CN1274725A - Preparation of hexamethl disilamine from hexamethyl disiloxane - Google Patents
Preparation of hexamethl disilamine from hexamethyl disiloxane Download PDFInfo
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- CN1274725A CN1274725A CN 00107494 CN00107494A CN1274725A CN 1274725 A CN1274725 A CN 1274725A CN 00107494 CN00107494 CN 00107494 CN 00107494 A CN00107494 A CN 00107494A CN 1274725 A CN1274725 A CN 1274725A
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- hexamethyldisiloxane
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- ammonia
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229940073561 hexamethyldisiloxane Drugs 0.000 title abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 238000005915 ammonolysis reaction Methods 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000001035 drying Methods 0.000 description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005051 trimethylchlorosilane Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229940107816 ammonium iodide Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229960004839 potassium iodide Drugs 0.000 description 2
- 235000007715 potassium iodide Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
The preparation includes the first reaction of hexamethyl disiloxane and phosphorous pentoxide in liquid organic compound as solvent, the ammonoloysis reaction in the said reaction system by adding halide as catalyst and leading ammonia gas in, sucking or pressing filtering to separate solid from liquid and collection of 124-126 deg.c fraction as hexamethyl disilamine. The preparation process of the present invention has the advantages of less investment in equipment, simple technological process, easy operation and low production cost.
Description
The present invention relates to a kind of method of producing hexamethl disilamine, specifically, the present invention relates to the method for preparing hexamethl disilamine by reaction and follow-up catalysis ammonolysis reaction, belong to meticulous field of chemical technology with hexamethyldisiloxane and Vanadium Pentoxide in FLAKES.
Hexamethl disilamine is a kind of important silylating reagent in organic synthesis, is indispensable important source material in medicine industry.One of traditional preparation method be make trimethylchlorosilane in inert solvent with ammonia gas react, then after filtration, rectifying prepares hexamethl disilamine.Present domestic trimethylchlorosilane main source is a component when synthesizing chlorosilane as organosilicon industry direct method, and this component generally only accounts for 3～5%, and it is limited to originate; The ammonium chloride that generates when traditional in addition method ammonia is separated is unformed solid, and the loss of sepn process product is bigger, and productive rate is generally about 70%.Medicine industry has the hexamethyldisiloxane by product of a great deal of to generate again in a large amount of use hexamethl disilamines in the production process.Therefore need a kind of method that is suitable for hexamethyldisiloxane is changed into hexamethl disilamine.
It is known in technical literature and patent documentation by the synthetic hexamethl disilamine of stepwise reaction to go out hexamethyldisiloxane.Document in 1948 has just been reported makes hexamethyldisiloxane and excessive oleum prepared in reaction go out the silica-based ester of sulfuric acid front three earlier, it is dissolved in the method for carrying out ammonia in the ether and separating then (sees Journal of American Chemical Society, 1948, the 70th volume, the 445th page).The normal at present method that adopts is earlier hexamethyldisiloxane to be converted into trimethylchlorosilane, and then carries out ammonia by traditional method and separate.Reported respectively that as Japanese Patent JP 78147030 (1978) and European patent EP 0461597 A2 (1990) hexamethyldisiloxane and dimethyldichlorosilane(DMCS) prepare the method for trimethylchlorosilane under different catalysts catalysis; German patent DE 3013920 (1981) and Japanese Patent JP 8092392 (1980) have then gone out trimethylchlorosilane by the prepared in reaction of hexamethyldisiloxane and hydrogen chloride gas respectively.Above-mentioned two kinds of methods all must at first prepare and isolate intermediate product, and then it is dissolved in implements ammonolysis reaction in the inert solvent, so these two kinds of preparation methods invest greatly, complex process, and cost is higher.
The objective of the invention is to propose a kind of method for preparing hexamethl disilamine by hexamethyldisiloxane, preparation process is purified without the separation of intermediate product, simplify production technique, reduce operation steps, and the hexamethyldisiloxane of recovery is recycled, thereby reduce the production cost of hexamethl disilamine.
The method for preparing hexamethl disilamine that the present invention proposes, one of main raw material is a hexamethyldisiloxane, it can be the by product of medicine industry, but is not limited only to the medicine industry by product.It is characterized in that this method comprises following each step:
(1) makes the reaction of hexamethyldisiloxane and Vanadium Pentoxide in FLAKES, and the adding liquid organic compound is made solvent, solvent comprises that boiling range is 40～90 ℃ sherwood oil, a benzene,toluene,xylene, wherein the mol ratio of Vanadium Pentoxide in FLAKES and hexamethyldisiloxane is 1: 4～20, the water content of hexamethyldisiloxane is smaller or equal to 200ppm, and the weight ratio of hexamethyldisiloxane and solvent is 1: 0～1.5.Temperature of reaction is 50～100 ℃, and the reaction times is 10～50 hours.
(2) add halogenide in the system after above-mentioned reaction finishes as the ammonolysis reaction catalyzer, halogenide is the compound of monovalence bromine or monovalence iodine, directly with pressed powder or to be mixed with weight concentration be to add after 5% the organic solution, the solvent of preparation organic solution can be non-proton polar organic compounds such as methyl-sulphoxide or dimethyl formamide, and halid add-on is 0.05～0.5% of a Vanadium Pentoxide in FLAKES weight.
(3) feed ammonia in the above-mentioned system that contains catalyzer and carry out ammonolysis reaction, ammonia dewaters through the potassium hydroxide drying tower before feeding system, and feeding speed is 1～10 milliliters/second, and temperature of reaction is 30～100 ℃, and the reaction times is 2～12 hours.
(4) with suction filtration or press filtration method solid and liquid separation in step (3) product.
(5) liquid portion with step (4) carries out atmospheric distillation, collects 124～126 ℃ of cuts, is hexamethl disilamine of the present invention.
The solids that obtains at last in the above-mentioned reaction, the also recyclable hexamethyldisiloxane that can be recycled.Step is as follows:
(1) solids is used solvent extraction 2～5 times then with the water dissolution of 1～5 times of himself weight, and solvent is that boiling range is 40～90 ℃ sherwood oil, ether, benzene, toluene or a dimethylbenzene, and its consumption is 20～100% of a water weight.
(2) above-mentioned extraction liquid siccative drying, siccative is calcium chloride, anhydrous sulfate or molecular sieve, its consumption is 1～10% of an extraction liquid weight.
(3) aforesaid liquid is carried out air distillation, collect 98～101 ℃ of cuts, be hexamethyldisiloxane.
The hexamethyldisiloxane (98～101 ℃ of cuts) that (5) step rectifying is collected in the above-mentioned reaction can be recycled.
What the present invention proposed prepares the method for hexamethl disilamine by hexamethyldisiloxane, be characterized in purifying without the separation of intermediate product, esterification is promptly directly carried out ammonolysis reaction after finishing in same reactor, the hexamethyldisiloxane that reclaims in the while preparation process can be used as raw material of the present invention and recycles, therefore compare with branch one-step preparation method commonly used, have that facility investment is few, production technique simple, a processing ease, advantage that production cost is low.
Esterification and ammonolysis reaction can carry out under the condition that does not add other solvents among the present invention in addition, in the case, do not introduce other components in the preparation process except that little amount of catalyst, make the higher hexamethl disilamine product of purity easily.Through gas chromatographic analysis hexamethl disilamine content greater than 97%.
Introduce embodiments of the invention below.One of raw materials used is commercially available hexamethyldisiloxane or purified medicine industry by product, and its content of gas chromatographic detection is 96.8%, and water content is smaller or equal to 200ppm.
Embodiment 1:
Get 162 gram hexamethyldisiloxanes (1 mole) and 28.4 and restrain Vanadium Pentoxide in FLAKESs (0.2 mole) and put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 60 ℃ of reactions 45 hours, the system for the treatment of stops heating when being chilled to 40 ℃, add 0.1 gram potassiumiodide, speed with 4 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia then, system temperature is fallen after rising, the logical ammonia of insulation and continuation when reducing to 40 ℃, stopped reaction when ammonolysis reaction proceeds to 7 hours.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 28.2 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 43.6 gram hexamethl disilamines, press Vanadium Pentoxide in FLAKES and calculate, productive rate is 44.9%, and the content that gas chromatographic analysis records hexamethl disilamine is 97.2%.
After filter cake dissolves with 150 ml distilled waters, tell organic phase, water is used 40 milliliters, 40 milliliters and 30 milliliters of extracted with diethyl ether respectively 3 times, organic phase and extraction liquid merge, with anhydrous sodium sulfate drying rectifying after 8 hours, collect 98～101 ℃ of cuts, obtain 32 gram hexamethyldisiloxanes, distillate was with the 4A molecular sieve drying of its weight 5% 24 hours, and recording its water content with Ka Erfeishi method (Karl Ficher Method) is 179ppm.
Embodiment 2:
Get 324 gram hexamethyldisiloxanes (2 moles) and 28.4 and restrain Vanadium Pentoxide in FLAKESs (0.2 mole) and put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 80 ℃ of reactions 28 hours, the system for the treatment of stops heating when being chilled to 45 ℃, add 0.08 gram ammonium iodide, speed with 3 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia then, system temperature is fallen after rising, the logical ammonia of insulation and continuation when reducing to 45 ℃, stopped reaction when ammonolysis reaction proceeds to 5 hours.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 184 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 67.7 gram hexamethl disilamines, productive rate is 70.1%.
Filter cake obtains 28.4 gram hexamethyldisiloxanes through handling with embodiment 1 same procedure.
Embodiment 3:
Get 226.5 gram hexamethyldisiloxanes (1.4 moles), put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger 28.4 gram Vanadium Pentoxide in FLAKES (0.2 mole) and 120 gram boiling ranges are 60～90 ℃ sherwood oil, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 80 ℃ of reactions 30 hours, the system for the treatment of stops heating when being chilled to 35 ℃, add 0.1 gram ammonium iodide, speed with 2 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia then, system temperature is fallen after rising, the logical ammonia of insulation and continuation when reducing to 35 ℃, stopped reaction when ammonolysis reaction proceeds to 9 hours.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, steams the solvent sherwood oil earlier, collects 98～101 ℃ of cuts then, obtains 87 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 65.5 gram hexamethl disilamines, productive rate is 67.8%.
Filter cake is told organic phase with after the 120 ml distilled waters dissolvings, and water is respectively 60～90 ℃ petroleum ether extraction 3 times with 30 milliliters of boiling ranges, organic phase and extraction liquid merge, with Calcium Chloride Powder Anhydrous rectifying after dry 8 hours, collect 98～101 ℃ of cuts, obtain 27 gram hexamethyldisiloxanes.
Embodiment 4:
Get 162 gram hexamethyldisiloxanes (1 mole), 28.4 gram Vanadium Pentoxide in FLAKESs (0.2 mole) and 162 gram dimethylbenzene are put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 100 ℃ of reactions 16 hours.The system for the treatment of stops heating when being chilled to 80 ℃, add 0.8 gram weight concentration and be the N of 5% ammonium iodide, dinethylformamide solution, the speed with 2 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia, stopped reaction when ammonolysis reaction proceeds to 4 hours then.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 37.4 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 61.8 gram hexamethl disilamines, productive rate is 63.4%.
Filter cake is told organic phase after dissolving with 150 ml distilled waters, and water is used 30 milliliters of xylene extraction 3 times respectively, and organic phase and extraction liquid merge, and with Calcium Chloride Powder Anhydrous rectifying after dry 8 hours, collects 98～101 ℃ of cuts, obtains 18.7 gram hexamethyldisiloxanes.
Embodiment 5:
Get 324 gram hexamethyldisiloxanes (2 moles) and 28.4 and restrain Vanadium Pentoxide in FLAKESs (0.2 mole) and put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 90 ℃ of reactions 24 hours.The system for the treatment of stops heating when being chilled to 60 ℃, add 0.05 gram potassiumiodide, and the speed with 3 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia, stopped reaction when ammonolysis reaction proceeds to 5 hours then.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 180 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 64 gram hexamethl disilamines, productive rate is 65.8%.
Filter cake obtains 30.1 gram hexamethyldisiloxanes through handling with embodiment 1 same procedure.
Embodiment 6:
Get 364.5 gram hexamethyldisiloxanes (2.25 moles) and 21.3 and restrain Vanadium Pentoxide in FLAKESs (0.15 mole) and put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 100 ℃, react after 16 hours and to add the dimethyl sulphoxide solution that 2.3 gram weight concentration are 5% brometo de amonio, speed with 2 milliliters/second feeds equably through potassium hydroxide drying tower exsiccant ammonia, stopped reaction when ammonolysis reaction proceeds to 3.5 hours then.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 252 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 48.3 gram hexamethl disilamines, productive rate is 66%.
Filter cake obtains 25 gram hexamethyldisiloxanes through handling with embodiment 1 same procedure.
The comparative example
Catalysts is separated in not ammonification in the present embodiment, directly feeds ammonia after the esterification and carries out ammonia and separate.
Get 324 gram hexamethyldisiloxanes (2 moles) and 28.4 and restrain Vanadium Pentoxide in FLAKESs (0.2 mole) and put into 500 milliliters of round-bottomed flasks that have electric mixer, reflux exchanger, connect a sodium hydroxide drying tube on the condenser and communicate with atmosphere.Be heated to 100 ℃ of reactions 16 hours.Treat that the speed that system temperature is reduced to after 60 ℃ directly with 3 milliliters/second feeds through potassium hydroxide drying tower exsiccant ammonia, system temperature is fallen after rising, insulation and continue logical ammonia after reducing to 60 ℃, and ammonolysis reaction reaches 5 hours stopped reaction.Be chilled to room temperature, suction filtration moves into filtrate 500 milliliters of round-bottomed flasks and carries out atmospheric distillation, collects 98～101 ℃ of cuts, obtains 202 gram hexamethyldisiloxanes; Collect 124～126 ℃ of cuts, obtain 31.3 gram hexamethl disilamines, productive rate is 34.2%.
Filter cake obtains 35 gram hexamethyldisiloxanes after handling with embodiment 1 same procedure.
Claims (1)
1. one kind prepares the method for hexamethl disilamine by hexamethyldisiloxane, it is characterized in that this anti-method comprises following each step:
(1) makes the reaction of hexamethyldisiloxane and Vanadium Pentoxide in FLAKES, and the adding liquid organic compound is made solvent, solvent is sherwood oil or dimethylbenzene, wherein the mol ratio of Vanadium Pentoxide in FLAKES and hexamethyldisiloxane is 1: 4～20, the water content of hexamethyldisiloxane is smaller or equal to 200ppm, the weight ratio of hexamethyldisiloxane and solvent is 1: 0～1.5, and temperature of reaction is 50～100 ℃, and the reaction times is 10～50 hours;
(2) add halogenide in the system after above-mentioned reaction finishes as the ammonolysis reaction catalyzer, halogenide is the compound of monovalence bromine or monovalence iodine, directly with pressed powder or to be mixed with weight concentration be to add after 5% the organic solution, the solvent of preparation organic solution is the non-proton polar organic compound of methyl-sulphoxide or dimethyl formamide, and halid add-on is 0.05～0.5% of a Vanadium Pentoxide in FLAKES weight:
(3) feed ammonia in the above-mentioned system that contains catalyzer and carry out ammonolysis reaction, ammonia dewaters through super-dry before feeding system, and the feeding speed of ammonia is 1～10 milliliters/second, and temperature of reaction is 30～100 ℃, and the reaction times is 2～12 hours;
(4) with suction filtration or press filtration method with solid and liquid separation in above-mentioned steps (3) product;
(5) liquid portion with step (4) carries out atmospheric distillation, collects 124～126 ℃ of cuts, is hexamethl disilamine of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107494A CN1092200C (en) | 2000-05-19 | 2000-05-19 | Preparation of hexamethl disilamine from hexamethyl disiloxane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107494A CN1092200C (en) | 2000-05-19 | 2000-05-19 | Preparation of hexamethl disilamine from hexamethyl disiloxane |
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| CN1092200C CN1092200C (en) | 2002-10-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237601A (en) * | 2014-06-30 | 2016-01-13 | 上虞新和成生物化工有限公司 | Synthetic method for 5-methyluridine |
| CN108017038A (en) * | 2016-10-28 | 2018-05-11 | 中昊晨光化工研究院有限公司 | One kind removes F22The method of fluorine ion in by-product hydrochloric acid |
| CN114805422A (en) * | 2022-05-17 | 2022-07-29 | 山东博苑医药化学股份有限公司 | Method for recovering silicon ether from alkylamine kettle residue |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3013920C2 (en) * | 1980-04-11 | 1986-03-27 | Bayer Ag, 5090 Leverkusen | Process for the preparation of triorganomonochlorosilane |
| JP3593367B2 (en) * | 1994-09-21 | 2004-11-24 | 三菱レイヨン株式会社 | Carbon fiber reinforced thermosetting resin prepreg |
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2000
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237601A (en) * | 2014-06-30 | 2016-01-13 | 上虞新和成生物化工有限公司 | Synthetic method for 5-methyluridine |
| CN105237601B (en) * | 2014-06-30 | 2018-05-15 | 上虞新和成生物化工有限公司 | A kind of synthetic method of 5-methyl-uridin |
| CN108017038A (en) * | 2016-10-28 | 2018-05-11 | 中昊晨光化工研究院有限公司 | One kind removes F22The method of fluorine ion in by-product hydrochloric acid |
| CN114805422A (en) * | 2022-05-17 | 2022-07-29 | 山东博苑医药化学股份有限公司 | Method for recovering silicon ether from alkylamine kettle residue |
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| CN1092200C (en) | 2002-10-09 |
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