• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1496310 Alkyl halides produced from organohalosilanes and alkanols WACKER-CHEMIE GmbH 11 May 1976 [15 May 1975] 19363/76 Heading C2C [Also in Division C3] A process for the manufacture of an organosiloxane and an alkyl halide comprises passing an organohalogenosilane having one or two halogen atoms into a reaction bed of inert packing material maintained at a temperature of from 60‹ to 150‹ C. causing it there to react with methanol or ethanol to produce an alkyl halide and a mixture comprising water and an organosiloxane, causing the said mixture to issue from the reaction bed and separating it into an aqueous phase and an organosiloxane phase, returning a part of the aqueous phase to the reaction bed such that the amount of the aqueous phase returned is from 1-6 litres per mole of the organohalogenosilane initially passed into the reaction bed, and causing the organosiloxane phase to react with an additional 2-10% wt. of the organohalogenosilane based on the organosiloxane phase, and separating the organosiloxane produced. The organohalogenosilane is preferably one of the formulµ R m H n SiX 4-m-n and R 2 XSi-R<SP>1</SP>-SiXR 2 where X is Cl, Br or I, R denotes an unsubstituted or substituted monovalent hydrocarbon radical, R<SP>1</SP> denotes an unsubstituted or substituted bivalent hydrocarbon radical, m is 1-3, n is 0 or 1 and m+n is 2 or 3. The preferred organohalosilane is dimethyldichlorosilane. The organohalosilane having 1 or 2 halogen atoms may be used in admixture with up to 10% wt. of one or more other halosilanes, e.g. SiCl 4 or methyltrichlorosilane. The alkanol may be passed into the reaction bed or may be manufactured in situ, e.g. by the hydrolysis of a carboxylic acid ester of 2-4 C atoms, e.g. methyl acetate. Suitable packing materials are of ceramics or carbon, sintered powder of polyolefins and silica Xerogels. The reaction bed may also contain Lewis acids and cation-exchangers in the H form. The reaction is preferably carried out at atmospheric pressure. The organohalosilane and alkanol may be fed to the reaction bed co- or counter-currently. Part of the aqueous phase not returned to the reaction bed may be distilled and the alkanol obtained recycled. The alkyl halide may be removed from the top of the reaction tower, if used. The organosiloxane produced may be subjected to steam distillation and any undesired organosiloxane returned to the reactiod bed. The process is preferably carried out continuously. In a preferred continuous process liquid dimethyldichlorosilane is fed through pipes 1 and 1α to evaporator 2 and the resultant vapour passed via pipe 3 into heat reaction tower 4 filled with packing material. Liquid CH 3 OH flows through pipe 6 from inlet pipe 11 into tower 4. Gaseous unreacted CH 3 OH and CH 3 Cl passes out of tower 4 into condenser 7 and the condensed CH 3 OH runs back into tower 4 via pipe 8, and the CH 3 Cl passes into wash tower 10 where it is washed with CH 3 OH and then passes out of tower 10 to a condenser via pipe 12. Material issuing from the lower end of tower 4 is separated into an upper polydimethylsiloxane layer and lower aqueous layer consisting of water, HCl and CH 3 OH. Part of the lower layer is returned via pipes 14 and 16 to tower 4. The rest is conveyed to distillation device 28 and the gaseous methanol issuing from the top of device 28 is condensed in condenser 30 and part of it returned to methanol supply line 11. The upper organosiloxane layer in vessel 13 is mixed in pipe 17 with additional dimethyldichlorosilane brought via pipe 1b and passes into mixing vessel 18 and thence into distillation device 23 where the low boiling point fractions are separated and returned to tower 4 via pipe 34 after separation from the aqueous phase. The linear dimethylpolysiloxanes which are OH- terminated and which are substantially free from alkoxy groups and may have viscosities ranging from 70-200 cS at 25‹ C. are drawn off through pipe 33.
    公开号:SU753362A3
    申请号:SU762353456
    申请日:1976-04-26
    公开日:1980-07-30
    发明作者:Шперк Хельмут；Штрассер Рудольф；Ридле Рудольф；Яквюс Вольфганг；Ваас Иоханн
    申请人:Вакер Хеми Гмбх (Фирма)；
    IPC主号:
    专利说明:

    organo-halosilane, taken in an amount of 2-10% by weight, based on the mixture, at a temperature that organopolysiloxanes have after they are separated from the water-alcohol phase. The process is carried out when recirculating the hydroalcoholic phase into a packed column in an amount of 1-6 l per every mole of organohalogenesilane introduced into the column.
    The distinctive features of the method include the treatment of a mixture of organopolysiloxanes with the original organohalogenesilane. The process of recycling the water-alcohol phase to the packed column in the amount of 1-6 liters per mole of organohalogenesilane introduced into the column.
    The described method allows to increase the productivity of the process and the quality of the target products.
    For example, for 1 hour in a device similar to the well-known, 31 liters of dimethyldichlorosilane and 19.1 liters of methanol can be consumed and 10.9 m of methyl chloride containing only 1.7% of di-alkyl ether is isolated
    In the packed column used, the packing must be inert under the reaction conditions, especially acid-resistant. Examples of suitable nozzles are ceramics-based or carbon-based nozzles as Raschig rings, and protrusions rings made from ceramics and graphite moldings, such as graphite rings. Other examples of nozzles used are sintered powders of polyolefins and / or other acid-resistant plastics, as well as silica xerogels.
    The use of substances that intensively promote the interaction of alkanols with organohalogenosilanes with the formation of organosiloxanes and alkyl halides as Lewis acids, for example zinc chloride or sulfuric acid, is not excluded. The use of substances that promote this interaction as cation-exchangers in the H-form is also not excluded. The use of such substances is not preferable, since such substances can also contribute to the breaking of Si-C bonds.
    Mixtures of different attachments can also be used. A suitable amount of packing is at least 50% by volume of the total volume of reaction components and reaction products in contact with the packing. The length of the layer (s) of the packing is at least 30 cm / l of the total amount of organohalogenosilane and alkanol passed through the layer (s) of the packing. In height, the length of the layer (s) of the packing is not limited.
    Preferably, the layers of the nozzles are maintained at 70-120 C.
    temperatures below the interaction of organohalogenosilanes with alkanols with the formation of organopolysiloxanes and alkyl halides proceeds undesirably slowly. At temperatures above 150 ° C, the quality of the organosiloxanes may deteriorate, for example, due to the rupture of S i-C-const.
    The aqueous phase, separated from the orOp of ganopolisiloxane that leaves the layer (s) and returned back to the column in an amount of 1-6 liters per mole of the organohalogenesilane introduced into the layer (s), is at least 70% by weight of water and hydrogen halide, most often hydrogen chloride, with the amount of hydrogen chloride being most often 21-26 wt.% with respect to the total amount of water and hydrogen chloride.
    0 According to a preferred embodiment of the method, 1-6 l / mol of an organohalogenesilane packing introduced into the layer (s), an aqueous phase separated from the exiting layer or
    5 layers of the nozzle of organopolysiloxane, directly returned to the layer (s) of the nozzle, did not remove previously an integral part of this aqueous phase, for example alkanol.
    Q Due to the return, according to the invention, of 1-6 l / mol of the aqueous phase introduced into the layer or layers of the nozzle of an organohalogenesilane separated from the nozzle of an organo siloxane, leaving the layer (s) with 1–1.75 mol of alkanol a halogen atom in the silane introduced into the reactor, in the layer (s) of the packing, in addition to the alkanol contained in the recovered aqueous phase, the alkanol in the layer or packing layers
    0 is in a concentration of 7-50 wt.%, Preferably 20-30 wt.% With respect to the total weight of alkanol, water and hydrogen halide.
    The layer or layers of the nozzle are
    5 in the tubular space of the reactor, which is preferably located vertically, therefore it is a column reactor, but it can also be located horizontally
    Q or tilt. If a column reactor is used as the reactor, the alcohol is preferably introduced above the site of introduction of the organohalogenosilane into the column reactor and the organosiloxane is withdrawn from the bottom of the column or at least from the bottom third of the column. Preferably, the site of introduction of the organohalogenesilane is at least 20 cm away from the site of introduction of the alkanol.
    0 The described method is preferably carried out under a pressure of about atmospheric, therefore, at 760 mm Hg. or at about 760 mmHg. (abs) because
    5 this flow-resistant material is less. However, the process can also be carried out at elevated or reduced pressures. Preferably, the pressure and temperature are chosen so that the water present in the nozzle layer (s) and the water supplied to the nozzle layer (s) is in the liquid phase, Organohalogenesilane and alkanol can be introduced directly or countercurrently in counterflow. Excess alkanol, which separates the organopolysiloxane leaving the layer of the packing and does not enter the aqueous phase returning to the packing layer (s) of the packing, can be reintroduced into the reactor after separation from the aqueous phase. In addition to organopolysiloxanes and alkyl halides, only small amounts of aqueous hydrohalic acid are formed in the process described, dialkyl esters are present in insignificant amounts. The yield of organopolysiloxanes is almost quantitative. The yield of alkyl halide is above 93% of theory. The organopolysiloxanes obtained according to the process of the present invention can be linear and / or cyclic. If linear organopolysiloxanes are desired, cyclic organopolysiloxanes, after separation from the nozzle from the layer (s) of the packing and the organopolysiloxane mixture separated from the aqueous phase, should be returned to the packing (s) of the packing. If cyclic organopolysiloxanes are desired, then linear organopolysiloxanes, after separation from the nozzle coming out of the layer (s) and the mixture of organopolysilok sans separated from the aqueous phase, will again be returned to the nozzle layer (s). If, as an example, for a preferred embodiment of the method, at least one layer of the packing is maintained at 100 ° C at a pressure of 760 mm Hg. and dimethyldichlorosilane is used as organohalogenesilane and methanol as alkanol. Moreover, there is always excess methanol in contact with the packing, while dimethyldichlorosilane is introduced into the packing layer (s), then after separation of the cyclic dimethylpolysiloxane, hydrogen chloride and methyl chloride, linear dimethylpolysiloxide with viscosity from 70 to 200 cP at 25 ° C is obtained. The viscosity of dimethylpolysiloxane is quite low, so that transportation by means of a pump is carried out without any difficulties. On the other hand, it is quite high, so dimethylpolysiloxane can be processed directly with conventional condensation catalysts, like phosphorus nityl chlorides, into high molecular weight dimethylpolysiloxanes suitable for producing elastomers, without the need or expediency of precondensation before this further processing. In addition to the hydrogen halide introduced into the packing layer (s) along with the returned aqueous phase, hydrogen halide of the same type as the hydrogen halide that is in the aqueous phase returned to the layer (layers) can be introduced into the packing layer (s) of the packing. ) nozzles. Due to this measure, a further alkyl halide is formed and it is even realized that it is difficult to use the Hydrogen Hydrogen Halide. The preferred embodiment of the proposed method is illustrated in the attached diagram. Pipeline 1 provides liquid dimethyldichlorosilane to evaporator 2. The evaporated dimethyldichlorosilane via line 3 enters the column reactor 4, the column reactor 4 is filled with a nozzle and heated by a circulation evaporator 5. Liquid line methanol is fed through line 6 to the column reactor 4. The vaporous unreacted methanol, together with the 4 methylene chloride formed in the column reactor, flows from the upper part of the column to the condenser 7. Condensed methanol through line 8 returns to the column reactor. The uncondensed methanol, as well as methyl chloride, through conduit 9 enters the scrubber 10, where methyl chloride is washed with fresh methanol from conduit 11. The washed methyl chloride from the scrubber 10 through conduit 12 is fed to a condensation unit. The product leaving the lower part of the column reactor 4, B, the separator 13 is divided into an upper layer, which consists mainly of dimethyl polysiloxane, and a lower layer, which represents the iodine phase, consisting mainly of water, hydrogen chloride and methanol. The part of the lower layer, which is formed in the blower 13, through the adjustable height controller layers at the interface 14 through the pipeline 15 through the pump 16 and through the pipeline 17 enters the distiller 18. The distillation residue obtained in the distiller 18 consists mainly out of 20% by weight of aqueous hydrochloric acid and discharged through conduit 19. Methanol leaving the upper part of the distiller 18 goes through conduit 20 to condenser 21. Part of the methanol condensed in condenser 21 of methanol via conduit 22 again goes to Distillo 18. The residue of the condensed methanol condenser 8 through line 23 is combined with fresh methanol in line 11 and fed to the scrubber 10, from which it is fed back to the column reactor 4 again. The remainder of the bottom layer, which is formed in separator 13, through the pipeline 24 by pumping-som 25 and through pipeline 26 is supplied to the upper part of the column reactor in the bed (s) of the packing. The top layer, which is formed in the separator 13, through the pipeline 27 together with the dosing pump 29 supplied from the pipeline 28 and the dimethyl dichlorosilane via the pipeline 30 is fed to the mixer 31. The interaction obtained according to the invention is thus also by pumping dimethyl polysiloxane mixed with dimethyl dichlorosilane with by means of pump 32, pipeline 33 is fed to distiller 34. In this distiller, by means of extractive distillation with water vapor at a temperature of 112 ° C, the introduction of which into the distiller 34 is not shown, low boiling dimethyl polysiloxane, therefore, mainly under cyclic dimethyl polysiloxane. Hydrogen chloride (approximately 30 g / L of dimethylpolysiloxane and conduit 33). Methylene chloride and also methanol are separated from nonvolatile, linear dimethylpolysilox. Non-volatile linear dimethylpolysiloxane is withdrawn from the distiller via conduit 35. Cyclic dimethylpolysiloxane after it is separated from the aqueous phase in a separator (not tested) via conduit 36 returns to the column reactor 4. Example 1: As a column reactor 4 are 12 sets perpendicular to each other and flanged connections connected to each other through intermediate parts with a length of 400 mm and a conditional passage of 300 mm, see the circumstances of glass tubes of 1000 mm length, which have a conditional passage of 300 m and filled with ceramic rings, broadened by 3.81 cm, fitted with hook-shaped protrusions that are held on perforated carbon plates. This nozzle goes on sale under the appointment Novalox. In the intermediate parts, there is no nozzle. The total height of the column is 14,500 mm. Pipeline 6, which is connected to column reactor 4 is 6000 mm above its lower end, the column is filled with liquid methanol from line 11. Liquid methanol is supplied through line 6 until methanol is circulated through pipelines 24 and 26 as through the separator 13 in the form of a stream of equal force. Then, through line 1, liquid dimethyldichlorosilane is fed to the evaporator 2. Evaporated dimethyldichlorosilane through line 3, which is connected to column reactor 4 1,500 mm above its lower end, is fed into column reactor 4. As soon as dimethyldichlorosilane enters column reactor 4, a supply of methanol from a pipe b 1 mol of methanol per immole dimethyldichlorosilane from pipe hydrogen is set. , and the contents of the column are heated by means of a steam-heated circulation evaporator 5 made of glass up to 10.0s. As soon as the temperature reaches 100 ° C, the flow of methanol from line 6 rises at the rate of 2 moles of methanol per mole of dimethyldichlorosilane from line 3. Vaporous, unreacted methanol together with methyl chloride / formed in the column reactor 30 minutes after the start of the addition of dimethyldichlorosilane, from the top columns to condenser 7. Condensed methanol through conduit 8 returns to the column reactor. The uncondensed methanol, like methyl chloride, is fed through conduit 9 to scrubber 10, where methyl chloride is washed countercurrently. The scrubber 10 consists of a perpendicularly located, 2000mm high tube with a nominal passage of 150 mm. The tube is filled with the same nozzle that is in the column reactor 4, and is equipped with a reflux condenser operating with a temperature of approximately 12 ° C. Pipeline 9 is attached to the scrubber 10 400 mm above its lower end. Methyl chloride, washed with methanol from line II and 23, from scrubber 10 through line 12 enters the condenser. The product leaving the bottom of the column reactor 4 enters separator 13, which consists of a perpendicular length of 900 mm tube with a nominal passage of 300 mm, through a pipeline connected to separator 13 at a distance of 600 mm above its lower end. In the separator 13 product, the exit from the lower part of the column reactor is divided into an upper layer, which consists mainly of dimethyl polysiloxane, and a lower layer, which is an aqueous phase. 1000 l / h of the lower layer, which is formed in the separator 13, through the pipeline 24 by the centrifugal pump 25 and through the pipeline 26 at a distance of 500 mm below the upper end of the column 4 the reactor returns to the layers with a nozzle, so that in these layers the methanol is at a concentration of 25% relative to the total weight of water, methanol and chlorine, then hydrogen. The rest of the lower layer, which is formed in the separator 13, through an adjustable height controller layers at the interface 14 through line 15 by pump 16 and through line 17 is introduced into the distiller 18 at a distance of approximately 1200 m above its lower end. The distiller 18 consists of 5 located perpendicularly to each other and flanged connections connected to each other in detail, glass tubes 1000 mm long, which are filled with Jntagox supports extended by 1.27 cm and has a total height of 5300 mm. Vaporous methanol coming from the top of the distiller 18 comes through the conduit 20 to the condenser 21. 80% by weight of methanol condensed in the condenser 21 through pipe 22 enters the distiller 18 again. 20% by weight of the methanol condensed 21 comes in tr 23. boprovod CIRCL l-insulating relationship with the distillation of methanol is 1: 4. The residue after distillation through line 19 is removed from the bottom of the distiller 1B. The methanol of conduit 23 is combined with fresh methanol in conduit 13 and enters the scrubber 1 from which it again enters the column reactor 4 through conduit 4. The upper layer, which is formed in separator 13, through conduit 2 which starts 850 mm above the lower the end of the separator 1.3, together with dimethyldichlorosilane supplied from the pipeline 28 by the dosing pump 29 and through the pipeline 30 In the amount of 3.9% relative to the weight of dimeti through the pipeline 27 Balance after 744 hours slave Reaction components dimethyldichlorosilane ny), methanol (liquid): -. a molar ratio of (CH), 1.88 olisiloksana is supplied to the mixer 1, whose volume was 18 liters. The product of the interaction, obtained in this way and by pumping using the center of a 3-stage pump 32 mixed with dimethyldichlorosilane and methyl polysiloxane, goes through pipeline 3 to the distiller 34. In this istiltor, the extractive steam is pumped from 112C, the input to the distiller 34 is not Diethylpolysiloxane, hydrogen chloride, methylated methyl, and also methanol are shown to be non-volatile linear dimethylpolysiloxane shown. The desired, non-volatile linear dimethylpolysiloxane is removed from conduit 35 via conduit 35. The cyclic dimethylpolysiloxanes, after they are separated from the aqueous phase in a separator (not shown), are returned via conduit 36 to column reactor 4 at a distance of 7000 mm above its lower end. . After the reaction reaches a constant flow from pipeline 1 to pipeline 28 and evaporator 2, a total of 31.0 liters of dimethyldichlorosilane per hour flows, from pipeline 1 to the evaporator 2 and column reactor 4 receives 29.3 liters of dimethyldichlorosilane per hour. From pipe 28 to h. 1.7 l of dimethyldichlorosilane is fed through pump 29 via conduit 30. 20 b of methanol is supplied via conduit b to column reactor 4. Scrabber 10 is supplied with 9.2 l of fresh methanol, which is fed into pipeline 11, and 0.8 l of reverse methanol from the pipeline 23. The pipeline 36 hours per column re actor 4 returns 27.72 kg of cyclic organopolysiloxanes. 18.78 kg of the dimethylpolysiloxane dimethylpolysiloxane containing one Si-bonded hydroxyl group with a viscosity of 120 cP at 25 ° C less than 1 mg of hydrogen chloride and at most one Si-bonded methoxy group per 350 are obtained from the pipeline 22 per hour. Si-bonded hydroxyl groups, which, after heating for 2 hours at 250 ° C, has a weight reduction of 0.25%. From conduit 12, 10.9 m of methyl chloride is obtained, which contains less than 1 mg of hydrogen chloride per kg and only 1.7% of dimethyl ether. per mole l kg 23064 24447 189.5 14285 11428
    Balance after .744 hours of work: Dioxymethylpolysiloxane reaction products
    Output 98% of theory.
    Methylene chloride in 1000 l (gaseous)
    The output of 93.2% of theory. Comparative Experience For a comparison with the known method, the method described in the present example is repeated with the change in that the pipes 28, 24, 26, 30, as well as the pumps 25 and 29 do not work, therefore, in the case of nozzles it does not return no aqueous phase, separated from the organosilox, coming out of the nozzle layer, and also separated from the aqueous phase, organopolysiloxane is not reacted with organohalogenosilanes. Dashoy, unlike the present example, the layers of the junction are maintained at a temperature not at b5-68® C, since without returning the nozzle to the layer separated from the aqueous phase leaving the layers of the organopolysiloxane cannot maintain a high temperature without using pressure and without a device suitable for applying pressure. Per hour Can interact with just 10 liters of dimethyldichlorosilane and 7.2 liters of methanol. From a pipeline 35 per hour, only b kg of one containing Si-bonded hydrostrong group of dimethylpolysiloxane with a viscosity of 50-60 centipoise at 25 s and at least two S i-associated methoxy groups per 100 Si-sv from the hydroxyl groups and from the pipeline 12 per hour only 3 are obtained, methyl chloride, which contains 3.2% dimethyl ether. Example 2. A 1 liter glass flask equipped with a stirring device and connected to a 24 mm inner diameter glass tube located on a flask and 1.5 m high, which is filled with Raschig rings 3x3 mm in size, is used as a reaction vessel. At the head of the column there is a reflux condenser, taken up with water at a temperature of approximately, which is connected to a scrubber, an organic solution of sodium hydroxide, as well as from a device.
    185.8 per (CHT), jSiO.
    8109 17840
    353.3 A solution for the condensation of ethyl chloride, namely with a device in which a low temperature is maintained by cooling with frozen carbon dioxide (dry ice) in ethyl alcohol. In a glass flask, the mixture consisting of 50% water, 20% HC1 and 30% ethanol is heated at the boiling point with stirring so that the temperature in this flask and in the glass tube on it is set to approximately. A pipeline, located 500 mm above the lower end of the glass tube located on the flask and entering this tube, is fed 260 g of dimethyldichlorosilane to the nozzle layer for 2 hours. 185 g of ethanol is fed into the nozzle layer through 2 piping entering the glass tube and located 1000 mm above the lower end of this tube. Through a lateral overflow device from a glass flask, used as part of the reaction vessel, a mixture consisting mainly of water, ethyl alcohol, HC and dimethylpolysiloxane enters the separation vessel. From the aqueous phase, which consists essentially of water, ethyl alcohol and NSW, which forms in the separation vessel as a lower layer, within 2 hours, 5000 ml is returned through a nozzle layer 70 mm below the reflux condenser. 146 g (97.9% of the theoretically calculated value) of dimethylpolysiloxane with a viscosity of 5.5 centipoise at a temperature of 25 ° C are obtained, which is immediately mixed with 10 g of dimethylchlorosilane and heated for 10 minutes at a temperature. In a device for the condensation of ethyl chloride, 196.2 g of 96.3% ethyl chloride are obtained (75.4% of the theoretically calculated
    cheni), which contains 2.4% diethyl ether.
    Example 3. In a glass flask, also designed as in Example 2, is heated at reflux to a 50% water level, 20% NSB and 30% ethanol, and through a pipeline entering the glass tube located on the flask and being 1000 mm above the lower end of this tube, 185 g of ethanol is fed into the nozzle layer for 2 hours. A pipeline located 500 mm above the lower end of the glass tube on the flask and entering this tube is fed 320 g of diethyl dichlorosilane to the nozzle layer for 2 hours.
    From the aqueous phase, which is formed in the separation vessel in the form of a 20 lower layer, for 2 hours through the nozzle layer, located 70 mm below the reflux condenser, return. Schi 5000 ml.
    187.5 g (92.5% of the theoretically calculated value) of diethyl polysiloxane are obtained, which is then immediately mixed with 15 g of diethyl dichlorosilane and heated at 30–60 ° C for 10 minutes.
    In a device for the condensation of ethyl chloride, 185 g of 94% ethyl chloride are obtained (68.3% of the theoretically calculated value), which contains 2.8% diethyl ether.
    Example 4. Prior 1 is repeated with the following changes. Q
     The return of the cyclic organosiloxane via line 36 to reaction tower 4 is interrupted. Instead, cyclic organosiloxane is released, according to a drawing not shown, from pipe 36. The methanol recovery through pipelines 15, 17, 20, 22 and 23 is equally turned off by pump 16, distillation apparatus 18 and refrigerator 21. Outlet 19 is directly connected to the controller of the height of the interface 14.
    After reaching a stable reaction course from pipeline 1, a total of 31 liters of dimethyldichlorosilane per hour, 30, 3 l / hour of dimethyldichlorosilane goes to evaporator 2 to pipeline 28 and evaporator 2. From pipe 28 every hour by pump 29 to pipeline 30 from 60 leads 0.7 liters (2 wt.% Calculated on organosiloxane) of dimethyldichlorosilane; through the scrubber 10 and line 6, 20 liters of methanol are partly sent to the reaction tower. Out of separation-- 65
    torus 13 via pipelines 24 and 26 by pump 25 returns 1,500 l / h to the reaction tower (about 6 l / mol of the hydroalcoholic phase separated from the organosiloxane.
    11.27 kg of cyclic organopolysiloxane is supplied from pipe 36 every hour. From the pipeline 35, every hour, 7.51 kg of dimethylpolysiloxane is contained, containing at the ends of the molecules one hydroxyl group bound to silicon, with a viscosity of 120 mm / sec, containing less than 1 mg of hydrogen chloride and maximally one methoxyl group bound to silicon. 350 silicon bound hydroxyl groups, after 2 hours of exposure, with the weight decreasing by 0.25%. The content of organopolysiloxanes from pipeline 36 contains less than 1 mg of hydrogen chloride to a maximum of 8% of chain-forming fractions, a density of 0.979, an octamethylcyclotetrasiloxane content of 50%, a decamethylcyclopentasiloxane of 40%, and a residue with cyclic siloxanes with 3,6,7 and 8 dimethyl siloxane units. Pipeline 12 supplies 10.9 methyl chloride containing less than 1 mg of hydrogen chloride / kg and only 1.7% dimethylether.
    Example 5. Example 4 is repeated with the following changes.
    Pipeline 1 sends hourly 27.0 liters of dimethyldichlorosilane to reaction tower 4, through evaporator 2, 28 4.0 liters / h (about 10 wt.%, Calculated on organosiloxane) dimethyldichlorosilane through the pipeline, the latter is fed into the tower by pump 29 to pipeline 30.
    Instead of 1500 l / h of the water-alkanol phase, only 235 l / h (about 1 l / mol per dimethyldichlorosilane) are returned to the reaction tower. Supply is provided by pump 25 through lines 24 and 26.
    Results for the product are comparable to those in Example 4.
    权利要求:
    Claims (2)
    [1]
     1. Andrianov K.A., Khananashvili L.M. Technologists of organoelement monomers and polymers, M., Himi, 1973, p.146.
    [2]
    2. US patent 3803195, cl. 260-448.2, pub. 1974 (prototype).
    if
    ie
    类似技术:
    公开号 | 公开日 | 专利标题
    SU753362A3|1980-07-30|Method of preparing organopolysiloxanes and alkyl halides
    US4298753A|1981-11-03|Continuous process for preparing silanes and siloxanes having SiOC groups
    US2832794A|1958-04-29|Hydrolysis of organosilanes
    US7514518B2|2009-04-07|Process for continuously preparing low-alkoxy silicone resins
    US4609752A|1986-09-02|Process and apparatus for continuously synthesizing alkoxypolysiloxanes
    JPH07216088A|1995-08-15|Silicone resin and its preparation
    US3803195A|1974-04-09|Process for the production of organosiloxanes
    CN100357298C|2007-12-26|Continuous hydrolysis process of organic dichlorosilane
    JP2006206589A|2006-08-10|METHOD FOR CONTINUOUSLY PRODUCING SiOC-CONTAINING COMPOUND
    US5527935A|1996-06-18|Organopolysiloxanes having bifunctional terminal siloxane units
    JP3802587B2|2006-07-26|Improved siloxane cracking process
    US20050113591A1|2005-05-26|Process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorsilanes
    CA1121369A|1982-04-06|Hydrocarbonoxy polysiloxanes prepared by continuousreflux process
    JP2778258B2|1998-07-23|Method for producing partially alkoxylated polysiloxane
    US4366324A|1982-12-28|Process for concurrent preparation of organosiloxanes and methyl chloride
    CN106749383A|2017-05-31|A kind of production technology of alkoxy silane
    KR20130109242A|2013-10-07|Continuous process for preparing sioc-containing compounds
    JP3356306B2|2002-12-16|Production method of organosiloxane
    JP2002508382A|2002-03-19|Production and apparatus of alkylmonohydrohalosilane by redistribution reaction and then distillation
    US4417067A|1983-11-22|Method of cleaving organosiloxanes
    US4060537A|1977-11-29|Preparation of organosiloxanes
    US4497942A|1985-02-05|Process for hydrolyzing chlorosilanes
    US4348532A|1982-09-07|Monoorganosiloxy containing siloxane fluids
    US4448981A|1984-05-15|Method of making organosiloxanes and alkyl halides from dialkyldialkoxysilanes
    RU2080323C1|1997-05-27|Process for preparing phenylethoxy silanes
    同族专利:
    公开号 | 公开日
    IT1061277B|1983-02-28|
    JPS5637997B2|1981-09-03|
    ES447918A1|1977-06-01|
    FR2311023B1|1980-10-24|
    AU503124B2|1979-08-23|
    DE2521742B2|1978-04-27|
    CA1050036A|1979-03-06|
    GB1496310A|1977-12-30|
    NL7604371A|1976-11-17|
    DE2521742A1|1976-11-25|
    FR2311023A1|1976-12-10|
    MX3232E|1980-08-04|
    BE841839A|1976-11-16|
    AU1393776A|1977-11-17|
    JPS51146424A|1976-12-16|
    US4032557A|1977-06-28|
    IN142758B|1977-08-27|
    DE2521742C3|1978-12-21|
    DD123473A5|1976-12-20|
    BR7602965A|1977-05-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE789272A|1971-09-29|1973-03-26|Wacker Chemie Gmbh|ORGANOSILOXANE PREPARATION PROCESS|DE2557624C3|1975-12-20|1979-05-03|Bayer Ag, 5090 Leverkusen|Process for the preparation of organosiloxanes|
    US4108882A|1977-10-27|1978-08-22|Dow Corning Corporation|Method of preparing methylsiloxanes and methylchloride|
    DE2806036A1|1978-02-14|1979-08-16|Wacker Chemie Gmbh|PROCESS FOR MANUFACTURING POLYSILOXANES WITH RESIDUAL CARBON RESIDUES BONDED TO SILICON OVER OXYGEN|
    BE885473A|1979-06-05|1981-01-16|Gen Electric|PROCESS FOR THE PREPARATION OF POLYDIMETHYLSILOXANES WITH METHOXY TERMINATIONS|
    JPS6328893B2|1980-11-25|1988-06-10|Shinetsu Chem Ind Co|
    US4329483A|1981-07-10|1982-05-11|Dow Corning Corporation|Preparation of cyclotetrasiloxanes aliphatic chlorides and acyl chlorides|
    US4395563A|1981-10-29|1983-07-26|General Electric Company|Hydrolysis of alkoxysilanes|
    DE3425067C1|1984-07-07|1986-01-23|Th. Goldschmidt Ag, 4300 Essen|Process and device for the continuous production of alkoxypolysiloxanes|
    DE3632875C2|1986-09-26|1988-08-11|Wacker-Chemie Gmbh, 8000 Muenchen, De|
    US5110972A|1991-07-18|1992-05-05|Tremco Incorporated|Process for recycling silicone scrap and products relating thereto|
    DE4124802A1|1991-07-26|1993-01-28|Bayer Ag|METHOD FOR PRODUCING ORGANOSILOXANES|
    DE4343033A1|1993-12-16|1995-06-29|Wacker Chemie Gmbh|Process for the preparation of polydimethylsiloxanes|
    US6316655B1|2001-02-20|2001-11-13|Dow Corning Corporation|Method of making hydroxy end-terminated linear siloxanes|
    DE102005032947A1|2005-07-14|2006-08-24|Wacker Chemie Ag|Procedure for processing mixtures comprising hydrochloric acid, water and siloxane, in the presence of fluorinated vinylpolymer fillers|
    DE102007023052A1|2007-05-16|2008-11-20|Wacker Chemie Ag|Process for the preparation of chloromethane with recycled hydrogen chloride|
    WO2010102139A2|2009-03-05|2010-09-10|Dow Global Technologies, Inc.|Methods and assemblies for liquid-phase reactions|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2521742A|DE2521742C3|1975-05-15|1975-05-15|Process for the preparation of organosiloxanes|
    [返回顶部]