CN102675358B - Preparation method of methylphenyl-cyclosiloxane - Google Patents
Preparation method of methylphenyl-cyclosiloxane Download PDFInfo
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Abstract
The invention relates to a preparation method of methylphenyl-cyclosiloxane, which comprises the following steps: hydrolyzing methylphenyl-dialkoxysilane under normal pressure, and distilling to continuously remove the hydrolysate alcohol compound; and when the density of distillate is approximate to that of water, stopping distillation and refluxing for some time, carrying out oil/water-phase separation, heating the oil phase under reduced pressure to remove water and low-boiling substances, continuing raising the temperature, enhancing the vacuum degree to carry out vacuum distillation, and collecting the methylphenyl-cyclosiloxane fraction. The method provided by the invention does not use any catalyst or neutralizer in the reaction process, and does not need filtering and water washing. The methylphenyl-cyclosiloxane prepared by the method has the advantages of high yield, high purity and good quality.
Description
Technical field
The present invention relates to a kind of method of preparing methyl phenyl ring siloxane, belong to organic compound preparing technical field.
Background technology
In methyl phenyl ring siloxane, be uniform-distribution with phenyl group, can stop the low temperature crystallization of dimethyl chain link, the high-and low-temperature resistance performance of material is largely increased (70 ℃ ~ 350 ℃).Compare with traditional silicon materials, radiation resistance, fire-retardant fireproof performance, damping characteristics containing phenyl chain link silicon materials are more excellent, therefore be widely used in numerous sophisticated technologies fields such as aerospace industry, nuclear industry, new forms of energy, become indispensable important new and high technology material.
The method of preparing methyl phenyl ring siloxane mainly comprises large class, the one, and the method by hydrolysis obtains, and another is that method by cracking obtains.
Methyl phenyl ring siloxane is prepared in hydrolysis: the production method that General Electric (U.S.A.) in 1998 discloses a kind of octaphenylcyclotetrasiloxane is (referring to United States Patent (USP) 5739370, CN1197073), in the mixed solvent of acetone and water, add micro-basic catalyst hydrolysis dimethoxydiphenylsilane to obtain octaphenylcyclotetrasiloxane.Inventor thinks does not affect the basic catalyst that contains trace in product the fusing point of product, and claims this method to can be used for A
4preparation.The Japan Qun Ma Masafumi Unno of university discloses a kind of method (Masafumi Unno Bull.Chem.Soc.Jpn. for preparing methyl phenyl ring siloxane, 2005,78,1105 – 1109): potassium hydroxide solution is splashed in the tetrahydrofuran solution of dichloromethyl phenylsilane, after reaction finishes, remove tetrahydrofuran (THF), through extracted with diethyl ether, repeatedly washing, dry, concentrated, after rectifying, obtain A
3, A
4and A
5.The deficiency of above method is that preparation process produces oil-containing sour water; Need washing, neutralization, dry.
CN 101503421A discloses a kind of preparation method of methyl phenyl ring siloxane, dichloromethyl phenylsilane is hydrolyzed in heterogeneous solvent to aminomethyl phenyl ring body and the partial line body that can obtain 80% above yield.The method need to need washing with a large amount of, multiple organic solvent, unfavorable to environmental protection.
Cracking is for methyl phenyl ring siloxane: within 1969, United States Patent (USP) 3484469 discloses a kind of method of preparing tetramethyl tetraphenyl cyclotetrasiloxane, dichloromethyl phenylsilane is hydrolyzed, washing, sodium carbonate neutralization, anhydrous sodium sulphate water suction, filter, obtain viscosity 700CS(20 ℃), refractive index 1.5482(20 ℃) hydrolyzate.Then add sodium carbonate (potassium, lithium) cracking, flask is heated to 250 ℃-290 ℃ (3mmHg), collects water and benzene in deep cooling bottle, collects thick product refractive index 1.544(20 ℃).Then rectifying A
3150-200 ℃ (0.35mmHg), A
4200-203 ℃ (0.35mmHg), refractive index 1.5448.Wherein A4 yield 63%.United States Patent (USP)s 3558681 in 1971 disclose a kind of method of methyl phenyl ring siloxane, first be that dichloromethyl phenylsilane is hydrolyzed, washing, calcium chloride is dry, then add lithium hydroxide or silanol lithium to carry out cracking, rectifying obtains product, the highlyest can obtain 88.6% yield, and can mutually change between A3 and A4.Within 2011, Chinese patent CN102134259 discloses a kind of method of preparing methyl phenyl ring siloxane, changes the catalyzer of cracking into organic acid lithium salts or organic acid sodium salt, think can so that scission reaction steadily carry out.The deficiency of above method is that preparation process produces oil-containing sour water; Need washing, neutralization, dry; Need basic catalyst cracking.
Within 1976, United States Patent (USP) 3989733 discloses one piece of method (United States Patent (USP) 3989733) of preparing methyl phenyl ring siloxane, by the hydrolyzate of dichloromethyl phenylsilane continuous join rectifying tower middle part, rectifying tower upper part filling material, lower part is equipped with lithium hydroxide particle.Thereby realize cracking rectifying continuous in rectifying tower.Within 2007, CN101125860A discloses a kind of method of preparing methyl phenyl ring siloxane.The methyl phenyl silicone of take containing phenyl silica tri functional chain, as raw material is under base catalysis, first removes the low-boiling-point substance that tri functional chain forms, and then obtains methyl phenyl ring siloxane.Within 2009, CN101503422 discloses a kind of method of preparing methyl phenyl ring siloxane.The aminomethyl phenyl diethoxy silane that the prepared by sodium condensation method of take generates, as raw material is hydrolyzed under alkaline condition, then obtains ring body by hydrolyzate with lithium hydroxide cracking.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of methyl phenyl ring siloxane.
Terminological interpretation:
Methyl phenyl ring siloxane typically refers to 1,3,5-trimethylammonium-1,3,5 triphenyl cyclotrisiloxane (A
3), 1,3,5,7-tetramethyl--1,3,5,7 tetraphenyl cyclotetrasiloxane (A
4), 1,3,5,7,9-pentamethyl--1,3,5,7,9 pentapheneyl D5 (A
5) mixture.A wherein
3, A
4, A
5all exist multiple not isomorphic map, as A3 exists 2 kinds of conformations, see Fig. 1 (a) (b), and its content ratio is about 1:3, A
4exist 4 kinds of conformations see Fig. 1 (c) (d) (e) (f) and its content ratio be about 1:4:2:1, A
5also have 4 kinds of conformations, and its content ratio is about 1:5:5:5.
It is A that the present invention makes methyl phenyl ring siloxane product
3, A
4, A
5mixture, various conformation has performance, A on gas chromatogram
32 peaks, A
44 peaks, A
54 peaks.
Technical scheme of the present invention is as follows:
A preparation method for methyl phenyl ring siloxane, is hydrolyzing methyl phenyl dialkoxy silicane under condition of normal pressure, by distilling, constantly removes hydrolysate alcohol compound.When the density of overhead product approaches the density of water, stop distillation and reflux for some time again, water oil content phase then, oil phase intensification decompression dehydration and low-boiling-point substance, then continue to improve temperature, and gas clean-up underpressure distillation, collects methyl phenyl ring siloxane cut.
More detailed, a kind of preparation method of methyl phenyl ring siloxane, comprises that step is as follows:
(1) aminomethyl phenyl dialkoxy silicane is added in reaction vessel and is hydrolyzed and reacts by 1:0.1～1 mass ratio with pure water, 60 ℃～200 ℃ of hydrolysis temperatures, stir, constantly steam the mixed solution of the first alcohol and water of reaction generation, when distillate volume density reaches 0.9～1g/ml, stop distillation, the 0.5～4h that refluxes, separates lower floor's oil phase hydrolyzate.
(2) the oil phase hydrolyzate that step (1) obtained moves into reactor and carries out decompression dehydration, deviates from low-boiling-point substance, and pressure range is-0.05MPa～-0.098MPa, and temperature range is 80 ℃～200 ℃, and the time is 0.5h～8h.
(3) dewater, deviate from after low-boiling-point substance, continue to heat up, underpressure distillation methyl phenyl ring siloxane, temperature range is 200 ℃～400 ℃, pressure range is-0.098MPa～-0.0999MPa.Collect methyl phenyl ring siloxane cut.
After above-mentioned underpressure distillation methyl phenyl ring siloxane, residual hydrolyzate is transparent dark brown, can be used as preparing resistance to irradiation phenyl silicone oil, or continues to add cracking catalyst to prepare methyl phenyl ring siloxane.
Raw material aminomethyl phenyl dialkoxy silicane of the present invention, wherein alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy.Described aminomethyl phenyl dialkoxy silicane is one of aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl diisopropoxy silane or combination.
According to the present invention, preferred:
In described hydrolysis reaction, aminomethyl phenyl dialkoxy silicane is 1:0.5～1 with the quality of water than scope.
Described hydrolysis temperature is 80 ℃～120 ℃.Described return time scope is 0.5h～3h.
The temperature range that described oil phase dewaters, deviates from low-boiling-point substance is 100 ℃～200 ℃, and pressure range is-0.08MPa～-0.098MPa that the time is 2h～6h.
The temperature range of described distillation methyl phenyl ring siloxane is 200 ℃～300 ℃, and pressure range is-0.0990MPa～-0.0999MPa.
It is A that the present invention makes methyl phenyl ring siloxane product
3, A
4, A
5mixture, A
3, A
4, A
5between ratio substantially at A3:A4:A5=2:5:1.
Method of the present invention is by hydrolyzing methyl phenyl dialkoxy silicane, obtains and take methyl phenyl ring siloxane composition as main hydrolyzate, then by underpressure distillation, obtains aminomethyl phenyl ring body.In whole process, do not use acidity or basic catalyst and neutralizing agent, do not need washing and filter, reaction is easy to control, and product purity is higher than 99.0%.
Beneficial effect of the present invention is as follows:
1, in reaction process, do not use catalyzer and neutralizing agent, do not need to filter and washing.
2, ring body yield is high, and purity is high, and quality is good.
3, owing at high temperature there is no alkaline katalysis, so to destroyed the lacking of silicon phenyl, avoid producing a large amount of by product benzene.
Accompanying drawing explanation
Fig. 1 is methyl phenyl ring siloxane A
3and A
4not isomorphic map formula.
Fig. 2 is the molecular weight distribution color atlas of embodiment 1 hydrolyzate.
Fig. 3 is the molecular weight distribution color atlas of the product methyl phenyl ring siloxane of embodiment 1 preparation.
Fig. 4 is the gas chromatogram of the product methyl phenyl ring siloxane of embodiment 1 preparation.
Fig. 5 is the molecular weight distribution color atlas of contrast experiment's 2 alkaline hydrolysis gained hydrolyzates.
Embodiment
Below by embodiment, the present invention is described further.
In embodiment, the analytical results of gas-chromatography obtains on Agilent 7890A gas chromatograph, sample size 1ul; Splitting ratio 100:1; 250 ℃ of injector temperatures; Carrier gas is helium; Hydrogen flameionization detects, 300 ℃ of detector temperatures; Chromatographic column Hp-5; Molecular weight distribution data is the data that obtain more than waters 1515 gel chromatographies; On 20 ℃ of refractive index numerical value Shi Shang Nereid section Abbe refractometers, obtain; The viscosity numerical value of 25 ℃ obtains on the permanent flat NDJ-5S rotational viscosimeter in Shanghai.
Embodiment 1: the preparation method of methyl phenyl ring siloxane, and step is as follows:
(1) get aminomethyl phenyl dimethoxy silane (GC purity 99.742%, refractive index (20 ℃) 1.4794) 1200g adds in 3L four-hole round-bottomed flask, the long Webster fractional column of 40cm is housed on four-hole boiling flask, then add 1200g pure water, open and stir, slowly be heated to 80 ℃, constantly steam the mixing solutions of the first alcohol and water of generation, and constantly improve temperature to 100 ℃, after 10h, record distillate volume density and reach 0.996g/ml, then reflux after 0.5h and separate lower floor's oil phase hydrolyzate, the molecular weight distribution color atlas of hydrolyzate is shown in Fig. 2, and analytical results is in Table 1.
Table 1 hydrolyzate molecular weight distribution analytical results
| Retention time | Peak molecular weight | Area percentage (%) | Molecular weight distribution coefficient |
| 27.033 | 3687 | 1.81 | 1.28 |
| 30.210 | 453 | 98.19 | 1.10 |
From Fig. 2 and table 1, can find out that the product of small molecules amount surpasses 98%, accounts for absolute majority.And the product content of high molecular is few.
(2) get hydrolyzate that step (1) obtains and get 332g and join in 1L round-bottomed flask, slowly decompression, to-0.095MPa, is slowly warmed up to 200 ℃ simultaneously, observes and constantly has water and low-boiling-point substance to be collected in cold-trap.After 4h, gas clean-up arrives 3mmHg post (approximately-0.0996MPa), and is slowly warmed up to 280 ℃, has observed cut and has produced.Distillation finishes rear cooling and weighs, analyzes.In flask, remaining hydrolyzate 77.9g, accounts for 22% of total input amount.Wherein remaining hydrolyzate is transparent dark brown, viscosity (25 ℃) 9520mpas, test refractive index (20 ℃) 1.5520.The aminomethyl phenyl ring body cut refractive index (20 ℃) 1.5449 of collecting, purity 99.343%.In cold-trap, micro-benzene detected and water is miscible.The molecular weight distribution color atlas of methyl phenyl ring siloxane product is shown in Fig. 3, and analytical results is in Table 2, and gas chromatogram is shown in Fig. 4, and analytical results is in Table 3.
Table 2 molecular weight of product distributional analysis result
| Retention time (min) | Peak molecular weight | Area percentage (%) | Molecular weight distribution coefficient |
| 30.192 | 458 | 100.00 | 1.10 |
Table 3 product gas chromatographic analysis result
| Retention time (min) | Peak name | Area percentage (%) |
| 15.152 | A 3 | 6.578 |
| 16.587 | A 3 | 16.725 |
| 23.318 | A 4 | 8.928 |
| 24.648 | A 4 | 32.222 |
| 24.916 | A 4 | 15.249 |
| 25.217 | A 4 | 8.148 |
| 30.708 | A 5 | 0.806 |
| 31.966 | A 5 | 3.664 |
| 32.357 | A 5 | 3.508 |
| 32.932 | A 5 | 3.515 |
By the molecular weight distribution data comparison of molecular weight distribution data and Fig. 2 and the table 1 of Fig. 3 and table 2 product, by retention time, peak molecular weight, distribution coefficient information, can judge that what in hydrolyzate, account for absolute majority is methyl phenyl ring siloxane.
The known A of gas chromatographic analysis data of Fig. 4 and table 3 product
3, A
4, A
5the aminomethyl phenyl ring body of totally 10 kinds of conformations all occurs, and proportionlity is substantially identical.
Contrast experiment 1:
(1) 500g dichloromethyl phenylsilane is slowly added drop-wise in 750g water, then 70 ℃ are reacted 0.5h, and the hydrolyzate obtaining, after layering, reaches neutral through 5 washings.
(2) getting the hydrolyzate 200g that step (1) obtains joins in four-hole boiling flask, add 3.0g lithium hydroxide to be heated to 250～300 ℃ and carry out scission reaction, reach-0.0998MPa of negative pressure, fractionation obtains aminomethyl phenyl ring body purity 99.64%, refractive index (20 ℃) 1.5447.Residual hydrolyzate at the bottom of still (account for input amount 20%) and lithium hydroxide particle are bundled together, and the transparency is poor, and viscosity is very high, is difficult to clear up.In cold-trap, collect 0.7g benzene.
Contrast experiment 2:
The sodium hydroxide solution of 576g aminomethyl phenyl dimethoxy silane and 576g 1% joins respectively in the four-hole round-bottomed flask of 2L, the long Webster fractional column of 20cm is housed on four-hole boiling flask, open and stir, be heated to 80 ℃, constantly there is the mixing solutions of methanol-water to be distillated, after 10h, distillate density reaches 0.96g/ml, continues backflow 2h.After washing 5 times, hydrolyzate is neutral, and vacuum is deviate from moisture and low-boiling-point substance wherein.Tested viscosity (25 ℃) 2060mpas, specific refractory power (20 ℃) 1.5510, fugitive constituent (150 ℃ * 3h) 0.10%.Molecular weight distribution color atlas is shown in Fig. 5.
PSI by high molecular in known Fig. 5 of contrast of Fig. 5 and Fig. 2 accounts for absolute majority, and the content of methyl phenyl ring siloxane is less, and these are significantly different from the result of Fig. 2.
Embodiment 2: the preparation method of methyl phenyl ring siloxane, and step is as follows:
(1) getting aminomethyl phenyl diethoxy silane 500g adds in 1L four-hole round-bottomed flask, the long Webster fractional column of 40cm is housed on four-hole boiling flask, open and stir, be heated to 80 ℃, then slowly drip 200g pure water, in dropping process, constantly slowly heat up, make the mixing solutions of second alcohol and water constantly be distilled out of, after 5h, record distillate volume density and reach 0.92g/ml, after the 4h that then refluxes, separate lower floor's oil phase hydrolyzate.
(2) get hydrolyzate that step (1) obtains and get 180g and join in 500mL round-bottomed flask, slowly decompression, to-0.08MPa, is slowly warmed up to 100 ℃ simultaneously, observes and constantly has water and low-boiling-point substance to be collected in cold-trap.After 4h, gas clean-up arrives 2mmHg post (approximately-0.0997MPa), and is slowly warmed up to 260 ℃, has observed cut and has produced.Distillation finishes rear cooling and weighs, analyzes.The aminomethyl phenyl ring body cut refractive index (20 ℃) 1.5447 of collecting, purity 99.53%.In cold-trap, micro-benzene detected and water is miscible.
Embodiment 3: the preparation method of methyl phenyl ring siloxane, and step is as follows:
(1) 200g pure water adds in 2L four-hole round-bottomed flask, the long Webster fractional column of 40cm is housed on four-hole boiling flask, open and stir and be heated to 100 ℃, then slowly drip 1200g aminomethyl phenyl dimethoxy silane, in dropping process, constantly there is the mixing solutions of first alcohol and water to be distilled out of, after 9h, record distillate volume density and reach 0.93g/ml, after the 2h that then refluxes, separate lower floor's oil phase hydrolyzate.
(2) get the hydrolyzate 260g that step (1) obtains and join in 500mL round-bottomed flask, slowly decompression, to-0.095MPa, is slowly warmed up to 150 ℃ simultaneously, observes and constantly has water and low-boiling-point substance to be collected in cold-trap.After 4h, gas clean-up arrives 2mmHg post (approximately-0.0997MPa), and is slowly warmed up to 260 ℃, has observed cut and has produced.Distillation finishes rear cooling and weighs, analyzes.The aminomethyl phenyl ring body cut refractive index (20 ℃) 1.5445 of collecting, purity 99.61%, cracking yield 85%.
Claims (7)
1. a preparation method for methyl phenyl ring siloxane, comprises that step is as follows:
(1) aminomethyl phenyl dialkoxy silicane is added in reaction vessel and is hydrolyzed and reacts by 1:0.1～1 mass ratio with pure water, 60 ℃～200 ℃ of hydrolysis temperatures, stir, constantly steam the mixed solution of first alcohol and water or the mixed solution of second alcohol and water that reaction produces, when distillate volume density reaches 0.9～1g/mL, stop distillation, the 0.5～4h that refluxes, separates lower floor's oil phase hydrolyzate;
(2) the oil phase hydrolyzate that step (1) obtained moves into reactor and carries out decompression dehydration, deviates from low-boiling-point substance, and pressure range is-0.05MPa～-0.098MPa, and temperature range is 80 ℃～200 ℃, and the time is 0.5h～8h;
(3) dewater, deviate from after low-boiling-point substance, continue to heat up, underpressure distillation methyl phenyl ring siloxane, temperature range is 200 ℃～400 ℃, pressure range is-0.098MPa～-0.0999 MPa; Collect methyl phenyl ring siloxane cut;
Described raw material aminomethyl phenyl dialkoxy silicane is aminomethyl phenyl dimethoxy silane or aminomethyl phenyl diethoxy silane;
Gained methyl phenyl ring siloxane product is A
3, A
4, A
5mixture, wherein, A
31,3,5-trimethylammonium-1,3,5 triphenyl cyclotrisiloxane, A
41,3,5,7-tetramethyl--1,3,5,7 tetraphenyl cyclotetrasiloxanes, A
51,3,5,7,9-pentamethyl--1,3,5,7,9 pentapheneyl D5s.
2. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, is characterized in that in described hydrolysis reaction, aminomethyl phenyl dialkoxy silicane is 1:0.5～1 with the quality of water than scope.
3. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, is characterized in that described hydrolysis temperature is 80 ℃～120 ℃.
4. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, is characterized in that the described return time scope of step (1) is 0.5h～3h.
5. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, the temperature range of it is characterized in that the described oil phase dehydration of step (2), deviating from low-boiling-point substance is 100 ℃～200 ℃, pressure range is-0.08MPa～-0.098MPa that the time is 2h～6h.
6. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, is characterized in that the temperature range of the distillation methyl phenyl ring siloxane that step (3) is described is 200 ℃～300 ℃, and pressure range is-0.0990MPa～-0.0999 MPa.
7. the preparation method of methyl phenyl ring siloxane as claimed in claim 1, it is characterized in that residual hydrolyzate after step (3) underpressure distillation methyl phenyl ring siloxane, for the preparation of resistance to irradiation phenyl silicone oil or continue to add cracking catalyst to prepare methyl phenyl ring siloxane.
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| CN105622663A (en) * | 2016-02-29 | 2016-06-01 | 山东东岳有机硅材料有限公司 | Preparation method of methylphenylcyclosiloxane |
| CN111072715A (en) * | 2019-12-31 | 2020-04-28 | 仙桃市格瑞化学工业有限公司 | Preparation method of bis (phenylcyclosiloxane) |
| CN115124824A (en) * | 2022-08-01 | 2022-09-30 | 太仓市华鼎塑料有限公司 | High-shading PC modified material and preparation method thereof |
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| CN101074284A (en) * | 2007-05-22 | 2007-11-21 | 杭州师范大学 | Production of polymethylphenylsilixane containing trifunctional phenyl-silox-chain |
| CN101343285A (en) * | 2008-08-28 | 2009-01-14 | 杭州师范大学 | Methyl-phenyl hybrid ring siloxane preparing method |
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| CN101074284A (en) * | 2007-05-22 | 2007-11-21 | 杭州师范大学 | Production of polymethylphenylsilixane containing trifunctional phenyl-silox-chain |
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