JPS62241879A - Manufacture of inorganic layer porous body - Google Patents
Manufacture of inorganic layer porous bodyInfo
- Publication number
- JPS62241879A JPS62241879A JP8473286A JP8473286A JPS62241879A JP S62241879 A JPS62241879 A JP S62241879A JP 8473286 A JP8473286 A JP 8473286A JP 8473286 A JP8473286 A JP 8473286A JP S62241879 A JPS62241879 A JP S62241879A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- inorganic
- layered porous
- porous material
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 23
- 150000002484 inorganic compounds Chemical class 0.000 claims description 21
- -1 cationic inorganic compound Chemical class 0.000 claims description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910021647 smectite Inorganic materials 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002363 hafnium compounds Chemical class 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- UTEKWVTZAYINIU-UHFFFAOYSA-N [F].[Si].[Si].[Si].[Si] Chemical compound [F].[Si].[Si].[Si].[Si] UTEKWVTZAYINIU-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- XYWJNTOURDMTPI-UHFFFAOYSA-N procodazole Chemical compound C1=CC=C2NC(CCC(=O)O)=NC2=C1 XYWJNTOURDMTPI-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/20—Mica; Vermiculite
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔技術分野〕
この発明は、断熱性に優れた無機層状多孔体の製法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing an inorganic layered porous material having excellent heat insulation properties.
空隙を有する層状化合物として、膨潤性層状化合物の層
間に水酸化物等の異種物質を挿入反応させたインターカ
レーション物質がある（たとえば、特開昭５４−５８８
４号公報および特開昭５４−１６３８６号公報参照）。As a layered compound having voids, there is an intercalation material in which a different substance such as hydroxide is inserted between the layers of a swellable layered compound (for example, Japanese Patent Application Laid-Open No. 54-588
4 and JP-A-54-16386).
ところが、このものは、層間距離が１０Å以下と小さい
ため、吸着水の影♂を受けやすく、また、断熱性の点で
もあまり優れているとは言えないものである。However, since this material has a small interlayer distance of 10 Å or less, it is easily affected by adsorbed water, and it cannot be said to have very good heat insulation properties.
これに対し、微細多孔質粘土材料として、スメクタイト
型鉱物に水溶性高分子化合物を混合したものを使用し、
それに、陽イオン性酸化物あるいは重合体状シリカをイ
ンターカレーションすることが、特開昭６０−１３１８
７８号公報、特開昭６０−１３７８１２号公報、特開昭
６０−１３７８１３号公報、特開昭６０−１５５５２６
号公報、ならびに、特開昭６０−１６６２１７号公報等
に示されている。これらの方法によれば、層間距離を前
述のインターカレーション物質の場合の１０Å以下から
、３０人程度にまで拡げることができる。しかしながら
、この方法によって形成された層状多孔体では、前述し
たように層間距離を３０人程度にまで拡げることができ
ても、その空隙内に水分が吸着されやすいため、この水
分の吸着による各層間の熱的な短絡が発生することがさ
けられず、熱物性の向上が期待できない。In contrast, we used a mixture of smectite minerals and water-soluble polymer compounds as microporous clay materials.
In addition, intercalation of cationic oxide or polymeric silica has been proposed in JP-A-60-1318.
78, JP 60-137812, JP 60-137813, JP 60-155526
No. 60-166217, etc. According to these methods, the interlayer distance can be increased from 10 Å or less in the case of the above-mentioned intercalation material to about 30. However, in the layered porous body formed by this method, even if the interlayer distance can be increased to about 30 people as described above, moisture is likely to be adsorbed within the pores. It is unavoidable that a thermal short circuit will occur, and no improvement in thermal properties can be expected.
この発明は、このような事情に鑑みてなされたものであ
って、層間に比較的大きな空隙を有し、断熱効果に優れ
た無機層状多孔体を製造する方法を提供することを目的
としている。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing an inorganic layered porous body having relatively large voids between layers and having an excellent heat insulating effect.
以上の目的を達成するため、この発明は、膨潤させた膨
潤性層状化合物の層間に、水溶性高分子化合物および第
４級アンモニウム塩のうちの少なくとも一方を挿入する
とともに、あらかじめエステル化したコロイド状無機化
合物に陽イオン性無機化合物を付加反応させて得られる
反応物をも挿入し、乾燥、焼成を行って前記層間に微細
な空隙を形成するようにする無機層状多孔体の製法を要
旨としている。In order to achieve the above object, the present invention inserts at least one of a water-soluble polymer compound and a quaternary ammonium salt between the layers of a swollen layered compound, and a pre-esterified colloidal compound. The gist is a method for producing an inorganic layered porous material in which a reactant obtained by addition-reacting a cationic inorganic compound to an inorganic compound is also inserted, followed by drying and firing to form fine voids between the layers. .
以下に、この発明を、そのｌ実施例をあられす図面を参
照しつつ詳しく説明する。Hereinafter, embodiments of the present invention will be explained in detail with reference to the accompanying drawings.
構造を模式化してあられした第１図にみるように、この
発明の無機層状多孔体の製法によって得られる無機層状
多孔体Ａは、無機層状化合物の層１．１間に、無機化合
物２が挿入固定されている。そのため、その層間の空隙
３が３０〜６００人に保持されている。As shown in FIG. 1, which schematically shows the structure, the inorganic layered porous material A obtained by the method for producing an inorganic layered porous material of the present invention has an inorganic compound 2 inserted between the layers 1.1 of the inorganic layered compound. Fixed. Therefore, the gap 3 between the layers is maintained between 30 and 600 people.
この発明に用いられる膨潤性層状化合物としては、Ｎａ
−モンモリロナイト、 Ｃａ−モンモリロナイト、酸性
白土、３−八面体合成スメクタイト、Ｎａ−ヘクトライ
ト、Ｌｉ−ヘクトライト、 Ｎａ−テニオライト、Ｌｉ
−テニオライト、および、合成雲母（Ｎａフッ素四ケイ
素雲母）等が挙げられるが、膨潤性層状化合物でありさ
えすれば、これらに限られるものではない。Ｃａ−モン
モリロナイトおよび酸性白土等のような膨潤性層状化合
物を主材として用いる場合には、強い剪断力を加えない
と膨潤しにくいので、膨潤時には混錬する必要がある。The swelling layered compound used in this invention includes Na
-Montmorillonite, Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, Na-hectorite, Li-hectite, Na-teniolite, Li
- teniolite, synthetic mica (Na fluorine tetrasilicon mica), etc., but the compound is not limited to these as long as it is a swellable layered compound. When a swellable layered compound such as Ca-montmorillonite or acid clay is used as the main material, it is difficult to swell unless a strong shearing force is applied, so it is necessary to knead it during swelling.
無機化合物となる反応物としては、あらかじめエステル
化されたコロイド状無機化合物に、陽イオン性無機化合
物を付加反応させたものが用いられる。コロイド状無機
化合物としては、５ｉ０２、Ｓｂｚ ０３ 、Ｆｅｚ
Ｏｚ ＋ Ａｌ１０３ 、ＴｉＯ２、および、ＺｒＯ，
などが挙げられ、これらが単独で、あるいは、？ｊ［Ｂ
混合して用いられる。このようなコロイド状無機化合物
をエステル化する方法も特に限定されず、通常、一般に
行われているエステル化法を適用することができる。エ
ステル化に用いられる有機化合物の種類も特に限定はさ
れず、メタノール、エタノール、ブタノール。As the reactant to become an inorganic compound, a product obtained by subjecting a colloidal inorganic compound that has been esterified in advance to an addition reaction with a cationic inorganic compound is used. Colloidal inorganic compounds include 5i02, Sbz 03, Fez
Oz + Al103, TiO2, and ZrO,
etc., and these alone or? j[B
Used in combination. The method of esterifying such a colloidal inorganic compound is not particularly limited, and a commonly used esterification method can be applied. The type of organic compound used for esterification is also not particularly limited, and includes methanol, ethanol, and butanol.
イソプロパツール、ノルマルプロパツール等の化合物を
単独で、あるいは、２挿具ユ、混合して用いることがで
きる。Compounds such as isopropanol and normal propazole can be used alone or in combination.
以上のように、コロイド状無機化合物をエステル化する
のは、このコロイド状無機化合物と、前記陽イオン性無
機化合物との付加反応を円滑に行うためである。すなわ
ち、このようなコロイド状無機化合物は、通常、その表
面がマイナスに帯電しており、それによってコロイド状
態が破壊される恐れがあるため、Ｎ ａ＋やＮＨ，”等
を配合して、前記コロイド状無機化合物を有効に単分散
させ、コロイド状態の安定化をはかっている。ところが
、このようなコロイド状無機化合物では、その表面付近
にある前記Ｎａ゛やＮｉｂ”等が障害となって、前記陽
イオン性無機化合物との付加反応を円滑に進行させるこ
とができない。そこで、この発明では、このようなＮａ
＋やＮＨ，”等を、エステル化によってＣ１ｌ、やＣ：
ｌＨ’１等の官能基にあらかじめ置換しておいてから、
あらためて、前記陽イオン性無機化合物と付加反応させ
るようにし、この付加反応を円滑に進行さ−Ｕるように
したのである。As described above, the reason why the colloidal inorganic compound is esterified is to smoothly perform the addition reaction between the colloidal inorganic compound and the cationic inorganic compound. In other words, the surface of such colloidal inorganic compounds is usually negatively charged, which may destroy the colloidal state. In this method, the colloidal inorganic compound is effectively monodispersed to stabilize its colloidal state. However, in such a colloidal inorganic compound, the above-mentioned Na', Nib', etc. near the surface become an obstacle, and the above-mentioned Addition reactions with cationic inorganic compounds cannot proceed smoothly. Therefore, in this invention, such Na
+, NH,” etc., by esterification to C1l, C:
After substituting in advance with a functional group such as lH'1,
Once again, an addition reaction was carried out with the cationic inorganic compound, and this addition reaction was made to proceed smoothly.
この発明に使用できる陽イオン性無機化合物としては、
ＴｉＣｌ４等のチタン系化合物、Ｚｒ００１□等のジル
コニウム系化合物、ハフニウム系化合物、リン系化合物
、ホウ素系化合物等が挙げられる。そして、これらが単
独で、あるいは、複数混合して、用いられる。Cationic inorganic compounds that can be used in this invention include:
Examples include titanium compounds such as TiCl4, zirconium compounds such as Zr001□, hafnium compounds, phosphorus compounds, and boron compounds. These may be used alone or in combination.
以上のような反応物とともに、前記膨潤性層状化合物の
眉間に挿入される水溶性高分子化合物としては種々のも
のが考えられるが、たとえば、ポリビニルアルコール、
ポリエチレングリコール。Various water-soluble polymer compounds can be considered to be inserted between the eyebrows of the swellable layered compound together with the above-mentioned reactants, such as polyvinyl alcohol,
Polyethylene glycol.
ポリエチレンオキサイド、メチルセルＩ′：１−ス、カ
ルボキシメチルセルロース、ポリアクリル酸ソーダ、ポ
リビニルピロリドン等が、好ましいものとしてあげられ
る。Preferred examples include polyethylene oxide, methylcellulose I':1-s, carboxymethylcellulose, sodium polyacrylate, and polyvinylpyrrolidone.
また、第４級アンモニウム塩としても、種々のものが考
えられるが、その中でも、オクタデシル基、ヘキサデシ
ル基、テトラデシル基、および、ドデシル基等の基を有
するものが好ましい。このような第４級アンモニウム塩
としては、っぎのような化合物があるが、眉間を押し拡
げて前記反応物の挿入を助け、焼成によって気化して層
間に空隙を残し、しかも、前記反応物と混合可能（すな
わち、混合してもゲル化しない）で、がっ、カチオン性
であれば、これ以外のものを使用することもできる。Moreover, various kinds of quaternary ammonium salts can be considered, but among them, those having groups such as octadecyl group, hexadecyl group, tetradecyl group, and dodecyl group are preferable. As such quaternary ammonium salts, there are compounds such as 《》, which expand the glabella to help insert the reactant, vaporize by calcination, leave a gap between the layers, and furthermore, they Other materials can also be used as long as they are mixable (ie, do not gel when mixed) and are cationic.
オクタデシルトリメチルアンモニウム塩、ジオクタデシ
ルジメチルアンモニウム塩、ヘキサデシルトリメチルア
ンモニウム塩、ジオクタデシルジメチルアンモニウム塩
、テトラデシルトリメチルアンモニウム塩、ジオクタデ
シルジメチルアンモニウム塩。Octadecyltrimethylammonium salt, dioctadecyldimethylammonium salt, hexadecyltrimethylammonium salt, dioctadecyldimethylammonium salt, tetradecyltrimethylammonium salt, dioctadecyldimethylammonium salt.
つぎに、この発明の無機層状多孔体の製法について、そ
の１実施例を模式化して表した図面にもとづいて、詳し
く説明する。Next, a method for producing an inorganic layered porous body according to the present invention will be explained in detail based on drawings schematically showing one embodiment thereof.
膨潤性粘土鉱物のような物質は、第２図に示すように、
膨潤性層状化合物Δ１の集まりでできている。主材たる
この化合物Ａ、を水などの溶媒と混合（必要に応じて混
錬）して、第３図にみるように、層１．１間に溶媒４を
含ませて、あらかじめ、膨潤させておく。溶媒としては
、一般に水が用いられるが、それ以外の極性溶媒、たと
えば、メタノール、ＤＭＦ、ＤＭＳＯ等を単独で、ある
いは、複数混合して用いるようにしてもかまわない。Substances such as swellable clay minerals, as shown in Figure 2,
It is made up of a collection of swellable layered compounds Δ1. This compound A, which is the main material, is mixed with a solvent such as water (kneaded if necessary), and as shown in Figure 3, the solvent 4 is impregnated between the layers 1 and 1 to swell it in advance. I'll keep it. Water is generally used as the solvent, but other polar solvents such as methanol, DMF, DMSO, etc. may be used alone or in combination.
つぎに、前述したように、あらかじめエステル化された
コロイド状無機化合物を陽イオン性無機化合物と付加反
応させる。この付加反応によって、第４図（ａ）にみる
ように、陽イオン性無機化合物中の陽イオンにより、そ
の表面がプラスにチャージした反応物２′が得られる。Next, as described above, the previously esterified colloidal inorganic compound is subjected to an addition reaction with a cationic inorganic compound. Through this addition reaction, a reactant 2' whose surface is positively charged due to the cations in the cationic inorganic compound is obtained, as shown in FIG. 4(a).
こうしてできた反応物２′に、前記水溶性高分子化合物
および第４級アンモニウム塩のうちの少なくとも一方を
ソフトピラー５として配合し、第４図Ｔｂ）にみるよう
に、充分均一になるまでｔ捏合する。At least one of the water-soluble polymer compound and the quaternary ammonium salt is blended into the reaction product 2' thus produced as soft pillars 5, and as shown in FIG. Knead.
得られた混合物を、あらかじめ、膨潤させておいた前記
膨潤性層状化合物と混合して、第５図にみるように層状
化合物の層１．１間に挿入（インターカレーション）す
る。そうすると、水溶性高分子化合物や第４級アンモニ
ウム塩がソフトピラー５として、ごの層１．１間を押し
拡げて保持し、それとともに、反応物２′の動きを鈍く
して、この層１，１間にとどめる働きをする。とどめら
れた反応物２′は、その表面の正電荷が層１表面のマイ
ナス部分と電気的に結合して、それによって、層１．１
間を押し拡げたまま保持することができると考えられる
。混合時の温度は、この発明では特に限定されないが、
６０〜７０℃前後であることが好ましい。The resulting mixture is mixed with the swellable layered compound which has been swollen in advance and inserted (intercalated) between the layers 1.1 of the layered compound as shown in FIG. Then, the water-soluble polymer compound and the quaternary ammonium salt act as soft pillars 5 to spread and hold the space between the layers 1 and 1, and at the same time, slow the movement of the reactant 2', and , works to keep it within one hour. The retained reactant 2' has a positive charge on its surface that is electrically coupled to a negative portion on the surface of layer 1, thereby forming layer 1.1.
It is thought that it is possible to hold the space while expanding it. The temperature during mixing is not particularly limited in this invention, but
Preferably, the temperature is around 60 to 70°C.
この反応溶液を遠心分離して脱水を行ったのち、ヘラ等
で板状に配向させる。この板状材を６０°Ｃ程度の温度
で温風乾燥等によって乾燥したあと、さらに、３００〜
６００℃、好ましくは４５０〜５５０℃で焼成する。こ
の焼成によって、前記水溶性高分子化合物や第４級アン
モニウム塩はＣＯｚ 、 Ｎ１１３． ｆＩｚ Ｏ等
に変化して除去され、これらが存在した空間は、そのま
ま空隙３となり、第１図に示したように、層１，１間に
無機化合物２が挿入された板状の無機層状多孔体を得る
ごとができる。This reaction solution is dehydrated by centrifugation, and then oriented into a plate shape using a spatula or the like. After drying this plate material by hot air drying at a temperature of about 60°C,
Calcination is performed at 600°C, preferably 450-550°C. By this calcination, the water-soluble polymer compound and quaternary ammonium salt are converted to COz, N113. fIz O, etc. and removed, and the space where these existed remains as a void 3, and as shown in Figure 1, a plate-shaped inorganic layered porous structure in which an inorganic compound 2 is inserted between layers 1 and 1 is formed. You can do it every time you get a body.
このようにして得られた無機層状多孔体は、その全体の
４０％以上が層間隔３０〜６００人を保持しており、第
１図矢印Ｂ方向の断熱性に優れている。The inorganic layered porous material thus obtained has a layer spacing of 30 to 600 in more than 40% of the total, and has excellent heat insulation properties in the direction of arrow B in FIG.
なお、以上の実施例では、反応物とソフトピラーとを混
合しておいてから、膨潤性層状化合物の層間に挿入して
いるが、これは、別々に、前記層間に挿入されるようで
あってもかまわない。In the above examples, the reactant and the soft pillar are mixed and then inserted between the layers of the swellable layered compound, but this is different from the case where the soft pillar is inserted between the layers separately. It doesn't matter.
つぎに、この発明の実施例について、比較例とあわせて
説明する。Next, examples of the present invention will be described together with comparative examples.
（実施例１）
エステル化されたコロイド状無機化合物として、メタノ
ールシリカゾル（日照化学工業０菊製：平均粒系１３０
人）の２０重量％溶液を調整した。(Example 1) As the esterified colloidal inorganic compound, methanol silica sol (manufactured by Nissei Kagaku Kogyo 0 Kiku: average particle size 130
A 20% by weight solution of the following was prepared.
この溶液に対し、２Ｎ塩酸に陽イオン性無機化合物であ
る塩化チタンの４ｍｏｌ水溶液を加えて充分に混合した
もの（塩化チタン中のＴｉと塩酸の配合比は、重量比で
０．０７１：１）を添加し、かく拌を行って反応物を得
た。得られた反応物に対し、４級アンモニウム塩である
オクタデジルトリメチルアンモニウム塩（日本油脂０１
製ニソサンカチオンＡ［３）を加えて混合物を作成した
。この混合物を、あらかじめ、水で膨潤させておいたＮ
ａ−モンモリロナイト （クニミネ工業（奎荀製りニビ
アＦ）に加え、約６０℃で混合反応させた。挿入反応後
、これを遠心分離し、ヘラで板状に配向させ、６０℃の
温度で温風乾燥させた。これを電気炉中に入れ、４５０
℃で焼成し、厚み１．５ ａｍの板状無機層状多孔体試
料を得た。なお、最終構成比は、モル比で、Ｎａ−モン
モリロナイト：シリカニ酸化チタン＝１：１０：１であ
った。To this solution, 4 mol aqueous solution of titanium chloride, a cationic inorganic compound, was added to 2N hydrochloric acid and mixed thoroughly (the blending ratio of Ti and hydrochloric acid in titanium chloride was 0.071:1 by weight). was added and stirred to obtain a reaction product. The obtained reaction product was treated with octadecyltrimethylammonium salt (NOF 01), which is a quaternary ammonium salt.
A mixture was prepared by adding Nisosane cation A [3] produced by Nisosane. This mixture was preliminarily swollen with water.
a-Montmorillonite (Nivia F manufactured by Kunimine Kogyo Co., Ltd.) was mixed and reacted at about 60°C. After the insertion reaction, it was centrifuged, oriented into a plate shape with a spatula, and heated at a temperature of 60°C. It was air-dried. It was placed in an electric furnace and heated at 450
C. to obtain a plate-like inorganic layered porous material sample having a thickness of 1.5 am. The final composition ratio was Na-montmorillonite:silica titanium oxide=1:10:1 in terms of molar ratio.
（実施例２）
エステル化されたコロイド状無機化合物として、イソプ
ロパツールシリカゾルを使用した以外は、実施例１と同
様にして板状無機層状多孔体試料を得た。(Example 2) A plate-like inorganic layered porous material sample was obtained in the same manner as in Example 1, except that isopropatol silica sol was used as the esterified colloidal inorganic compound.
（実施例３）
エステル化されたコロイド状無機化合物として、ノルマ
ルプロパツールシリカゾルを使用した以外は、実施例１
と同様にして板状無機層状多孔体試料を得た。(Example 3) Example 1 except that normal propatool silica sol was used as the esterified colloidal inorganic compound.
A plate-like inorganic layered porous material sample was obtained in the same manner as above.
（実施例４）
第４級アンモニウム塩として、ジオクタデシルジメチル
アンモニウムクロライドとジオクタデシルジメチルアン
モニウムクロライドとを７５＝２４の割合で混合したも
の（ライオンアグゾ０鴫製アーカード２ＨＴ−７５）を
使用した以外は、実施例１と同様にして板状無機層状多
孔体試料を得た（実施例５）
膨潤性層状化合物として、合成雲母（ドビー化学工業型
グイモナイトＨＧ）を用いた以外は、実施例１と同様に
して板状無機層状多孔体試料を得た。(Example 4) Except for using a mixture of dioctadecyldimethylammonium chloride and dioctadecyldimethylammonium chloride at a ratio of 75=24 (Lion Agzo 0 Tsuzuku Alucard 2HT-75) as the quaternary ammonium salt, A plate-like inorganic layered porous material sample was obtained in the same manner as in Example 1 (Example 5) A sample was obtained in the same manner as in Example 1 except that synthetic mica (Dobby Chemical Industries type Guimonite HG) was used as the swelling layered compound. A plate-like inorganic layered porous material sample was obtained.
（実施例６）
ソフトピラーとして、水溶性高分子化合物であるポリビ
ニルアルコールを使用した以外は、実施例１と同様にし
て板状無機層状多孔体試料を得た（比較例１）
コロイド状無機化合物としてエステル化していないコロ
イダルシリカ（平均粒度１３０人、２０重量％水溶液）
を、膨潤性層状化合物としてＮａ −モンモリロナイト
（クニミネ工業■製りニピアＦ）を、それぞれ使用し、
これを水溶性高分子化合物であるポリエチレンオキサイ
ド（明成化学ａｖＪ製アルコックスＥ７５．平均分子量
１５０万〜２２０万）および水とともに７０℃で４０分
間混合した。この混合物をヘラなどで板状に配向させ感
想後、４００℃、２時間の焼成を行い、板状無機層状多
孔体試料を得た。(Example 6) A plate-like inorganic layered porous material sample was obtained in the same manner as in Example 1, except that polyvinyl alcohol, which is a water-soluble polymer compound, was used as the soft pillar (Comparative Example 1) Colloidal inorganic compound Colloidal silica (average particle size 130, 20% by weight aqueous solution) that is not esterified as
and using Na-montmorillonite (Nipia F manufactured by Kunimine Industries) as a swelling layered compound, respectively.
This was mixed with a water-soluble polymer compound, polyethylene oxide (Alcox E75 manufactured by Meisei Kagaku avJ, average molecular weight 1.5 million to 2.2 million), and water at 70° C. for 40 minutes. This mixture was oriented into a plate shape using a spatula or the like, and after impression, it was fired at 400°C for 2 hours to obtain a plate-shaped inorganic layered porous material sample.
なお、Ｎａ−モンモリロナイト、水、コロイダルシリカ
、ポリエチレンオキサイドの配合比は、重量比で１：１
０：３：０．１であった。The blending ratio of Na-montmorillonite, water, colloidal silica, and polyethylene oxide is 1:1 by weight.
The ratio was 0:3:0.1.
これら実施例ならびに比較例で得られた板状無機層状多
孔体試料の開孔率２層間距離、密度、熱伝導率を測定し
、その結果を、石膏ボードおよび砂の成形体の２つの比
較例と併せて第１表に示す、なお、開孔率はつぎのよう
な式
によって得られる。比表面積は窒素吸着法におけるＢＥ
Ｔの方法を、平均層間距離（細孔分布）は窒素吸着法に
おけるＣＩ法を、それぞれ、用いて得た。窒素吸着装置
はカンタクローム社のオートソープ６を用いた。熱伝導
測定は、キセノンフラッシュ法による熱伝導測定装置を
用いた。The porosity, interlayer distance, density, and thermal conductivity of the plate-like inorganic layered porous material samples obtained in these Examples and Comparative Examples were measured, and the results were compared to the two Comparative Examples of plasterboard and sand moldings. The porosity is also shown in Table 1, and the porosity is obtained by the following formula. The specific surface area is BE in the nitrogen adsorption method.
The average interlayer distance (pore distribution) was obtained using the CI method in the nitrogen adsorption method, respectively. The nitrogen adsorption device used was Autosoap 6 manufactured by Quantachrome. The thermal conductivity measurement was performed using a thermal conductivity measuring device using the xenon flash method.
この発明の無機層状多孔体の製法は、以上のように構成
されているため、無機化合物によって全体の４０％以上
が層間隔を３０〜６００人に保持されて開孔率が３０％
以上になっており、低熱伝導率であって断熱材等に有用
な断熱性に非常にすぐれた無機層状多孔体を確実に得る
ことができるようになる。Since the method for manufacturing an inorganic layered porous material of the present invention is configured as described above, the layer spacing is maintained at 30 to 600 in more than 40% of the total by the inorganic compound, and the porosity is 30%.
As described above, it is possible to reliably obtain an inorganic layered porous body that has low thermal conductivity and has excellent heat insulating properties that are useful for heat insulating materials and the like.
第１図は無機層状多孔体の模式的側面図、第２図は膨潤
性層状化合物の模式的側面図、第３図はその膨潤に至る
状態を説明する説明図、第４図（ａ）はエステル化した
コロイド状無機化合物の表面に陽イオン性無機化合物を
付加反応させた状態を説明する説明図、第４図（ｂ）は
第４図（ａ）の反応物にさらにソフトピラーを加えた状
態を説明する説明図、第５図は第４図（ｂ）の混合物を
膨潤性層状化合物の層間に挿入した状態を説明する説明
図である。
Ａ・・・無機層状多孔体 Ａ１・・・膨潤性層状化合物
１・・・層 ２′・・・反応物 ３・・・空隙 ５・・
・ソフトピラー
代理人 弁理士 松 本 武 彦
第１図
第２図
＠３図
第５図Figure 1 is a schematic side view of an inorganic layered porous material, Figure 2 is a schematic side view of a swellable layered compound, Figure 3 is an explanatory diagram illustrating the state leading to swelling, and Figure 4 (a) is An explanatory diagram illustrating the state in which a cationic inorganic compound is subjected to an addition reaction on the surface of an esterified colloidal inorganic compound. Figure 4 (b) is a diagram in which soft pillars are further added to the reaction product of Figure 4 (a). FIG. 5 is an explanatory diagram illustrating a state in which the mixture of FIG. 4(b) is inserted between layers of a swellable layered compound. A... Inorganic layered porous material A1... Swellable layered compound 1... Layer 2'... Reactant 3... Voids 5...
・Soft Pillar Agent Takehiko Matsumoto, Patent Attorney Figure 1 Figure 2 @ Figure 3 Figure 5
Claims (6)
分子化合物および第４級アンモニウム塩のうちの少なく
とも一方を挿入するとともに、あらかじめエステル化し
たコロイド状無機化合物に陽イオン性無機化合物を付加
反応させて得られる反応物をも挿入し、乾燥、焼成を行
って前記層間に微細な空隙を形成するようにする無機層
状多孔体の製法。(1) At least one of a water-soluble polymer compound and a quaternary ammonium salt is inserted between the layers of the swollen layered compound, and a cationic inorganic compound is inserted into the colloidal inorganic compound that has been esterified in advance. A method for producing an inorganic layered porous body in which a reactant obtained by an addition reaction is also inserted, dried and fired to form fine voids between the layers.
Ｏ＿３、Ｆｅ＿２Ｏ＿３、Ａｌ＿２Ｏ＿３、ＴｉＯ＿２
、および、ＺｒＯ＿２からなる群より選ばれた少なくと
も１つである特許請求の範囲第１項記載の無機層状多孔
体の製法。(2) The colloidal inorganic compound is SiO_2, Sb_2
O_3, Fe_2O_3, Al_2O_3, TiO_2
The method for producing an inorganic layered porous material according to claim 1, which is at least one selected from the group consisting of , and ZrO_2.
コニウム系化合物、ハフニウム系化合物、リン系化合物
、および、ホウ素系化合物からなる群より選ばれた少な
くとも１つである特許請求の範囲第１項または第２項記
載の無機層状多孔体の製法。(3) Claim 1, wherein the cationic inorganic compound is at least one selected from the group consisting of titanium compounds, zirconium compounds, hafnium compounds, phosphorus compounds, and boron compounds. Or the method for producing an inorganic layered porous material according to item 2.
ポリエチレングリコール、ポリエチレンオキサイド、メ
チルセルロース、カルボキシメチルセルロース、ポリア
クリル酸ソーダ、および、ポリビニルピロリドンからな
る群より選ばれた少なくとも１つであり、第４級アンモ
ニウム塩が、オクタデシル基、ヘキサデシル基、テトラ
デシル基、および、ドデシル基からなる群より選ばれた
少なくとも１つの基を有するものである特許請求の範囲
第１項から第３項までのいずれかに記載の無機層状多孔
体の製法。(4) The water-soluble polymer compound is polyvinyl alcohol,
At least one selected from the group consisting of polyethylene glycol, polyethylene oxide, methylcellulose, carboxymethylcellulose, sodium polyacrylate, and polyvinylpyrrolidone, and the quaternary ammonium salt is an octadecyl group, a hexadecyl group, a tetradecyl group, and The method for producing an inorganic layered porous material according to any one of claims 1 to 3, wherein the inorganic layered porous material has at least one group selected from the group consisting of , and dodecyl groups.
Ｃａ−モンモリロナイト、酸性白土、３−八面体合成ス
メクタイト、Ｎａ−ヘクトライト、Ｌｉ−ヘクトライト
、Ｎａ−テニオライト、Ｌｉ−テニオライト、および、
合成雲母からなる群より選ばれた少なくとも１つである
特許請求の範囲第１項から第４項までのいずれかに記載
の無機層状多孔体の製法。(5) The swelling layered compound is Na-montmorillonite,
Ca-montmorillonite, acid clay, 3-octahedral synthetic smectite, Na-hectorite, Li-hectite, Na-teniolite, Li-teniolite, and
A method for producing an inorganic layered porous material according to any one of claims 1 to 4, which is at least one selected from the group consisting of synthetic mica.
項から第５項までのいずれかに記載の無機層状多孔体の
製法。(6) Claim 1 in which the void is 30 to 600 Å
A method for producing an inorganic layered porous body according to any one of Items 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8473286A JPS62241879A (en) | 1986-04-11 | 1986-04-11 | Manufacture of inorganic layer porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8473286A JPS62241879A (en) | 1986-04-11 | 1986-04-11 | Manufacture of inorganic layer porous body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62241879A true JPS62241879A (en) | 1987-10-22 |
Family
ID=13838865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8473286A Pending JPS62241879A (en) | 1986-04-11 | 1986-04-11 | Manufacture of inorganic layer porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62241879A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003004412A1 (en) * | 2001-07-06 | 2003-01-16 | The University Of Queensland | Metal oxide nanoparticles in an exfoliated silicate framework |
-
1986
- 1986-04-11 JP JP8473286A patent/JPS62241879A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003004412A1 (en) * | 2001-07-06 | 2003-01-16 | The University Of Queensland | Metal oxide nanoparticles in an exfoliated silicate framework |
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