JPH03271114A - Silylating agent and modified silica particle silylated with same agent - Google Patents
Silylating agent and modified silica particle silylated with same agentInfo
- Publication number
- JPH03271114A JPH03271114A JP6999690A JP6999690A JPH03271114A JP H03271114 A JPH03271114 A JP H03271114A JP 6999690 A JP6999690 A JP 6999690A JP 6999690 A JP6999690 A JP 6999690A JP H03271114 A JPH03271114 A JP H03271114A
- Authority
- JP
- Japan
- Prior art keywords
- silylating agent
- silylated
- silica particles
- agent
- modified silica
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 239000002245 particle Substances 0.000 title description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 229920005862 polyol Polymers 0.000 abstract description 10
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 150000003377 silicon compounds Chemical class 0.000 abstract description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 abstract 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 abstract 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 aromatic compound silanes Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006884 silylation reaction Methods 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-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
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 108010011222 cyclo(Arg-Pro) Proteins 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RKHQZMOCQHXUBC-UHFFFAOYSA-N phenol;potassium Chemical compound [K].OC1=CC=CC=C1 RKHQZMOCQHXUBC-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Silicon Compounds (AREA)
Abstract
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１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。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silylating agent and modified silica particles treated with the same. More specifically, in the present invention, the surface of silica is silylated using a silylating agent represented by a specific chemical structural formula and the silylating agent. The present invention relates to silica particles that can be homogeneously redispersed in organic solvents.
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１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、トリフェニルリロルシ
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 silylating agents, low molecular weight chain compounds or aromatic compound silanes 1 such as methyltrichlorosilane, vinyltrichlorosilane, triphenyllylorsilane, benzyltrimethoxysilane, etc. have been used (especially (Refer to Publication No. 2-1090). However, the silyl groups formed by bonding these silylating agents to the surface of silica etc. will undergo hydrolysis if moisture remains.
Therefore, this silylated product had the problem of lacking stability.
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 with 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 that can be homogeneously dispersed in an organic solvent using the silylating agent.
本発明の１つは、一般式
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れた変性シリカ粒子に
関する。One aspect of the present invention relates to modified silica particles obtained by treating 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。 The silylating agent according to the present invention has the general formula:
式中、ｎ＝７〜１５
ｍ＝１０以上
Ｒ□＝炭素数Ｏ〜６の範囲のアルキレン基（炭素数Ｏの
場合はＲ工が存在しない
ことを表わす）
Ｒ，＝炭素数１〜４の範囲のアルキル基Ｒ，＝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。In the formula, n = 7 to 15 m = 10 or more R□ = alkylene group having a carbon number of O to 6 (if the carbon number is O, it means that R is not present) R, = a group having a carbon number of 1 to 4 Alkyl group in the range R, = carbon number 1
It relates to a silylating agent represented by an alkyl group in the range of .about.4.
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１ｍ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Ｏの場合はＲ工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
、Ｒ１が炭素数ｌ〜４の範囲のアルキル基で表わされる
化合物である。In the formula, n is in the range of 7 to 15, preferably 8
~12, and 1 m is 10 or more, preferably 15
~25, R1 is an alkylene group having 0 to 6 carbon atoms (if the number of carbon atoms is O, it means that R is not present), and R2 is an alkyl group having 1 to 4 carbon atoms. and R1 is a compound represented by an alkyl group having 1 to 4 carbon atoms.
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よりも大きい場合は、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 in the aliphatic diols that are the starting materials for synthesizing the compound. If the value of n is 6 or less, the redispersibility of the inorganic particles obtained by the silylation treatment into the organic solvent is poor, which is not preferable. Moreover, when the value of n is larger than 15, the dispersibility of the compound in an organic solvent becomes poor, 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 degree of polymerization of the polyol. If the value of m is less than 10, it is undesirable because a silylating agent having the desired three-dimensional structure cannot be obtained.
また、式中Ｒ１は、炭素数１〜６のフルキレン基または
、炭素数がＯ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Ｒ
３は、メチル基、エチル基、プロピル基、またはブチル
基を示す。In addition, R1 in the formula represents a fullkylene group having 1 to 6 carbon atoms or a carbon number O and no alkylene group, that is, oxygen and Si are directly bonded, and R2 and R
3 represents 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。The silylating agent according to the present invention has a unique steric structure, so when it is bonded to the surface of silica etc., steric hindrance occurs on the surface, so it is not easily affected by the OH groups remaining on the surface and is stable. A silylated product is obtained. Furthermore, the silyl group formed by bonding the silylating agent to the surface of silica particles has a characteristic that hydrolysis does not easily 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）ｎＯＨ３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〔■〕を
もつポリオールを合成する。Such a silylating agent can be obtained, for example, by heating aliphatic diols [HO(CH2)nOH3] in the presence of a base such as potassium phenol to synthesize a polyol having the following structural unit [■].
このポリオール（ｎ）に
（Ａ）ジェトキシジメチルシランのような一般式％式％
）
で表わされるケイ素化合物を、好ましくは１００−１５
０℃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
％式％）
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。This polyol (n) has a general formula such as (A) jetoxydimethylsilane.
) Preferably a silicon compound represented by 100-15
Method of reacting at 0°C to convert into silyl ether, (B) allyl halide
It is synthesized by a method such as reacting to form an allyl ether, and adding a silicon compound represented by the general formula %, such as ethoxydimethylsilane.
本発明に係るシリル化剤は、シリカ、チタニャ、アルミ
ナ、マグネシャ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 silylation agent according to the present invention can be effectively used for silylation of inorganic substances such as silica, titania, alumina, and magnesia. In particular, modified silica particles surface-treated with the silylating agent are homogeneously 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 conventional silylation method. For example, the silylating agent is dispersed in an organic solvent, organosilica sol is added thereto, heated to 80 to 200°C and reacted for 1 to 50 hours, and then the solvent is removed by evaporation or the like to obtain a silylated modified silica. Get 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５〜３００ｎｍ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 preferably colloidal particles with an average particle size in the range of 5 to 300 nm.
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。Organosilica sol can be prepared by a known method, for example, by substituting a normal silica sol using water as a dispersion medium with an organic solvent.
本発明のシリル化処理した変性シリカ粒子は。The silylated modified silica particles of the present invention are as follows.
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 surface of silica is silylated with a silylating agent that has a unique three-dimensional structure, and is not easily affected by the OH groups remaining on the surface, so it is stable even if the silylation rate of the silica surface is small, ketones, ethers, aromatics,
Disperses homogeneously in most organic solvents such as hydrocarbons and aliphatic hydrocarbons. These modified silica particles are used as fillers for modifying various resins, as reactants 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。EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例１
１．１０−デカンジオールから得られたポリオール［Ｉ
ｒ −１）（２，５６ｇ）を共沸脱水後、ジェトキシジ
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）５０ｍ
Ｑをフラスコに仕込み、１４０℃で１２時間反応させた
。Example 1 Polyol obtained from 1.10-decanediol [I
After azeotropic dehydration of r-1) (2,56 g), jetoxydimethylsilane (DEDMS) (5,01 g) and 50 m of dehydrated tetrahydrofuran (THF) as a solvent were added.
Q was charged into a flask and reacted at 140°C for 12 hours.
その後、真空減圧下で溶媒と過剰分のＤＥＤＮＳを蒸発
させ、生成物であるシリルエーテル化ポリマー（１−１
）を得た。（スキーム１）〔Ｕ−１）
ｒＩ−１）（スキームｌ）
次に、このシリル化剤、シリルエーテル化ポリマーＣＩ
−１）（０，３３ｇ）を脱水したジメトキシエタン（
ＤＭＥ）５０−に分散させ、この分散液を、あらかじめ
ＳｉＯ□として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、１４
０℃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。Thereafter, the solvent and excess DEDNS were evaporated under reduced pressure in vacuum, and the product silyl etherified polymer (1-1
) was obtained. (Scheme 1) [U-1]
rI-1) (Scheme 1) Next, this silylating agent, silyl etherified polymer CI
-1) (0.33g) was dehydrated in dimethoxyethane (
This dispersion was placed in an eggplant-shaped flask filled with silica sol containing DME as a dispersion medium, which is equivalent to 0.2 g of SiO□.
The reaction was carried out at 0°C for 9 hours under reflux. After the reaction was completed, 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ＤＭＨ
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 contain DMH, which is a solvent during the reaction.
In addition to being homogeneously redispersed in chloroform and THF solvents, no precipitate was observed even after 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［Ｉ
［−２）（３，０２ｇ）を共沸脱水後、ジェトキシジメ
チルシラン（７，１０ｇ）と溶媒の脱水ＴＨＦ（５０ｍ
Ｒ）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ェ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
［１−２３を得た。（スキーム２）（ＩＩ−２）
［１−２］（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（１
−２）（０，５５ｇ）を脱水ＤＭＥ（１５ｍ１２）に分
散させ、あらかじめＤ肚分散ゾル（Ｓｏｎ中のＳｉＯ□
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１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 [I
[-2) (3.02 g) was azeotropically dehydrated, then jetoxydimethylsilane (7.10 g) and the solvent dehydrated THF (50 m
R) was charged and reacted at 140°C for 12 hours. Thereafter, the solvent and excess jetoxydimethylsilane were evaporated under vacuum to obtain the product silyl etherified polymer [1-23. (Scheme 2) (II-2)
[1-2] (Scheme 2) Next, this silylating agent, silyl etherified polymer (1
-2) (0.55 g) was dispersed in dehydrated DME (15 m12), and the SiO
(0.22 g) was placed in an eggplant-shaped flask, and refluxed at 130°C for 24 hours. After one reaction, the solvent was evaporated under reduced pressure 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ＤＭＨ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 DMH, which is a solvent during the reaction, but also 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（Ｉ
Ｉ −１）（２，８５ｇ）を共沸脱水後、ソディユウム
エトキシド（２，０５ｇ）と無水エタノール（５０＋＋
＋Ｑ）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
して得た固型物を口頭フラスコに移し、乾燥した窒素雰
囲気下、アリルクロリド（１５ｇ）と脱水ＤＭＥ（５０
ｔＩ２）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Ｎａ（Ｊｌ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
、ＮａＣＱを除去した。さらに残留したＮａＣβ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（Ｉｎ −１）を得た。（スキーム３）
（ＩＩ−１３［１１１−１］
（スキーム３）
続いて、アリルエーテル化ポリマー（ｍ−１）（２，２
１ｇ）を口頭フラスコに入れ、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 （３
０ｍ１２）を加えた。さらに触媒としてＨ２Ｐｔ（４１
６Ｈ２０エタノール溶液（０，０６ｗｔ％、０．２ｍＱ
）を加え、水冷下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
ムを加えで振り混ぜた後、ろ過することにより除去した
９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（１−３３を得た。（スキーム４）
〔ｍ−１） （１−３］
（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
ゴ（０，４０ｇ）を脱水ＤＭＥ （２５ｗｕ） ４Ｃ分
散させ、あらかじめＤＭＥ分散ゾルＣ３ｏＱ中のＳｉＯ
□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。反応後了
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 (I
After azeotropic dehydration of I-1) (2.85g), sodium ethoxide (2.05g) and absolute ethanol (50++
+Q) was added to make a homogeneous solution. Next, this homogeneous solution was evaporated under vacuum and reduced pressure, and then heated to 100° C. for 1 hour to completely remove ethanol. The solid thus obtained was transferred to a neck flask, and under a dry nitrogen atmosphere, allyl chloride (15 g) and dehydrated DME (50
tI2) was added, and the mixture was stirred and refluxed at 80°C for 20 hours. Since Na(Jl) is generated in the product obtained in this way, an operation to remove this was performed next.First, suction filtration was performed to remove NaCQ.Furthermore, in order to remove the remaining NaCβ, allyl chloride After evaporating DME under reduced pressure, ether was added to perform extraction. After separating the ether layer, it was evaporated and further azeotroped to obtain an allyl etherified polymer (In-1). (Scheme 3) (II-13[111-1] (Scheme 3) Subsequently, allyl etherified polymer (m-1) (2,2
1 g) was placed in a neck flask, and ethoxydimethylsilane (1.98 g) and dehydrated DME (3
0 m12) was added. Furthermore, H2Pt (41
6H20 ethanol solution (0.06wt%, 0.2mQ
) and stirred for 1 hour under water cooling. Thereafter, the mixture was stirred at room temperature for 5 hours, and further refluxed at 80°C for 12 hours. Here, black by-products are produced in the system, but after adding anhydrous magnesium sulfate and shaking, the 9 filtrate removed by filtration is evaporated under vacuum and reduced pressure, and the allyl ether silylated polymer (1 -33 was obtained. (Scheme 4) [m-1) (1-3]
(Scheme 4) Next, this silylating agent allylsilylated polymer (I-3
SiO (0.40g) was dispersed in dehydrated DME (25wu) 4C, and SiO
0.21 g) was placed in an eggplant-shaped flask, and the mixture was stirred and refluxed at 130° C. for 24 hours. After the reaction was completed, the solvent was evaporated under reduced pressure to obtain modified silica fine particles with redispersibility.
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ＤＭＨ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 DMH, which is a solvent during the 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、ソディユウ
ムエトキシド（５，５７ｇ）と無水エタノール（５０ｍ
ｕ）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。Example 4 Polyol obtained from 1.8-octanediol ['
After azeotropic dehydration of II-2) (5.07 g), sodium ethoxide (5.57 g) and absolute ethanol (50 m
u) was added to make a homogeneous solution. Next, this was evaporated under vacuum and reduced pressure, and further heated to 100° C. for 1 hour to completely remove ethanol.
こうして得た固型物を口頭フラスコに移し、乾燥した窒
素雰囲気下、アリルクロリド（１５ｇ）と脱水ＤＭＥ（
５０ａ＋Ｑ）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Ｎａｆｊｌｌ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、Ｎａ（、Ｒを除去した。さらに残留したＮａＣ
Ｑ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）
［１１１）
［ｍ−２）
（スキーム５）
続いて、アリルエーテル化ポリマー（ｍ−２）（１，５
９ｇ）を口頭フラスコに入れ、乾燥窒素雰囲気下でエト
キシジメチルシラン（１，８９ｇ）と脱水下ＨＦ （５
０ｍ１２）を加えた。さらに触媒としてＨ２ＰｔＣＱ、
・５ｎ２ｏエタノール溶液（０，０６ｗｔ％、０．２ｍ
Ｒ）を加え、水冷下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ＣＩ −４）を得た。The solid thus obtained was transferred to a neck flask, and under a dry nitrogen atmosphere, allyl chloride (15 g) and dehydrated DME (
50a+Q) was added, and the mixture was stirred and refluxed at 80°C for 20 hours. Since Nafjll was generated in the product obtained in this way, an operation to remove this was performed next. First, suction filtration was performed to remove Na(,R).Furthermore, the remaining NaC
In order to remove Q, allyl chloride and DME were evaporated under vacuum and then extracted with ether. After the ether layer was separated, it was evaporated and further subjected to azeotropy to obtain allyl etherified polymer (III-2). (Scheme 5)
[111) [m-2) (Scheme 5) Subsequently, allyl etherified polymer (m-2) (1,5
9g) was placed in a neck flask and mixed with ethoxydimethylsilane (1.89g) under dry nitrogen atmosphere and HF (5g) under dehydration.
0 m12) was added. Furthermore, H2PtCQ as a catalyst,
・5n2o ethanol solution (0.06wt%, 0.2m
R) was added and stirred for 1 hour under water cooling. Thereafter, the mixture was stirred at room temperature for 5 hours and further refluxed at 80°C for 12 hours. Here, black byproducts were produced in the system, but they were removed by adding anhydrous magnesium sulfate, shaking, and filtering. The filtration was performed by evaporation under vacuum and reduced pressure to obtain allyl ether silylated polymer CI-4).
（スキーム６）
に分散させ、あらかしめＤＭＥ分散ゾル（ＳｏＱ中のＳ
ｉｎ、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。(Scheme 6) DME dispersion sol (S in SoQ)
(in, 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 reduced pressure to obtain modified silica fine particles with redispersibility.
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、ＤＭＨの有機溶媒に均質に分散した。The obtained silylated modified silica particles were treated with THF,
It was homogeneously dispersed in organic solvents such as chloroform and DMH.
比較例１
１．６−へ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、 ＤＥＤＮＳ（７，１
０ｇ）と溶媒の脱水ＴＨＦ （５０ｍ１２）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ＤＥＤＮＳ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）
（ＩＩＩ−２） （１−４
）（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（２５１
１氾）（ＩＸ）
（Ｘ）
（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 （５０ｍ文）に分散
させ、あらかじめＤＭＥ分散ゾル（ＳｏＱ中の５ｉｎ２
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１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
) (3,05 g) was azeotropically dehydrated, DEDNS (7,1
0g) and the solvent dehydrated THF (50m12),
The reaction was carried out at 140°C for 12 hours. Thereafter, the solvent and excess DEDNS were evaporated under vacuum to obtain a product, silyl etherified polymer (X). (Scheme 7)
(III-2) (1-4
) (Scheme 6) Next, this silylating agent aryl ether-silylated polymer (I-4) (0.5 g) was dissolved in dehydrated DME (251
1 flood) (IX) (X) (Scheme 7) Next, this silylating agent, the silyl etherified polymer (X
) (0.54g) was dispersed in dehydrated DME (50m) and preliminarily dissolved in DME dispersion sol (5in2 in SoQ).
0.2g) into an eggplant-shaped flask,
After one reaction was completed by refluxing at 130° C. for 24 hours, 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１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。The obtained modified silica particles were mixed with DME, which was the solvent for 1 reaction.
When the mixture was dispersed into a container, some precipitate was observed at the bottom of the container after being allowed to stand for 48 hours.
クロロホルム、ＴＨＦでもＤＭＨの場合と同様に一部沈
殿物が見られた。Some precipitates were also observed in chloroform and THF as in the case of DMH.
Claims (1)
の場合はＲ＿１が存在しない ことを表わす） Ｒ＿２＝炭素数１〜４の範囲のアルキル基 Ｒ＿３＝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。 ２、請求項１記載のシリル化剤でシリカ粒子を処理する
ことにより得られた変性シリカ粒子。[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. Number 0
(indicates that R_1 does not exist) R_2 = alkyl group having 1 to 4 carbon atoms R_3 = silylating agent represented by an alkyl group having 1 to 4 carbon atoms. 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 true JPH03271114A (en) | 1991-12-03 |
| JPH0798657B2 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 (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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI501808B (en) | 2010-07-12 | 2015-10-01 | Dainippon Ink & Chemicals | Use of dispersion agent for inorgainc micro particle, inorganic micro particle dispersion liquid, and inorganic micro particle dispersion using dispersion agent for inorganic micro particle, paint and cured article |
| 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 |
-
1990
- 1990-03-20 JP JP6999690A patent/JPH0798657B2/en not_active Expired - Fee Related
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798657B2 (en) | 1995-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4455415A (en) | Polymeric tertiary and secondary amines with a silica-type backbone, processes for their preparation, and use | |
| US6624236B1 (en) | Cyclosiloxane-based cross-linkable monomers, production thereof and use thereof in polymerizable materials | |
| AU667638B2 (en) | Metal-oxide polymer composites | |
| US6096903A (en) | Hydrolysable and polymerizable oxetane silanes | |
| JP2001525833A (en) | Organosilane-oligomer | |
| EP0669362A2 (en) | Method for the preparation of organic solvent-soluble polytitanosiloxanes | |
| JPH069659A (en) | Formation of siloxane bond | |
| EP0478284B1 (en) | Organic silicon compounds and cosmetic compositions | |
| JPS6058991A (en) | Organic silicon compound, manufacture and use | |
| Agaskar | Facile, high yield synthesis of functionalized spherosilicates: precursors of novel organolithic macromolecular materials | |
| JPS6017214B2 (en) | Soluble methylpolysiloxane and its manufacturing method | |
| JPH1087674A (en) | Production of cyclic silane ester and its solvolysis product, production of cyclic organosilane ester, compound thus obtained, its hydrolysis product and alcoholysis product, crosslinking agent, adhesive and phase mediating agent composed of the same product and modifier for polymer material having ester group | |
| KR100543488B1 (en) | Organosilane oligomer | |
| US4469881A (en) | [2-(p-t-Butylphenyl)ethyl]silanes and method of making the same | |
| JPS61272238A (en) | Functionalized phenylene group-containing organopolysiloxaneand its production | |
| CN101228211B (en) | Silicon- and polysilyl cyanurates and -cyanurates, their preparation and their use | |
| JPH11512378A (en) | Preparation of organic functionalized airgel | |
| JPH0798657B2 (en) | Silylating agent and modified silica particles silylated by the method | |
| US4645848A (en) | Phenylene group-containing organopolysiloxanes and method for their preparation | |
| Brondani et al. | A new trialkoxysilylation reaction, the cross-coupling of (tri-isopropyloxysilyl) methyl grignard reagent with organic halides | |
| EP0414186B1 (en) | Novel fluorinated organic silicon compounds and a method for making them | |
| JP2001504859A (en) | High purity branched alkyl silsesquioxane liquid | |
| JPS6158086B2 (en) | ||
| US5478546A (en) | Process for preparing powder of silicon compound | |
| CA2175415A1 (en) | Modified hydrogen silsesquioxane resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071025 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081025 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091025 Year of fee payment: 14 |
|
| LAPS | Cancellation because of no payment of annual fees |