CN101225170B

CN101225170B - Method for synthesizing short-chain hydroxyl silicone oil

Info

Publication number: CN101225170B
Application number: CN2008100142223A
Authority: CN
Inventors: 蔺存国; 王利
Original assignee: 725th Research Institute of CSIC
Current assignee: 725th Research Institute of CSIC
Priority date: 2008-01-26
Filing date: 2008-01-26
Publication date: 2011-04-13
Anticipated expiration: 2028-01-26
Also published as: CN101225170A

Abstract

The invention relates to a synthetic method for short-chain hydroxyl silicone oil. Firstly, the materials are proportionally measured according to raw materials components, then adding acid clay, water, and cyclotetrasiloxanes to a three-mouth flask with a reflux device, adding concentrated sulfuric acid in agitation condition, and reacting by controlling the reaction temperature, when the reaction is completed, adding magnesia and agitating about 10 minutes, then processing pumping filtration, distilling and recovering acetone using a rotary evaporimeter used for filtrating under the temperature of 45 DEG C, then adding sodium carbonate solution for neutralization under controllable temperature for stratification; then watering and washing the organic layer on the upper layer once or twice, then discharging water through stratification, and then feeding the organic layer into the rotary evaporimeter for warming up to 95 DEG C, depressing and detracting low-boiling residues, obtaining micromolecule hydroxyl silicone oil. The synthetic method for short-chain hydroxyl silicone oil has the advantages of simple technological process, easy controllable reaction condition, low cost and easily available raw materials, fast reaction generating speed, good product quality and high reactivity, and wide application range.

Description

A kind of synthetic method of short-chain hydroxyl silicone oil

Technical field:

The present invention relates to a kind of synthetic method of short-chain hydroxyl silicone oil, particularly a kind of is that dual catalytic agent synthetic side group is hydrogen, C with the acidic white earth and the vitriol oil ₁-C ₇Alkyl chain or the method for the micromolecular hydroxyl silicone oil of vinyl, nitrile ethyl.

Background technology:

Short-chain hydroxyl silicone oil is a kind of constitution controller of high-temperature silicon disulfide rubber, also can be used for the synthetic of silicone resin or organic compound, at present, its main synthetic method has following several: (1) U.S. Patent Publication No. USP3853932, open day in October, 1974, title is a kind of with acidic white earth catalysis hexamethyl cyclotrisiloxane (D for the process patent of producing the low-molecular-weight silicon hydroxyl terminated polymer discloses ₃) method of the synthetic low-molecular-weight hydroxyl silicone oil of method; (2) Chinese patent Granted publication CN 1025861C, on September 7 1994 Granted publication day, name is called α, and the patent of the preparation of ω-two-hydroxyl oxygen dimethyl silicone pdms is used octamethylcyclotetrasiloxane (D ₄), distilled water is raw material synthesis of hydroxy silicone oil under polyethylene homogeneous phase cation sulfonate film (PECM) catalysis.(3) Chinese patent publication number CN1821284A, open day on August 23rd, 2006, name is called potassium hydroxide catalysed octamethylcyclotetrasiloxane ring-opening polymerization method, and this patent has been set forth the method for present production hydroxy silicon oil in background technology simultaneously: (4) methyl cyclosiloxane and acetic anhydride ring-opening polymerization method under an acidic catalyst; (5) write in " organosilicon macromolecule and the application " that Chemical Industry Press publishes with dimethyldichlorosilane(DMCS) hydrolytic polymerization method synthesis of hydroxy silicone oil by Feng Shengyu etc. etc.Wherein, D in the method (1) ₃Output is few, and the price height is used octamethylcyclotetrasiloxane (D cheaply instead ₄), common acidic white earth is effectively catalysis again; The viscosity of method (2) synthetic hydroxy silicon oil is at 350-3500CS/25 ℃, and viscosity is too high, and hydroxy radical content is too low, is not suitable for the demand of organic synthesis; Will neutralize with a large amount of sodium hydroxide catalysis with a large amount of sulfuric acid in the method (3), cost is higher; Method (4) will be done end-capping reagent with acetic anhydride, except the price height, adopts this method technology stability poor, wayward.The chlorosilane hydrolysis reaction is too violent in the method (5), and technology is wayward, and producing a large amount of spent acid needs post-processed, and cost is higher.In addition, more than five kinds of method synthetic be the short hydroxy silicon oil that side group is a methyl, and do not comprise hydrogen, C ₂-C ₇The sense side chain of feature richness such as alkyl chain, vinyl and nitrile ethyl, can not satisfy the demand of special industry.

Summary of the invention:

The objective of the invention is to overcome the shortcoming that exists in the prior art, seek to provide a kind of easy to operate, synthetic low-cost, lower molecular weight dimethyl end hydroxyl silicone oil and contain the synthetic method of the low molecular weight hydroxy-terminated silicone oil of function side group.

To achieve these goals, the present invention acidic white earth and sulphuric acid catalysis synthesizing small molecular hydroxy silicon oil, the employing cyclotetrasiloxane is a raw material, with tetrahydrofuran (THF) or acetone is reaction solvent, with the acidic white earth and the vitriol oil is the dual catalytic agent, with the aqueous sodium carbonate is that neutralizing agent carries out ring-opening polymerization in water, makes the micromolecular hydroxyl silicone oil that viscosity is 5-25CS; Earlier measure various raw materials by starting material component proportioning, respectively acidic white earth, water, acetone, cyclotetrasiloxane are added then and be equipped with in the there-necked flask of reflux, under whipped state, add the vitriol oil, under the control reaction temperature condition, react, after having reacted, add magnesium oxide and stirred 10 minutes, suction filtration, filtrate is distilled recovery acetone with Rotary Evaporators down at 45 ℃, and then the adding aqueous sodium carbonate neutralizes standing demix under the temperature control condition; Organic layer to the upper strata adds water cleaning 1～2 time again, and standing demix is put and anhydrated again, then organic layer is sent into Rotary Evaporators and is warming up to 95 ℃, and low-boiling-point substance is sloughed in decompression, makes micromolecular hydroxyl silicone oil.

Starting material constituent mass part proportioning of the present invention is: cyclotetrasiloxane 100 mass parts, acidic white earth 1～10 mass parts, the vitriol oil 0.1～1.5 mass parts, acetone or tetrahydrofuran (THF) 70～140 mass parts, yellow soda ash 0.2～1.8 mass parts, water 1～10 mass parts and magnesium oxide 1～5 mass parts;

Reaction process control condition of the present invention: 40～65 ℃ of temperature of reaction, in 8～20 hours reaction times, water cleans 30～60 ℃ of neutral temperatures, in and 1～4 hour time, 80 rev/mins of mixing speed.

The present invention compared with prior art, its technological process is simple, reaction conditions is convenient to control, material cost is low and be easy to get, the reaction formation speed is fast, good product quality is active high, applied range.

Embodiment:

The present invention will be further described below by embodiment.

Embodiment 1:

With 5g acidic white earth, 3g water, 110g acetone, 100gD ₄Add and be equipped with in the there-necked flask of reflux, under whipped state,, reacted 16 hours down at 50～60 ℃ with adding the 1.0g vitriol oil; After having reacted, add 5g magnesium oxide and stirred 10 minutes, suction filtration, with filtrate with Rotary Evaporators 45 ℃ down distillation reclaim acetone, and then add aqueous sodium carbonate 150ml 30～60 ℃ down in and 3 hours, standing demix.The organic layer on upper strata adds water 200ml and cleans 1～2 time, and standing demix is put and anhydrated again, then organic layer is sent into Rotary Evaporators and is warming up to 95 ℃, and low-boiling-point substance is sloughed in decompression, and the micromolecular hydroxyl silicone oil viscosity that makes is 19.4CS, productive rate 98.0%.

Embodiment 2:

With 2g acidic white earth, 8g water, 110g acetone, 100gD ₄Add and be equipped with in the there-necked flask of reflux, under whipped state,, reacted 24 hours down at 50～60 ℃ with adding the 1.0g vitriol oil; All the other process conditions are identical with embodiment 1, and the micromolecular hydroxyl silicone oil viscosity that makes is 10.5CS, productive rate 85.5%.

Embodiment 3:

With 10g acidic white earth, 4g water, 110g acetone, 80gD ₄, 20g tetraethyl-cyclotetrasiloxane adds and to be equipped with in the there-necked flask of reflux, under whipped state with adding the 0.65g vitriol oil, 50～60 ℃ of reactions 16 hours down; All the other process conditions are identical with embodiment 1, and the micromolecular hydroxyl silicone oil viscosity that makes is 11.5CS, productive rate 82.2.0%.

Claims

1. the synthetic method of a short-chain hydroxyl silicone oil, with acidic white earth and sulphuric acid catalysis synthesizing small molecular hydroxy silicon oil, the employing cyclotetrasiloxane is a raw material, with tetrahydrofuran (THF) or acetone is reaction solvent, with the acidic white earth and the vitriol oil is the dual catalytic agent, with the aqueous sodium carbonate is that neutralizing agent carries out ring-opening polymerization in water, makes the micromolecular hydroxyl silicone oil that viscosity is 5～25CS; It is characterized in that measuring various raw materials by starting material component proportioning earlier, respectively acidic white earth, water, acetone, cyclotetrasiloxane are added then and be equipped with in the there-necked flask of reflux, under whipped state, add the vitriol oil, be to react 8～20 hours under 40～65 ℃ the condition in control reaction temperature, after having reacted, adding magnesium oxide stirred 10 minutes, suction filtration, filtrate is distilled recovery acetone with Rotary Evaporators down at 45 ℃, and then add aqueous sodium carbonate under 30～60 ℃ of conditions in and 1～4 hour, standing demix; Organic layer to the upper strata adds water cleaning 1～2 time again, and standing demix is put and anhydrated again, then organic layer is sent into Rotary Evaporators and is warming up to 95 ℃, and low-boiling-point substance is sloughed in decompression, makes micromolecular hydroxyl silicone oil.

2. the synthetic method of short-chain hydroxyl silicone oil according to claim 1, it is characterized in that starting material constituent mass part proportioning is: cyclotetrasiloxane 100 mass parts, acidic white earth 1～10 mass parts, the vitriol oil 0.1～1.5 mass parts, acetone or tetrahydrofuran (THF) 70～140 mass parts, yellow soda ash 0.2～1.8 mass parts, water 1～10 mass parts and magnesium oxide 1～5 mass parts.