JPH0798657B2 - Silylating agent and modified silica particles silylated by the method - Google Patents
Silylating agent and modified silica particles silylated by the methodInfo
- Publication number
- JPH0798657B2 JPH0798657B2 JP6999690A JP6999690A JPH0798657B2 JP H0798657 B2 JPH0798657 B2 JP H0798657B2 JP 6999690 A JP6999690 A JP 6999690A JP 6999690 A JP6999690 A JP 6999690A JP H0798657 B2 JPH0798657 B2 JP H0798657B2
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- Prior art keywords
- silylating agent
- silica particles
- modified silica
- silylated
- solvent
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、シリル化剤およびそれにより処理された変性
シリカ粒子に関するものである。さらに詳しくは、本発
明は、特定の化学構造式で表わされるシリル化剤および
該シリル化剤でシリカの表面をシリル化処理した、有機
溶剤に均質に再分散可能なシリカ粒子に関するものであ
る。TECHNICAL FIELD The present invention relates to a silylating agent and modified silica particles treated with the silylating agent. More specifically, the present invention relates to a silylating agent represented by a specific chemical structural formula, and silica particles that have been subjected to a silylation treatment on the surface of silica with the silylating agent and can be homogeneously redispersed in an organic solvent.
従来、シリル化剤としては、低分子量の鎖状化合物又
は、芳香族化合物のシラン類、例えばメチルトリクロル
シラン、ビニルトリクロルシラン、トリフェニルクロル
シラン、ベンジルトリメトキシシラン等が使用されてい
る（特公平２−1090号公報参照）。しかし、これらのシ
リル化剤がシリカなどの表面に結合して形成されたシリ
ル基は、水分が残存する場合には加水分解がおこり、そ
のためこのシリル化物は、安定性に欠ける憾みがあっ
た。Conventionally, as the silylating agent, low molecular weight chain compounds or silanes of aromatic compounds such as methyltrichlorosilane, vinyltrichlorosilane, triphenylchlorosilane, benzyltrimethoxysilane, etc. have been used. 2-1090). However, the silyl group formed by bonding these silylating agents to the surface of silica or the like is hydrolyzed in the presence of residual water, so that the silylated product is not stable enough.
本発明の目的は、安定性に優れた新規なシリル化剤を提
供する点にある。An object of the present invention is to provide a novel silylating agent having excellent stability.
本発明の他の目的は、前記シリル化剤を使用して、有機
溶剤に均質に分散可能な、シリカ粒子を提供する点にあ
る。Another object of the present invention is to provide silica particles which can be uniformly dispersed in an organic solvent using the silylating agent.
本発明の１つは、一般式 式中、ｎ＝７〜15 ｍ＝10以上 R1＝炭素数０〜６の範囲のアルキレン基（炭素数０の場
合はR1が存在しないことを表わす） R2＝炭素数１〜４の範囲のアルキル基 R3＝炭素数１〜４の範囲のアルキル基 で表わされるシリル化剤に関する。One of the inventions is the general formula In the formula, n = 7 to 15 m = 10 or more R 1 = alkylene group having a carbon number of 0 to 6 (in the case of 0 carbon, R 1 does not exist) R 2 = C 1 to 4 Alkyl group in the range R 3 = alkyl group in the range of 1 to 4 carbon atoms
本発明のもう１つは、請求項１記載のシリル化剤でシリ
カ粒子を処理することにより得らえた変性シリカ粒子に
関する。Another aspect of the present invention relates to modified silica particles obtained by treating the silica particles with the silylating agent according to claim 1.
本発明に係るシリル化剤は、一般式、 で表わされ、式中、ｎが７〜15の範囲、好ましくは８〜
12の範囲で、ｍが10以上の範囲、好ましくは15〜25の範
囲であり、R1が炭素数０〜６の範囲のアルキレン基（炭
素数０の場合はR1が存在しないことを意味する）で、R2
が炭素数１〜４の範囲のアルキル基で、R3が炭素数１〜
４の範囲のアルキル基で表わされる化合物である。The silylating agent according to the present invention has the general formula: In the formula, n is in the range of 7 to 15, preferably 8 to
In the range of 12, m is 10 or more, preferably 15 to 25, and R 1 is an alkylene group having a carbon number of 0 to 6 (in the case of 0 carbon, it means that R 1 does not exist). To R 2
Is an alkyl group having 1 to 4 carbon atoms, and R 3 is 1 to 4 carbon atoms.
It is a compound represented by an alkyl group in the range of 4.
上記式中のｎの値は、該化合物を合成する際の出発原料
である脂肪族ジオール類のアルキレン基の数を選択する
ことにより任意に調節することができる。このｎの値が
６以下の場合は、シリル化処理して得られる無機物粒子
の有機溶媒への再分散性が悪いので好ましくない。また
ｎの値が15より大きい場合は、該化合物の有機溶媒への
分散性が悪くなるので望ましくない。The value of n in the above formula can be arbitrarily adjusted by selecting the number of alkylene groups of the aliphatic diol which is a starting material for synthesizing the compound. When the value of n is 6 or less, the redispersibility of the inorganic particles obtained by the silylation treatment in an organic solvent is poor, which is not preferable. On the other hand, when the value of n is more than 15, the dispersibility of the compound in an organic solvent is deteriorated, which is not desirable.
上記式中のｍの値は、ポリオールの重合度を調節するこ
とにより、任意に調節することができる。このｍの値が
10より小さい場合は、所望の立体構造を有するシリル化
剤が得られないので望ましくない。The value of m in the above formula can be arbitrarily adjusted by adjusting the polymerization degree of the polyol. This value of m
When it is less than 10, a silylating agent having a desired steric structure cannot be obtained, which is not desirable.
また、式中R1は、炭素数１〜６のアルキレン基または、
炭素数が０でアルキレン基が存在しないこと、即ち酸素
とSiが直接結合していることを示し、R2およびR3は、メ
チル基、エチル基、プロピル基、またはブチル基を示
す。R 1 in the formula is an alkylene group having 1 to 6 carbon atoms, or
It shows that the number of carbon atoms is 0 and no alkylene group exists, that is, oxygen and Si are directly bonded, and R 2 and R 3 represent a methyl group, an ethyl group, a propyl group, or a butyl group.
本発明に係るシリル化剤は、特異な立体構造を有するた
めシリカなどの表面に結合させた場合、その表面に立体
障害が生じるので、その表面に残存するOH基の影響を受
けにくく、安定なシリル化物が得られる。また、該シリ
ル化剤がシリカ粒子などの表面に結合して形成されたシ
リル基は、加水分解が起こりにくい特徴を有する。Since the silylating agent according to the present invention has a unique three-dimensional structure, when it is bonded to the surface of silica or the like, steric hindrance occurs on the surface, so that it is less susceptible to the OH group remaining on the surface and is stable. A silylated product is obtained. Further, the silyl group formed by bonding the silylating agent to the surface of silica particles or the like has a characteristic that hydrolysis is unlikely to occur.
このようなシリル化剤は、たとえば、脂肪族ジオール類
〔HO（CH2）nOH〕をフェノールカリウムのような塩基の
存在下で加熱して下記に示す構造単体〔Ｉ〕をもつポリ
オールを合成する。As such a silylating agent, for example, an aliphatic diol [HO (CH 2 ) nOH] is heated in the presence of a base such as phenol potassium to synthesize a polyol having a structural unit [I] shown below. .
このポリオール〔II〕に （Ａ）ジエトキシジメチルシランのような一般式 （R3）2Si（OR2）２ で表わされるケイ素化合物を、好ましくは100〜150℃で
反応させ、シリルエーテル化する方法、 （Ｂ）ハロゲン化アリル（allyl halide）を反応させて
アリルエーテル化し、エトキシジメチルシランのような
一般式 （R3）2SiH（OR2） で表わされるケイ素化合物を付加させるなどの方法によ
り合成する。 The polyol [II] is reacted with a silicon compound represented by the general formula (R 3 ) 2 Si (OR 2 ) 2 such as (A) diethoxydimethylsilane, preferably at 100 to 150 ° C. to form a silyl ether. Method (B) by reacting an allyl halide to form an allyl ether, and adding a silicon compound represented by the general formula (R 3 ) 2 SiH (OR 2 ) such as ethoxydimethylsilane. To synthesize.
本発明に係るシリル化剤は、シリカ、チタニヤ、アルミ
ナ、マグネシヤなどの無機物のシリル化に有効に使用で
きる。特に該シリル化剤で表面処理した変性シリカ粒子
は有機溶剤に均質に分散して安定なシリカ分散液とな
る。The silylating agent according to the present invention can be effectively used for silylation of inorganic substances such as silica, titania, alumina, and magnesia. In particular, the modified silica particles surface-treated with the silylating agent are uniformly dispersed in an organic solvent to form a stable silica dispersion.
本発明に係るシリル化処理した変性シリカ粒子は通常の
シリル化処理の方法で製造することができる。たとえ
ば、該シリル化剤を有機溶媒に分散させ、次いで、オル
ガノシリカゾルを加え80〜200℃に加熱し１〜50時間反
応させた後、溶媒を蒸発などにより除去してシリル化処
理された変性シリカ粒子を得る。The silylated modified silica particles according to the present invention can be produced by a usual silylation method. For example, the silylating agent is dispersed in an organic solvent, and then organosilica sol is added and the mixture is heated to 80 to 200 ° C. and reacted for 1 to 50 hours, and then the solvent is removed by evaporation and the like to obtain a silylated modified silica. Get the particles.
シリカ粒子としては、コロイド次元の粒子径のものが望
ましく、平均粒子径が５〜30nmの範囲のコロイド粒子が
好ましい。The silica particles preferably have a colloidal particle size, and colloidal particles having an average particle size of 5 to 30 nm are preferred.
オルガノシリカゾルは、公知の方法で調製することがで
き、たとえば水を分散媒とする通常のシリカゾルを有機
溶媒で溶媒置換して調製される。The organosilica sol can be prepared by a known method, for example, a conventional silica sol having water as a dispersion medium is solvent-substituted with an organic solvent.
本発明のシリル化処理した変性シリカ粒子は、特異な立
体構造を有するシリル化剤でシリカの表面がシリル化さ
れ、その表面に残存するOH基の影響を受けにくいため
に、シリカ表面のシリル化の割合が少なくても安定であ
り、アルコール、ケトン、エーテル、芳香族、炭化水
素、脂肪族炭化水素などほとんどの有機溶媒に均質に分
散する。この変性シリカ粒子は、各種樹脂の改質用フィ
ラー、各種樹脂との反応剤などとして使用される。The modified silica particles subjected to the silylation treatment of the present invention are silylated on the silica surface because the surface of the silica is silylated with a silylating agent having a unique three-dimensional structure and is less susceptible to the OH groups remaining on the surface. It is stable even if the proportion of is small, and is homogeneously dispersed in most organic solvents such as alcohols, ketones, ethers, aromatics, hydrocarbons and aliphatic hydrocarbons. The modified silica particles are used as a filler for modifying various resins, a reaction agent with various resins, and the like.
以下に実施例を示し本発明をさらに具体的に説明する。Hereinafter, the present invention will be described more specifically with reference to examples.
実施例１ 1,10−デカンジオールから得られたポリオール〔II−
１〕（2.56g）を共沸脱水後、ジエトキシジメチルシラ
ン（DEDMS）（5.01g）と溶媒としての脱水したテトラハ
イドロフラン（THF）50mlをフラスコに仕込み、140℃で
12時間反応させた。その後、真空減圧下で溶媒と過剰分
のDEDMSを蒸発させ、生成物であるシリルエーテル化ポ
リマー〔Ｉ−１〕を得た。（スキーム１） 次に、このシリル化剤、シリルエーテル化ポリマー〔Ｉ
−１〕（0.33g）を脱水したジメトキシエタン（DME）50
mlに分散させ、この分散液を、あらかじめSiO2としての
0.2gに相当するDMEを分散媒とするシリカゾルを張り込
んだナス型フラスコに入れ、140℃で９時間還流を行い
ながら反応させた。反応終了後、真空減圧で溶媒を蒸発
して、シリル化処理した変性シリカ粒子を得た。Example 1 Polyol obtained from 1,10-decanediol [II-
1] (2.56 g) was azeotropically dehydrated, and diethoxydimethylsilane (DEDMS) (5.01 g) and 50 ml of dehydrated tetrahydrofuran (THF) as a solvent were placed in a flask at 140 ° C.
The reaction was carried out for 12 hours. Then, the solvent and the excess DEDMS were evaporated under reduced pressure in vacuum to obtain the product silyl etherified polymer [I-1]. (Scheme 1) Next, this silylating agent and silyl etherified polymer [I
-1] (0.33g) dehydrated dimethoxyethane (DME) 50
ml and disperse this dispersion in advance as SiO 2 .
The mixture was placed in an eggplant-shaped flask in which a silica sol containing 0.2 g of DME as a dispersion medium was placed, and the mixture was reacted at 140 ° C. for 9 hours under reflux. After completion of the reaction, the solvent was evaporated under reduced pressure to obtain silylated modified silica particles.
得られた変性シリカ粒子は、反応時の溶媒であるDMEに
均質に再分散するほか、クロロホルム、THFの溶媒にも
均質に再分散し、長時間静置しても沈殿物は見られなか
った。The obtained modified silica particles were homogeneously redispersed in DME which is a solvent at the time of reaction, and also homogeneously redispersed in a solvent of chloroform and THF, and no precipitate was observed even when left standing for a long time. .
実施例２ 1,8−オクタンジオールから得られたポリオール〔II−
２〕（3.02g）を共沸脱水後、ジエトキシジメチルシラ
ン（7.10g）と溶媒の脱水THF（50ml）を仕込み、140℃
で12時間反応させた。その後、真空減圧下で溶媒と過剰
分のジエトキシジメチルシランを蒸発させ、生成物であ
るシリルエーテル化ポリマー〔Ｉ−２〕を得た。（スキ
ーム２） 次に、このシリル化剤、シリルエーテル化ポリマー〔Ｉ
−２〕（0.55g）を脱水DME（15ml）に分散させ、あらか
じめDME分散ゾル（Sol中のSiO2は0.22g）を仕込んでお
いたナス型フラスコに入れ、130℃で24時間還流を行
い、反応終了後、真空減圧下で溶媒を蒸発して、再分散
性のある変性シリカ微粒子を得た。Example 2 Polyol obtained from 1,8-octanediol [II-
2) (3.02g) was azeotropically dehydrated, then diethoxydimethylsilane (7.10g) and dehydrated THF (50ml) as a solvent were charged, and the temperature was adjusted to 140 ° C.
And reacted for 12 hours. Then, the solvent and excess diethoxydimethylsilane were evaporated under reduced pressure in vacuum to obtain a product silyl etherified polymer [I-2]. (Scheme 2) Next, this silylating agent and silyl etherified polymer [I
-2] (0.55 g) was dispersed in dehydrated DME (15 ml), and the mixture was placed in an eggplant-shaped flask in which a DME dispersion sol (0.22 g of SiO 2 in Sol) had been charged in advance, and refluxed at 130 ° C for 24 hours. After completion of the reaction, the solvent was evaporated under reduced pressure in vacuum to obtain redispersible modified silica fine particles.
得られたシリル化処理した変性シリカ粒子は、反応時の
溶媒であるDMEに均質に再分散するのはもちろんのこ
と、クロロホルム、THFにも均質に再分散した。The obtained silylated modified silica particles were not only uniformly redispersed in DME, which is a solvent at the time of reaction, but also uniformly redispersed in chloroform and THF.
実施例３ 1,10−デカンジオールから得られたポリオール〔II−
１〕（2.85g）を共沸脱水後、ソディュウムエトキシド
（2.05g）と無水エタノール（50ml）を加え、均一な溶
液とした。次に、この均一な溶液を真空減圧下で蒸発
後、さらに100℃まで加熱してエタノールを完全に除去
する操作を１時間行った。こうして得た固型物を四頭フ
ラスコに移し、乾燥した窒素雰囲気下、アリルクロリド
（15g）と脱水DME（50ml）を加え、80℃で20時間撹拌還
流させた。こうして得た生成物中にはNaClが発生するの
で、これを除く操作を次に行った。まづ始めに吸引ろ過
を行い、NaClを除去した。さらに残留したNaClを除くた
め、アリルクロリド、DMEを真空減圧下で蒸発させた後
にエーテルを加えて抽出を行った。エーテル層を分取
後、これを蒸発させ、さらに共沸を行いアリルエーテル
化ポリマー〔III−１〕を得た。（スキーム３） 続いて、アリルエーテル化ポリマー〔III−１〕（2.21
g）を四頭フラスコに入れ、乾燥窒素雰囲気中でエトキ
シジメチルシラン（1.98g）と脱水DME（30ml）を加え
た。さらに触媒としてH2PtCl6・6H2Oエタノール溶液
（0.06wt％、0.2ml）を加え、氷冷下１時間撹拌した。
その後室温で５時間撹拌し、さらに80℃で12時間還流を
行った。ここで系内には黒色の副生物を生じるが、無水
硫酸マグネシウムを加えて振り混ぜた後、ろ過すること
により除去した。ろ液は真空減圧下で蒸発を行ない、ア
リルエーテルシリル化ポリマー〔Ｉ−３〕を得た。（ス
キーム４） 次に、このシリル化剤アリルシリル化ポリマー〔Ｉ−
３〕（0.40g）を脱水DME（25ml）に分散させ、あらかじ
めDME分散ゾル（Sol中のSiO2は0.21g）を仕込んでおい
たナス型フラスコに入れ、130℃で24時間撹拌還流を行
なった。反応終了後、真空減圧下で溶媒を蒸発して、再
分散性のある変性シリカ微粒子を得た。Example 3 Polyol obtained from 1,10-decanediol [II-
1) (2.85 g) was azeotropically dehydrated, and then sodium ethoxide (2.05 g) and absolute ethanol (50 ml) were added to obtain a uniform solution. Next, this uniform solution was evaporated under reduced pressure in a vacuum, and then heated to 100 ° C. to completely remove ethanol for 1 hour. The solid product thus obtained was transferred to a four-headed flask, and under a dry nitrogen atmosphere, allyl chloride (15 g) and dehydrated DME (50 ml) were added, and the mixture was stirred and refluxed at 80 ° C. for 20 hours. Since NaCl was generated in the product thus obtained, an operation for removing this was carried out next. First, suction filtration was performed to remove NaCl. Further, in order to remove the remaining NaCl, allyl chloride and DME were evaporated under vacuum and reduced pressure, and then ether was added for extraction. After separating the ether layer, this was evaporated and further azeotropically distilled to obtain an allyl etherified polymer [III-1]. (Scheme 3) Then, allyl etherified polymer [III-1] (2.21
g) was placed in a four-headed flask, and ethoxydimethylsilane (1.98 g) and dehydrated DME (30 ml) were added in a dry nitrogen atmosphere. Further, H 2 PtCl 6 .6H 2 O ethanol solution (0.06 wt%, 0.2 ml) was added as a catalyst, and the mixture was stirred for 1 hour under ice cooling.
Then, the mixture was stirred at room temperature for 5 hours, and further refluxed at 80 ° C for 12 hours. Here, a black by-product is generated in the system, but it was removed by adding anhydrous magnesium sulfate, shaking, and then filtering. The filtrate was evaporated under reduced pressure in vacuum to obtain an allyl ether silylated polymer [I-3]. (Scheme 4) Next, this silylating agent allylsilylated polymer [I-
3) (0.40 g) was dispersed in dehydrated DME (25 ml), and the mixture was placed in an eggplant-shaped flask in which DME dispersion sol (SiO 2 in Sol was 0.21 g) had been charged in advance, and stirred and refluxed at 130 ° C for 24 hours. It was After completion of the reaction, the solvent was evaporated under reduced pressure in vacuum to obtain redispersible modified silica fine particles.
得られたシリル化処理した変性シリカ粒子は反応時の溶
媒であるDMEに均質に再分散するのはもちろんのことク
ロロホルム、THFにも均質に再分散した。The obtained silylated modified silica particles were homogeneously redispersed not only in DME which was a solvent at the time of reaction, but also in chloroform and THF.
実施例４ 1,8−オクタンジオールから得られたポリオール〔II−
２〕（5.07g）を共沸脱水後、ソディュウムエトキシド
（5.57g）と無水エタノール（50ml）を加え、均一な溶
液とした。次にこれを真空減圧下で蒸発後、さらに100
℃まで加熱してエタノールを完全に除去する操作を１時
間行った。こうして得た固型物を四頭フラスコに移し、
乾燥した窒素雰囲気下、アリルクロリド（15g）と脱水D
ME（50ml）を加え、80℃で20時間撹拌還流させた。こう
して得た生成物中にはNaClが発生するので、これを除く
操作を次に行った。まづ始めに吸引ろ過を行い、NaClを
除去した。さらに残留したNaClを除くため、アリルクロ
リド、DMEを真空減圧下で蒸発させた後に、エーテル抽
出を行った。エーテル層を分取後、これを蒸発させ、さ
らに共沸を行いアリルエーテル化ポリマー〔III−２〕
を得た。（スキーム５） 続いて、アリルエーテル化ポリマー〔III−２〕（1.59
g）を四頭フラスコに入れ、乾燥窒素雰囲気下でエトキ
シジメチルシラン（1.89g）と脱水THF（50ml）を加え
た。さらに触媒としてH2PtCl6・6H2Oエタノール溶液
（0.06wt％、0.2ml）を加え、氷冷下１時間撹拌した。
その後室温で５時間撹拌し、さらに80℃で12時間還流し
た。ここで系内には黒色の副生物を生じるが、無水硫酸
マグネシウムを加えて振り混ぜ、ろ過することで除去し
た。ろ過は真空減圧下で蒸発を行い、アリルエーテルシ
リル化ポリマー〔Ｉ−４〕を得た。（スキーム６） 次に、このシリル化剤アリールエーテルーシリル化ポリ
マー〔Ｉ−４〕（0.5g）を脱水DME（25ml）に分散さ
せ、あらかじめDME分散ゾル（Sol中のSiO2は0.2g）を仕
込んでおいたナス型フラスコに入れ、130℃で24時間還
流を行なった。反応終了後、真空減圧下で溶媒を蒸発し
て、再分散性のある変性シリカ微粒子を得た。Example 4 Polyol obtained from 1,8-octanediol [II-
2) (5.07 g) was azeotropically dehydrated, and then sodium ethoxide (5.57 g) and absolute ethanol (50 ml) were added to obtain a uniform solution. It was then evaporated under vacuum and further 100
The operation of heating to 0 ° C. to completely remove ethanol was performed for 1 hour. Transfer the solid thus obtained to a four-headed flask,
Allyl chloride (15g) and dehydrated D under a dry nitrogen atmosphere
ME (50 ml) was added, and the mixture was stirred and refluxed at 80 ° C for 20 hr. Since NaCl was generated in the product thus obtained, an operation for removing this was carried out next. First, suction filtration was performed to remove NaCl. To remove the remaining NaCl, allyl chloride and DME were evaporated under reduced pressure in vacuum and then extracted with ether. After the ether layer was collected, it was evaporated and azeotropically distilled to give an allyl etherified polymer [III-2].
Got (Scheme 5) Then, allyl etherified polymer [III-2] (1.59
g) was placed in a four-headed flask, and ethoxydimethylsilane (1.89 g) and dehydrated THF (50 ml) were added under a dry nitrogen atmosphere. Further, H 2 PtCl 6 .6H 2 O ethanol solution (0.06 wt%, 0.2 ml) was added as a catalyst, and the mixture was stirred for 1 hour under ice cooling.
Then, the mixture was stirred at room temperature for 5 hours, and further refluxed at 80 ° C for 12 hours. Here, a black by-product is generated in the system, but it was removed by adding anhydrous magnesium sulfate, shaking and filtering. Filtration was performed under reduced pressure in a vacuum to obtain an allyl ether silylated polymer [I-4]. (Scheme 6) Next, this silylating agent aryl ether-silylated polymer [I-4] (0.5 g) was dispersed in dehydrated DME (25 ml), and DME dispersion sol (SiO 2 in Sol was 0.2 g) was charged in advance. The mixture was placed in an eggplant-shaped flask, and refluxed at 130 ° C. for 24 hours. After completion of the reaction, the solvent was evaporated under reduced pressure in vacuum to obtain redispersible modified silica fine particles.
得られたシリル化処理した変性シリカ粒子は、THF、ク
ロロホルム、DMEの有機溶媒に均質に分散した。The obtained silylated modified silica particles were uniformly dispersed in an organic solvent such as THF, chloroform and DME.
比較例１ 1,6−ヘキサジオールから得られたポリオール〔IX〕
（3.05g）を共沸脱水後、DEDMS（7.10g）と溶媒の脱水T
HF（50ml）を仕込み、140℃で12時間反応させた。その
後、真空減圧下で溶媒と過剰分のDEDMSを蒸発させ、生
成物であるシリルエーテル化ポリマー〔Ｘ〕を得た。
（スキーム７） 次にこのシリル化剤、シリルエーテル化ポリマー〔Ｘ〕
（0.54g）を脱水DME（50ml）に分散させ、あらかじめDM
E分散ゾル（Sol中のSiO2は0.2g）を仕込んでおいたナス
型フラスコに入れ、130℃で24時間還流を行い、反応終
了後、真空減圧下で溶媒を蒸発してシリル化処理した変
性シリカ粒子を得た。Comparative Example 1 Polyol obtained from 1,6-hexadiol [IX]
After azeotropic dehydration of (3.05g), dehydration of DEDMS (7.10g) and solvent T
HF (50 ml) was charged and reacted at 140 ° C for 12 hours. Then, the solvent and excess DEDMS were evaporated under reduced pressure in vacuum to obtain the product silyl etherified polymer [X].
(Scheme 7) Next, this silylating agent and silyl etherified polymer [X]
Disperse (0.54g) in dehydrated DME (50ml) and DM
E-dispersed sol (SiO 2 in Sol was 0.2 g) was placed in an eggplant-shaped flask and refluxed at 130 ° C. for 24 hours. After the reaction was completed, the solvent was evaporated under vacuum reduced pressure for silylation treatment. Modified silica particles were obtained.
得られた変性シリカ粒子は、反応時の溶媒であるDMEへ
分散したところ、48時間静置後に容器の底に一部沈殿物
が見られた。When the obtained modified silica particles were dispersed in DME which is a solvent at the time of reaction, a precipitate was partially seen at the bottom of the container after standing for 48 hours.
クロロホルム、THFでもDMEの場合と同様に一部沈殿物が
見られた。As with DME, some precipitates were seen with chloroform and THF.
Claims (2)
合はR1が存在しないことを表わす） R2＝炭素数１〜４の範囲のアルキル基 R3＝炭素数１〜４の範囲のアルキル基 で表わさせるシリル化剤。1. A general formula In the formula, n = 7 to 15 m = 10 or more R 1 = alkylene group having a carbon number of 0 to 6 (in the case of 0 carbon, R 1 does not exist) R 2 = C 1 to 4 Alkyl group in the range R 3 = silyl group represented by an alkyl group in the range of 1 to 4 carbon atoms.
処理することにより得られた変性シリカ粒子。2. Modified silica particles obtained by treating silica particles with the silylating agent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6999690A JPH0798657B2 (en) | 1990-03-20 | 1990-03-20 | Silylating agent and modified silica particles silylated by the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6999690A JPH0798657B2 (en) | 1990-03-20 | 1990-03-20 | Silylating agent and modified silica particles silylated by the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03271114A JPH03271114A (en) | 1991-12-03 |
| JPH0798657B2 true JPH0798657B2 (en) | 1995-10-25 |
Family
ID=13418799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6999690A Expired - Fee Related JPH0798657B2 (en) | 1990-03-20 | 1990-03-20 | Silylating agent and modified silica particles silylated by the method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798657B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014175369A1 (en) | 2013-04-24 | 2014-10-30 | Dic株式会社 | Inorganic fine particle composite body, method for producing same, composition and cured product |
| US8962727B2 (en) | 2010-07-12 | 2015-02-24 | Dic Corporation | Inorganic fine particle dispersant and inorganic fine particle dispersion using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5683501A (en) * | 1993-11-09 | 1997-11-04 | Nippon Shokubai Co., Ltd. | Compound fine particles and composition for forming film |
-
1990
- 1990-03-20 JP JP6999690A patent/JPH0798657B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8962727B2 (en) | 2010-07-12 | 2015-02-24 | Dic Corporation | Inorganic fine particle dispersant and inorganic fine particle dispersion using the same |
| WO2014175369A1 (en) | 2013-04-24 | 2014-10-30 | Dic株式会社 | Inorganic fine particle composite body, method for producing same, composition and cured product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03271114A (en) | 1991-12-03 |
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