CN1019805B - The method for making of α W siloxane glycol - Google Patents
The method for making of α W siloxane glycolInfo
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- CN1019805B CN1019805B CN90105777A CN90105777A CN1019805B CN 1019805 B CN1019805 B CN 1019805B CN 90105777 A CN90105777 A CN 90105777A CN 90105777 A CN90105777 A CN 90105777A CN 1019805 B CN1019805 B CN 1019805B
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- water
- acid
- organoalkoxysilane
- hydrolysis
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Abstract
The present invention is a kind of method of producing lower molecular weight α, ω siloxane glycol, and (general formula is (RO) with organoalkoxysilane
2SiR ' R ", wherein R is Me, Et; R ', R " be respectively H; Me, Et, Ph; Vi etc.) be raw material; with acid (as oxalic acid, hydrochloric acid, phosphoric acid or acetic acid etc.) is catalyzer, in excessive water, is lower than and carries out twice hydrolysis under 50 ℃ of temperature; each 1～2 minute reaction times; product mean polymerisation degree 2～10, hydroxy radical content 1～14%, residual alkoxyl group few (below 0.2%) or nothing.Suitablely especially make silicon rubber structured control agent, also as release paper coatings, releasing agent and room temperature vulcanized silicone rubber.Present method technology is simple, and the polymerization degree is easy to control, and energy consumption is little.
Description
The present invention is a kind of preparation method about α, ω siloxane glycol, is to make through twice hydrolysis in the presence of acid catalyst by organoalkoxysilane and water.By α, ω siloxane glycol that the present invention makes, molecular weight is low, the hydroxy radical content height, and the suitable especially antistructurizing agent of making silicon rubber also can be used as release paper coatings, releasing agent and room temperature vulcanized silicone rubber etc.
The general formula of α, ω siloxane glycol is HO(SiR ' R " O) nH R ' wherein, R " is respectively Me, Et, Ph, Vi, H, n=2～10.The method for making of α, ω siloxane glycol in the prior art, the following several method of main employing:
(1) chlorosilane hydrolysis: general formula be RnSiX4-n(wherein R be Me, Et, Ph or Vi, X=Cl, n=2～3) chlorosilane, owing to generate a large amount of hydrogenchloride during hydrolysis, make hydrolysis and polycondensation speed restive, be difficult to make the very low α of molecular weight, ω siloxane glycol, also have a large amount of ring bodies to produce simultaneously.Ger.Offen2,403,303 adopt at NH
2-NH
4Be hydrolyzed in the Cl solution, can make α, the ω siloxane glycol of SiOH content 22.4%, but operate complicated.
(2) annular siloxane ring-opening polymerization: the available annular siloxane has hexamethyl cyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D4) etc., D3 difficulty produces, usually all be raw material with D4, its ring opening catalyst generally adopts strong acid such as sulfuric acid, acidic white earth or strongly acidic cation-exchange etc.It is catalyzer that Rom.RO75237 adopts sulfuric acid, and in 15～135 minutes reaction times, the products therefrom molecular weight is 25,000～120,000, and remaining about 10% unreacted ring body in the product; USP4,066,680 to adopt acidic white earth be catalyzer, by at AC
2Refluxed 4 hours among O and the ACOH, generate the intermediate product acetoxysilane earlier, add NaHCO then
3Aqueous hydrolysis, the α that makes, ω siloxane glycol mean polymerisation degree 6～7 are as silicon rubber structured control agent.But this method complicated operation, hydrolysis is difficult for thoroughly.
(3) organoalkoxysilane hydrolysis: general hydrolysis reaction is with alkali as a catalyst or without catalyzer, USP2, and 415,389 to adopt general formulas be (RO)
2SiR ' R " (R, R ', R " is a low alkyl group) organoalkoxysilane, with a small amount of alkali as a catalyst, add less water and be hydrolyzed, the siloxane glycol that makes, molecular weight is higher.It is very slow not add catalyzer [J.Am, Chem, Soc., 75,2712-14(1953)] organoalkoxysilane hydrolysis rate.USP4,395,563 is catalyzer with periodictable II a family metal oxide (as MgO etc.), can make viscosity is 25.6Cst(20 ℃), the product of mean polymerisation degree 3.4, SiOH content 11.5%.This method speed of response is slower, needs after reactant stirs evenly to place 21 hours, contains unhydrolysed alkoxyl group 1～3% in the product.
The object of the present invention is to provide a kind of lock out operation easy, the product yield height, the method of producing α, ω siloxane glycol that the polymerization degree is easy to control, the product that makes has molecular-weight average low (mean polymerisation degree 2～10), hydroxy radical content height (SiOH content 3～15%), unreacted alkoxy group content seldom or not wait characteristics.
It is raw material that the present invention adopts organoalkoxysilane, with acid is catalyzer, in the presence of excessive water, be hydrolyzed, mixture reacted 1～20 minute being lower than under 50 ℃ the temperature, divide disacidify water after, add acid and excessive water in the organic layer again, under the same conditions, carry out the hydrolysis second time, divide the disacidify water layer, organic layer adds alkali neutralization, drying, decolouring makes α, ω siloxane glycol.
The used organoalkoxysilane general formula of the present invention is (RO) nSiR ' R ", wherein R is Me, Et; R ', R " is respectively H, Me, Et, Ph, Vi etc., n=2.
Advantages such as the acid catalyst kind that the organoalkoxysilane hydrolysis is suitable for is more, and as oxalic acid, phosphoric acid, acetic acid, hydrochloric acid etc., it is the most suitable to experimental results show that with hydrochloric acid, and it is few to have a consumption, and speed of response is fast, is easy to control, and is inexpensive.Be hydrolyzed as catalyzer with hydrochloric acid, the consumption of hydrochloric acid is generally 0.05～1%(weight of water consumption), but with 0.1～0.25%(weight) for well.
The used in amounts of water substantially exceeds the requirement of alkoxyl group hydrolysis, and the amount ratio of organoalkoxysilane and water is 1: a 3～20(mol ratio usually), with 1: 5～15(mol ratio) be good.The organoalkoxysilane hydrolysis condensation reaction is as follows:
The temperature range that this reaction is suitable for is very wide, the temperature of reaction height, and the speed of hydrolysis and polycondensation is fast, the molecular weight of product height, hydroxy radical content is low.For obtaining the high product of hydroxy radical content, temperature of reaction is unsuitable too high, generally is no more than 50 ℃, usually with 10～40 ℃ for well.
The hydrolysis of organoalkoxysilane, polycondensation process are carried out simultaneously.In the prior art, for ease of control, the general slower alkali as a catalyst of speed of response that all adopts, according to data J.Am.Chem.Sec., 76,3408-14(1954) to report, the silicon hydroxyl condensation reaction speed that with hydrochloric acid is catalyzer is than fast 500 times with KOH, therefore it is generally acknowledged that it is to be difficult to control that hydrochloric acid is done the reaction of catalyzer, the product of particularly desiring to make high hydroxyl content is more difficult.The method that the present invention adopts can make rapid reaction be effectively controlled, the α that makes, ω siloxane glycol hydroxy radical content height (3～15%), and the polymerization degree low (2-10) can also provide tetramethyl-dihydroxyl sily oxide crystalline compounds when needing.
Because the present invention adopts hydrochloric acid to make catalyzer, speed of response is very fast, only need stir at normal temperatures 1～20 minute, and entire reaction just can be finished.By reaction formula (1) as can be seen, the organoalkoxysilane hydrolysis is a reversible reaction, therefore, always has the part alkoxyl group to be difficult to remove.For making the very low product of alkoxy group content, the method that the present invention adopts twice hydrolysis i.e. mixture after the hydrolysis first time, left standstill 0.5～2 hour, allow after its layering, divide the disacidify water layer to remove the ROH of generation, and then add hydrochloric acid and water carries out hydrolysis reaction second time, and passing through twice hydrolysis like this, almost the whole hydrolysis of remaining alkoxyl group can be fallen.According to one's analysis, through the product of twice hydrolysis, (OR) remaining quantity is below 0.2%, even do not have for alkoxyl group.
The acid of hydrolysis for the second time and water consumption generally equate with the first time, also can suitably reduce.Because ROH content is less in the sour water layer after the hydrolysis for the second time, therefore can be used as the hydrolysis first time of next batch of material, can reduce the water dissolution loss of α, ω siloxane glycol like this, improve yield.
Mixture behind second time hydrolysis reaction was placed after 0.5～1 hour, divided the disacidify water layer, added appropriate bases solution in the organic layer and neutralized.Can be used for neutral alkali NaOH, KOH, NH are arranged
2, NaHCO
3Deng, but with NaHCO
3The most suitable, use in the caustic alkali and the wayward just in time neutrality that arrives, can cause α, the further polycondensation of ω siloxane glycol like this, thereby reduce the SiOH content of product.Neutralization is advisable with about 1% with the concentration of alkaline solution.The lixiviating water layer is divided in neutralization back, adds Calcium Chloride Powder Anhydrous and carry out drying in organic layer, and the elimination siccative can add product volume 0～2%(weight in case of necessity) gac, place a few hours, decolour, the elimination gac obtains finished product then.
By above result as can be seen, α of the present invention, ω siloxane glycol preparation method, technology is reasonable, and the hydrolysis lock out operation is extremely simple, and speed of response is fast, transforms thoroughly, the product yield height, energy consumption is low, and raw material consumption is few, and product degree of polymerization is easy to control.The product mean polymerisation degree that makes is 2～10, hydroxy radical content can be regulated on demand up to 14%(), unreacted alkoxy group content is lower than 0.2% in the product, does not contain or only contain seldom to measure ring body, and the crystalline compounds of tetramethyl-dihydroxyl sily oxide also can be provided when needed.
The α that the present invention makes, ω siloxane glycol, because hydroxy radical content height (can regulate) 1～14%, alkoxyl group less residue (below 0.2%), catalyzer can thoroughly be removed, therefore product excellent storage stability is suitable for doing the antistructurizing agent of silicon rubber especially, also can be according to different requirements, make and be suitable for release paper coatings, the product of releasing agent and room temperature vulcanized silicone rubber etc.
Embodiment 1
In the enamel still of 300 liters, add dimethyldiethoxysilane 120Kg, water 100Kg, hydrochloric acid 0.556Kg(concentration 36%), stirred 15 minutes down at 35 ℃, stop to stir, left standstill 0.5～1 hour, divide disacidify water, add entry 100Kg in the organic layer again, the hydrochloric acid 0.556Kg of concentration 36% is under 35 ℃, stirred 15 minutes, standing demix, the sour water of telling can be used for the hydrolysis first time of next batch of material, and organic layer adds the Calcium Chloride Powder Anhydrous drying, the activated carbon decolorizing that adds product 1% then gets product 43.2Kg.Product hydroxy radical content 11.05%, oxyethyl group content is below 0.2%.
Embodiment 2
Experimental installation, operation are with example 1, and feeding quantity is with example 1, and 45 ℃ of temperature of reaction get product 45.1Kg, product hydroxy radical content 9.08%, and oxyethyl group content is below 0.2%.
Embodiment 3
Reaction unit, operation adds dimethyldiethoxysilane 120Kg with example 1, water 100Kg, 36% concentrated acid 1.12Kg, 45 ℃ of temperature of reaction, after twice of the same terms hydrolysis product 47.0Kg, product hydroxy radical content 5.25%, oxyethyl group content is below 0.2%.
Claims (6)
1, a kind of by organoalkoxysilane and water hydrolysis in the presence of catalyzer produce the method for α, ω siloxane glycol, it is characterized in that:
(1) the organoalkoxysilane general formula is (RO) nSiR ' R ", R is Me in the formula, Et; R ', R " be respectively H, Me, Et, n=2,
(2) organoalkoxysilane mixes with the ratio of water with 1: 4～20 (mol ratios), adds acid catalyst 0.05～1% (based on the water yield, weight percentage), stirs 1～20 minute being lower than under 50 ℃ the temperature, divides disacidify water,
(3) organic layer adds water, acid with (2) the same terms under, carry out hydrolysis second time, the organic layer of telling adds alkali and neutralizes drying.
2,, it is characterized in that acid catalyst is a hydrochloric acid according to the described method of claim 1.
3, according to claim 1 or 2 described methods, it is characterized in that the hydrochloric acid consumption be 0.1～0.25%(based on the water yield, weight percentage).
4, according to claim 1 or 2 described methods, it is characterized in that the organoalkoxysilane and the ratio of water are 1: 5～15(mol ratio).
5,, it is characterized in that temperature of reaction is 10～40 ℃ according to claim 1 or 2 described methods.
6, according to claim 1 or 2 described methods, it is characterized in that organic layer neutralizes with sodium bicarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105777A CN1019805B (en) | 1990-03-02 | 1990-03-02 | The method for making of α W siloxane glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105777A CN1019805B (en) | 1990-03-02 | 1990-03-02 | The method for making of α W siloxane glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044100A CN1044100A (en) | 1990-07-25 |
| CN1019805B true CN1019805B (en) | 1992-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105777A Expired CN1019805B (en) | 1990-03-02 | 1990-03-02 | The method for making of α W siloxane glycol |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323101C (en) * | 2005-09-16 | 2007-06-27 | 浙江新安化工集团股份有限公司 | Prepn process of mixable silicon rubber structure controlling agent |
| CN103897191B (en) * | 2014-02-20 | 2016-05-11 | 合肥市科天化工有限公司 | A kind of preparation method of hydroxy-terminated polysiloxane polyalcohol |
-
1990
- 1990-03-02 CN CN90105777A patent/CN1019805B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1044100A (en) | 1990-07-25 |
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