The synthetic method of a kind of trimethylammonium three (3,3,3-fluoropropyl) ring three silazaneTechnical field:
The present invention relates to the synthesis technical field of compound, especially the synthetic method of trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.
Background technology:
Since organosilicon macromolecule comes out, especially trifluoropropyl siloxane, due to features such as it have high-low temperature resistant, oil resistant, becomes a class type material gradually, in aviation, and space flight, the field extensive application such as automobile[1].And fluorine silazane is as the auxiliary agent of trifluoropropyl siloxane processing, can not only serves as antistructurizing agent, and cross-linked rubber thermotolerance and physical strength are increased.Trimethylammonium three (3,3,3-fluoropropyl) ring three silazane are common fluorine silazane, extensive application in Rubber processing.Its synthesis technique is rarely found, and the synthetic cost of existing synthesis technique is high, yield is low, and some also has environmental pollution.
Summary of the invention:
For prior art problem, the invention provides the synthetic method of the trimethylammonium three that a kind of productive rate is high, cost is low (3,3,3-fluoropropyl) ring three silazane.
The present invention will solve the problems of the technologies described above and be achieved by following technical scheme:
The synthetic method of a kind of trimethylammonium three (3,3,3-fluoropropyl) ring three silazane, step is: A, methyl (3,3,3-fluoropropyl) dichlorosilane is joined in gasoline, stir with 0.020～0.025m3the speed of/h passes into ammonia, and the logical too fast meeting of ammonia causes polymkeric substance to become many, crosses long response time long; Make reaction system remain on 20～30 ℃, it is slack-off that temperature is crossed low reaction, and cost is large, excess Temperature, and the many yields of impurity are low; Pass into ammonia to not absorbing; B, in the solution of steps A gained, add sodium hydroxide solution, stir and make chloride leach, be divided into the oil phase on upper strata and the water of lower floor, trimethylammonium three (3,3,3-fluoropropyl) ring three silazane products are dissolved in after gasoline lighter than sodium hydroxide solution.C, lower floor's water in step B is given up, upper oil phase is dry with Calcium Chloride Powder Anhydrous, and rectification under vacuum, intercepts 134～140 ℃ of cuts, encircles three silazane thereby obtain trimethylammonium three (3,3,3-fluoropropyl).Water and oil phase are generally all stratification, then use conventional water and oil-phase separating method, such as the conventional separating funnel of those skilled in the art separates, also have separator water phase separated and oil phase etc.
Further: in the synthetic method of above-mentioned trimethylammonium three (3,3,3-fluoropropyl) ring three silazane, in steps A, methyl (3,3,3-fluoropropyl) volume ratio of dichlorosilane and gasoline is 1:7, than lower than 1:7 yield step-down, becomes large higher than 1:8 cost.In the system of steps A, pass into ammonia when not absorbing, more complete in order to guarantee reaction, raw material can be wrapped in ammonium chloride, needs to continue logical ammonia 2 ± 0.5h stopped reaction, and steps A total reaction time is 6～7 hours.In step B, the weight that adds sodium hydroxide solution is 20%～25% of steps A gained solution weight, and this calculates according to calculated amount is excessive, excessive as far as possible point, and concentration of sodium hydroxide solution is 20%～25%, and the low yield of concentration is low, and the basic constant cost of the high yield of concentration is large.Water in B step is given up, and oil phase Calcium Chloride Powder Anhydrous is dry, and rectification under vacuum, intercepts 134～140 ℃ of cuts, thereby obtains trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.
Compared with prior art, trimethylammonium three (3 of the present invention, 3, 3-fluoropropyl) ring three silazane synthetic method, take the common gasoline being easy to get as solvent, logical ammonia gas react under the condition stirring again, and pass into ammonia when not absorbing, more complete in order to guarantee reaction, raw material can be wrapped in ammonium chloride, need to continue just stopped reaction of logical ammonia 2 ± 0.5h, because ammonium chloride can affect quality product and yield, so finally with in sodium hydroxide and ammonium chloride material, , trimethylammonium three (3, 3, 3-fluoropropyl) ring three silazane products are dissolved in after gasoline lighter than sodium hydroxide and ammonia chloride mixing solutions, whole system is divided into the oil phase on upper strata and the water of lower floor.Because there is a small amount of moisture in gasoline, so oil phase is dry with Calcium Chloride Powder Anhydrous, rectification under vacuum, intercept 134～140 ℃ of cuts, just can collect the cut of relevant temperature such as being placed with thermometer at the tower top of rectifying setting, seeing the temperature that slips out liquid, thereby obtain trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.Synthesis technique of the present invention is simple, cost is low, easy to operate, non-environmental-pollution, and the product yield of gained is high.
Embodiment:
Purport of the present invention is by take gasoline as solvent, and the volume proportion of solvent and raw material is 7:1, and logical ammonia speed is 0.020～0.025m3/ h, temperature of reaction is 20～30 ℃, reaction obtains trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.The method process is simple, consuming time short, cost-saving and safe and reliable.Below in conjunction with embodiment, content of the present invention is described in further detail, in embodiment, mentioned content is not limitation of the invention, and in synthetic method, the selection of each step parameter can be suited measures to local conditions and result be there is no to substantial effect.
Embodiment 1
Methyl (3,3,3-fluoropropyl) dichlorosilane solvent is joined in the four-hole boiling flask of 5000ml band stirring, stir and pass into ammonia with the speed of 0.020～0.025m3/h, make reaction system remain on 20～30 ℃, pass into ammonia to not absorbing; Because reaction process is thermopositive reaction, must use the cooling guarantee temperature of reaction system of ice-water bath at 20～30 ℃, then add sodium hydroxide solution, stir and make chloride leach, be divided into the oil phase on upper strata and the water of lower floor; Upper oil phase is dry with Calcium Chloride Powder Anhydrous, and rectification under vacuum, intercepts 134～140 ℃ of cuts, thereby obtains trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.Different solvent ratio, final trimethylammonium three (3,3,3-fluoropropyl) ring three silazane have different yield (calculate theoretical weight according to reaction formula, then the product weight obtaining with real reaction just obtaining yield divided by theoretical weight) as shown in table 1 below:
Table 1:
| Methyl 3-fluoropropyl dichlorosilane: gasoline (volume ratio) | Yield % |
| 1：4 | 50 |
| 1：5 | 58 |
| 1：6 | 65 |
| 1：7 | 68 |
| 1：8 | 68 |
| 1：9 | 63 |
Embodiment 2
On the basis of embodiment 1, in the system of steps A, pass into ammonia when not absorbing, continue logical ammonia 2 ± 0.5h stopped reaction, steps A total reaction time is 6～7 hours.Final trimethylammonium three (3,3,3-fluoropropyl) ring three silazane yields have increased by 2% left and right.
Embodiment 3
By methyl (3,3,3-fluoropropyl) dichlorosilane 2mol and 1400ml petrolic solvent join in the four-hole boiling flask that 5000ml band stirs, and 1mol volume of material approximates 100ml, stirs and passes into ammonia, cooling with ice-water bath, because reaction process is thermopositive reaction, must remains on certain temperature by the cooling guarantee reaction system of ice-water bath, then add sodium hydroxide solution, stirring makes chloride leach, is divided into the oil phase on upper strata and the water of lower floor; Upper oil phase is dry with Calcium Chloride Powder Anhydrous, and rectification under vacuum, intercepts 134～140 ℃ of cuts, thereby obtains trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.Different temperature has different yields to show as table 2:
Table 2:
| Temperature/℃ | Time/h that reaction is reached home | Yield/% |
| 0～10 | 9 | 70 |
| 10～20 | 6 | 68 |
| 20～30 | 4.5 | 68 |
| More than 30 | 2 | 60 |
Embodiment 4
Methyl (3,3,3-fluoropropyl) dichlorosilane is joined in gasoline, stir with 0.020～0.025m3the speed of/h passes into ammonia, makes reaction system remain on 20～30 ℃, passes into ammonia to not absorbing; The volume ratio of methyl (3,3,3-fluoropropyl) dichlorosilane and gasoline is 1:7.Add sodium hydroxide solution, the amount that adds sodium hydroxide solution is aforementioned amount of solution 22%, stirs and makes chloride leach, is divided into the oil phase on upper strata and the water of lower floor; Lower floor's water is given up, and upper oil phase is dry with Calcium Chloride Powder Anhydrous, and rectification under vacuum, intercepts 134～140 ℃ of cuts, thereby obtains trimethylammonium three (3,3,3-fluoropropyl) ring three silazane.The alkali lye of different concns, can obtain different yields:
| Concentration of lye/% | Product yield/% |
| 10 | 52 |
| 15 | 63 |
| 20 | 68 |
| 25 | 68 |
Can find out from above-described embodiment, preferred processing parameter is: A, methyl (3,3,3-fluoropropyl) dichlorosilane is joined in gasoline, stir with 0.020～0.025m3the speed of/h passes into ammonia, makes reaction system remain on 20～30 ℃, passes into ammonia to not absorbing; Continue logical ammonia 2 ± 0.5h stopped reaction, steps A total reaction time is 6～7 hours, and the volume ratio of methyl (3,3,3-fluoropropyl) dichlorosilane and gasoline is 1:7.The amount that adds sodium hydroxide solution is 20%～25% of steps A gained amount of solution, and concentration of sodium hydroxide solution is 20%～25%.Yield 70% left and right of synthetics, and stable.