分後得られた透明溶液を密閉容器に
移し、40℃の恒温槽中に保持したところ約８時間後に固
化した。固化した試料を更に数時間熟成し、蒸留水とエ
タノールで数回洗浄した後、60℃で乾燥した。乾燥した
試料には１μｍ程度の揃った細孔が絡み合い構造で存在
していた。反応溶液中のポリエチレングリコール、１規
定硝酸水溶液及びエタノールの濃度や反応温度を変化さ
せることにより細孔径を制御することができた。これら
の乾燥した試料に所定の熱処理を行なうことにより、ほ
ぼ同様の構造を持った多孔質シリカガラスが得られた。Example 3-2 First, a neutral polymer polyethylene oxide (manufactured by Aldrich, product number 18199-4: molecular weight 200,000) was dissolved in 6.61 g of 1N aqueous nitric acid solution to make 13.1% by weight. 7 ml of tetraethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 8 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. The dried sample had entangled structures with uniform pores of about 1 μm. The pore diameter could be controlled by changing the concentrations of polyethylene glycol, 1N nitric acid aqueous solution and ethanol in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例３−３ まず中性高分子であるポリエチレングリコール（和光
純薬工業（株）製商品番号16812221:分子量４万〜６
万）を、１規定硝酸水溶液6.61gに溶解して12.6重量％
とした。この溶液に攪拌下でテトラエトキシシラン7ml
を加えて加水分解反応を行なった。数分後得られた透明
溶液を密閉容器に移し、40℃の恒温槽中に保持したとこ
ろ約８時間後に固化した。固化した試料を更に数時間熟
成し、蒸留水とエタノールで数回洗浄した後、60℃で乾
燥した。乾燥した試料には２μｍ程度の揃った細孔が絡
み合い構造で存在していた。反応溶液中のポリエチレン
グリコール、１規定硝酸水溶液及びエタノールの濃度や
反応温度を変化させることにより細孔径を制御すること
ができた。これらの乾燥した試料に所定の熱処理を行な
うことにより、ほぼ同様の構造を持った多孔質シリカガ
ラスが得られた。Example 3-3 First, a neutral polymer polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., product number 16812221: molecular weight 40,000-6)
10,000) dissolved in 6.61 g of 1N nitric acid aqueous solution to yield 12.6% by weight
And 7 ml of tetraethoxysilane under stirring in this solution
Was added to carry out hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 8 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the dried sample, uniform pores of about 2 μm were present in an entangled structure. The pore diameter could be controlled by changing the concentrations of polyethylene glycol, 1N nitric acid aqueous solution and ethanol in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例３−４ まず中性高分子であるポリエチレングリコール（林純
薬工業（株）製：分子量２万）を、１規定硝酸水溶液6.
61gに溶解して12.0重量％水溶液とした。この溶液に攪
拌下でテトラエトキシシラン7mlを加えて加水分解反応
を行なった。数分後得られた透明溶液を密閉容器に移
し、40℃の恒温槽中に保持したところ約８時間後に固化
した。固化した試料を更に拾数時間熟成し、蒸留水とエ
タノールで数回洗浄した後、60℃で乾燥した。乾燥した
試料には１μｍ程度の揃った細孔が絡み合い構造で存在
していた。反応溶液中のポリエチレングリコール、１規
定硝酸水溶液及びエタノールの濃度や反応温度を変化さ
せることにより細孔径を制御することができた。これら
の乾燥した試料に所定の熱処理を行なうことにより、ほ
ぼ同様の構造を持った多孔質シリカガラスが得られた。Example 3-4 First, a neutral polymer polyethylene glycol (manufactured by Hayashi Pure Chemical Industries, Ltd .: molecular weight 20,000) was added to a 1N aqueous nitric acid solution 6.
It was dissolved in 61 g to give a 12.0 wt% aqueous solution. 7 ml of tetraethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 8 hours. The solidified sample was further picked up and aged for several hours, washed with distilled water and ethanol several times, and then dried at 60 ° C. The dried sample had entangled structures with uniform pores of about 1 μm. The pore diameter could be controlled by changing the concentrations of polyethylene glycol, 1N nitric acid aqueous solution and ethanol in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例３−５ まず中性高分子であるポリエチレングリコール（林純
薬工業（株）製：分子量6000）を、１規定硝酸水溶液6.
16gに溶解して7.03重量％水溶液とした。この溶液に攪
拌下でテトラエトキシシラン7mlを加えて加水分解反応
を行なった。数分後得られた透明溶液を密閉容器に移
し、40℃の恒温槽中に保持したところ約８時間後に固化
した。固化した試料を更に拾数時間熟成し、蒸留水とエ
タノールで数回洗浄した後、60℃で乾燥した。乾燥した
試料には１μｍ程度の揃った細孔が絡み合い構造で存在
していた。反応溶液中のポリエチレングリコール、１規
定硝酸水溶液及びエタノールの濃度や反応温度を変化さ
せることにより細孔径を制御することができた。これら
の乾燥した試料に所定の熱処理を行なうことにより、ほ
ぼ同様の構造を持った多孔質シリカガラスが得られた。Example 3-5 First, a neutral high molecular weight polyethylene glycol (Hayashi Pure Chemical Industries, Ltd .: molecular weight 6000) was added to a 1N aqueous nitric acid solution 6.
It was dissolved in 16 g to give a 7.03% by weight aqueous solution. 7 ml of tetraethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 40 ° C., whereupon it solidified after about 8 hours. The solidified sample was further picked up and aged for several hours, washed with distilled water and ethanol several times, and then dried at 60 ° C. The dried sample had entangled structures with uniform pores of about 1 μm. The pore diameter could be controlled by changing the concentrations of polyethylene glycol, 1N nitric acid aqueous solution and ethanol in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例4;有機高分子としてポリビニルピロリドンを用い
る場合 実施例４−１ まず中性高分子であるポリビニルピロリドン（アルド
リッチ製商品番号85645−2:分子量１万）を、１規定硝
酸水溶液5.51gに溶解して21.4重量％とした。この溶液
に攪拌下でテトラメトキシシラン5mlを加えて加水分解
反応を行なった。数分後得られた透明溶液を密閉容器に
移し、60℃の恒温槽中に保持したところ約１時間後に固
化した。固化した試料を更に拾数時間熟成し、蒸留水と
エタノールで数回洗浄した後、60℃で乾燥した。乾燥し
た試料には３μｍ程度の揃った細孔が絡み合い構造で存
在していた。反応溶液中の高分子の濃度や反応温度を変
化させることによって、異なる細孔径を持つ多孔体が得
られた。これらの乾燥した試料を100℃/hの昇温速度で9
00℃まで加熱してこの温度に２時間保持したところ、ほ
ぼ同様の構造を持った多孔質シリカガラスが得られた。Example 4; When using polyvinylpyrrolidone as an organic polymer Example 4-1 First, polyvinylpyrrolidone (Aldrich product number 85645-2: molecular weight 10,000), which is a neutral polymer, is dissolved in 5.51 g of a 1N aqueous nitric acid solution. To be 21.4% by weight. 5 ml of tetramethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was transferred to a closed container and kept in a constant temperature bath at 60 ° C., whereupon it solidified after about 1 hour. The solidified sample was further picked up and aged for several hours, washed with distilled water and ethanol several times, and then dried at 60 ° C. In the dried sample, uniform pores of about 3 μm existed in an entangled structure. Porous substances having different pore sizes were obtained by changing the concentration of the polymer in the reaction solution and the reaction temperature. These dried samples were heated at a heating rate of 100 ° C / h for 9
When heated to 00 ° C. and kept at this temperature for 2 hours, a porous silica glass having a substantially similar structure was obtained.
実施例４−２ まず中性高分子であるポリビニルピロリドン（アルド
リッチ製商品番号85656−8:分子量４万）を蒸留水5.0g
に溶解して23.1重量％とした。この溶液に攪拌下でテト
ラメトキシシラン5mlを加えて加水分解反応を行なっ
た。数分後得られた透明溶液を密閉容器に移し、60℃の
恒温槽中に保持したところ約30分以内に固化した。固化
した試料を更に数時間熟成し、蒸留水とエタノールで数
回洗浄した後、60℃で乾燥した試料には0.3μｍ程度の
揃った細孔が絡み合い構造で存在していた。なお、第３
図水銀圧入法で測定した細孔径分布を示す。反応溶液中
の高分子の濃度や反応温度を変化させることによって、
異なる細孔径を持つ多孔体が得られた。これらの乾燥し
た試料に所定の熱処理を行なうことにより、ほぼ同様の
構造を持った多孔質シリカガラスが得られた。Example 4-2 First, 5.0 g of distilled water was added to polyvinylpyrrolidone (Aldrich product number 85656-8: molecular weight 40,000), which is a neutral polymer.
To 23.1% by weight. 5 ml of tetramethoxysilane was added to this solution with stirring to carry out a hydrolysis reaction. After a few minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C, whereupon it solidified within about 30 minutes. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the sample, uniform pores of about 0.3 μm were present in an entangled structure. The third
Figure shows the pore size distribution measured by mercury porosimetry. By changing the concentration of the polymer in the reaction solution and the reaction temperature,
Porous bodies with different pore sizes were obtained. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例5;有機高分子としてポリアリルアミンを用いる場
合 実施例５−１ まず側鎖に第一アミンのみを有するポリアリルアミン
（日東紡績製 PAA−HCL−L:分子量8000〜11000）を、0.
5規定硝酸水溶液に溶解して11.8重量％とした。この溶
液10.51gに攪拌下でテトラメトキシシラン5mlを加え
て、加水分解反応を行なった。数分後得られた透明溶液
を密閉容易に移し、40℃の恒温槽中に保持したところ約
２時間以内に固化した。固化した試料を更に数時間熟成
し、蒸留水とエタノールで数回洗浄した後、60℃で乾燥
した。乾燥した試料には３μｍ程度の揃った細孔が絡み
合い構造で存在していた。反応溶液中の高分子の濃度や
反応温度を変化させることによって、異なる細孔径を持
つ多孔体が得られた。これらの乾燥した試料を100℃/h
の昇温速度で900℃まで加熱してこの温度に２時間保持
したところ、ほぼ同様の構造を持った多孔質シリカガラ
スが得られた。Example 5; When polyallylamine is used as the organic polymer Example 5-1 First, polyallylamine having only a primary amine in the side chain (PAA-HCL-L manufactured by Nitto Boseki: molecular weight 8000 to 11000) was used.
It was dissolved in 5N aqueous nitric acid solution to make 11.8% by weight. To 10.51 g of this solution, 5 ml of tetramethoxysilane was added with stirring to carry out a hydrolysis reaction. The transparent solution obtained after a few minutes was easily transferred in a sealed manner and kept in a constant temperature bath at 40 ° C., whereupon it solidified within about 2 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the dried sample, uniform pores of about 3 μm existed in an entangled structure. Porous substances having different pore sizes were obtained by changing the concentration of the polymer in the reaction solution and the reaction temperature. These dried samples were run at 100 ° C / h
When heated to 900 ° C. at a heating rate of and held at this temperature for 2 hours, a porous silica glass having almost the same structure was obtained.
実施例５−２ まず側鎖に第一アミンのみを有するポリアリルアミン
の塩酸塩（日東紡績製 PAA−HCL−H:分子量50000〜6500
0）を、0.5規定硝酸水溶液に溶解して3.67重量％とし
た。この溶液10.51gに攪拌下でテトラメトキシシラン3m
lを加えて、加水分解反応を行なった。数分後得られた
透明溶液を密閉容器に移し、60℃の恒温槽中に保持した
ところ約１時間以内に固化した。固化した試料を更に数
時間熟成し、蒸留水とエタノールで数回洗浄した後、60
℃で乾燥した。乾燥した試料には0.5μｍ程度の揃った
細孔が絡み合い構造で存在していた。反応溶液中の高分
子の濃度や反応温度を変化させることによって、異なる
細孔径を持つ多孔体が得られた。これらの乾燥した試料
を所定の熱処理を行なうことにより、ほぼ同様の構造を
持った多孔質シリカガラスが得られた。Example 5-2 First, a polyallylamine hydrochloride having only a primary amine in a side chain (PAA-HCL-H manufactured by Nitto Boseki: molecular weight 50000 to 6500).
0) was dissolved in 0.5N nitric acid aqueous solution to make 3.67% by weight. To 10.51 g of this solution was added 3 m of tetramethoxysilane under stirring.
l was added to carry out a hydrolysis reaction. After a few minutes, the obtained transparent solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C. When it was solidified within about 1 hour. The solidified sample is aged for several more hours, washed with distilled water and ethanol several times, and then 60
It was dried at ° C. In the dried sample, uniform pores of about 0.5 μm existed in an entangled structure. Porous substances having different pore sizes were obtained by changing the concentration of the polymer in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
実施例6;有機高分子としてポリエチレンイミンを用いる
場合 実施例６−１ まず主鎖に窒素原始を有するポリエチレンイミンの50
重量％水溶液（アルドリッチ製商品番号18197−８）を2
0重量％に希釈し、この溶液6.25gに62重量％の濃硝酸2.
54gと水1mlを加えて均一溶液とした。この溶液に攪拌下
でテトラメトキシシラン5mlを加えて、加水分解反応を
行なった。数分後得られた透明溶液を密閉容器に移し、
60℃の高温槽中に保持したところ約２時間以内に固化し
た。固化した試料を更に数時間熟成し、蒸留水とエタノ
ールで数回洗浄した後、60℃で乾燥した。乾燥した試料
には0.1μｍ程度の揃った細孔が絡み合い構造で存在し
ていた。反応溶液中の高分子の濃度や反応温度を変化さ
せることによって、異なる細孔径を持つ多孔体が得られ
た。これらの乾燥した試料を所定の熱処理を行なうこと
により、ほぼ同様の構造を持った多孔質シリカガラスが
得られた。Example 6; Using polyethyleneimine as an organic polymer Example 6-1 First, 50 of polyethyleneimine having a nitrogen primitive in its main chain is used.
2% by weight aqueous solution (Aldrich product number 18197-8)
Dilute to 0 wt% and add to this solution 6.25 g 62 wt% concentrated nitric acid 2.
54 g and 1 ml of water were added to make a homogeneous solution. 5 ml of tetramethoxysilane was added to this solution under stirring to carry out hydrolysis reaction. After a few minutes transfer the resulting clear solution to a closed container,
When kept in a high temperature bath at 60 ° C, it solidified within about 2 hours. The solidified sample was further aged for several hours, washed several times with distilled water and ethanol, and then dried at 60 ° C. In the dried sample, uniform pores of about 0.1 μm existed in an entangled structure. Porous substances having different pore sizes were obtained by changing the concentration of the polymer in the reaction solution and the reaction temperature. By subjecting these dried samples to a predetermined heat treatment, porous silica glass having a substantially similar structure was obtained.
上述の実施例では、原料がテトラアルコキシシランで
あったため多孔質シリカガラスが得られたが、テトラア
ルコキシシランに少量の他の金属アルコキシドを添加し
た原料を用いれば同様にして各種のSiO2系多孔質セラミ
ックスが得られる。また、昇温速度や最高加熱温度を多
少変更しても同様な多孔質セラミックスが得られる。In the above-mentioned examples, since the raw material was tetraalkoxysilane, porous silica glass was obtained, but if a raw material obtained by adding a small amount of other metal alkoxide to tetraalkoxysilane is used, various SiO 2 -based porous materials are similarly obtained. Quality ceramics can be obtained. Further, similar porous ceramics can be obtained even if the temperature rising rate and the maximum heating temperature are changed to some extent.
［比較例］ テトラエトキシシラン250mlに0.01規定の塩酸200mlを
加え攪拌した。次いでこれに10〜50重量％のポリ酢酸ビ
ニルエマルジョンを加えて分散させた。次いでこれにア
ンモニアを添加し、pH値を〜3.5〜6.6に調整した後、密
閉容器に入れ、20〜30℃で放置しゲル化させた。次いで
これを焼成し多孔質ガラスを製造した。この多孔質ガラ
スについて細孔径を測定した結果を第１図に▽印でプロ
ットした。同図から明らかなように、この細孔径は広い
範囲に分布している。[Comparative Example] To 250 ml of tetraethoxysilane, 200 ml of 0.01N hydrochloric acid was added and stirred. Then, 10 to 50% by weight of polyvinyl acetate emulsion was added and dispersed therein. Then, ammonia was added to this to adjust the pH value to ˜3.5 to 6.6, then put in a closed container and left at 20 to 30 ° C. for gelation. Then, this was fired to produce a porous glass. The results of measuring the pore size of this porous glass are plotted in FIG. As is clear from the figure, the pore diameters are distributed in a wide range.
［発明の効果］ 本発明によれば、サブミクロンから数拾ミクロンの範
囲の揃った細孔径を有する多孔質セラミックスを容易に
提供できる。[Effects of the Invention] According to the present invention, it is possible to easily provide a porous ceramic having a uniform pore size in the range of submicron to several micron.
第１図、第２図、第３図は、細孔径分布図を示す図であ
る。FIG. 1, FIG. 2 and FIG. 3 are diagrams showing pore diameter distribution charts.
Claims (2)
機高分子とを含む反応溶液を準備し、該溶液中で該金属
アルコキシド又はそのオリゴマーを加水分解・重合して
ゲルを作成し、該ゲルを焼成して多孔質ガラスを製造す
る方法であって、該有機高分子は、該金属アルコキシド
又はそのオリゴマーの溶液と相溶性を有し、該加水分解
・重合の工程で、相分離を生じ、かつ実質的に沈殿を生
じないものである多孔質ガラスの製造法。1. A reaction solution containing a metal alkoxide or an oligomer thereof and an organic polymer is prepared, and a gel is prepared by hydrolyzing and polymerizing the metal alkoxide or an oligomer thereof in the solution and baking the gel. A method for producing a porous glass by using the organic polymer, wherein the organic polymer is compatible with the solution of the metal alkoxide or its oligomer, phase separation occurs in the hydrolysis / polymerization step, and A method for producing a porous glass which does not cause precipitation in the glass.
酸ナトリウム、ポリアクリル酸、ポリアリルアミン、ポ
リエチレンイミン、ポリエチレンオキシド又はポリビニ
ルピロリドンである請求項（１）記載の多孔質ガラスの
製造法。2. The method for producing a porous glass according to claim 1, wherein the organic polymer is sodium polystyrene sulfonate, polyacrylic acid, polyallylamine, polyethyleneimine, polyethylene oxide or polyvinylpyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1245947A JPH0829952B2 (en) | 1988-09-28 | 1989-09-21 | Porous glass manufacturing method |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24553288 | 1988-09-28 | ||
| JP63-245532 | 1988-09-28 | ||
| JP5688689 | 1989-03-08 | ||
| JP1-56886 | 1989-03-08 | ||
| JP1245947A JPH0829952B2 (en) | 1988-09-28 | 1989-09-21 | Porous glass manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH038729A JPH038729A (en) | 1991-01-16 |
| JPH0829952B2 true JPH0829952B2 (en) | 1996-03-27 |
Family
ID=27296071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1245947A Expired - Lifetime JPH0829952B2 (en) | 1988-09-28 | 1989-09-21 | Porous glass manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829952B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7217359B2 (en) | 2003-07-30 | 2007-05-15 | Ngk Insulators, Ltd. | Columns for chromatograph |
| US7291383B2 (en) | 2004-01-23 | 2007-11-06 | Ngk Insulators, Ltd. | Supports for solid phase extraction |
| WO2013187398A1 (en) | 2012-06-14 | 2013-12-19 | ダイソー株式会社 | Support for antibody purification, manufacturing method for same, and application for same |
| WO2018207932A1 (en) | 2017-05-12 | 2018-11-15 | 国立大学法人広島大学 | Cancer diagnosis device |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4559813B2 (en) * | 2004-10-05 | 2010-10-13 | 株式会社トクヤマ | Method for producing dual pore silica beads |
| JP4745706B2 (en) * | 2005-04-13 | 2011-08-10 | Ｄｉｃ株式会社 | Water-based coating composition and method for producing coating film |
| JP4684813B2 (en) * | 2005-09-05 | 2011-05-18 | 国立大学法人 千葉大学 | Method for producing dual pore silica |
| JP4985112B2 (en) * | 2007-06-04 | 2012-07-25 | Ｄｉｃ株式会社 | Organic-inorganic hybrid resin aqueous dispersion, curable resin composition, paint and paint |
| JP4985460B2 (en) * | 2007-07-27 | 2012-07-25 | Ｄｉｃ株式会社 | Organic-inorganic hybrid resin aqueous dispersions, paints and painted products |
| JP4226050B1 (en) * | 2007-09-12 | 2009-02-18 | 株式会社Ｒｅｉメディカル | Absorption column for body fluid purification treatment |
| CN102834355B (en) * | 2010-03-04 | 2015-06-24 | 地方独立行政法人东京都立产业技术研究中心 | Process for producing porous silica, and porous silica |
-
1989
- 1989-09-21 JP JP1245947A patent/JPH0829952B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7217359B2 (en) | 2003-07-30 | 2007-05-15 | Ngk Insulators, Ltd. | Columns for chromatograph |
| US7291383B2 (en) | 2004-01-23 | 2007-11-06 | Ngk Insulators, Ltd. | Supports for solid phase extraction |
| WO2013187398A1 (en) | 2012-06-14 | 2013-12-19 | ダイソー株式会社 | Support for antibody purification, manufacturing method for same, and application for same |
| WO2018207932A1 (en) | 2017-05-12 | 2018-11-15 | 国立大学法人広島大学 | Cancer diagnosis device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH038729A (en) | 1991-01-16 |
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