JPH0687871A - Method for purifying cyclic siloxane - Google Patents
Method for purifying cyclic siloxaneInfo
- Publication number
- JPH0687871A JPH0687871A JP24084592A JP24084592A JPH0687871A JP H0687871 A JPH0687871 A JP H0687871A JP 24084592 A JP24084592 A JP 24084592A JP 24084592 A JP24084592 A JP 24084592A JP H0687871 A JPH0687871 A JP H0687871A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyl group
- siloxane
- chain
- terminal
- group
- 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.)
- Pending
Links
- -1 cyclic siloxane Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 78
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 22
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 229920006294 polydialkylsiloxane Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UEHOWTBIFIIEBO-UHFFFAOYSA-N 2,2,4,4,6,6-hexaoctyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCCCCCCC[Si]1(CCCCCCCC)O[Si](CCCCCCCC)(CCCCCCCC)O[Si](CCCCCCCC)(CCCCCCCC)O1 UEHOWTBIFIIEBO-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CVAGYCLEIYGJQT-UHFFFAOYSA-N dichloro(dioctyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)CCCCCCCC CVAGYCLEIYGJQT-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
(57)【要約】
【目的】 環状シロキサンと末端に水酸基を有する鎖状
シロキサンとの混合物から、環状シロキサンの損失を低
減して末端に水酸基を有する鎖状シロキサンを除去す
る。
【構成】環状シロキサンと末端に水酸基を有する鎖状シ
ロキサンの混合物を、シリコン原子又はアルミニウム原
子に結合した水酸基を表面に有する無機化合物、例え
ば、シリカ、アルミナと接触させることにより、末端に
水酸基を有する鎖状シロキサンを除去する。(57) [Summary] [Object] To remove a chain siloxane having a terminal hydroxyl group from a mixture of a cyclic siloxane and a chain siloxane having a terminal hydroxyl group, thereby reducing the loss of the cyclic siloxane. [Structure] A mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal is brought into contact with an inorganic compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface, for example, silica or alumina, to thereby have a hydroxyl group at the terminal. The chain siloxane is removed.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、環状シロキサンの精製
方法に関する。FIELD OF THE INVENTION The present invention relates to a method for purifying cyclic siloxanes.
【０００２】[0002]
【従来の技術】ポリプロピレン（以下、ＰＰと略す。）
は、汎用樹脂として広く使用されているが、衝撃強度が
低いという欠点を有している。この欠点を補うため、長
鎖アルキル基を側鎖に有する高分子量のポリジアルキル
シロキサンをＰＰに添加することが行われている。この
方法により、剛性を低下させることなく耐衝撃性を向上
させることができる。2. Description of the Related Art Polypropylene (hereinafter abbreviated as PP)
Is widely used as a general-purpose resin, but has the drawback of low impact strength. In order to make up for this drawback, it has been practiced to add a high molecular weight polydialkylsiloxane having a long chain alkyl group as a side chain to PP. By this method, impact resistance can be improved without lowering rigidity.
【０００３】しかしながら、この効果は、上記ポリジア
ルキルシロキサンが高分子量でなければ発現しないた
め、ポリジアルキルシロキサンを高分子量化する必要が
ある。However, this effect does not appear unless the polydialkylsiloxane has a high molecular weight, and therefore it is necessary to make the polydialkylsiloxane have a high molecular weight.
【０００４】一方、ポリジアルキルシロキサンのモノマ
ーである環状シロキサンの合成において、末端に水酸基
を有する鎖状シロキサンオリゴマーが副生する。末端に
水酸基を有する鎖状シロキサンオリゴマーは重合停止剤
として働くため、ポリジアルキルシロキサンの高分子量
化のためには、これを除去しなければならない。ポリジ
アルキルシロキサンのアルキル基がメチル基の場合に
は、環状シロキサンや末端に水酸基を有する鎖状シロキ
サンオリゴマーの分子量が小さく沸点も比較的低いため
蒸留による分離も可能であるが、アルキル基が長鎖アル
キル基の場合には蒸留が不可能となる。On the other hand, in the synthesis of cyclic siloxane which is a monomer of polydialkylsiloxane, a chain siloxane oligomer having a hydroxyl group at the terminal is produced as a by-product. Since the chain-like siloxane oligomer having a hydroxyl group at the terminal acts as a polymerization terminator, it must be removed in order to increase the molecular weight of the polydialkylsiloxane. When the alkyl group of the polydialkylsiloxane is a methyl group, the cyclic siloxane or chain siloxane oligomer having a hydroxyl group at the terminal has a small molecular weight and a relatively low boiling point, so separation by distillation is possible, but the alkyl group has a long chain. Distillation becomes impossible in the case of an alkyl group.
【０００５】特開年3-292329号公報には、長鎖のアルキ
ル基を側鎖に持つ環状シロキサンから副生物を除去する
方法として溶媒抽出による方法が示されている。しか
し、この方法では、鎖状シロキサンオリゴマーを問題に
ならないレベルまで除去するためには、抽出操作をかな
りの回数繰り返し行わねばならず、単に操作が煩雑であ
るばかりでなく、目的物である環状シロキサンの損失も
大きい。Japanese Unexamined Patent Publication No. 3-292329 discloses a method by solvent extraction as a method for removing a by-product from a cyclic siloxane having a long-chain alkyl group as a side chain. However, in this method, in order to remove the chain siloxane oligomer to a level at which it does not pose a problem, the extraction operation must be repeated a considerable number of times, and not only the operation is complicated, but also the target cyclic siloxane. The loss of is also large.
【０００６】[0006]
【発明が解決しようとする課題点】この様に、現在行わ
れている環状シロキサンから末端水酸基を有する鎖状シ
ロキサンオリゴマーを除去する方法は、操作が煩雑であ
るという他に環状シロキサンの回収率が低いという問題
点があり、さらに効率の良い環状シロキサンの精製方法
の出現が強く望まれていた。As described above, the method for removing a chain siloxane oligomer having a terminal hydroxyl group from a cyclic siloxane that is currently used is complicated in operation and has a recovery rate of the cyclic siloxane. There is a problem that it is low, and the advent of a more efficient method for purifying a cyclic siloxane has been strongly desired.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の技
術的課題を解決すべく鋭意検討を行って来た。その結
果、末端に水酸基を有する鎖状シロキサンを含む環状シ
ロキサンを、シリコン原子又はアルミニウム原子に結合
した水酸基を表面に有する無機化合物と接触させると、
効率良く環状シロキサンから末端に水酸基を有する環状
シロキサンを除去できることを見出し、本発明を完成す
るに至った。Means for Solving the Problems The present inventors have made extensive studies to solve the above technical problems. As a result, when a cyclic siloxane containing a chain siloxane having a hydroxyl group at the terminal is brought into contact with an inorganic compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface,
The inventors have found that the cyclic siloxane having a hydroxyl group at the terminal can be efficiently removed from the cyclic siloxane, and have completed the present invention.
【０００８】即ち、本発明は、環状シロキサンと末端に
水酸基を有する鎖状シロキサンの混合物を、シリコン原
子又はアルミニウム原子に結合した水酸基を表面に有す
る無機化合物と接触させることにより、末端に水酸基を
有する鎖状シロキサンを除去することを特徴とする環状
シロキサンの精製方法である。That is, according to the present invention, a mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal is brought into contact with an inorganic compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface to thereby have a hydroxyl group at the terminal. A method for purifying cyclic siloxane, which comprises removing chain siloxane.
【０００９】本発明における環状シロキサンは、下記一
般式（１）で示されるものである。The cyclic siloxane in the present invention is represented by the following general formula (1).
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】（但し、Ｒ1およびＲ2は同種又は異種のア
ルキル基であって、ｎは、３又は４である。）上記一般
式（１）中、Ｒ1およびＲ2は同種又は異種のアルキル基
である。Ｒ1およびＲ2は、鎖状、分岐状および環状のア
ルキル基を用いることができ、また、その炭素数は特に
制限されるものではない。しかし、末端に水酸基を有す
る鎖状シロキサンの除去効率の点から、炭素数１６以下
のアルキル基であることが好適である。(However, R 1 and R 2 are the same or different alkyl groups and n is 3 or 4.) In the above general formula (1), R 1 and R 2 are the same or different. It is an alkyl group. R 1 and R 2 may be chain, branched or cyclic alkyl groups, and the number of carbon atoms is not particularly limited. However, an alkyl group having 16 or less carbon atoms is preferable from the viewpoint of removal efficiency of chain siloxane having a hydroxyl group at the terminal.
【００１２】本発明で好適に使用される環状シロキサン
の側鎖アルキル基を例示すれば、メチル基，エチル基，
ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，ｔ−
ブチル基，イソブチル基，アミル基，ｎ−ヘキシル基，
２−ヘキシル基，ｎ−ペチル基，ｎ−オクチル基，ノニ
ル基，デシル基，ウンデシル基，ドデシル基，トリデシ
ル基，テトラデシル基，ペンタデシル基およびヘキサデ
シル基などが挙げられる。また、上記一般式（１）にお
いてｎは３又は４である。Examples of the side chain alkyl group of the cyclic siloxane preferably used in the present invention include methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, t-
Butyl group, isobutyl group, amyl group, n-hexyl group,
Examples thereof include 2-hexyl group, n-petyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group. In the general formula (1), n is 3 or 4.
【００１３】本発明で除去の対象となる末端に水酸基を
有する鎖状シロキサンは、分子の末端に水酸基を有する
鎖状のシロキサンであれば特に限定されないが、一般的
には、この末端に水酸基を有する鎖状シロキサンは、下
記一般式（２）で示されるものである。The chain-like siloxane having a hydroxyl group at the terminal to be removed in the present invention is not particularly limited as long as it is a chain-like siloxane having a hydroxyl group at the terminal of the molecule, but generally, a hydroxyl group at this terminal is The chain siloxane has is represented by the following general formula (2).
【００１４】[0014]
【化２】 [Chemical 2]
【００１５】（但し、Ｒ1およびＲ2は同種又は異種のア
ルキル基であって、ｍは２以上の自然数である。）上記
の末端に水酸基を有する鎖状シロキサンは、環状シロキ
サンを合成する時の副生物であると考えられる。(However, R 1 and R 2 are the same or different alkyl groups, and m is a natural number of 2 or more.) The above chain siloxane having a hydroxyl group at the terminal is used when synthesizing a cyclic siloxane. Considered to be a by-product of.
【００１６】上記一般式（２）において、Ｒ1およびＲ2
は、一般式（１）におけるＲ1およびＲ2の説明と同じで
ある。また、上記一般式（２）において、ｍは２以上の
自然数であれば特に限定されないが、末端に水酸基を有
するシロキサンの除去効率の点からｍは２〜５の範囲で
あることが好適である。末端に水酸基を有する鎖状シロ
キサンは、１種類でもよく、また、種類の異なるものの
混合物であっても良い。In the above general formula (2), R 1 and R 2
Is the same as the description of R 1 and R 2 in the general formula (1). In the general formula (2), m is not particularly limited as long as it is a natural number of 2 or more, but it is preferable that m is in the range of 2 to 5 from the viewpoint of removal efficiency of siloxane having a hydroxyl group at the terminal. . The chain siloxane having a hydroxyl group at the terminal may be one type or a mixture of different types.
【００１７】本発明において環状シロキサンと末端に水
酸基を有する鎖状シロキサンの混合物の混合割合も特に
限定されないが、水酸基を有する鎖状シロキサンの濃度
が、１０モル％以下であることが好適である。末端に水
酸基を有する鎖状シロキサンの濃度が上記範囲を超える
場合には、鎖状シロキサン濃度が上記範囲内になるよ
う、溶媒抽出などの前処理を行うのが好適である。In the present invention, the mixing ratio of the mixture of the cyclic siloxane and the chain siloxane having a hydroxyl group at the terminal is not particularly limited, but the concentration of the chain siloxane having a hydroxyl group is preferably 10 mol% or less. When the concentration of the chain siloxane having a hydroxyl group at the terminal exceeds the above range, it is preferable to perform a pretreatment such as solvent extraction so that the chain siloxane concentration is within the above range.
【００１８】また、本発明で用いる無機化合物は、シリ
コン原子またはアルミニウム原子に結合した水酸基を表
面に有するものであれば特に限定されない。本発明で好
適に使用できる無機化合物を例示すれば、シリカ；ケイ
酸カルシウム、ケイ酸ナトリウム、ケイ酸アルミニウム
等のケイ酸塩；アルミナ；ゼオライトなどが挙げられ
る。The inorganic compound used in the present invention is not particularly limited as long as it has a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface. Examples of inorganic compounds that can be suitably used in the present invention include silica; silicates such as calcium silicate, sodium silicate, and aluminum silicate; alumina; zeolite.
【００１９】本発明において、末端に水酸基を有する鎖
状シロキサンの除去は、鎖状シロキサンがシリコン原子
またはアルミニウム原子に結合した水酸基を表面に有す
る無化合物に吸着あるいは末端水酸基と表面の水酸基の
反応を介して選択的に固定化されることを利用したもの
である。従って、末端に水酸基を有する鎖状シロキサン
を環状シロキサンから除去するためには、該鎖状シロキ
サンを表面に水酸基を有する無機化合物に接触させる必
要がある。接触の方法は特に限定されるものではない
が、一般には、環状シロキサンと末端に水酸基を有する
鎖状シロキサンとの混合物をそのまま、あるいは溶媒で
希釈したものを、表面に水酸基を有する無機化合物と混
合する方法、あるいは、該混合物をそのまま、あるいは
溶媒で希釈したものを、表面に水酸基を有する無機化合
物の固定層を通過させる方法を用いるのが好適である。
この時、鎖状シロキサンの末端水酸基と無機化合物の表
面水酸基の反応を促進するために加熱したり、微量の酸
又はアルカリを溶媒として加えることもできる。また、
これら接触方法において溶媒を使用する場合、用いる溶
媒は環状シロキサンと末端に水酸基を有する鎖状シロキ
サンの混合物を溶解するものであれば特に限定されず、
ヘキサン等の炭化水素系溶媒、メチルイソブチルケトン
等の含酸素系溶媒あるいはクロロホルムなどのハロゲン
系溶媒が好適に使用される。In the present invention, the chain siloxane having a hydroxyl group at the end is removed by adsorbing the chain siloxane on a compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface or reacting the terminal hydroxyl group with the hydroxyl group on the surface. It utilizes that it is selectively immobilized via the. Therefore, in order to remove the chain siloxane having a hydroxyl group at the terminal from the cyclic siloxane, it is necessary to bring the chain siloxane into contact with an inorganic compound having a hydroxyl group on the surface. The method of contact is not particularly limited, but generally, a mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal as it is or diluted with a solvent is mixed with an inorganic compound having a hydroxyl group on the surface. It is preferable to use the above method or a method of passing the mixture as it is or diluted with a solvent through a fixed layer of an inorganic compound having a hydroxyl group on the surface.
At this time, heating may be performed to accelerate the reaction between the terminal hydroxyl group of the chain siloxane and the surface hydroxyl group of the inorganic compound, or a trace amount of acid or alkali may be added as a solvent. Also,
When a solvent is used in these contact methods, the solvent used is not particularly limited as long as it dissolves a mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal,
A hydrocarbon solvent such as hexane, an oxygen-containing solvent such as methyl isobutyl ketone, or a halogen solvent such as chloroform is preferably used.
【００２０】これら接触方法において用いる表面に水酸
基を有する無機化合物の量は、その表面水酸基の総量が
精製したい混合物中に含まれる末端に水酸基を有する鎖
状シロキサンのモル数の半分以上であれば特に限定され
ないが、鎖状シロキサンの末端水酸基と無機化合物の表
面水酸基との反応効率および操作性を考慮すると、無機
化合物の表面水酸基の総和が末端に水酸基を有する鎖状
シロキサンのモル数の１〜１０，０００倍の範囲の量で
あるのが好適である。この時、混合物中に含まれる末端
に水酸基を有する鎖状シロキサンの量は、Ａｐｐ．Ｓｐ
ｅｃｔｒｏｓｃ．，４５，４７７（１９９１）に記載さ
れている様に、混合物中のフリーのＳｉ−ＯＨの吸収ピ
ークをフーリエ変換赤外吸収スペクトル（以下、ＦＴＩ
Ｒという）により定量することにより知ることができ
る。また、無機化合物の表面水酸基の量は、無機化合物
の表面積および結晶構造などから求めることができる。The amount of the inorganic compound having a hydroxyl group on the surface used in these contacting methods is particularly preferably such that the total amount of the surface hydroxyl group is at least half the number of moles of the chain-like siloxane having a hydroxyl group at the terminal contained in the mixture to be purified. Although not limited, in consideration of the reaction efficiency between the terminal hydroxyl group of the chain siloxane and the surface hydroxyl group of the inorganic compound and the operability, the sum of the surface hydroxyl groups of the inorganic compound is 1 to 10 of the number of moles of the chain siloxane having a terminal hydroxyl group. Amounts in the range of 1,000 times are preferred. At this time, the amount of the chain-like siloxane having a hydroxyl group at the end contained in the mixture is App. Sp
electrosc. , 45, 477 (1991), the absorption peak of free Si—OH in the mixture is converted into a Fourier transform infrared absorption spectrum (hereinafter referred to as FTI).
It can be known by quantifying by R). The amount of surface hydroxyl groups of the inorganic compound can be determined from the surface area and crystal structure of the inorganic compound.
【００２１】これらの方法により、環状シロキサンと末
端に水酸基を有する鎖状シロキサンを表面に水酸基を有
する無機化合物と接触させた後、ろ過等の操作により末
端に水酸基を有する鎖状シロキサンを無機化合物ととも
に分離することにより該鎖状シロキサンを環状シロキサ
ンから除去することができる。According to these methods, after the cyclic siloxane and the chain siloxane having a hydroxyl group at the terminal are brought into contact with the inorganic compound having a hydroxyl group on the surface, the chain siloxane having a hydroxyl group at the terminal is combined with the inorganic compound by an operation such as filtration. By separating, the chain siloxane can be removed from the cyclic siloxane.
【００２２】[0022]
【発明の効果】本発明の精製方法により、環状シロキサ
ンから末端に水酸基を有する鎖状シロキサンを効率良く
除去することができる。このことにより、ＰＰの対衝撃
性改良剤として有効な、高分子量のポリジアルキルシロ
キサンを効率的に得ることが可能となる。Industrial Applicability According to the purification method of the present invention, a chain siloxane having a hydroxyl group at the terminal can be efficiently removed from the cyclic siloxane. This makes it possible to efficiently obtain a high molecular weight polydialkylsiloxane that is effective as a PP impact modifier.
【００２３】[0023]
【実施例】本発明を更に具体的に説明するため、以下実
施例及び比較例を挙げて説明するが、本発明はこれら実
施例に限定されるものではない。EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples.
【００２４】実施例１ 特開平３−２９２３２９号公報記載の製造例に従って得
たジオクチルジクロルシランの加水分解物１２４６ｇ
を、アセトン１．５Ｌとメタノール０．５Ｌからなる混
合溶媒で３回洗浄を行った後、真空乾燥させてヘキサオ
クチルシクロトリシロキサン，オクタオクチルシクロテ
トラシロキサンおよび末端に水酸基を有する鎖状ジオク
チルシロキサンの混合物９０８ｇを得た。この混合物を
Ａｐｐｌ．Ｓｐｅｃｔｒｏｓｃ．，４５．４７７（１９
９１）記載の方法に従ってＦＴＩＲで分析を行い、Ｓｉ
−ＯＨの吸収強度から、この混合物に含まれる末端に水
酸基を有する鎖状ジオクチルシロキサンの量を求めたと
ころ、その量は混合物１ｇ当り１．８０×１０-2ミリモ
ルであった。この値は約１．２モル％の濃度に相当す
る。また、この混合物をＧＰＣで分析したところヘキサ
オクチルシクロトリシロキサン含有量は約９５モル％，
オクタオクチルシクロテトラシロキサンの含有量は約４
モル％であった。Example 1 1246 g of hydrolyzate of dioctyldichlorosilane obtained according to the production example described in JP-A-3-292329.
Was washed three times with a mixed solvent consisting of 1.5 L of acetone and 0.5 L of methanol, and then vacuum dried to obtain hexaoctylcyclotrisiloxane, octaoctylcyclotetrasiloxane and a chain dioctylsiloxane having a hydroxyl group at the end. 908 g of a mixture was obtained. This mixture was added to Appl. Spectrosc. , 45.477 (19
91) FTIR analysis according to the method described in
The amount of chain dioctylsiloxane having a hydroxyl group at the end contained in this mixture was determined from the absorption strength of —OH, and the amount was 1.80 × 10 −2 mmol per 1 g of the mixture. This value corresponds to a concentration of about 1.2 mol%. When this mixture was analyzed by GPC, the hexaoctylcyclotrisiloxane content was about 95 mol%,
The content of octaoctylcyclotetrasiloxane is about 4
It was mol%.
【００２５】この環状シロキサンと末端にＯＨ基を有す
る鎖状シロキサンの混合物２０ｇをヘキサン２００ｃｃ
に溶解し、シリカゲル（和光純薬工業社製 ワコーゲル
Ｃ−２００）を３０ｇ（表面の水酸基の量が鎖状ジオク
チルシロキサンの２００倍モルに相当）加え、還流下で
約２時間攪拌を行った。その後、ろ過によりシリカゲル
を除いた後、ろ液中のヘキサンをロータリーエバポレー
ターで除去した。さらに１００℃で５時間真空乾燥を行
い、冷却したところ１９．５ｇの白色固体が回収でき
た。この回収物をＦＴＩＲで分析したところ、Ｓｉ−Ｏ
Ｈの吸収は観測されなかった。なお、この時のＦＴＩＲ
法でのＳｉ−ＯＨの検出限界は、混合物１ｇ当り２×１
０-4ミリモルである。20 g of a mixture of this cyclic siloxane and a chain siloxane having an OH group at the end was added with 200 cc of hexane.
And 30 g of silica gel (Wako gel C-200 manufactured by Wako Pure Chemical Industries, Ltd.) (the amount of hydroxyl groups on the surface corresponds to 200 times mol of chain dioctyl siloxane) was added, and the mixture was stirred under reflux for about 2 hours. Then, silica gel was removed by filtration, and then hexane in the filtrate was removed by a rotary evaporator. Vacuum drying was further performed at 100 ° C. for 5 hours, and when cooled, 19.5 g of a white solid could be recovered. When this collected product was analyzed by FTIR, Si--O
No absorption of H was observed. FTIR at this time
The detection limit of Si-OH by the method is 2 x 1 per 1 g of the mixture.
It is 0 -4 mmol.
【００２６】実施例２〜７ 実施例１において、加水分解するのに用いたクロルシラ
ンの種類を表１に示すように変えた他は実施例１と同様
にして、環状シロキサンと末端に水酸基を有する鎖状シ
ロキサンの混合物を得、これをシリカゲルで処理した。
シリカゲルの使用量は、表面水酸基の量が鎖状シロキサ
ンの水酸基の４００倍モルとなるようにした。処理前、
後の試料１ｇ中に含まれた末端に水酸基を有する環状シ
ロキサンの濃度および鎖状シロキサンの回収率を併せて
表１に示した。Examples 2 to 7 In the same manner as in Example 1 except that the type of chlorosilane used for hydrolysis was changed as shown in Table 1, a cyclic siloxane and a hydroxyl group at the end were prepared. A mixture of linear siloxanes was obtained, which was treated with silica gel.
The amount of silica gel used was such that the amount of surface hydroxyl groups was 400 times the molar amount of the hydroxyl groups of the chain siloxane. Before processing,
The concentration of the cyclic siloxane having a hydroxyl group at the terminal and the recovery rate of the chain siloxane contained in 1 g of the sample described later are also shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】比較例１ 実施例１で得た末端に水酸基を有する鎖状ジオクチルシ
ロキサン濃度が１．８０×１０-2ミリモル／ｇである混
合物５０ｇを、アセトン１５０ｃｃとメタノール５０ｃ
ｃからなる混合溶媒でさらに３回洗浄を行った。その
後、１００℃で５時間真空乾燥を行い、回収物中に含ま
れる末端に水酸基を有する環状シロキサンの定量を行っ
たところ、回収物１ｇに含まれる鎖状シロキサン量は
７．５１×１０-3ミリモル／ｇであった。なお、この時
の環状シロキサンの回収率は７３％であった。Comparative Example 1 50 g of a mixture obtained in Example 1 having a hydroxyl group-terminated dioctylsiloxane concentration of 1.80 × 10 -2 mmol / g was added to 150 cc of acetone and 50 c of methanol.
Washing was further performed three times with the mixed solvent consisting of c. Then, vacuum drying was carried out at 100 ° C. for 5 hours to quantify the cyclic siloxane having a hydroxyl group at the end contained in the recovered product. The amount of chain siloxane contained in 1 g of the recovered product was 7.51 × 10 −3. It was mmol / g. The recovery rate of cyclic siloxane at this time was 73%.
【００２９】実施例８ 実施例１において、シリカゲルの代りにアルミナ（和光
純薬工業社製）３０ｇ（表面水酸基の量が鎖状シロキサ
ンの２００倍モルに相当する）を用いた他は同様にして
回収物の分析を行ったところ、回収物１ｇ中に含まれる
末端に水酸基を有する鎖状シロキサンの量は３．９５×
１０-3ミリモル／ｇであった。またこの時の環状シロキ
サンの回収率は９６％であった。Example 8 In the same manner as in Example 1, except that 30 g of alumina (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of silica gel (the amount of surface hydroxyl groups corresponded to 200 times the molar amount of chain siloxane). Analysis of the recovered product showed that the amount of chain-like siloxane having a hydroxyl group at the end contained in 1 g of the recovered product was 3.95 ×.
It was 10 −3 mmol / g. The recovery rate of cyclic siloxane at this time was 96%.
【手続補正書】[Procedure amendment]
【提出日】平成４年１０月９日[Submission date] October 9, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】本発明において、末端に水酸基を有する鎖
状シロキサンの除去は、鎖状シロキサンがシリコン原子
またはアルミニウム原子に結合した水酸基を表面に有す
る無機化合物に吸着あるいは末端水酸基と表面の水酸基
の反応を介して選択的に固定化されることを利用したも
のである。従って、末端に水酸基を有する鎖状シロキサ
ンを環状シロキサンから除去するためには、該鎖状シロ
キサンを表面に水酸基を有する無機化合物に接触させる
必要がある。接触の方法は特に限定されるものではない
が、一般には、環状シロキサンと末端に水酸基を有する
鎖状シロキサンとの混合物をそのまま、あるいは溶媒で
希釈したものを、表面に水酸基を有する無機化合物と混
合する方法、あるいは、該混合物をそのまま、あるいは
溶媒で希釈したものを、表面に水酸基を有する無機化合
物の固定層を通過させる方法を用いるのが好適である。
この時、鎖状シロキサンの末端水酸基と無機化合物の表
面水酸基の反応を促進するために加熱したり、微量の酸
又はアルカリを触媒として加えることもできる。また、
これら接触方法において溶媒を使用する場合、用いる溶
媒は環状シロキサンと末端に水酸基を有する鎖状シロキ
サンの混合物を溶解するものであれば特に限定されず、
ヘキサン等の炭化水素系溶媒、メチルイソブチルケトン
等の含酸素系溶媒あるいはクロロホルムなどのハロゲン
系溶媒が好適に使用される。In the present invention, the chain siloxane having a hydroxyl group at the end is removed by adsorbing the chain siloxane to an inorganic compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface or reacting the terminal hydroxyl group with the surface hydroxyl group. It utilizes that it is selectively immobilized via the. Therefore, in order to remove the chain siloxane having a hydroxyl group at the terminal from the cyclic siloxane, it is necessary to bring the chain siloxane into contact with an inorganic compound having a hydroxyl group on the surface. The method of contact is not particularly limited, but generally, a mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal as it is or diluted with a solvent is mixed with an inorganic compound having a hydroxyl group on the surface. It is preferable to use the above method or a method of passing the mixture as it is or diluted with a solvent through a fixed layer of an inorganic compound having a hydroxyl group on the surface.
At this time, heating may be performed to accelerate the reaction between the terminal hydroxyl group of the chain siloxane and the surface hydroxyl group of the inorganic compound, or a trace amount of acid or alkali may be added as a catalyst. Also,
When a solvent is used in these contact methods, the solvent used is not particularly limited as long as it dissolves a mixture of a cyclic siloxane and a chain siloxane having a hydroxyl group at the terminal,
A hydrocarbon solvent such as hexane, an oxygen-containing solvent such as methyl isobutyl ketone, or a halogen solvent such as chloroform is preferably used.
Claims (1)
状シロキサンの混合物を、シリコン原子又はアルミニウ
ム原子に結合した水酸基を表面に有する無機化合物と接
触させることにより、末端に水酸基を有する鎖状シロキ
サンを除去することを特徴とする環状シロキサンの精製
方法。1. A chain siloxane having a terminal hydroxyl group is obtained by bringing a mixture of a cyclic siloxane and a chain siloxane having a terminal hydroxyl group into contact with an inorganic compound having a hydroxyl group bonded to a silicon atom or an aluminum atom on the surface. A method for purifying a cyclic siloxane, which comprises removing the cyclic siloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24084592A JPH0687871A (en) | 1992-09-09 | 1992-09-09 | Method for purifying cyclic siloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24084592A JPH0687871A (en) | 1992-09-09 | 1992-09-09 | Method for purifying cyclic siloxane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0687871A true JPH0687871A (en) | 1994-03-29 |
Family
ID=17065566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24084592A Pending JPH0687871A (en) | 1992-09-09 | 1992-09-09 | Method for purifying cyclic siloxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0687871A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0760373A3 (en) * | 1995-09-01 | 1998-03-11 | Corning Incorporated | Method for purifying polyalkylsiloxanes and the resulting products |
| CN113522361A (en) * | 2020-04-22 | 2021-10-22 | 江西蓝星星火有机硅有限公司 | Immobilized catalyst for purifying cyclosiloxane |
-
1992
- 1992-09-09 JP JP24084592A patent/JPH0687871A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0760373A3 (en) * | 1995-09-01 | 1998-03-11 | Corning Incorporated | Method for purifying polyalkylsiloxanes and the resulting products |
| CN113522361A (en) * | 2020-04-22 | 2021-10-22 | 江西蓝星星火有机硅有限公司 | Immobilized catalyst for purifying cyclosiloxane |
| CN113522361B (en) * | 2020-04-22 | 2023-02-03 | 江西蓝星星火有机硅有限公司 | Immobilized catalyst for purifying cyclosiloxane |
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