JPH0193411A - Production of highly water repellent compound using silicate compound as raw material - Google Patents
Production of highly water repellent compound using silicate compound as raw materialInfo
- Publication number
- JPH0193411A JPH0193411A JP24769287A JP24769287A JPH0193411A JP H0193411 A JPH0193411 A JP H0193411A JP 24769287 A JP24769287 A JP 24769287A JP 24769287 A JP24769287 A JP 24769287A JP H0193411 A JPH0193411 A JP H0193411A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid
- silicate
- manufacturing
- product
- 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.)
- Granted
Links
- -1 silicate compound Chemical class 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002994 raw material Substances 0.000 title claims description 8
- 239000005871 repellent Substances 0.000 title description 17
- 230000002940 repellent Effects 0.000 title description 12
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000003518 caustics Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims abstract description 6
- 239000010425 asbestos Substances 0.000 claims abstract description 6
- 229910052895 riebeckite Inorganic materials 0.000 claims abstract description 6
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 14
- 238000006884 silylation reaction Methods 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MNTALGTVSQTALQ-UHFFFAOYSA-N trihydroxy(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](O)(O)O MNTALGTVSQTALQ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分舒］
本発明はケイ酸塩化合物を原料とした高撥水性化合物の
製造方法に係り、特に蛇紋岩、石綿以外のケイ酸塩化合
物を原料として、有機溶媒に可溶で撥水性に優れた生成
物を高収率で得ることができる方法に関する。[Detailed Description of the Invention] [Industrial Application] The present invention relates to a method for producing a highly water-repellent compound using a silicate compound as a raw material. , relates to a method capable of obtaining a product soluble in organic solvents and having excellent water repellency in high yield.
［従来の技術］
ケイ酸塩化合物を原料として、これをシラン化合物と反
応させてシリル基を導入することにより（本明細書にお
いて、この処理を「シリル化」ということがある、）、
有機溶剤に可溶で撥水性のある化合物を得る方法は既に
公知である。例えば、特公昭４９−４０６３９号には、
ケイ酸ナトリウム化合物又はケイ酸マグネシウム化合物
を原料とし、これをトリメチルクロルシランによりトリ
メチルシリル化してトリメチルシリルシリケートを製造
する方法が開示されている。トリメチルシリルシリケー
トは撥水性、防水性及び塗膜形成能を有するため、各種
撥水剤として極めて有用である。[Prior Art] By using a silicate compound as a raw material and reacting it with a silane compound to introduce a silyl group (in this specification, this process is sometimes referred to as "silylation"),
Methods for obtaining water-repellent compounds that are soluble in organic solvents are already known. For example, in Special Publication No. 49-40639,
A method for producing trimethylsilylsilicate by using a sodium silicate compound or a magnesium silicate compound as a raw material and trimethylsilylating the same with trimethylchlorosilane is disclosed. Trimethylsilyl silicate is extremely useful as various water repellents because it has water repellency, waterproof property, and coating film forming ability.
［発明が解決しようとする問題点］
ケイ酸塩化合物を直接シリル化処理する上記特公昭４９
−４０６３９号公報記載の方法では、ケイ酸塩化合物の
種類によっては目的とする生成物の収量が著しく悪く、
工業的、経済的に不利である。[Problems to be Solved by the Invention] The above-mentioned Japanese Patent Publication No. 1983, in which a silicate compound is directly silylated
In the method described in Publication No. 40639, the yield of the desired product is extremely low depending on the type of silicate compound;
It is industrially and economically disadvantageous.
［問題点を解決するための手段］
本発明は上記従来の問題点を解消し、ケイ酸塩化合物を
原料としそ、有機溶媒に可溶で撥水性の高い化合物を高
収率で製造することができる方法を提供するものであっ
て、蛇紋岩及び石綿以外のケイ酸塩化合物を酸分解した
後、酸の存在下シラン化合物と反応させる、即ちシリル
化することにより、高撥水性化合物を製造することを特
徴とする。[Means for Solving the Problems] The present invention solves the above-mentioned conventional problems, and uses a silicate compound as a raw material to produce a compound that is soluble in organic solvents and has high water repellency at a high yield. This method provides a method for producing a highly water-repellent compound by acid decomposing a silicate compound other than serpentine and asbestos, and then reacting it with a silane compound in the presence of an acid, that is, silylating it. It is characterized by
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の方法においては、まずケイ酸塩化合物を酸分解
する。本発明において用いるケイ酸塩化金物は蛇紋岩及
び石綿以外のケイ酸塩化合物であって、例えば、タルク
、セピオライト等のケイ酸マグネシウム、カオリナイト
、ゼオライト等のケイ酸アルミニウム、フライアッシエ
、高炉スラグ等のケイ酸塩副産物、又はその他のケイ酸
塩化合物が挙げられる。また、これらのケイ酸塩化合物
の酸分解に使用される酸としては特に制限はないが、一
般には塩酸、硫酸等が用いられる。酸の使用量はケイ酸
塩化合物の種類によって異なり、ケイ酸塩化合物が完全
に分解するように適宜その使用量を決定する。ケイ酸塩
化合物に酸を加えて酸分解して得られる生成物は、酸に
溶けず、残漬として残るので、ろ過、遠心分離等の分離
操作を行うことにより容易に回収することができる。In the method of the present invention, the silicate compound is first subjected to acid decomposition. The silicate metal used in the present invention is a silicate compound other than serpentine and asbestos, such as magnesium silicate such as talc and sepiolite, aluminum silicate such as kaolinite and zeolite, fly assier, blast furnace slag, etc. Includes silicate by-products or other silicate compounds. There are no particular restrictions on the acid used for acid decomposition of these silicate compounds, but hydrochloric acid, sulfuric acid, etc. are generally used. The amount of acid used varies depending on the type of silicate compound, and is appropriately determined so that the silicate compound is completely decomposed. A product obtained by adding an acid to a silicate compound and decomposing it with acid is not dissolved in the acid and remains as a residue, so it can be easily recovered by performing separation operations such as filtration and centrifugation.
ケイ酸塩化合物の酸分解により得られた生成物は、必要
に応じて乾燥した後、シリル化に先立ち、好ましくは苛
性アルカリに溶解して苛性アルカリ溶液とする。即ち、
上記酸分解により回収した残漬を、適当な濃度、例えば
０．６〜１．ＯＮ程度に調製した苛性アルカリ水溶液に
室温で溶解させる。この場合、特に加温する必要はなく
、室温において容易に溶解させることができる。用いる
苛性アルカリとしては特に制限はないが、一般には苛性
ソーダが使用される。なお、酸分解残渣の中には、苛性
アルカリに溶けない物質も含まれている場合もある。こ
の場合には、不溶部を除去して酸分解生成物の苛性アル
カリ溶液を得る。The product obtained by acid decomposition of the silicate compound, after optionally drying, is preferably dissolved in caustic alkali to form a caustic solution prior to silylation. That is,
The residue recovered by the above acid decomposition is adjusted to an appropriate concentration, for example 0.6 to 1. Dissolve at room temperature in a caustic alkali aqueous solution prepared to ON level. In this case, there is no particular need for heating, and it can be easily dissolved at room temperature. There are no particular restrictions on the caustic alkali used, but caustic soda is generally used. Note that the acid decomposition residue may also contain substances that are insoluble in caustic alkali. In this case, the insoluble portion is removed to obtain a caustic alkaline solution of the acid decomposition product.
次いで、得られた酸分解生成物の苛性アルカリ溶液を、
シリル化する。即ち、別途調製した酸、有機溶媒及びシ
ラン化合物（本明細書において、これを「シリル化剤」
ということがある。）を含む混合溶液に滴下して、室温
ないし５０℃程度の加温下で反応を行なう。Next, a caustic alkaline solution of the obtained acid decomposition product was
to silylate. That is, separately prepared acids, organic solvents, and silane compounds (herein referred to as "silylating agents")
There is a thing. ) is added dropwise to a mixed solution containing the following components, and the reaction is carried out at room temperature to about 50°C.
この場合、混合溶液の酸濃度は酸分解生成物の苛性アル
カリ溶液のアルカリ濃度の７倍以上、好ましくは１０倍
以上とすることにより、反応効率を高めることができる
。また、シリル化剤の使用量は特に制限はないが、苛性
アリカリ溶液中の酸分解生成物の主成分であるシリカの
５ｉ０２換算のモル数に対する、シリル化剤中のＳｉの
モル数の比（以下、「シリル他剤比率」という。）が１
以上となるようにすれば、シリル化が完全に行なわれ、
撥水性の高い生成物が得られる。In this case, the reaction efficiency can be increased by setting the acid concentration of the mixed solution to at least 7 times, preferably at least 10 times, the alkaline concentration of the caustic alkaline solution of the acid decomposition product. The amount of the silylating agent to be used is not particularly limited, but the ratio of the number of moles of Si in the silylating agent to the number of moles of silica, which is the main component of the acid decomposition product in the caustic alkali solution, in terms of 5i02 ( Hereinafter referred to as "silyl and other drug ratio") is 1
By doing the above, silylation will be completed,
A highly water-repellent product is obtained.
混合溶液の調製に用いられる酸としては、硫酸、塩酸等
が適宜選択される。有機溶媒については、テトラヒドロ
フラン、２−ブタノール、ジメチルホルムアミド等の水
に可溶の極性溶媒と、ヘキサン、石油エーテル等の水に
不溶の溶媒を併用するのが好ましい。シラン化合物につ
いては、特に限定はないが、トリメチルクロロシランの
使用が一般的である。特にシラン化合物としてはビニル
基を有する単官能性のクロロシラン類１例えばビニルジ
メチルクロロシランを使用するのが好ましい。ビニル基
を有する単官能性のクロロシラン類が望ましい理由は、
得られる生成化合物が撥水処理する対象物にビニル基を
利用して架橋することにより、耐久撥水性が著しく向上
するからである。As the acid used for preparing the mixed solution, sulfuric acid, hydrochloric acid, etc. are appropriately selected. As for the organic solvent, it is preferable to use a water-soluble polar solvent such as tetrahydrofuran, 2-butanol, and dimethylformamide together with a water-insoluble solvent such as hexane and petroleum ether. The silane compound is not particularly limited, but trimethylchlorosilane is generally used. In particular, as the silane compound, it is preferable to use monofunctional chlorosilanes having a vinyl group, such as vinyldimethylchlorosilane. The reason why monofunctional chlorosilanes having a vinyl group are desirable is as follows.
This is because the durable water repellency is significantly improved by crosslinking the obtained product compound to the object to be water repelled using vinyl groups.
本発明において、使用可能なシリル化剤としては、下記
一般式で示されるものが挙げられる。In the present invention, examples of silylating agents that can be used include those represented by the following general formula.
（上記式中、Ｒ１，Ｒ２１Ｒ３，Ｒ４１Ｒ＋３゜Ｒ６は
メチル、エチル、ブチル、メトキシ、エトキシ、ビニル
、アリル、フェニル等の置換基を示す、）
酸分解生成物の苛性アルカリ溶液を前記混合溶液に滴下
、反応させて得られた反応液は２層に分離するので、上
層の有機溶媒層を分液して回収し、不溶物を除去後、有
機溶媒を留去して乾燥することにより、本発明の目的と
する生成物を得る。この生成物は、必要に応じてアセト
ン、テトラヒドロフラン等の有機溶媒に溶解させ、水中
で再沈精製することにより精製することができる。(In the above formula, R1, R21R3, R41R+3゜R6 represents a substituent such as methyl, ethyl, butyl, methoxy, ethoxy, vinyl, allyl, phenyl, etc.) A caustic alkaline solution of the acid decomposition product is dropped into the mixed solution. The reaction solution obtained by the reaction is separated into two layers, so the upper organic solvent layer is separated and collected, the insoluble matter is removed, and the organic solvent is distilled off and dried. The desired product is obtained. This product can be purified by dissolving it in an organic solvent such as acetone or tetrahydrofuran, if necessary, and purifying it by reprecipitation in water.
得られる生成物は、前記シリル他剤比率が３以上である
と概ね黄色いグリス状となり、３未満であると白色粉末
となる。特に、シリル他剤比率が１以上であると、著し
く強い撥水性を有するものとなる。When the silyl-other-agent ratio is 3 or more, the resulting product becomes a yellow grease-like product, and when it is less than 3, it becomes a white powder. In particular, when the ratio of silyl and other agents is 1 or more, it has extremely strong water repellency.
［作 用］
本発明の方法によれば、有機溶媒に可溶で撥水性の高い
生成物を高収率で得ることができる。[Function] According to the method of the present invention, a product that is soluble in organic solvents and has high water repellency can be obtained in high yield.
しかして、得られるケイ素含有化合物は、水ガラスを原
料として製造されるトリメチルシリルシリケート（特公
昭４９−４０６３９）に比し、極めて複雑な構造を有す
るため、その撥水性は著しく高い。The resulting silicon-containing compound has a much more complex structure than trimethylsilyl silicate (Japanese Patent Publication No. 49-40639) produced using water glass as a raw material, so its water repellency is significantly higher.
［実施例コ 以下、実施例及び比較例について説明する。[Example code] Examples and comparative examples will be described below.
実施例１〜４
カオリナイト（栃木製産）、ベントナイト（新潟集塵）
、タルク（埼玉系ａ）、ゼオライト（秋田集塵）、の粉
砕品各々８０ｇを６Ｍ塩酸６００ｍ１中に入れ、５０℃
で２４Ｈｒ攪拌し、分解した。分解後、遠心分離により
約３０ｇ〜Ｂｏｇの残渣を回収し、水で洗浄後乾燥した
。得られた残漬を適当量、０．８Ｍカセイソーダ水１０
０ｍ１ｌ中で３Ｈｒ溶解し、不溶部を除去後、ＳｉＯ２
濃度１０ｇ／１００ｍｕのケイ酸アルカリ溶液を得た。Examples 1 to 4 Kaolinite (produced in Tochigi), bentonite (Niigata dust collection)
, talc (Saitama type a), and zeolite (Akita Dust Collection) were placed in 600 ml of 6M hydrochloric acid and heated at 50°C.
The mixture was stirred for 24 hours and decomposed. After the decomposition, approximately 30 g of Bog residue was collected by centrifugation, washed with water, and then dried. Appropriate amount of the obtained residue, 10% of 0.8M caustic soda water
After dissolving in 0ml for 3 hours and removing the insoluble part, SiO2
An alkaline silicate solution with a concentration of 10 g/100 mu was obtained.
得られたケイ酸アルカリ溶液を、それぞれ下記第１表に
示す組成の混合溶液中に５ｍ１Ｌ１分程度の速度で滴下
し、１２Ｈｒ反応させた。反応後、有機溶媒層を分液回
収し、有機溶媒を留去して乾燥し、生成物を得た。The resulting alkali silicate solutions were added dropwise at a rate of about 5 ml/liter to a mixed solution having the composition shown in Table 1 below at a rate of about 1 minute, and reacted for 12 hours. After the reaction, the organic solvent layer was separated and collected, and the organic solvent was distilled off and dried to obtain a product.
得られた生成物の性状及び収量は第１表に示す通りであ
った。The properties and yield of the obtained product were as shown in Table 1.
また、各生成物を撥水剤として、その撥水性を下記方法
で調べた。結果を第１表に示す。In addition, each product was used as a water repellent and its water repellency was examined by the following method. The results are shown in Table 1.
ｌ木１１旦旦１１
被処理布 ：ナイロンタフタ
撥水剤の調合：撥水剤 ５％
トリクロロエチレン ９５％
処 理 ：被処理布を撥水剤に浸漬後、良く絞り乾
燥させる
撥水性評価方法：ＪＩＳ Ｌ−１０９２比較例１〜４
実施例１〜４で使用したケイ酸塩化合物それぞれについ
て、５ｉ０２含量１０ｇとなる量を採取して、以下の組
成の混合溶液中に投入して、直接シリル化反応を行った
。Treated fabric: Nylon taffeta Water repellent formulation: Water repellent 5% Trichlorethylene 95% Treatment: After soaking the treated fabric in the water repellent, thoroughly squeeze and dry Water repellency evaluation method: JIS L-1092 Comparative Examples 1 to 4 For each of the silicate compounds used in Examples 1 to 4, an amount with a 5i02 content of 10 g was collected and added to a mixed solution having the following composition to perform a direct silylation reaction. I did it.
混合溶液の組成
硫酸（１８Ｍ） １００ｍｆＬ水
１００ｍｆテト
ラヒドロフラン ｓｏｍｘヘキサン
５０ｍｆＬトリメチルクロロシラン
５４．２ｇ反応後の溶液は２層に分離し、有機溶媒
層は白濁していた。有機溶媒層を回収し、不溶部を除去
後有機溶媒を留去し、乾燥後生成物を得たが、収量は下
記第２表のとおりで、いずれも実施例１〜４と比較して
著しく少なかった。Composition of mixed solution Sulfuric acid (18M) 100mfL water
100mf tetrahydrofuran somx hexane
50mfL trimethylchlorosilane
The solution after 54.2g reaction was separated into two layers, and the organic solvent layer was cloudy. The organic solvent layer was collected, the insoluble portion was removed, the organic solvent was distilled off, and the product was obtained after drying. There weren't many.
第 ２ 表
比較例２
水ガラス３号（市販品）を５ｉＯａ分として１０ｇ／１
００ｍｆｔの濃度となるよう調整し、実施例１のカオリ
ナイトのシリル止剤条件と同じ条件でシリル化反応を行
った。Table 2 Comparative Example 2 Water Glass No. 3 (commercial product) 10g/1 as 5iOa
The silylation reaction was carried out under the same conditions as the silyl inhibitor conditions for kaolinite in Example 1.
生成物は白色粉末で収量は１４．２ｇであった。また、
この生成物の撥水性能を実施例１と同じ条件で試験した
ところ、スプレーテスト評価点数は７０で実施例１より
もかなり劣ってし）た。The product was a white powder with a yield of 14.2 g. Also,
When the water repellency of this product was tested under the same conditions as Example 1, the spray test evaluation score was 70, which was considerably inferior to Example 1).
実施例５〜８
実施例１〜４で行ったシリル化におし）て、シリル化剤
をビニルジメチルクロロシランに変え、その他の条件は
同じにして反応させ、下記第３表の結果を得た。Examples 5 to 8 In the silylation performed in Examples 1 to 4, the silylation agent was changed to vinyldimethylchlorosilane, and the reaction was carried out under the same conditions except for the results shown in Table 3 below. .
各生成物について実施例１と同様の方法で撥水性能を調
べた結果を第３表に示す。Table 3 shows the results of examining the water repellency of each product in the same manner as in Example 1.
なお、実施例１〜４及び実施例５〜８について下記方法
により耐久撥水性能を調べたところ、第４表に示す如く
、シリル化剤としてビニルジメチルクロロシランを用い
た実施例５〜８のものの方が優れていた。In addition, when the durable water repellent performance of Examples 1 to 4 and Examples 5 to 8 was examined by the following method, as shown in Table 4, the results of Examples 5 to 8 using vinyldimethylchlorosilane as the silylation agent were found. was better.
耐久撥水性能試験 法
被処理布 ：ナイロンタフタ
撥水剤の調合：撥水剤 ５％
トリクロロエチレン ９５％
処 理 ：被処理布を撥水剤に浸漬後、良く絞り乾
燥させる
架 橋 ：イソシアネート系架橋剤を使用（実施例
５〜８のみ）
耐久撥水性評価法：ＪＩＳ Ｌ−０２１７−第 ４
表
［発明の効果］
以上詳述した通り、本発明のケイ酸塩化合物を原料とし
た高撥水性化合物の製造方法は蛇紋岩及び石綿以外のケ
イ酸塩化合物を酸分解後、シリル化処理するものであっ
て、分子構造が複雑で撥水性が著しく高い生成物を高収
率で容易に製造することができる。従って、本発明によ
れば、高性能撥水剤を高い生産効率で製造することがで
き、工業的に極めて有利である。Durable water repellent performance test Treated fabric: Nylon taffeta Water repellent formulation: Water repellent 5% Trichlorethylene 95% Treatment: After soaking the treated fabric in the water repellent, thoroughly squeeze and dry Crosslinking: Isocyanate crosslinking (Examples 5 to 8 only) Durable water repellency evaluation method: JIS L-0217-No. 4
Table [Effects of the Invention] As detailed above, the method for producing a highly water-repellent compound using a silicate compound as a raw material of the present invention involves acid decomposition of silicate compounds other than serpentine and asbestos, and then silylation treatment. A product with a complex molecular structure and extremely high water repellency can be easily produced in high yield. Therefore, according to the present invention, a high performance water repellent can be produced with high production efficiency, which is extremely advantageous industrially.
代理人 弁理士 重 野 剛Agent: Patent attorney Tsuyoshi Shigeno
Claims (1)
た後、酸の存在下シラン化合物と反応させることを特徴
とするケイ酸塩化合物を原料とした高撥水性化合物の製
造方法。 （２）シラン化合物がトリメチルクロロシランであるこ
とを特徴とする特許請求の範囲第１項に記載の製造方法
。 （３）ケイ酸塩化合物がケイ酸アルミニウム化合物、ケ
イ酸マグネシウム化合物又はケイ酸塩側産物であること
を特徴とする特許請求の範囲第１項又は第２項に記載の
製造方法。（４）ケイ酸アルミニウム化合物がゼオライ
ト又はカオリナイトであることを特徴とする特許請求の
範囲第３項に記載の製造方法。 （５）ケイ酸マグネシウム化合物がタルク又はセピオラ
イトであることを特徴とする特許請求の範囲第３項に記
載の製造方法。 （６）ケイ酸塩副産物がフライアッシュ又は高炉スラグ
であることを特徴とする特許請求の範囲第３項に記載の
製造方法。 （７）ケイ酸塩化合物を酸分解後、苛性アルカリと反応
させて苛性アルカリ溶液とし、該苛性アルカリ溶液を酸
の存在下シラン化合物と反応させることを特徴とする特
許請求の範囲第１項ないし第６項にいずれか１項に記載
の製造方法。 （８）苛性アルカリ溶液を酸、有機溶媒及びシラン化合
物を含む混合溶液に添加混合して反応させることを特徴
とする特許請求の範囲第７項に記載の製造方法。 （９）混合溶液の酸濃度は苛性アルカリ溶液のアルカリ
濃度の７倍以上であることを特徴とする特許請求の範囲
第８項に記載の製造方法。 （１０）苛性アルカリ溶液中のシリカのＳｉＯ＿２換算
値とシラン化合物中のＳｉのモル比が１：１以上である
ことを特徴とする特許請求の範囲第８項又は第９項に記
載の製造方法。[Scope of Claims] (1) High water repellency using a silicate compound as a raw material, which is characterized by acid decomposing a silicate compound other than serpentine and asbestos, and then reacting it with a silane compound in the presence of an acid. Method of manufacturing the compound. (2) The manufacturing method according to claim 1, wherein the silane compound is trimethylchlorosilane. (3) The manufacturing method according to claim 1 or 2, wherein the silicate compound is an aluminum silicate compound, a magnesium silicate compound, or a silicate side product. (4) The manufacturing method according to claim 3, wherein the aluminum silicate compound is zeolite or kaolinite. (5) The manufacturing method according to claim 3, wherein the magnesium silicate compound is talc or sepiolite. (6) The manufacturing method according to claim 3, wherein the silicate by-product is fly ash or blast furnace slag. (7) After the silicate compound is decomposed with an acid, it is reacted with a caustic alkali to form a caustic alkaline solution, and the caustic alkaline solution is reacted with a silane compound in the presence of an acid. The manufacturing method according to any one of Item 6. (8) The manufacturing method according to claim 7, characterized in that a caustic alkaline solution is added to and mixed with a mixed solution containing an acid, an organic solvent, and a silane compound to react. (9) The manufacturing method according to claim 8, wherein the acid concentration of the mixed solution is 7 times or more the alkaline concentration of the caustic alkaline solution. (10) The manufacturing method according to claim 8 or 9, characterized in that the molar ratio of the SiO_2 equivalent value of silica in the caustic alkaline solution to Si in the silane compound is 1:1 or more. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24769287A JPH0653799B2 (en) | 1987-09-30 | 1987-09-30 | Method for producing highly water repellent compound using silicate compound as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24769287A JPH0653799B2 (en) | 1987-09-30 | 1987-09-30 | Method for producing highly water repellent compound using silicate compound as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0193411A true JPH0193411A (en) | 1989-04-12 |
| JPH0653799B2 JPH0653799B2 (en) | 1994-07-20 |
Family
ID=17167224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24769287A Expired - Fee Related JPH0653799B2 (en) | 1987-09-30 | 1987-09-30 | Method for producing highly water repellent compound using silicate compound as raw material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653799B2 (en) |
-
1987
- 1987-09-30 JP JP24769287A patent/JPH0653799B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653799B2 (en) | 1994-07-20 |
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