JPH0470253B2 - - Google Patents
Info
- Publication number
- JPH0470253B2 JPH0470253B2 JP20888888A JP20888888A JPH0470253B2 JP H0470253 B2 JPH0470253 B2 JP H0470253B2 JP 20888888 A JP20888888 A JP 20888888A JP 20888888 A JP20888888 A JP 20888888A JP H0470253 B2 JPH0470253 B2 JP H0470253B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- formula
- parts
- group
- ketene acetal
- 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
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- LTVRSJBNXLZFGT-UHFFFAOYSA-N 2-silylethenone Chemical compound [SiH3]C=C=O LTVRSJBNXLZFGT-UHFFFAOYSA-N 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- -1 silylketene acetal compound Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002560 ketene acetals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle 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
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Description
［産業上の利用分野］
本発明は疎水性シリカの製造方法、特には毒性
や腐蝕性のある残存不純物量が極めて少ないの
で、電子電気部品、精密材料部品、医療用部品な
どに使用されるシリコーン樹脂、シリコーンゴム
製品の充填剤として有用とされる疎水性シリカの
製造方法に関するものである。
［従来の技術］
粉末状のシリカ充填剤を表面改質する方法につ
いてはすでに各種の方法が提案されており、これ
については例えばシリカ粉末をヘキサメチルジシ
ラザンで処理する方法［J.of phy.Chem.72−８，
P.2750（1968）］、ヒユームドシリカをアンモニア
接触させたのちシリル化窒素化合物と接触させる
方法（特公昭49−20739号公報参照）、シクロトリ
シロキサンにアミンまたはアンモニアを用いる方
法（特公昭45−12567号公報参照）、ハロゲン化シ
ランで処理する方法（特開昭51−14900号公報参
照）などが知られている。
しかし、これらの方法はいずれも窒素含有化合
物、ハロゲン化シラン化合物などを用いるもので
あるために、シリカとの反応時にアミン、アンモ
ニア、塩酸などの腐蝕性物質を生ずるという不利
があり、このために工程用の機器の損傷が早めら
れ、これらの方法で製造された表面改質シリカ、
疎水性シリカについては十分な注意と技術によつ
てこれらの化合物を取り除く必要があるし、この
ような処理をしたシリカもこれをシリコーンゴム
の充填剤として使用した場合には硬化触媒として
使用する白金またはロジウムがこの不純物で被毒
して硬化速度が遅くなつたり、得られたシリコー
ンゴム成形物の変質が早められ、さらには未硬化
ゴムコンパウンドの可塑化戻り現象（クリープハ
ードニング）が促進されるという不利があるの
で、このシリカ充填剤の表面改質についてはこの
ような不利を伴なわない方法の開発が望まれてい
る。
［発明の構成］
本発明はこのような不利を解決することのでき
る疎水性シリカの製造方法に関するものであり、
これはシリカ粉末100重量部を、１分子中に式
[Industrial Application Field] The present invention relates to a method for producing hydrophobic silica, and in particular, since the amount of residual impurities that are toxic and corrosive is extremely small, silicone used in electronic and electrical parts, precision material parts, medical parts, etc. The present invention relates to a method for producing hydrophobic silica, which is useful as a filler for resins and silicone rubber products. [Prior Art] Various methods have already been proposed for surface modifying powdered silica fillers, such as a method of treating silica powder with hexamethyldisilazane [J.of phy. Chem.72−8,
P.2750 (1968)], a method in which fumed silica is brought into contact with ammonia and then a silylated nitrogen compound (see Japanese Patent Publication No. 49-20739), a method in which cyclotrisiloxane is used with an amine or ammonia (Japanese Patent Publication No. 45-12567). (see Japanese Patent Application Laid-Open No. 14900/1983), and a method of treatment with a halogenated silane (see Japanese Patent Application Laid-Open No. 14900/1983). However, since all of these methods use nitrogen-containing compounds, halogenated silane compounds, etc., they have the disadvantage of producing corrosive substances such as amines, ammonia, and hydrochloric acid during the reaction with silica. Damage to process equipment is accelerated and surface-modified silica produced by these methods,
As for hydrophobic silica, it is necessary to remove these compounds with sufficient care and technique, and when silica treated in this way is used as a filler in silicone rubber, it may be difficult to remove platinum, which is used as a curing catalyst. Alternatively, rhodium may be poisoned by these impurities, slowing down the curing speed, accelerating the deterioration of the obtained silicone rubber molding, and further promoting the replasticization phenomenon (creep hardening) of the uncured rubber compound. Because of this disadvantage, there is a desire to develop a method for surface modification of silica fillers that does not involve such disadvantages. [Structure of the Invention] The present invention relates to a method for producing hydrophobic silica that can solve these disadvantages.
This formula contains 100 parts by weight of silica powder in one molecule.
【式】で示される基を１個以上含有す
るシリルケテンアセタール化合物１〜50重量部を
用いて25〜400℃の温度で処理することを特徴と
するものである。
すなわち、本発明者らはシリカ粉末の疎水化処
理において腐蝕性物質を発生しない処理剤を用い
る方法について種々検討した結果、上記した式
It is characterized by treating at a temperature of 25 to 400°C using 1 to 50 parts by weight of a silylketene acetal compound containing one or more groups represented by the formula. That is, the present inventors have studied various methods of using processing agents that do not generate corrosive substances in the hydrophobization treatment of silica powder, and have found that the above formula
【式】で示される基を１分子中に少な
くとも１個有するシリルケテンアセタール化合物
を使用すると、
一般にWhen using a silyl ketene acetal compound having at least one group represented by the formula in one molecule, generally
【式】（Ｒは１価炭化水素
基）で表わされるシリルケテンアセタール化合物
はシリカ中に存在するアルコール性OH基、シラ
ノール基と反応してこれをシリル化してシリカを
疎水化するが、このシリルケテンアセタールは
The silyl ketene acetal compound represented by the formula (R is a monovalent hydrocarbon group) reacts with the alcoholic OH group and silanol group present in silica to silylate it and make the silica hydrophobic. Ketene acetal is
【式】で表わされるエステル化合物
となり、このものは全く腐蝕性を有しないので従
来法における不利が解決されるということを見出
すと共に、この方法で得られた疎水性シリカを充
填剤として使用したシリコーン樹脂、シリコーン
ゴムは電子、電気部品、精密材料部品、医療用部
品などとして使用しても何ら不利を生じることが
ないということを確認して本発明を完成させた。
つぎにこれをさらに詳述する。
本発明の方法において始発材とされるシリカは
化学的には実質的にSiO2で表わされるものであ
ればよいし、これは一般にはシリコーンゴムの充
填剤として用いられている補強性、準補強性のも
のとすればよく、これは非補強性のものであつて
もよいが、実用面からは比表面積が50m2／ｇ以上
のヒユームドシリカ、沈降性シリカ、粒子径が
0.1〜100μmのシリカ粉末、特にはヒユームドシ
リカ、沈降性シリカとすればよい。
また、このシリカを処理するために使用される
シリルケテンアセタール化合物は１分子中に式
It was discovered that the disadvantages of the conventional method were solved by forming an ester compound represented by the formula: This compound has no corrosive properties, and silicone using the hydrophobic silica obtained by this method as a filler. The present invention was completed after confirming that resins and silicone rubbers do not cause any disadvantage when used as electronic, electrical parts, precision material parts, medical parts, etc. Next, this will be explained in more detail. The silica used as the starting material in the method of the present invention may chemically be substantially represented by SiO2 , and this is generally used as a reinforcing or semi-reinforcing filler for silicone rubber. It may be a non-reinforcing material, but from a practical point of view, fumed silica with a specific surface area of 50 m 2 /g or more, precipitated silica, and particle size
Silica powder of 0.1 to 100 μm, particularly fumed silica or precipitated silica, may be used. In addition, the silyl ketene acetal compound used to treat this silica has a formula in one molecule.
【式】で示される基を少なくとも１個
含有するものであればよく、これには下記
It is sufficient that it contains at least one group represented by [Formula], which includes the following:
【式】【formula】
のものが例示され、このけい素原子に結合してい
る有機基は目的によつてはビニル基、フエニル
基、トリフルオロプロピル基に置換したものとし
てもよいが、本発明の目的からこれらはＮ，Ｐ，
Ｓなどの元素は含有しないものとする必要があ
る。
このシリルケテンアセタール化合物によるシリ
カの処理は、シリカとシリルケテンアセタールを
混合して25〜400℃、好ましくは50〜200℃で反応
させればよいが、このシリルケテンアセタール化
合物が沸点の低いものであるときにはこれを気相
でシリカ中に吹き込んでもよく、これによればシ
リカに含有されているアルコール性OH基または
シラノール基が次式
（R1，R2，R3，R4は１価炭化水素基）によつて
表わされる様にシリル化されるので、このシリカ
は疎水性され、この場合シリルケテンアセタール
もエステル化合物に変成されるのがこの変成物は
全く腐蝕性を有しないので、このものはシリカ中
に残存してもシリカの実用面に不利を与えるおそ
れはない。
なお、ここに使用されるシリルケテンアセター
ル化合物は例えば式 The organic group bonded to the silicon atom may be substituted with a vinyl group, phenyl group, or trifluoropropyl group depending on the purpose, but for the purpose of the present invention, these are substituted with N ,P,
It is necessary that elements such as S are not contained. Silica can be treated with this silyl ketene acetal compound by mixing silica and silyl ketene acetal and reacting at 25 to 400°C, preferably 50 to 200°C. However, if this silyl ketene acetal compound has a low boiling point, In some cases, it may be blown into silica in the gas phase, and according to this method, the alcoholic OH group or silanol group contained in the silica has the following formula: (R 1 , R 2 , R 3 , and R 4 are monovalent hydrocarbon groups), so this silica is made hydrophobic, and in this case, the silyl ketene acetal is also converted into an ester compound. This modified product has no corrosive properties, so even if it remains in the silica, there is no risk of any disadvantage to the practical aspects of the silica. Note that the silylketene acetal compound used here has the formula
【式】で示さ れる化合物を式Indicated by [formula] Formula
【式】によつて示
される化合物と反応させたのち、ハロシランと反
応させることにより次式
によつて容易に得ることができるし、これはまた
メタクリルエステルにウイルキンソン錯体の存在
下にハイドロジエンシランまたはシロキサンを付
加させることにより、次式
で表わされる様に容易に得ることができるので、
本発明の方法を容易にかつ安価に実施することが
できるという有利性が与えられる。
つぎに本発明の実施例をあげる。
実施例
比表面積200m2／ｇのヒユームドシリカ粉100重
量部に、式
で示されるシリルケテンアセタール化合物30重量
部を加え、フラスコ中で攪拌して均一化し、つい
で80℃に加熱して２時間反応させたのち、120
℃／１トールに減圧して余剰の化合物および副生
物を除去したところ、このようにして得たシリカ
はつぎのような物性を示した。After reacting with the compound represented by [Formula], the following formula is obtained by reacting with halosilane. It can also be easily obtained by the addition of a hydrogen silane or siloxane to a methacrylic ester in the presence of a Wilkinson complex. Since it can be easily obtained as shown in
The advantage is that the method of the invention can be carried out easily and inexpensively. Next, examples of the present invention will be given. Example: To 100 parts by weight of fumed silica powder with a specific surface area of 200 m 2 /g, the formula Add 30 parts by weight of the silyl ketene acetal compound represented by the formula, stir in a flask to homogenize, heat to 80°C and react for 2 hours,
When the excess compounds and by-products were removed by reducing the pressure to .degree. C./1 Torr, the silica thus obtained exhibited the following physical properties.
Claims (1)
【式】で示される基を１個以上含有す るシリルケテンアセタール化合物１〜50重量部を
用いて25〜400℃の温度範囲で処理することを特
徴とする疎水性シリカの製造方法。[Claims] 1. 100 parts by weight of silica powder at a temperature of 25 to 400°C using 1 to 50 parts by weight of a silyl ketene acetal compound containing one or more groups represented by the formula [formula] in one molecule. 1. A method for producing hydrophobic silica, which is characterized in that it is treated within a range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20888888A JPH0259417A (en) | 1988-08-23 | 1988-08-23 | Method for producing hydrophobic silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20888888A JPH0259417A (en) | 1988-08-23 | 1988-08-23 | Method for producing hydrophobic silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0259417A JPH0259417A (en) | 1990-02-28 |
| JPH0470253B2 true JPH0470253B2 (en) | 1992-11-10 |
Family
ID=16563785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20888888A Granted JPH0259417A (en) | 1988-08-23 | 1988-08-23 | Method for producing hydrophobic silica |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0259417A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0633343B2 (en) * | 1989-11-02 | 1994-05-02 | 信越化学工業株式会社 | Organosilicone-treated silica, composition containing the same, and method for producing the composition |
| DE69902223T2 (en) * | 1998-01-15 | 2003-01-23 | Cabot Corp., Boston | POLYFUNCTIONAL ORGANOSILANE TREATMENT OF SILICA |
| JP6884574B2 (en) * | 2016-12-28 | 2021-06-09 | ポーラ化成工業株式会社 | Method of modifying the surface of powder particles |
-
1988
- 1988-08-23 JP JP20888888A patent/JPH0259417A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259417A (en) | 1990-02-28 |
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