JP2820873B2 - Method for producing surface-treated silica - Google Patents
Method for producing surface-treated silicaInfo
- Publication number
- JP2820873B2 JP2820873B2 JP5276516A JP27651693A JP2820873B2 JP 2820873 B2 JP2820873 B2 JP 2820873B2 JP 5276516 A JP5276516 A JP 5276516A JP 27651693 A JP27651693 A JP 27651693A JP 2820873 B2 JP2820873 B2 JP 2820873B2
- Authority
- JP
- Japan
- Prior art keywords
- och
- silica
- group
- water
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面処理シリカの製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing surface-treated silica.
【０００２】[0002]
【従来の技術】シリカをオルガノアルコキシシラン（シ
ランカップリング剤）で表面処理する方法については従
来多くの提案がなされているが、大別すると乾式法と湿
式法に分けられる。乾式法は溶剤を使用しないのでコス
ト的には有利であり、湿式法は溶剤系あるいは水系で処
理を行うため、シリカの表面を均一に処理できるという
利点がある。2. Description of the Related Art There have been many proposals for surface treatment of silica with an organoalkoxysilane (silane coupling agent), but they are roughly classified into a dry method and a wet method. The dry method is advantageous in terms of cost since no solvent is used, and the wet method has an advantage that the silica surface can be uniformly treated because the treatment is carried out in a solvent or water system.
【０００３】[0003]
【発明が解決しようとする課題】しかし、乾式法にはシ
リカの表面を均一に処理できないという不利がある。ま
た、湿式法では加水分解触媒として酸あるいはアルカリ
性触媒（酢酸、塩酸、硫酸、アンモニア等）を使用しな
ければならず、有機官能基が損なわれる可能性がある
し、触媒が腐食性物質であるので工程用の機器の損傷が
早められ、かつ操作性、安全性もそれほど優れていると
はいえない。このように、従来は均一性、安定性に優
れ、かつ操作性、安全性にも優れた方法が見出されてい
なかった。本発明は上述の不利を解決しようとしてなさ
れたものである。However, the dry method has a disadvantage that the surface of silica cannot be uniformly treated. Further, in the wet method, an acid or alkaline catalyst (acetic acid, hydrochloric acid, sulfuric acid, ammonia, etc.) must be used as a hydrolysis catalyst, and organic functional groups may be damaged, and the catalyst is a corrosive substance. Therefore, damage to process equipment is hastened, and operability and safety are not so excellent. As described above, a method excellent in uniformity and stability and excellent in operability and safety has not been found conventionally. The present invention has been made to solve the above disadvantages.
【０００４】[0004]
【課題を解決するための手段】本発明者らは前記の課題
を解決するため鋭意検討の結果、水あるいは有機溶剤中
で行う湿式法において、触媒としてSi-F結合を有するフ
ッ素含有ケイ素化合物あるいはフッ素の塩化合物の存在
下、ケイ素原子に直結したアルコキシ基を有する有機ケ
イ素化合物とシリカとを反応させる方法によれば目的が
達成されることを見出して本発明に至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, in a wet method performed in water or an organic solvent, a fluorine-containing silicon compound having a Si-F bond as a catalyst or The present inventors have found that the object can be attained by a method of reacting an organic silicon compound having an alkoxy group directly bonded to a silicon atom with silica in the presence of a fluorine salt compound, thereby achieving the present invention.
【０００５】すなわち本発明は、ケイ素原子に直結した
アルコキシ基を有する有機ケイ素化合物を、Si-F結合を
有するフッ素含有ケイ素化合物あるいはフッ素の塩化合
物触媒の存在下、水あるいは含水有機溶剤中に分散させ
たシリカと反応させることを特徴とする表面処理シリカ
の製造方法、に関するものである。That is, according to the present invention, an organic silicon compound having an alkoxy group directly bonded to a silicon atom is dispersed in water or a water-containing organic solvent in the presence of a fluorine-containing silicon compound having a Si-F bond or a fluorine salt compound catalyst. A method for producing surface-treated silica, characterized by reacting the treated silica with the silica.
【０００６】以下に本発明について詳しく説明する。本
発明で使用するケイ素原子に直結したアルコキシ基を有
する有機ケイ素化合物は、典型的には一般式 YSiR1 a(OR
2)3-a で表され、式中のR1は非置換又は置換のアルキル
基及びフェニル基から選ばれる基であり、R2は炭素原子
数１〜４のアルキル基から選ばれる基である。Ｙは非置
換又は置換のアルキル基、アルケニル基、フェニル基、
Si-C結合でケイ素原子に結合した有機基であってエポキ
シ基、（メタ）アクリロキシ基、アミノ基、メルカプト
基、水酸基、シロキシ基、エーテル結合、ケトン基、エ
ステル結合、リン結合などから選ばれる官能基又は結合
を含む基及びSi-C結合でケイ素原子に結合した有機基で
あってポリ（ビニル芳香族）、ポリエーテル、ポリアミ
ドなどから選ばれるポリマーを含む基から選ばれるもの
である。また、ａは０〜２の整数である。なお、上記一
般式に含まれないものも勿論使用できる。Hereinafter, the present invention will be described in detail. The organosilicon compound having an alkoxy group directly bonded to a silicon atom used in the present invention typically has the general formula YSiR 1 a (OR
2 ) represented by 3-a , wherein R 1 is a group selected from an unsubstituted or substituted alkyl group and a phenyl group, and R 2 is a group selected from an alkyl group having 1 to 4 carbon atoms . Y is an unsubstituted or substituted alkyl group, alkenyl group, phenyl group,
Organic group bonded to silicon atom by Si-C bond, selected from epoxy group, (meth) acryloxy group, amino group, mercapto group, hydroxyl group, siloxy group, ether bond, ketone group, ester bond, phosphorus bond, etc. It is a group containing a functional group or a bond or an organic group bonded to a silicon atom by a Si-C bond, and is selected from a group containing a polymer selected from poly (vinyl aromatic), polyether, polyamide and the like. A is an integer of 0 to 2. In addition, those not included in the above general formula can of course be used.
【０００７】このようなケイ素原子に直結したアルコキ
シ基を有する有機ケイ素化合物の具体例としては下記の
ものが挙げられる。CH3Si(OCH3)3, (CH3)2Si(OCH3)2,
(CH3)3SiOCH3, CH3Si(OCH2CH3)3,(CH3)2Si(OCH2CH3)2,
(CH3)3SiOCH2CH3, CH3CH2Si(OCH3)3,(CH3CH2)2Si(OCH3)
2, (CH3CH2)3SiOCH3, CH3CH2Si(OCH2CH3)3,(CH3CH2)2Si
(OCH2CH3)2, (CH3CH2)3SiOCH2CH3, CH3CH2CH2Si(OC
H3)3,(CH3CH2CH2)2Si(OCH3)2, (CH3CH2CH2)3SiOCH3, CH
3CH2CH2Si(OCH2CH3)3,(CH3CH2CH2)2Si(OCH2CH3)2, (CH3
CH2CH2)3SiOCH2CH3,CH3CH2CH2CH2Si(OCH3)3, (CH3CH2CH
2CH2)2Si(OCH3)2,(CH3CH2CH2CH2)3SiOCH3, CH3CH2CH2CH
2Si(OCH2CH3)3,(CH3CH2CH2CH2)2Si(OCH2CH3)2, (CH3CH2
CH2CH2)3SiOCH2CH3,Specific examples of such organosilicon compounds having an alkoxy group directly bonded to a silicon atom include the following. CH 3 Si (OCH 3 ) 3 , (CH 3 ) 2 Si (OCH 3 ) 2 ,
(CH 3 ) 3 SiOCH 3 , CH 3 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 ,
(CH 3 ) 3 SiOCH 2 CH 3 , CH 3 CH 2 Si (OCH 3 ) 3 , (CH 3 CH 2 ) 2 Si (OCH 3 )
2 , (CH 3 CH 2 ) 3 SiOCH 3 , CH 3 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 CH 2 ) 2 Si
(OCH 2 CH 3 ) 2 , (CH 3 CH 2 ) 3 SiOCH 2 CH 3 , CH 3 CH 2 CH 2 Si (OC
H 3 ) 3 , (CH 3 CH 2 CH 2 ) 2 Si (OCH 3 ) 2 , (CH 3 CH 2 CH 2 ) 3 SiOCH 3 , CH
3 CH 2 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 CH 2 CH 2 ) 2 Si (OCH 2 CH 3 ) 2 , (CH 3
CH 2 CH 2 ) 3 SiOCH 2 CH 3 , CH 3 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 , (CH 3 CH 2 CH
2 CH 2 ) 2 Si (OCH 3 ) 2 , (CH 3 CH 2 CH 2 CH 2 ) 3 SiOCH 3 , CH 3 CH 2 CH 2 CH
2 Si (OCH 2 CH 3 ) 3 , (CH 3 CH 2 CH 2 CH 2 ) 2 Si (OCH 2 CH 3 ) 2 , (CH 3 CH 2
CH 2 CH 2 ) 3 SiOCH 2 CH 3 ,
【０００８】CH3CH2(CH3)CHSi(OCH3)3, [CH3CH2(CH3)C
H]2Si(OCH3)2,[CH3CH2(CH3)CH]3SiOCH3, CH3CH2(CH3)CH
Si(OCH2CH3)3,[CH3CH2(CH3)CH]2Si(OCH2CH3)2, [CH3CH2
(CH3)CH]3SiOCH2CH3,(CH3)2CHCH2Si(OCH3)3, [(CH3)2CH
CH2]2Si(OCH3)2, [(CH3)2CHCH2]3SiOCH3,(CH3)2CHCH2Si
(OCH2CH3)3, [(CH3)2CHCH2]2Si(OCH2CH3)2,[(CH3)2CHCH
2]3SiOCH2CH3, (CH3)3CSi(OCH3)3, [(CH3)3C]2Si(OCH3)
2,[(CH3)3C]3SiOCH3, (CH3)3CSi(OCH2CH3)3, [(CH3)3C]
2Si(OCH2CH3)2,[(CH3)3C]3SiOCH2CH3,CH 3 CH 2 (CH 3 ) CHSi (OCH 3 ) 3 , [CH 3 CH 2 (CH 3 ) C
H] 2 Si (OCH 3 ) 2 , [CH 3 CH 2 (CH 3 ) CH] 3 SiOCH 3 , CH 3 CH 2 (CH 3 ) CH
Si (OCH 2 CH 3 ) 3 , [CH 3 CH 2 (CH 3 ) CH] 2 Si (OCH 2 CH 3 ) 2 , [CH 3 CH 2
(CH 3 ) CH] 3 SiOCH 2 CH 3 , (CH 3 ) 2 CHCH 2 Si (OCH 3 ) 3 , [(CH 3 ) 2 CH
CH 2 ] 2 Si (OCH 3 ) 2 , [(CH 3 ) 2 CHCH 2 ] 3 SiOCH 3 , (CH 3 ) 2 CHCH 2 Si
(OCH 2 CH 3 ) 3 , [(CH 3 ) 2 CHCH 2 ] 2 Si (OCH 2 CH 3 ) 2 , [(CH 3 ) 2 CHCH
2 ] 3 SiOCH 2 CH 3 , (CH 3 ) 3 CSi (OCH 3 ) 3 , [(CH 3 ) 3 C] 2 Si (OCH 3 )
2 , [(CH 3 ) 3 C] 3 SiOCH 3 , (CH 3 ) 3 CSi (OCH 2 CH 3 ) 3 , [(CH 3 ) 3 C]
2 Si (OCH 2 CH 3 ) 2 , [(CH 3 ) 3 C] 3 SiOCH 2 CH 3 ,
【０００９】[0009]
【化１】 Embedded image
【００１０】CH2=CHSi(OCH3)3, CH2=CH(CH3)Si(OCH3)2,
CH2=CHSi(OCH2CH3)3,CH2=CH(CH3)Si(OCH2CH3)2, CH2=C
HCH2Si(OCH3)3, CH2=CHCH2(CH3)Si(OCH3)2,CH2=CHCH2Si
(OCH2CH3)3, CH2=CHCH2(CH3)Si(OCH2CH3)2,CH2=CH(CH2)
4Si(OCH3)3, CH2=CH(CH2)4(CH3)Si(OCH3)2,CH2=CH(CH2)
4Si(OCH2CH3)3, CH2=CH(CH2)4(CH3)Si(OCH2CH3)2,CH2=C
H(CH2)8Si(OCH3)3, CH2=CH(CH2)8Si(OCH2CH3)3,CH2=CHO
(CH2)3Si(OCH3)3, CH2=CHO(CH2)3Si(OCH2CH3)3,CH2=CHO
OC(CH2)10Si(OCH3)3, CH2=CHOOC(CH2)10Si(OCH2CH3)3,CH 2 = CHSi (OCH 3 ) 3 , CH 2 = CH (CH 3 ) Si (OCH 3 ) 2 ,
CH 2 = CHSi (OCH 2 CH 3 ) 3 , CH 2 = CH (CH 3 ) Si (OCH 2 CH 3 ) 2 , CH 2 = C
HCH 2 Si (OCH 3 ) 3 , CH 2 = CHCH 2 (CH 3 ) Si (OCH 3 ) 2 , CH 2 = CHCH 2 Si
(OCH 2 CH 3 ) 3 , CH 2 = CHCH 2 (CH 3 ) Si (OCH 2 CH 3 ) 2 , CH 2 = CH (CH 2 )
4 Si (OCH 3 ) 3 , CH 2 = CH (CH 2 ) 4 (CH 3 ) Si (OCH 3 ) 2 , CH 2 = CH (CH 2 )
4 Si (OCH 2 CH 3 ) 3 , CH 2 = CH (CH 2 ) 4 (CH 3 ) Si (OCH 2 CH 3 ) 2 , CH 2 = C
H (CH 2 ) 8 Si (OCH 3 ) 3 , CH 2 = CH (CH 2 ) 8 Si (OCH 2 CH 3 ) 3 , CH 2 = CHO
(CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHO (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , CH 2 = CHO
OC (CH 2 ) 10 Si (OCH 3 ) 3 , CH 2 = CHOOC (CH 2 ) 10 Si (OCH 2 CH 3 ) 3 ,
【００１１】[0011]
【化２】 Embedded image
【００１２】[0012]
【化３】 Embedded image
【００１３】CH2=C(CH3)COO(CH2)3Si(OCH3)3, CH2=C(CH
3)COO(CH2)3Si(OCH2CH3)3,CH2=C(CH3)COO(CH2)3(CH3)Si
(OCH3)2,CH2=C(CH3)COO(CH2)3(CH3)Si(OCH2CH3)2,CH2=C
HCOO(CH2)3Si(OCH3)3, CH2=CHCOO(CH2)3Si(OCH2CH3)3,C
H2=CHCOO(CH2)3(CH3)Si(OCH3)2, CH2=CHCOO(CH2)3(CH3)
Si(OCH2CH3)2,HS(CH2)3Si(OCH3)3, HS(CH2)3Si(OCH2C
H3)3, HS(CH2)3(CH3)Si(OCH3)2,HS(CH2)3(CH3)Si(OCH2C
H3)2, CH3O(CH2CH2O)10(CH2)3Si(OCH3)3,CH3O(CH2CH2O)
10(CH2)3Si(OCH2CH3)3, CF3(CH2)2Si(OCH3)3,．CF3(C
H2)2Si(OCH2CH3)3, CH3COCH2COO(CH2)3Si(OCH3)3,CH3CO
CH2COO(CH2)3Si(OCH2CH3)3,CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = C (CH
3) COO (CH 2) 3 Si (OCH 2 CH 3) 3, CH 2 = C (CH 3) COO (CH 2) 3 (CH 3) Si
(OCH 3 ) 2 , CH 2 = C (CH 3 ) COO (CH 2 ) 3 (CH 3 ) Si (OCH 2 CH 3 ) 2 , CH 2 = C
HCOO (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHCOO (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , C
H 2 = CHCOO (CH 2 ) 3 (CH 3 ) Si (OCH 3 ) 2 , CH 2 = CHCOO (CH 2 ) 3 (CH 3 )
Si (OCH 2 CH 3 ) 2 , HS (CH 2 ) 3 Si (OCH 3 ) 3 , HS (CH 2 ) 3 Si (OCH 2 C
H 3 ) 3 , HS (CH 2 ) 3 (CH 3 ) Si (OCH 3 ) 2 , HS (CH 2 ) 3 (CH 3 ) Si (OCH 2 C
H 3 ) 2 , CH 3 O (CH 2 CH 2 O) 10 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 3 O (CH 2 CH 2 O)
10 (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , CF 3 (CH 2 ) 2 Si (OCH 3 ) 3 ,. CF 3 (C
H 2 ) 2 Si (OCH 2 CH 3 ) 3 , CH 3 COCH 2 COO (CH 2 ) 3 Si (OCH 3 ) 3 , CH 3 CO
CH 2 COO (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 ,
【００１４】[0014]
【化４】 Embedded image
【００１５】CH2=C(CH3)OCH2CH2O(CH2)3Si(OCH3)3,CH2=
C(CH3)OCH2CH2O(CH2)3Si(OCH2CH3)3,CH2=C(CH3)COO(C
H2)11Si(OCH3)3, CH2=C(CH3)COO(CH2)11Si(OCH2CH3)3,H
2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3,H2N(CH2)3
(CH3)Si(OCH3)2, H2N(CH2)3(CH3)Si(OCH2CH3)2,CH3NH(C
H2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3,(CH3)2N(C
H2)3Si(OCH3)3, (CH3)2N(CH2)3Si(OCH2CH3)3,(CH3CH2CH
2CH2)2N(CH2)3Si(OCH3)3, (CH3CH2CH2CH2)2N(CH2)3Si(O
CH2CH3)3,H2N(CH2)2NH(CH2)3Si(OCH3)3, H2N(CH2)2NH(C
H2)3Si(OCH2CH3)3,H2N(CH2)2NH(CH2)3(CH3)Si(OCH3)2,
H2N(CH2)2NH(CH2)3(CH3)Si(OCH2CH3)2,H2N(CH2)6NH(C
H2)3Si(OCH3)3, H2N(CH2)6NH(CH2)3Si(OCH2CH3)3,H2N(C
H2)2NH(CH2)2NH(CH2)3Si(OCH3)3,H2N(CH2)2NH(CH2)2NH
(CH2)3Si(OCH2CH3)3,CH 2 = C (CH 3 ) OCH 2 CH 2 O (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 =
C (CH 3 ) OCH 2 CH 2 O (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , CH 2 = C (CH 3 ) COO (C
H 2 ) 11 Si (OCH 3 ) 3 , CH 2 = C (CH 3 ) COO (CH 2 ) 11 Si (OCH 2 CH 3 ) 3 , H
2 N (CH 2 ) 3 Si (OCH 3 ) 3 , H 2 N (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , H 2 N (CH 2 ) 3
(CH 3 ) Si (OCH 3 ) 2 , H 2 N (CH 2 ) 3 (CH 3 ) Si (OCH 2 CH 3 ) 2 , CH 3 NH (C
H 2 ) 3 Si (OCH 3 ) 3 , CH 3 NH (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 N (C
H 2 ) 3 Si (OCH 3 ) 3 , (CH 3 ) 2 N (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , (CH 3 CH 2 CH
2 CH 2 ) 2 N (CH 2 ) 3 Si (OCH 3 ) 3 , (CH 3 CH 2 CH 2 CH 2 ) 2 N (CH 2 ) 3 Si (O
CH 2 CH 3 ) 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , H 2 N (CH 2 ) 2 NH (C
H 2 ) 3 Si (OCH 2 CH 3 ) 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 3 (CH 3 ) Si (OCH 3 ) 2 ,
H 2 N (CH 2 ) 2 NH (CH 2 ) 3 (CH 3 ) Si (OCH 2 CH 3 ) 2 , H 2 N (CH 2 ) 6 NH (C
H 2 ) 3 Si (OCH 3 ) 3 , H 2 N (CH 2 ) 6 NH (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , H 2 N (C
H 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , H 2 N (CH 2 ) 2 NH (CH 2 ) 2 NH
(CH 2 ) 3 Si (OCH 2 CH 3 ) 3 ,
【００１６】[0016]
【化５】 Embedded image
【００１７】(CH3O)3Si(CH2)3NH(CH2)2NH(CH2)3Si(OC
H3)3,(CH3CH2O)3Si(CH2)3NH(CH2)2NH(CH2)3Si(OCH2CH3)
3,(CH3O)3Si(CH2)3NH(CH2)3Si(OCH3)3,(CH3CH2O)3Si(CH
2)3NH(CH2)3Si(OCH2CH3)3,(CH3)3SiOSi(OCH3)3, [(CH3)
3SiO]2Si(OCH3)2, [(CH3)3SiO]3SiOCH3,(CH3)3SiOSi(OC
H2CH3)3, [(CH3)3SiO]2Si(OCH2CH3)2,[(CH3)3SiO]3SiOC
H2CH3,(CH 3 O) 3 Si (CH 2 ) 3 NH (CH 2 ) 2 NH (CH 2 ) 3 Si (OC
H 3 ) 3 , (CH 3 CH 2 O) 3 Si (CH 2 ) 3 NH (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 2 CH 3 )
3 , (CH 3 O) 3 Si (CH 2 ) 3 NH (CH 2 ) 3 Si (OCH 3 ) 3 , (CH 3 CH 2 O) 3 Si (CH
2 ) 3 NH (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 3 SiOSi (OCH 3 ) 3 , ((CH 3 )
3 SiO] 2 Si (OCH 3 ) 2 , [(CH 3 ) 3 SiO] 3 SiOCH 3 , (CH 3 ) 3 SiOSi (OC
H 2 CH 3 ) 3 , [(CH 3 ) 3 SiO] 2 Si (OCH 2 CH 3 ) 2 , [(CH 3 ) 3 SiO] 3 SiOC
H 2 CH 3 ,
【００１８】[0018]
【化６】 Embedded image
【００１９】これらのケイ素原子に直結したアルコキシ
基を有する有機ケイ素化合物は１種単独で用いることも
２種以上併用することもできる。この有機ケイ素化合物
の使用量は特に限定されないが、シリカ 100重量部に対
して 0.001〜10重量部、特には0.01〜１重量部が好まし
い。この有機ケイ素化合物の使用量が 0.001重量部未満
であるとシリカ表面の処理が不十分になってくる。ま
た、10重量部を超えても効果はそれほど大きくならない
しコスト高になるために経済的に不利である。These organosilicon compounds having an alkoxy group directly bonded to a silicon atom can be used alone or in combination of two or more. The amount of the organosilicon compound is not particularly limited, but is preferably 0.001 to 10 parts by weight, particularly preferably 0.01 to 1 part by weight, based on 100 parts by weight of silica. If the amount of the organosilicon compound is less than 0.001 part by weight, the treatment of the silica surface becomes insufficient. If the amount exceeds 10 parts by weight, the effect is not so large and the cost is high, which is economically disadvantageous.
【００２０】また、上記のケイ素原子に直結したアルコ
キシ基を有する有機ケイ素化合物の他にも、下記に示す
ようなテトラアルコキシシランを併用あるいは前処理し
てもよい。 Si(OCH3)4, Si(OCH2CH3)4, Si(OCH2CH2CH3)4, Si(OCH2C
H2CH2CH3)4 上記テトラアルコキシシランを併用する場合、ケイ素原
子に直結したアルコキシ基を有する有機ケイ素化合物 1
00重量部に対して30重量部以下の量を添加するのがよ
い。30重量部を超えるとケイ素原子に直結したアルコキ
シ基を有する有機ケイ素化合物とテトラアルコキシシラ
ンとが縮合してしまい、シリカの表面をうまく処理でき
ず好ましくない。In addition to the organosilicon compound having an alkoxy group directly bonded to a silicon atom, a tetraalkoxysilane as shown below may be used in combination or pretreated. Si (OCH 3 ) 4 , Si (OCH 2 CH 3 ) 4 , Si (OCH 2 CH 2 CH 3 ) 4 , Si (OCH 2 C
H 2 CH 2 CH 3 ) 4 When the above tetraalkoxysilane is used in combination, an organosilicon compound having an alkoxy group directly bonded to a silicon atom 1
It is preferable to add an amount of 30 parts by weight or less based on 00 parts by weight. If it exceeds 30 parts by weight, an organosilicon compound having an alkoxy group directly bonded to a silicon atom and tetraalkoxysilane are condensed, and the surface of silica cannot be treated well, which is not preferable.
【００２１】反応系に添加する触媒はSi-F結合を分子内
に少なくとも１個有するフッ素含有ケイ素化合物あるい
はフッ素の塩化合物である。Si-F結合を分子内に少なく
とも１個有するフッ素含有ケイ素化合物としては、Si-F
結合を持つものであれば有機化合物でも無機化合物でも
よい。有機化合物系のものは例えば、FSi(OCH3)3, FSi
(OC2H5)3, FSi(OC3H7)3, FSi(OC4H9)3, F2Si(OCH3)2,F2
Si(OC2H5)2, F2Si(OC3H7)2, F2Si(OC4H9)2, F3SiOCH3,
F3SiOC2H5,F3SiOC3H7, F3SiOC4H9, FSi(CH3)3, FSi(C2H
5)3, FSi(C3H7)3, FSi(C4H9)3,F2Si(CH3)2, F2Si(C2H5)
2, F2Si(C3H7)2, F2Si(C4H9)2, F3SiCH3, F3SiC2H5,F3S
iC3H7, F3SiC4H9等を具体例としてあげることができる
が、Si-F結合を含有していればポリシロキサン、ポリシ
ラン化合物でもよい。また、無機化合物系のものでは、
例えばSiF4, H2SiF6, Na2SiF6, (NH4)2SiF6 等をあげる
ことができる。これらの化合物の中でコスト、操作性、
安全性などを考慮するとFSi(OCH3)3, FSi(OC2H5)3, (NH
4)2SiF6 などが特に好適である。The catalyst to be added to the reaction system is a fluorine-containing silicon compound or a fluorine salt compound having at least one Si-F bond in the molecule. Examples of the fluorine-containing silicon compound having at least one Si-F bond in a molecule include Si-F
An organic compound or an inorganic compound may be used as long as it has a bond. Organic compounds are, for example, FSi (OCH 3 ) 3 , FSi
(OC 2 H 5 ) 3 , FSi (OC 3 H 7 ) 3 , FSi (OC 4 H 9 ) 3 , F 2 Si (OCH 3 ) 2 , F 2
Si (OC 2 H 5 ) 2 , F 2 Si (OC 3 H 7 ) 2 , F 2 Si (OC 4 H 9 ) 2 , F 3 SiOCH 3 ,
F 3 SiOC 2 H 5 , F 3 SiOC 3 H 7 , F 3 SiOC 4 H 9 , FSi (CH 3 ) 3 , FSi (C 2 H
5 ) 3 , FSi (C 3 H 7 ) 3 , FSi (C 4 H 9 ) 3 , F 2 Si (CH 3 ) 2 , F 2 Si (C 2 H 5 )
2 , F 2 Si (C 3 H 7 ) 2 , F 2 Si (C 4 H 9 ) 2 , F 3 SiCH 3 , F 3 SiC 2 H 5 , F 3 S
Specific examples include iC 3 H 7 and F 3 SiC 4 H 9, but polysiloxane and polysilane compounds may be used as long as they contain a Si—F bond. In addition, in the case of inorganic compounds,
For example, SiF 4 , H 2 SiF 6 , Na 2 SiF 6 , (NH 4 ) 2 SiF 6 and the like can be mentioned. Among these compounds, cost, operability,
Considering safety, etc., FSi (OCH 3 ) 3 , FSi (OC 2 H 5 ) 3 , (NH
4 ) 2 SiF 6 and the like are particularly suitable.
【００２２】また、フッ素の塩化合物としては、例えば
LiF, NaF, KF, RbF, CsFなどＩ族元素のフッ化物、Be
F2, MgF2, CaF2, SrF2, BaF2などのII族元素のフッ化
物、BF3, AlF3, GaF3,InF3, TlF3などの III族元素のフ
ッ化物、CuF2, ZnF2, SnF2, PdF2, SbF3, CrF3, YF3 な
どのフッ化物、LaF3,CeF3, PrF3, NdF3, SmF3, EuF3, G
dF3, TbF3, DyF3, HoF3, ErF3などのランタノイド系の
フッ化物などをあげることができるが、これらの水和物
でもよい。また、(CH3)4N・F, (CH3CH2)4N・F, (CH3CH2CH
2)4N・F, (CH3CH2CH2CH2)4N・Fのようなフッ素のアンモニ
ウム塩化合物も例示することができる。これらの化合物
の中でコスト、水溶解性、操作性、安全性を考慮する
と、NaF,KF, (CH3CH2CH2CH2)4N・Fなどが特に好適であ
る。Examples of the fluorine salt compound include, for example,
Group I element fluoride such as LiF, NaF, KF, RbF, CsF, Be
Group 2 element fluoride such as F 2 , MgF 2 , CaF 2 , SrF 2 , BaF 2 , Group III element fluoride such as BF 3 , AlF 3 , GaF 3 , InF 3 , TlF 3 , CuF 2 , ZnF 2 , Fluoride such as SnF 2 , PdF 2 , SbF 3 , CrF 3 , YF 3 , LaF 3 , CeF 3 , PrF 3 , NdF 3 , SmF 3 , EuF 3 , G
Lanthanoid fluorides such as dF 3 , TbF 3 , DyF 3 , HoF 3 , and ErF 3 can be mentioned, but hydrates thereof may also be used. Also, (CH 3 ) 4 N ・ F, (CH 3 CH 2 ) 4 N ・ F, (CH 3 CH 2 CH
2 ) 4 N · F, (CH 3 CH 2 CH 2 CH 2 ) 4 N · F, etc. can also be exemplified. Among these compounds, NaF, KF, (CH 3 CH 2 CH 2 CH 2 ) 4 N · F, etc. are particularly preferable in consideration of cost, water solubility, operability and safety.
【００２３】本発明の方法においては、粉末状の球状あ
るいは無定形のシリカ、コロイダルシリカ、アルコキシ
シラン類を加水分解させて作成したシリカ、また、酸化
チタン、アルミナ等の無機酸化物の表面をシランカップ
リング剤で処理したものなどであれば処理することが可
能である。In the method of the present invention, powdery spherical or amorphous silica, colloidal silica, silica prepared by hydrolyzing alkoxysilanes, or the surface of an inorganic oxide such as titanium oxide or alumina is treated with silane. If it has been treated with a coupling agent, it can be treated.
【００２４】本発明の製造方法は湿式法であり、水ある
いは含水有機溶剤中で処理を行う。有機溶剤としては例
えば、メチルアルコール、エチルアルコール、１−プロ
ピルアルコール、２−プロピルアルコール等のアルコー
ル類、ジエチルエーテル、ジプロピルエーテル等のエー
テル類、酢酸メチル、酢酸エチル、アセト酢酸エチル等
のエステル類、アセトン、ジエチルケトン、イソプロピ
ルメチルケトン、メチルエチルケトン等のケトン類をあ
げることができる。溶媒の量は処理するシリカ 100重量
部に対して20〜1000重量部が好ましく、更に好ましくは
20〜500 重量部である。溶剤の量が1000重量部を超える
と反応装置などを大きくしなければならず、ポットイー
ルドも低下するため経済的に不利である。また、溶剤の
量が20重量部より少ないとシリカ表面を均一に処理する
ことが難しくなる。The production method of the present invention is a wet method, and the treatment is carried out in water or a water-containing organic solvent. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol and 2-propyl alcohol, ethers such as diethyl ether and dipropyl ether, and esters such as methyl acetate, ethyl acetate and ethyl acetoacetate. And ketones such as acetone, diethyl ketone, isopropyl methyl ketone and methyl ethyl ketone. The amount of the solvent is preferably 20 to 1000 parts by weight, more preferably 100 to 100 parts by weight of silica to be treated.
20 to 500 parts by weight. If the amount of the solvent exceeds 1000 parts by weight, the size of the reactor must be increased, and the pot yield is reduced, which is economically disadvantageous. If the amount of the solvent is less than 20 parts by weight, it becomes difficult to uniformly treat the silica surface.
【００２５】溶剤系への水の添加量はケイ素原子に直結
したアルコキシ基を有する有機ケイ素化合物のアルコキ
シ基対水のモル比で１対0.5 〜１対10が好ましい。水の
モル比が 0.5よりも少ないと加水分解せずに残るアルコ
キシ基の量が増加するため、シリカ表面をうまく処理で
きなくなってくるので好ましくない。また、水のモル比
が10を超えるとシリカが処理される前にケイ素原子に直
結したアルコキシ基を有する有機ケイ素化合物が自己縮
合するようになり、処理能力が低下するので好ましくな
い。The amount of water added to the solvent system is preferably from 1: 0.5 to 1:10 in terms of the molar ratio of the alkoxy group to water of the organosilicon compound having an alkoxy group directly bonded to a silicon atom. If the molar ratio of water is less than 0.5, the amount of alkoxy groups remaining without hydrolysis increases, and it is not preferable because the silica surface cannot be treated well. On the other hand, when the molar ratio of water exceeds 10, the organosilicon compound having an alkoxy group directly bonded to a silicon atom is self-condensed before the silica is treated, which is not preferable because the treatment capacity is reduced.
【００２６】触媒を反応系に添加する方法は、フッ素含
有ケイ素化合物の場合、このものが有機化合物の時はケ
イ素原子に直結したアルコキシ基を有する有機ケイ素化
合物に混合するのがよく、無機化合物の時は水、溶媒に
溶解させればよい。フッ素の塩化合物の場合は水、溶媒
に溶解させて使用する方法が好ましい。触媒の量はケイ
素原子に直結したアルコキシ基を有する有機ケイ素化合
物のSi対触媒の Fのモル比が 1.0対0.0001〜1.0 対2.0
の範囲となるようにすることが好ましい。Siに対する F
のモル比が1.0 対0.0001よりも小さいと触媒としての効
果があまりなく処理に長時間を要し、また、シリカの表
面を均一に処理することが難しくなるので好ましくな
い。逆にこのモル比が1.0 対2.0 よりも大きいとポット
イールドが低下し、高コストになってしまうためやはり
好ましくない。より好ましくはSi対 Fのモル比が 1.0対
0.001 〜 1.0対0.1 の範囲を満たすことである。The method of adding the catalyst to the reaction system is as follows. When the fluorine-containing silicon compound is an organic compound, it is preferably mixed with an organic silicon compound having an alkoxy group directly bonded to a silicon atom. In such a case, it may be dissolved in water or a solvent. In the case of a fluorine salt compound, a method of dissolving it in water or a solvent is preferable. The amount of the catalyst is such that the molar ratio of Si of the organosilicon compound having an alkoxy group directly bonded to the silicon atom to F of the catalyst is 1.0 to 0.0001 to 1.0 to 2.0.
It is preferable to set it in the range. F for Si
If the molar ratio is less than 1.0 to 0.0001, the effect as a catalyst is not so high, and a long time is required for the treatment, and it is difficult to uniformly treat the surface of the silica. Conversely, if the molar ratio is greater than 1.0 to 2.0, the pot yield decreases and the cost increases, which is not preferable. More preferably, the molar ratio of Si to F is 1.0 to
Satisfy the range of 0.001 to 1.0 to 0.1.
【００２７】実際の代表的な処理操作においては、シリ
カの水性懸濁液に所定量の触媒を加え、攪拌下にケイ素
原子に直結したアルコキシ基を有する有機ケイ素化合物
を室温で徐々に添加する。これによりシリカの表面はケ
イ素原子に直結したアルコキシ基を有する有機ケイ素化
合物によって速やかに処理される。上記操作によって表
面処理されたシリカをろ過等の方法によって懸濁液中か
ら分離し、溶媒、水等を揮発乾燥させると、目的とする
ケイ素原子に直結したアルコキシ基を有する有機ケイ素
化合物で表面処理されたシリカが得られる。また、スプ
レードライヤーなどの機器を利用して懸濁液から直接取
り出してもよい。In an actual representative treatment operation, a predetermined amount of a catalyst is added to an aqueous suspension of silica, and an organosilicon compound having an alkoxy group directly bonded to a silicon atom is gradually added at room temperature with stirring. Thereby, the surface of the silica is promptly treated with the organosilicon compound having an alkoxy group directly bonded to a silicon atom. The silica surface-treated by the above operation is separated from the suspension by a method such as filtration, and the solvent, water and the like are volatilized and dried, and the surface is treated with an organosilicon compound having an alkoxy group directly bonded to a target silicon atom. The resulting silica is obtained. Moreover, you may take out directly from a suspension using apparatuses, such as a spray dryer.
【００２８】[0028]
【実施例】実施例１ 球形シリカ20g 、メタノール100g、水2g、KF 0.01g(0.2
mmol) を攪拌機、温度計及び冷却器を備えた 500mlの反
応器に入れ攪拌混合した。ここにトリメチルメトキシシ
ラン2g(19mmol)を滴下し、室温で１時間攪拌熟成を行っ
た。ついで熟成後の懸濁液中の処理シリカをブフナーロ
ートで濾別し、蒸留水つづいてアセトンで洗浄した後、
真空乾燥機により80℃、10mmHgの条件で２時間処理して
溶媒を除去し、表面がトリメチルシリル化されたシリカ
を得た。このシリカの疎水化度を測定したところ、処理
前の球形シリカは０％であったが、処理されたシリカは
63.7％に達し、トリメチルメトキシシランで疎水化処理
されていることがわかった。なお、疎水化度（％）は、
水50ccにシリカ0.2gを入れ、そこにメタノールを少しづ
つ滴下して振とうし、静置後、シリカが混合液層に全て
湿潤する限界のメタノール濃度（％）で表した。EXAMPLES Example 1 20 g of spherical silica, 100 g of methanol, 2 g of water, 0.01 g of KF (0.2 g)
mmol) was placed in a 500 ml reactor equipped with a stirrer, thermometer and cooler and mixed with stirring. 2 g (19 mmol) of trimethylmethoxysilane was added dropwise thereto, and the mixture was aged at room temperature for 1 hour with stirring. Then, the treated silica in the aging suspension was filtered off with a Buchner funnel, washed with distilled water and then with acetone,
The solvent was removed by treating with a vacuum drier at 80 ° C. and 10 mmHg for 2 hours to obtain silica having a trimethylsilylated surface. When the degree of hydrophobicity of this silica was measured, the spherical silica before treatment was 0%, but the treated silica was
It reached 63.7%, indicating that it was hydrophobized with trimethylmethoxysilane. The degree of hydrophobicity (%) is
0.2 g of silica was put in 50 cc of water, methanol was added dropwise little by little, and the mixture was shaken. After standing, the methanol concentration (%) at which the silica was completely wetted in the mixed liquid layer was expressed.
【００２９】実施例２ KFを(NH4)2SiF6 0.005g(0.03mmol) とした以外は実施例
１と同様な反応及び処理を行った。この時の疎水化度は
52.4％であった。Example 2 The same reaction and treatment as in Example 1 were conducted except that KF was changed to 0.005 g (0.03 mmol) of (NH 4 ) 2 SiF 6 . The degree of hydrophobicity at this time is
52.4%.
【００３０】実施例３ メタノール100gを水100gにした以外は実施例１と同様な
反応及び処理を行った。この時の疎水化度は66.3％であ
った。Example 3 A reaction and treatment were carried out in the same manner as in Example 1 except that 100 g of methanol was changed to 100 g of water. At this time, the degree of hydrophobicity was 66.3%.
【００３１】比較例１ KFを36％ HCl水溶液0.1gとした以外は実施例１と同様な
反応及び処理を行った。この時の疎水化度は12％であっ
た。Comparative Example 1 The same reaction and treatment as in Example 1 were carried out except that KF was changed to 0.1 g of 36% HCl aqueous solution. At this time, the degree of hydrophobicity was 12%.
【００３２】実施例４ トリメチルメトキシシランをγ−グリシドキシプロピル
トリメトキシシラン2g(8.5mmol) とした以外は実施例１
と同様な反応及び処理を行った。疎水化度は52％であっ
た。また、チオ硫酸ソーダ法［実験化学講座 続５ 有
機化合物の定性確認法（上）p518（丸善）参照］による
呈色反応を行ったところ紅色を呈し、エポキシ基が保持
されていることがわかった。また、この表面処理シリカ
についてCPMAS 法による13C-NMR 測定をしたところ図１
に示すチャートが得られた。この結果からもエポキシ基
が損なわれずシリカ表面に被覆されていることが確認さ
れた。Example 4 Example 1 except that trimethylmethoxysilane was changed to 2 g (8.5 mmol) of γ-glycidoxypropyltrimethoxysilane.
The same reaction and treatment as described above were performed. The degree of hydrophobicity was 52%. In addition, when a color reaction was performed by the sodium thiosulfate method [Experimental Chemistry Lecture 5: Qualitative confirmation method of organic compounds (top), see p518 (Maruzen)], it turned out to be red and it was found that the epoxy group was retained. . 13 C-NMR measurement of this surface-treated silica by CPMAS method showed that
The chart shown in FIG. From this result, it was confirmed that the epoxy group was coated on the silica surface without being damaged.
【００３３】実施例５ トリメチルメトキシシランをビニルトリメトキシシラン
2g(13mmol)とした以外は実施例１と同様な反応及び処理
を行った。疎水化度は55％であった。また、過マンガン
酸カリウム法［実験化学講座 続５ 有機化合物の定性
確認法（上）p132（丸善株式会社）参照］による呈色反
応を行ったところ紫色であった液が脱色され、ビニル基
の存在が確認された。Example 5 Trimethylmethoxysilane was converted to vinyltrimethoxysilane
The same reaction and treatment as in Example 1 were performed except that the amount was changed to 2 g (13 mmol). The degree of hydrophobicity was 55%. When a color reaction was performed by the potassium permanganate method [Experimental Chemistry Lecture 5: Qualitative confirmation method of organic compounds (above), p. 132 (Maruzen Co., Ltd.)], the purple liquid was decolorized and the vinyl group was decolorized. Existence confirmed.
【００３４】実施例６ KFをFSi(OCH2CH3)3 0.04g(0.2mmol)とした以外は実施例
１と同様な反応及び処理を行った。この時の疎水化度は
51.2％であった。Example 6 The same reaction and treatment as in Example 1 were carried out except that KF was changed to FSi (OCH 2 CH 3 ) 3 0.04 g (0.2 mmol). The degree of hydrophobicity at this time is
51.2%.
【００３５】実施例７ トリメチルメトキシシランをγ−メタクリロキシプロピ
ルトリメトキシシラン2g(8mmol) とした以外は実施例１
と同様な反応及び処理を行った。疎水化度は56％であっ
た。過マンガン酸カリウム法（前出）による呈色反応を
行ったところ紫色であった液が脱色されたことからγ−
メタクリロキシプロピル基の存在が確認された。Example 7 Example 1 was repeated except that 2 g (8 mmol) of γ-methacryloxypropyltrimethoxysilane was used instead of trimethylmethoxysilane.
The same reaction and treatment as described above were performed. The degree of hydrophobicity was 56%. When the color reaction was performed by the potassium permanganate method (described above), the purple solution was decolorized.
The presence of a methacryloxypropyl group was confirmed.
【００３６】実施例８ トリメチルメトキシシランをアミノプロピルトリメトキ
シシラン2g(11mmol)とした以外は実施例１と同様な反応
及び処理を行った。第１アミンに対するRimini試験［実
験化学講座 続５ 有機化合物の定性確認法（下）p104
4 （丸善株式会社）参照］による呈色反応を行ったとこ
ろ紫赤色を呈したことからアミノ基の存在が確認され
た。Example 8 The same reaction and treatment as in Example 1 were performed except that trimethylmethoxysilane was changed to 2 g (11 mmol) of aminopropyltrimethoxysilane. Rimini test for primary amines [Experimental Chemistry Lecture 5 Sequential confirmation method for organic compounds (lower) p104
4 (Maruzen Co., Ltd.)], the color reaction turned purple-red, confirming the presence of an amino group.
【００３７】実施例９ トリメチルメトキシシランをトリメチルトリメトキシジ
シロキサン2g(9.5mmol) とした以外は実施例１と同様な
反応及び処理を行った。この時の疎水化度は60％であっ
た。Example 9 The same reaction and treatment as in Example 1 were carried out except that trimethylmethoxysilane was changed to 2 g (9.5 mmol) of trimethyltrimethoxydisiloxane. The degree of hydrophobicity at this time was 60%.
【００３８】[0038]
【発明の効果】本発明の製造方法によれば、温和な条件
で容易にしかも均一にシリカの表面処理を行うことがで
き、例えばエポキシ基のような反応性に富む有機官能基
でも損なうことなく安定に被覆させることができる。そ
して、酸あるいはアルカリ性触媒を用いる場合に比べ、
装置等の損傷もなくかつ操作性、安全性が格段に改善さ
れた。本発明の製造方法によれば、シリカ表面を所望の
密度で各種の有機官能基により被覆することができ、こ
のような被覆処理シリカは、カラムなどの充填剤や各種
の酵素、金属化合物などの担持用固体として有用であ
り、バイオリアクター、固定化酵素、固定化触媒、金属
回収用などの担体としての用途に好適である。また、こ
のような被覆処理シリカは各種フィラー用としても有用
である。According to the production method of the present invention, the surface treatment of silica can be easily and uniformly performed under mild conditions, and even a reactive organic functional group such as an epoxy group is not damaged. It can be coated stably. And, compared to the case of using an acid or alkaline catalyst,
There was no damage to the equipment and the operability and safety were significantly improved. According to the production method of the present invention, the silica surface can be coated with various organic functional groups at a desired density, and such coated silica can be used as a filler such as a column or various enzymes, a metal compound, or the like. It is useful as a supporting solid, and is suitable for use as a carrier for bioreactors, immobilized enzymes, immobilized catalysts, metal recovery, and the like. Such coated silica is also useful for various fillers.
【図１】実施例４で得た表面処理シリカのCPMAS 法によ
る13C-NMR 測定の結果を示す図である。FIG. 1 is a diagram showing the results of 13 C-NMR measurement of the surface-treated silica obtained in Example 4 by the CPMAS method.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C09C 1/00 - 3/12──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 6 , DB name) C09C 1/00-3/12
Claims (1)
する有機ケイ素化合物を、Si-F結合を有するフッ素含有
ケイ素化合物あるいはフッ素の塩化合物触媒の存在下、
水あるいは含水有機溶剤中に分散させたシリカと反応さ
せることを特徴とする表面処理シリカの製造方法。1. An organic silicon compound having an alkoxy group directly bonded to a silicon atom is converted into a fluorine-containing silicon compound having a Si-F bond or a fluorine salt compound catalyst in the presence of a catalyst.
A method for producing surface-treated silica, which comprises reacting with silica dispersed in water or a water-containing organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5276516A JP2820873B2 (en) | 1993-11-05 | 1993-11-05 | Method for producing surface-treated silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5276516A JP2820873B2 (en) | 1993-11-05 | 1993-11-05 | Method for producing surface-treated silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126549A JPH07126549A (en) | 1995-05-16 |
| JP2820873B2 true JP2820873B2 (en) | 1998-11-05 |
Family
ID=17570566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5276516A Expired - Fee Related JP2820873B2 (en) | 1993-11-05 | 1993-11-05 | Method for producing surface-treated silica |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2820873B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE496098T1 (en) * | 2000-10-21 | 2011-02-15 | Evonik Degussa Gmbh | RADIATION CURING PAINT SYSTEMS |
| EP1199335B1 (en) * | 2000-10-21 | 2010-12-22 | Evonik Degussa GmbH | Functionalized silicic acids |
| EP1199336B1 (en) | 2000-10-21 | 2014-01-15 | Evonik Degussa GmbH | Functionalized, structure modified silicic acids |
| JP5564752B2 (en) * | 2007-12-26 | 2014-08-06 | 東洋インキＳｃホールディングス株式会社 | Metal oxide dispersion, resin composition using the same, and molded article |
| JP5241279B2 (en) * | 2008-03-14 | 2013-07-17 | 旭化成イーマテリアルズ株式会社 | Inorganic filler |
-
1993
- 1993-11-05 JP JP5276516A patent/JP2820873B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07126549A (en) | 1995-05-16 |
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