CN101362774A - System and process for continuous industrial preparation of 3-glycidyl-oxypropylalkoxysilanes - Google Patents
System and process for continuous industrial preparation of 3-glycidyl-oxypropylalkoxysilanes Download PDFInfo
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Abstract
The invention relates to a device, a reactor and a method for continuously and industrially carrying out the following reactions, wherein allyl glycidyl ether A and His-compound B are reacted in the presence of a catalyst C and other optional addition agent, and the device is based on at least one multi-element reactor (5) at a reactant concentrating position (3) of components A(1) and B(2) at least, comprises at least two reactor units, that is a replaceable pre-reactor (5.1) and at least another reactor unit (5.3) connected with the pre-reactor, and is based on product post treatment (8).
Description
Technical field
The present invention relates to that continuous industryization prepares the new reactor and the device of 3-glycidyl oxygen base propyl group organoalkoxysilane by the reaction of glycidyl allyl ether and HSi-compound, and relevant therewith method.
Background technology
Organosilane, as vinyl chlorosilane or vinyl alkoxy silane (EP 0 456 901 A1, EP 0 806 427 A2), (DE-AS 28 15 316 for the chlorine alkyl chlorosilane, EP 0 519 181 A1, DE 195 34 853 A1, EP 0 823 434 A1, EP 1 020 473 A2), alkylalkoxy silane (EP 0 714 901 A1, DE 101 52 284 A1), fluoroalkyl organoalkoxysilane (EP 0 838467 A1, DE 103 01 997 A1), (DE-OS 27 53 124 for the aminoalkyl group organoalkoxysilane, EP 0 709 391 A2, EP 0 849 271 A2, EP 1 209 162 A2, EP 1 295 889 A2), glycidyl oxygen yl alkyl alkoxy silane (EP 1 070 721 A2, EP 0 934 947 A2), methacryloxy alkylalkoxy silane (EP 0 707 009 A1, EP 0 708 081 A2), polyoxyalkylene alkyl organoalkoxysilane (EP 0 387 689 A2), and other or the like, high technology and industrial requirement are arranged.Its preparation method and device are known already.These products are products of smaller tonnage, mainly prepare with interrupter method.Usually use reused device for this reason, thereby realize the high as far as possible load of intermittent type device.But, when replacement of products, must carry out the purification and the developing technique of trouble to such intermittent type device.Usually need the residence time of reaction mixture in the intermittent type device of large volume, costliness and individual propensities strong (personalintensiven) longer in addition, thereby reach enough productive rates.And described reaction usually is remarkable heat release, and reaction heat is 100～180kJ/mol.Therefore, when reaction, undesirable side reaction also can have a significant impact selectivity and productive rate.Described reaction is hydrosilylation, and therefore possible hydrogen separates higher to safety specifications.In addition, in the semibatch operation scheme, a kind of reactant adds with catalyzer, and is metered into another kind of reactant.In addition, less fluctuation also can cause productive rate to occur obvious deviation with quality product on different annexes (Ansatze) in the operational process of intermittence or semibatch device.If the result of laboratory/technology scale is transformed into intermittently scale (scale amplification), much difficulties then also occur.
The reactor of micro-structural itself for example is used for continuous production of polyether alcohols (DE 10 2,004 013551 A1) or synthetic especially ammonia, methyl alcohol, MTBE (WO 03/078052), is known.The microreactor that is used for catalyzed reaction also is known (WO 01/54807).But up to now, it is still blank that the microreactor technology is used for the preparation of industrialization organosilane, perhaps do not realize at least.At this, the tendency and corresponding the sticking in the organosilane preparation facilities of organoalkoxysilane and chlorosilane hydrolysis (under the small amount of moisture situation) may be regarded as persistent problem.
Summary of the invention
Therefore purpose is, for preparation of industrialization 3-glycidyl oxygen base propyl group organoalkoxysilane provides another kind of possibility.Particularly request provides and makes every effort to make the minimized another kind of possibility that is used for the such organosilane of preparation continuously of above-mentioned shortcoming.
According to the present invention, the purpose that is proposed is solved according to the explanation in claims.
Find surprisingly in the present invention, the composition B that contains HSi, hydrogen organoalkoxysilane particularly, hydrosilylation with glycidyl allyl ether (composition A), advantageously can be in the presence of catalyzer C, mode with simple and less expensive, carrying out in based on the device of multicomponent reactor (5) on the technical scale and continuously, wherein especially multicomponent reactor (5) comprises the reactor unit of at least two interchangeable pre-reactors (5.1) form and at least one and latter linked another reactor unit of described pre-reactor (5.3).
Therefore, in embodiments of the present invention, by using multicomponent reactor (5), can advantageously help to move continuously the inventive method, because multicomponent reactor of the present invention (5) can be changed pre-reactor on purpose, successively, wherein, after working time, isolate the hydrolysate of significant quantity, and new pre-reactor may be still under operational conditions.
Can use the Packed pre-reactor of outfit in particularly advantageous mode at this, thereby can more meet the point of destination with more effectively separate hydrolysate or-particle, therefore reduce because obstruction tendency that alluvial in the reactor and adhesion cause and the stoppage time of installing.
Different with the situation of batch charging, can also make reactant (Edukte) before described multicomponent reactor, directly carry out premix continuously in the present invention, premix can carry out by cold type in the case, next in the multicomponent reactor, heat, and there towards target and reaction continuously.Also can in reaction-ure mixture, add catalyzer.Next can carry out continuous aftertreatment to product, for example in evaporation, rectifying and/or in short distance or thin-film evaporator, only mention several possibilities.The reaction heat that discharges in reaction advantageously can deflect from heating agent through big surface and (if the stipulating in advance) with the proportional reactor wall of reactor volume in the multicomponent reactor.In addition, use under the multicomponent reactor situation, can obviously raise fast, the space-time yield of the reaction of heat effect in the present invention.This can be by than short mix reactant more under the interrupter method situation, the mean concns level that reactant is higher and realize that promptly be not subjected to the restriction that reactant lacks and/or temperature raises, this can play the extra effect of quickening of reaction that makes usually.In addition, the present invention can guarantee process safety fairly simple and economically.Therefore in the present invention, owing to higher transformation efficiency and selectivity make productive rate be increased to 20%, can realize significant process modification.Preferred of the present invention being reflected in the stainless steel multicomponent reactor carried out.Therefore in order to carry out described reaction, advantageously can omit and use special material (Sonderwerkstoffen).In addition,, can determine that the service hours of metal system reactor is longer, show more tired because described material is explained with respect to the intermittent operation mode by the continuously-running duty of the reaction under pressure, carried out.And repeatable during with respect to interrupter method for the comparable research be improved significantly.In addition, when the result to laboratory or technology scale transformed, there was obviously less amplification danger in the inventive method.Particularly when utilizing the continuation method of the present invention of apparatus of the present invention, wherein the multicomponent reactor comprises advantageously that at least one is interchangeable, preferably be filled with the pre-reactor of filler, can realize the device working time of surprising length, that is not by the shut-down that adheres to or alluvial causes.Find surprisingly that in addition particularly advantageously in the methods of the invention be, described multicomponent reactor washes with described reaction mixture before the real reaction of beginning, promptly pre-condition processing is particularly when it contains homogeneous catalyst.By this measure, can unexpectedly stable processing condition quick adjustment be arrived high level.
Therefore, theme of the present invention is a kind of device that continuous industryization is carried out following reaction that is used for, wherein, glycidyl allyl ether A and HSi-compd B react in the presence of catalyzer C and optional other auxiliary agent, and this device is at least based on the reactant habitat (3) of composition A (1) and B (2), at least one multicomponent reactor (5), itself comprise at least two reactor units, form is at least one interchangeable pre-reactor (5.1) and at least one and latter linked another reactor unit of this pre-reactor system (5.3), and based on product postprocessing (8).
Theme of the present invention also is a kind of hydrolyzable silane that is used to react, the multicomponent reactor (5) that particularly contains the unitary silane of H-Si-, itself comprise at least two reactor units, form is at least one interchangeable pre-reactor (5.1) and at least one and latter linked another reaction member of this pre-reactor system (5.3).
Preferably be equipped with Packed pre-reactor (5.1) at this.Appropriate filler for example-but be not only-be structurized filler, the rule or the irregular particle that promptly have identical or different size, preferred median size is corresponding be less than or equal to each reactor unit (5.1) cross-sectional area free cross section 1/3, preferred especially 1/5～1/100, and the average grain cross-sectional area is preferably 100～10
-6Mm
2, such as smear metal, fiber/wool, globe, fragment has the bar of circle or similar round or angular cross section, spiral, cylinder, pipe, bucket shape, saddle type, honeycomb, plate, grid, fabric, opening sponge, irregularly shaped body or ducted body, (structure) bulk cargo or the group's bundle (Gebinde) that is formed by the said structure body are by metal, metal oxide, pottery, the spheroplast that glass or plastics form, wherein said filler for example-but be not only-can be stainless steel, titanium by steel, copper, aluminium, titanium oxide, aluminum oxide, corundum, Si oxide, quartz, silicate, potter's clay, zeolite, alkali glass, boron glass, silica glass, porous ceramics, vitrifying pottery, special ceramics, SiC, Si
3N
4, BN, compositions such as SiBNC.
Brief Description Of Drawings
Fig. 1～6 expressions are as the device of the preferred embodiment for the present invention or the schema of device feature.
Therefore Fig. 1 represents a kind of preferred continuous apparatus, and wherein, reactant composition A and B are at list Assemble in the unit (3), add in the unit (5), this unit can contain immobilized catalyst, React at this, product is carried out post processing in unit (8).
Fig. 2 represents another preferred embodiment of continuous apparatus of the present invention, wherein catalyst C is added Enter among the composition B. But also catalyst can be added in the unit (3), perhaps as shown in Figure 3, Catalyst C will enter multicomponent reactor unit (5) before at the mixture of composition A and B Be metered into wherein.
Can in above-mentioned each logistics, add other optional auxiliary agent in addition.
At this, reactor unit refers to the element of multicomponent reactor (5), wherein each element All be zone or the reative cell for described reaction, for example referring to (the 5.1) (pre-reaction among Fig. 4 The reactor unit of device form) and (5.5) among Fig. 5 [integrated batch reactor (5.3.1 Reactor unit)] and (5.10) [reactor of microtubule fasolculus heat-exchanger reactor (5.9) Unit]. That is, the reactor unit of the multicomponent reactor (5) on the meaning of the present invention is not especially Rust steel wool tubule or quartz glass capillary, stainless steel tube or may be determined size stainless The steel reactor, pre-reactor (5.1) for example, microtubule fasolculus heat-exchanger reactor [for example (5.9)] In pipe (5.10) and integrated batch reactor [for example (5.3.1)] form in umwandete Zone (5.5). Inwall that in the case can application of reactive device element, coated with ceramic layer for example, By metal oxide, such as Al2O
3，TiO
2，SiO
2，ZrO
2, zeolite, the layer that silicate forms, Only mention a few, but organic polymer, particularly fluoropolymer polymer such as teflon also are possible .
Therefore, device of the present invention comprises one or more multicomponent reactors (5), itself Based at least 2～1000000 reactor units, comprise all therebetween natural numbers, excellent Select 3～10000, particularly 4～1000 reactor units.
In the case, the reactor chamber of at least one reactor unit or reative cell preferably have one Individual semicircle perpendicular to flow direction, half elliptic, circle, ellipse, triangle, four limits Shape, rectangle or trapezoidal cross section. The cross-sectional area that preferred such cross section has is 75 μ m2～75cm
2 Special preferred cross sectional area is 0.7～120mm2And therebetween owning Numerical value. The circular preferred diameter of cross-sectional area 〉=30 μ m～＜15mm, particularly 150 μ m～10 Mm. The preferred length of side of angular cross section be 〉=30 μ m～＜15mm, preferred 0.1～12mm. At this, in the multicomponent reactor (5) of apparatus of the present invention, can exist to have the difformity horizontal stroke The reactor unit in cross section.
In addition, the structure length in the reactor unit, i.e. reaction stream from reactor unit or product The entrance of logistics, for example referring to (5.1 and 5.1.1) or (5.5 and 5.5.1), until outlet, Referring to (5.1.2) or (5.5.2), be preferably 5cm～500m, comprise therebetween all Numerical value, especially preferred 〉=15cm～100m, more preferred 20cm～50m, particularly 25 Cm～30m.
Preferred such reactor unit in a kind of apparatus of the present invention, its reaction volume separately (being also referred to as reactor volume, i.e. the product of cross-sectional area and structure length) is 0.01ml～100 L comprises all therebetween numerical value. The reaction of the reactor unit of especially preferred apparatus of the present invention Body is long-pending to be 0.05ml～10l, more preferred 1ml～5l, and more preferred 3ml～2l, 5ml～500ml particularly.
Apparatus of the present invention can also be based on one or more multicomponent reactors (5), and they are preferred Parallel connection. But described multicomponent reactor (5) also can connect one by one, therefore, Can add entering of subsequently multicomponent reactor from the product of the multicomponent reactor of front Mouthful.
Multicomponent reactor of the present invention (5) advantageously can be transfused to reactant and become shunting (4) Or (5.2), they suitably be allocated to each the shunting, for example referring to (5.4) among Fig. 5 with And (5.11) among Fig. 6. After the reaction, product stream can flock together, for example referring to Fig. 5 In (5.7), (5.12) among Fig. 6 and (7), next advantageously single in post processing Carry out post processing in the unit (8). Such post-processing unit (8) at first can have condensation stage or Person's evaporation stage is one or more distillation levels then.
In addition, the multicomponent reactor (5) of apparatus of the present invention can also be based at least one, preferably at least two parallel connected stainless steel capillaries or based at least two parallel connected quartz glass capillaries or at least one tube bundle heat exchanger reactor (5.9) or batch reactor (5.3.1) that at least one is integrated.
Especially can use stainless steel capillary, reactor or the pre-reactor that advantageously constitutes at this by high strength, high temperature resistant and rustless stainless steel; Do not constitute by 1.4571 or 1.4462 shaped steel but for example do not get rid of pre-reactor, kapillary, batch reactor, tube bundle heat exchanger reactor etc., particularly also referring to steel according to DIN 17007 yet.In addition, stainless steel capillary or multicomponent reactor can also be equipped with polymer layer towards the surface of reaction chamber, for example fluorine-containing layer, especially teflon, and perhaps ceramic layer preferably optionally is porous SiO
2-, TiO
2-or Al
2O
3-layer is especially for holding catalyzer.
Especially advantageously can use integrated batch reactor, for example being designed to by definite structurized metal sheet (below be also referred to as the plane) can thermoregulated batch reactor, can be referring to http://www.heatric.com/pche-construction.html.
Prepare described structurized metal sheet or plane, can build batch reactor by it then, for example can be undertaken by other technology of burn into turning, cutting, milling, mold pressing, rolling, galvanic corrosion, laser processing, plasma technique or known fabrication method.Therefore, very will properly limit exactly and structure arranged on purpose, for example groove or seam are added in metal sheet, particularly on the side of the metal sheet of stainless steel.Find on each groove or the general end face of its beginning of seam at this, and on the metal sheet opposing end faces, finish usually at metal sheet.
Therefore Fig. 5 represents to have the plane of the integrated batch reactor (5.3.1) of a plurality of reactor units or element (5.5).At this, such plane is normally formed by metal substrate, has metallic walls (5.6) on it, this and metal system cover plate and be used for thermoregulated unit (6.5,6.6), and preferably another plane or structurized metal sheet define reaction chamber (5.5) together.Unit (5.3.1) goes back inclusion region (5.4) in addition, in order to finish (Aufgabe) reaction-ure mixture (5.2) and it be distributed in the reactor elements (5.5), and zone (5.7), in order to assemble product stream and carrying-off product flow (7) from conversion zone (5.5).Can also a plurality of above-mentioned such planes of overlapping connection in the scope of this external integrated batch reactor (5.3.1).Described connection for example can by (diffusion) weld or
Realize; For these and spendable other processing technology can also be referring to www.imm-mainz.de/seiten/de/u_050527115034_2679.php here? PHPSESSID=76a6285eb0433122b9cecaca3092dadb.In addition, so integrated batch reactor (5.3.1) is advantageously also surrounded by temperature adjustment unit (6.5,6.6), and it can heat or cool off batch reactor (5.3.1), i.e. on purpose heat conduction.For this reason, medium (D), for example Marlotherm or Mediatherm, can carry out temperature adjustment by interchanger (6.7), and and in the adding temperature adjustment unit (6.5) through pipeline (6.8), pump (6.9) and pipeline (6.1), pass through (6.6) and (6.2) by carrying-off, and add in the heat exchanger unit (6.7).At this, the reaction heat the best that discharges in integrated batch reactor (5.3.1) is controlled on the most funny path, thereby can avoid the reaction process of target is had the temperature spikes of disadvantageous effect.But also can design integrated batch reactor (5.3.1) and relevant therewith temperature adjustment unit (6.5 like this, 6.6), make and between two reactor elements planes, arranging a temperature adjustment plane respectively, it can make temperature control medium in zone (6.1,6.5) and (6.6,6.2) between directivity ground conduction is more arranged.
Especially preferred such multicomponent reactor (5) in apparatus of the present invention, its i) based at least one pre-reactor (5.1) and at least one and the latter linked stainless steel capillary of this pre-reactor (5.3), perhaps (ii) based at least one pre-reactor (5.1) and at least one and the latter linked quartz glass capillary of this pre-reactor (5.3), perhaps (iii) based at least one pre-reactor (5.1) and batch reactor that at least one is integrated (5.3 or 5.3.1), perhaps (iv) based at least one pre-reactor (5.1) and at least one microtubule fasolculus heat-exchanger reactor (5.3 or 5.9), referring to Fig. 4.In addition, pre-reactor (5.1) is also made can be suitably thermoregulated, can cool off and/or heatable (D, 6.3,6.4).
Usually, trace water has promptly caused organoalkoxysilane or chlorosilane reactant generation hydrolysis, therefore causes alluvial or adhesion.The special advantage of this embodiment of pre-reactor (5.1) in multicomponent reactor (5) scope reaction of silane (particularly for) is; except by on purpose separating and drainage water hydrolysis products or particle carry out this successive reaction, can also advantageously reduce unplanned stoppage time or stop time to greatest extent.Therefore, the pre-reactor (5.1) that is equipped with according to the present invention can also before connect and/or back connection strainer to carry out particle separation.
Generally speaking, be used for apparatus of the present invention that continuous industryization reacts based on the reactant habitat (3) that is used for composition A and B, at least one described multicomponent reactor (5) and based on product postprocessing (8), referring to Fig. 1,2 and 3, wherein multicomponent reactor (5) comprises at least two reactor units, and form is interchangeable pre-reactor (5.1), it preferably is equipped with filler and at least one and latter linked other reactor unit of this pre-reactor system (5.3).
At this, reactant composition A and B can be by pump and optional passing through
System and on purpose accumulating in continuously the zone (3) from storage unit respectively.Usually composition A and B preferably are metered under 10～40 ℃ at ambient temperature, and mix in zone (3).But also can at least a composition of preheating, two kinds of compositions or materials, perhaps corresponding mixture.Therefore described storage unit can carry out climatic regulation, and this storage vessel can be made into can be thermoregulated.In addition, the reactant composition can also flock together under pressure.Reaction-ure mixture can be added in the multicomponent reactor (5) continuously through pipeline (4).
At this, multicomponent reactor (5) is preferably by temperature control medium D (6.1,6.2) and reach or keep desirable operating temperature, therefore the undesirable temperature spikes recognized by the intermittent type device and temperature fluctuation can advantageously be avoided in device according to the present invention or become enough little.
Product stream or crude product stream (7) are added product postprocessing (8) continuously, for example in the rectification cell, wherein, for example can be with low-boiling products F through top (10), for example excessive use and silane capable of circulation best take out continuously and through bottom (9) high boiling point product E are taken out continuously.But also can from unit (8), take out effluent as product.
The reaction of branch A and B must be carried out in the presence of catalyzer C if hope for success, and then advantageously, homogeneous catalyst can be used for reactant flow by being metered into.But also can use suspended catalyst, it can be metered in the reactant flow equally.At this, the largest particle diameter of suspended catalyst advantageously should be less than 1/3 of the extension (Ausdehnung) of the minimum free cross-sectional area of the reactor unit of multicomponent reactor (5).
Therefore can see from Fig. 2, advantageously in zone (3), before the gathering, described catalyzer C is metered among the composition B at composition B and composition A.
Homogeneous catalyst C or suspended catalyst C, perhaps A that carries in pipeline (4) and the mixture of B preferably before will entering the multicomponent reactor, are metered into through pipeline (2.2), referring to Fig. 3.
Can be in the mode identical with homogeneous catalyst, also adding in reactant composition A and B mainly is other liquid auxiliary agent, for example-but be not only-activator, initiator, stablizer, inhibitor, solvent or thinner etc.
But also can select to be equipped with the multicomponent reactor (5) of immobilized catalyzer C, referring to Fig. 1.Catalyzer C can be for example in the case-but be not only-be present on the reaction chamber surface of each reactor elements.
Generally speaking, be used to choose wantonly described compd A and compd B continuous industryization react in the presence of catalyzer and other auxiliary agent apparatus of the present invention based at least one reactant habitat (3), at least one multicomponent reactor (5), itself comprise reactor unit of the present invention (5.1 and 5.3) and based on product postprocessing (8).Suitably, reactant or materials have been provided for reacting in storage unit, and add as required or be metered into.In addition, device of the present invention is equipped with measuring unit common in the technology, batching unit, brake unit, delivery unit, supply unit, monitoring unit, control unit and waste gas and waste material to remove equipment.In addition, such apparatus of the present invention advantageously can also be placed in the portable and stackable container, and can handle neatly.Therefore, for example device of the present invention also can be placed in each required reactant source or energy source place fast neatly.But also can bring all advantages of continuous product, and in the position that described product is further processed or further uses, for example directly under client's situation with device of the present invention.
Another the outstanding especially advantage of apparatus of the present invention that is used for the reaction of continuous industry enforcement glycidyl allyl ether (compd A) and HSi-compd B is, also can also prepare a small amount of specific product continuously neatly in the mode of simple and less expensive, deposition is 5kg～50000tp.a., preferred 10kg～10000tp.a..Unnecessary stoppage time be can advantageously avoid, productive rate, optionally temperature spikes and fluctuation influenced, and the oversize residence time, and then also have undesirable side reaction.Particularly such device sees it is to be used to prepare silane of the present invention best from economy, ecology and client close friend's angle.
Therefore another theme of the present invention is to be used for the method that continuous industryization prepares the 3-glycidyl oxygen base propyl group organoalkoxysilane of general formula (I)
H
2C(O)CHCH
2-O-(CH
2)
3-Si(R‘)
m(OR)
3-m (I)，
Wherein R ' represents C independently with R
1-～C
4-alkyl and m equal 0 or 1 or 2,
Wherein, be reflected at catalyzer C and optional other composition of reactant composition A and B exist down and carry out in multicomponent reactor (5), this multicomponent reactor itself is based at least two reactor units, and form is at least one interchangeable pre-reactor (5.1) and at least one and latter linked other reactor unit of this pre-reactor system (5.3).
Preferably this is reflected at least one multicomponent reactor (5) and carries out at this, its reactor unit is formed by stainless steel or silica glass, and perhaps its reaction chamber is limited by stainless steel or silica glass, wherein, the surface of reactor unit can be coated or coating, for example applies teflon.
Preferably use such reactor unit in addition in the methods of the invention, its cross section separately is designed to semicircle, half elliptic, circle, ellipse, trilateral, tetragon, rectangle or trapezoid.
Advantageously use such reactor unit at this, its cross-sectional area separately is 75 μ m
2～75cm
2
The such reactor unit of also preferred use, its scantling length is 5cm～200m, is preferably 10cm～120m especially, the more special 15cm～80m that is preferably, particularly 18cm～30m comprise all possible numerical value that is comprised by aforementioned region.
Therefore suitably use such reactor unit in the methods of the invention, its reaction volume separately is 0.01ml～100l, comprises all therebetween numerical value, preferred 0.1ml～50l, preferred especially 1ml～20l, more preferred 2ml～10l, particularly 5ml～5l.
In the methods of the invention, described reaction advantageously can be carried out in the device that has multicomponent reactor (5) equally, described multicomponent reaction device (i) is based at least two parallel connected pre-reactors (5.1) and at least one and the latter linked stainless steel capillary of this pre-reactor, perhaps (ii) based at least two parallel connected pre-reactors (5.1) and at least one and the latter linked quartz glass capillary of this pre-reactor, perhaps (iii) based at least two parallel connected pre-reactors (5.1) and batch reactor (5.3.1) that at least one is integrated, perhaps (iv) based at least two parallel connected pre-reactors (5.1) and at least one tube bundle heat exchanger reactor (5.9).
Preferred especially such multicomponent reactor (5), its comprise at least two interchangeable according to pre-reactor of the present invention (5.1), wherein, this pre-reactor is equipped with filler, filler as mentioned above particularly is in order to separate the hydrolysate of employed hydrolyzable silane.Preferred especially method of the present invention is carried out in the reactor unit of stainless steel.
Also preferred, in the methods of the invention, the surface of the reactor unit of the multicomponent reactor that the usefulness catalyst coated contacts with reactant/product mixture.
If carry out under the existence that is reflected at homogeneous catalyst C of composition A and B in the method for the invention, then shockingly find particularly advantageously to be, the multicomponent reactor moves this device by the one or many flushing process or the short period of time of the mixture using the mixture that formed by homogeneous catalyst C and composition B or formed by homogeneous catalyst C and composition A and B, for example moves 10～120 minutes and optionally carries out pre-condition processing with higher catalyst concn.
Being used for that the multicomponent reactor is carried out the material that pre-condition handles can be caught, and is metered in the reactant flow to small part subsequently, perhaps directly adds in the product postprocessing and carries out aftertreatment.
Handle by above-mentioned pre-condition, particularly when it is made by stainless steel, then can surprising and advantageously under the maximum yield situation, realize constant running status fast the multicomponent reactor.
In the methods of the invention, described reaction can be carried out in gas phase and/or liquid phase.Reaction mixture or product mixtures can single-phase, two-phase or three-phase existence.In the methods of the invention, preferred single-phase the carrying out of reaction particularly carries out in liquid phase.
Therefore the inventive method is that 10～250 ℃ and pressure are that 0.1～500bar (definitely) moves down using under the multicomponent reactor situation advantageously in temperature.At this, the reaction of preferred component A and B, particularly hydrosilylation, in the multicomponent reactor, it is 50～200 ℃ in temperature, be preferably 90～180 ℃, particularly 130～150 ℃ and pressure are 0.5～300bar (definitely), be preferably 1～200bar (definitely), be preferably especially under 2～50bar (definitely) and carry out.
Usually, the pressure difference in apparatus of the present invention, promptly the pressure difference between reactant habitat (3) and the product postprocessing (8) is 1～10bar (definitely).Advantageously can be for apparatus of the present invention are equipped with controlling valve, when particularly using Trimethoxy silane (TMOS).Preferred controlling valve is adjusted to 1～100bar (definitely), preferably until 70bar (definitely), especially preferably until the value of 40bar (definitely), particularly 10～35bar (definitely).
According to the present invention, this reaction can on-line velocity (LV) be 1～110
4h
-1I.N. carry out down.The velocity of flow of described logistics in reactor unit is preferably 0.0001～1m/si.N., and the institute in preferred especially 0.0005～0.7m/s, particularly 0.05～0.3m/s and the above-mentioned scope might numerical value.If relate to reactor surface (A) to the dominant ratio of reactor volume (V) in reaction of the present invention, then preferred A/V-ratio is 20～5000m
2/ m
3, comprise being positioned at all possible single numerical value of described scope, advantageously to carry out method of the present invention.The A/V-ratio is measuring of thermal conduction and possible heterogeneous (wall) influence at this.
Therefore in the methods of the invention, described reaction is 10 seconds～60 minutes at mean residence time (τ) advantageously, preferred 1～30 minute, preferred especially 2～20 minutes, particularly carries out under 5～10 minutes.Also indicate the disclosed all possible numerical value of described scope once more respectively at this.
In the methods of the invention, as composition A, advantageously use glycidyl allyl ether (H
2C (O) CHCH
2-O-CH
2CH=CH
2).
In the methods of the invention, particularly the hydrogen silane of general formula (II) is suitable as composition B
HSi(R’)
m(OR)
3-m (II)，
Wherein R ' and R represent C1-～C4-alkyl independently, and m equals 0 or 1 or 2, and preferred R represents methyl or ethyl, and R ' expression methyl.
So Trimethoxy silane preferably used according to the invention or methyl dimethoxysilane.
To be preferably A be 1: 5～100: 1 than B to the mol ratio of composition A of Shi Yonging and B in the methods of the invention, preferred especially 1: 4～5: 1, preferred more especially 1: 2～2: 1, particularly 1: 1.5～1.5: 1, comprise all possible numerical value in the above-mentioned scope, for example-but be not only-1 to 0.7～1.2.
The inventive method is preferably carried out in the presence of homogeneous catalyst C.But the inventive method also can be moved not adding under the catalyzer situation, and can expect that productive rate obviously descends this moment usually.
Particularly utilize the inventive method to carry out hydrosilylation reactions, with the organosilane of preparation formula (I), the homogeneous catalyst of Series P t-complex compound catalyst particularly wherein, those of Karstedt type for example, as Pt (0)-divinyl tetramethyl disiloxane, in dimethylbenzene, PtCl
4, H
2[PtCl
6] or H
2[PtCl
6] 6H
2O, preferred " Speyer-catalyzer ", cis-(Ph
3P)
2PtCl
2, those complex compound catalysts of the complex compound catalyst of Pd, Rh, Ru, Cu, Ag, Au, Ir or other transition metal or precious metal.Known complex compound catalyst can be dissolved in organic solvent, in the preferred polar solvent, (but being not only) ethers for example, as THF, ketone, as acetone, alcohols, as Virahol, aliphatic series or aromatic hydrocarbon are as toluene, dimethylbenzene.
Can in the solution of described homogeneous catalyst or homogeneous catalyst, add activator in addition, for example with organic or inorganic acid form, as HCl, H
2SO
4, H
3PO
4, monocarboxylic acid or di-carboxylic acid, HCOOH, H
3C～COOH, propionic acid, oxalic acid, succsinic acid, citric acid, phenylformic acid, phthalic acid is only mentioned several.
Add organic in this export-oriented reaction mixture or mineral acid can play other favourable function, for example as the stablizer or the inhibitor of trace scope impurity.
If use homogeneous catalyst or suspended catalyst in the methods of the invention, the mol ratio of then used alkene composition A and catalyzer (based on the metal meter) is preferably 2000000: 1～and 1000: 1, preferred especially 1000000: 1～4000: 1, particularly 500000: 1～10000: 1 and the interior all possible numerical value of above-mentioned scope.
But also can use the immobilized catalyst that forms by series transition metal or precious metal or heterogeneous catalyst or corresponding multielement catalyzer to be used to carry out hydrosilylation reactions.Therefore for example-but be not only-precious metal sludge or precious metal/gac can be used.But fixed bed also can be set hold the interior heterogeneous catalyst of multicomponent reactor area.Therefore for example-but be not only-can also with at carrier such as especially by SiO
2, TiO
2, Al
2O
3, ZrO
2Pack into the conversion zone of reactor unit of heterogeneous catalyst on the globe of making, bar, ball, cylinder, the stirrer etc.The example that has catalyst fixed bed integrated batch reactor is referring to http://www.heatric.com/iqs/sid.0833095090382426307150/mab_react ors.html.
In addition, can also use solvent or thinner as auxiliary agent, as alcohols, aliphatic series and aromatic hydrocarbon, ether, ester, ketone, CKW, FCKW only mentions several.These auxiliary agents for example can be removed from product in product is handled.
Can use inhibitor equally in the methods of the invention, as itself being known those or corresponding mixture, as extra auxiliary agent.
Generally speaking, followingly carry out method of the present invention:
Usually, at first be metered into reactant composition A, B and the C that chooses wantonly and other optional auxiliary agent, and mix.Make every effort to be metered into accuracy≤± 20% at this, the homogeneous catalyst of preferred≤± 10%.Under particular case, homogeneous catalyst and other optional auxiliary agent before will entering the multicomponent reactor, the mixture of composition A and B can be metered in this mixture.Next this reaction-ure mixture can be added in the multicomponent reactor, and the reaction under temperature control of described composition.But described multicomponent reactor also can be at first with containing the reactant of catalyzer or reaction-ure mixture washes or pre-condition is handled, regulate in advance then (
) temperature reacts.But the pre-condition of multicomponent reactor is handled also and can be carried out under the temperature that raises a little.Product that flock together or that obtain stream (crude product) subsequently can be with suitable manner in the product postprocessing of apparatus of the present invention in the multicomponent reactor, for example-but be not only-carry out aftertreatment by the distillation that has rectifying.The preferred operation continuously of this method.
Therefore, using under apparatus of the present invention situation, the inventive method advantageously can be moved continuously, and the product discharging is 5kg～50000tp.a., for example-but be not only-advantageously prepare 3-glycidyl oxygen base propyl trimethoxy silicane.
Explaining the present invention in more detail by following examples, is not to limit theme of the present invention.
Embodiment
Embodiment
The preparation of 3-glycidyl oxygen base propyl trimethoxy silicane
Be used to prepare the device of 3-glycidyl oxygen base propyl trimethoxy silicane mainly by the reactant storage vessel, surge pump, regulon, measuring unit and batching unit, the T-mixing tank, two parallel connected removable and be equipped with pre-reactor (the diameter 5mm of filler (the stainless steel bead of mean diameter 1.5mm), length 40mm, stainless steel), stainless steel capillary (1mm diameter, 50m length), be used for pre-reactor and the thermostatic bath that has temperature adjusting capillaceous, controlling valve is used N continuously
2The stripping tower and being used to of operation transmits reactant and the required pipeline of carrying-off product, recycle and waste gas is formed.At first at room temperature be metered into alkene (glycidyl allyl ether) and platinum catalyst [53g chloroplatinic acid-hexahydrate is in 1l acetone], mol ratio is alkene: Pt=270000: 1, mix, and in the T-mixing tank with hydrogen Trimethoxy silane (TMOS, Degussa AG) with mol ratio TMOS: alkene=mix at 0.9: 1, and add in the reactor assembly continuously.This moment, pressure was 25 ± 10bar.When this device of operation, should guarantee that this device does not have H as far as possible
2O and do not have O
2State.In addition, washed 2 hours with reaction-ure mixture A+C before the temperature of this device in the rising reactor assembly.When continuous flux was total up to 300g/h, the temperature during the rising temperature adjustment is bathed was adjusted to 130 ℃ at reactor assembly, and moves 14 days continuously.Behind this reactor assembly, from this pipe product stream, take a sample at interval with certain hour, and study with the GC-WLD-measurement.Transformation efficiency based on the TMOS meter is 79%, and the selectivity of based target product meter is about 86%.The reacting product stream that obtains like this added continuously use N
2In the stripping tower of operation, and take out the product of hydrosilylation continuously.
Claims (22)
1. be used for the device that continuous industryization is carried out following reaction, wherein, glycidyl allyl ether A and HSi-compd B are reacted in the presence of catalyzer C and optional other auxiliary agent, and this device is at least based on the reactant habitat (3) of composition A (1) and B (2), at least one multicomponent reactor (5), itself comprise at least two reactor units, form is at least one interchangeable pre-reactor (5.1) and at least one and latter linked another reactor unit of this pre-reactor system (5.3), and based on a product postprocessing (8).
2. according to the device of claim 1, it is characterized in that reactor unit (5.3), itself comprise 1～100 000 reactor unit.
3. according to the device of claim 1 or 2, it is characterized in that reactor unit, wherein, the free responding volume of pre-reactor (5.1) is 5ml～10 l, and the free responding volume summation of reactor unit (5.3) is 1ml～100 l.
4. according to the device of one of claim 1～3, it is characterized in that at least one multicomponent reactor (5), its (i) is based at least two parallel connected pre-reactors (5.1) and at least one and the latter linked stainless steel capillary of this pre-reactor, perhaps (ii) based at least two parallel connected pre-reactors (5.1) and at least one and the latter linked quartz glass capillary of this pre-reactor, perhaps (iii) based at least two parallel connected pre-reactors (5.1) and batch reactor (5.3.1) that at least one is integrated, perhaps (iv) based at least two parallel connected pre-reactors (5.1) and at least one microtubule fasolculus heat-exchanger reactor (5.9).
5. according to the device of one of claim 1～4, it is characterized in that at least two are equipped with Packed pre-reactor (5.1).
6. according to the device of one of claim 1～5, it is characterized in that multicomponent reactor (5), its comprise four to eight parallel connections and pile up Packed pre-reactor (5.1) and one with the latter linked integrated batch reactor of this pre-reactor (5.3.1), itself comprise 10～4 000 reactor units (5.5).
7. be used to react the multicomponent reactor (5) of hydrolyzable silane, itself comprise at least two reactor units, form is interchangeable pre-reactor (5.1) and at least one and latter linked another reaction member of this pre-reactor (5.3).
8. according to the device of one of claim 1～6 or according to the multicomponent reactor of claim 7, it is characterized in that pre-reactor (5.1), its accumulation has structurized filler (5.1.3).
9. be used for the method that continuous industryization prepares the 3-glycidyl oxygen base propyl group organoalkoxysilane of general formula (I)
H
2C(O)CHCH
2-O-(CH
2)
3-Si(R’)
m(OR)
3-m (I)，
Wherein R ' represents C independently with R
1-～C
4-alkyl and m equal 0 or 1 or 2,
Wherein, be reflected at catalyzer C and optional other composition of reactant composition A and B exist down and carry out in multicomponent reactor (5), this multicomponent reactor itself is based at least two reactor units, and form is at least one interchangeable pre-reactor (5.1) and at least one and latter linked other reactor unit of this pre-reactor system (5.3).
10. according to the method for claim 9, it is characterized in that this is reflected at least one multicomponent reactor (5) and carries out, wherein this reactor unit is designed to stainlessly, and is equipped with at least two pre-reactors (5.1) that have filler (5.1.3).
11. the method according to claim 9 or 10 is characterized in that, glycidyl allyl ether (composition A) reacts with the silane (composition B) of general formula (II),
HSi(R‘)
m(OR)
3-m (II)，
Wherein R ' represents C independently with R
1-～C
4-alkyl and m equal 0 or 1 or 2.
12. the method according to one of claim 9～11 is characterized in that, used composition B (hydrogen silane) is 0.7～1.2 to 1 with the mol ratio of A (alkene).
13. the method according to one of claim 9～12 is characterized in that, uses homogeneous catalyst C, and is 1～5 to 500000 based on the mol ratio of this catalyzer of precious metal meter and composition A.
14. the method according to one of claim 9～13 is characterized in that this is reflected at based on PtCl
4Or H
2PtCl
6Or H
2PtCl
66H
2Carry out under O or Speyer-catalyzer or the catalyst system existence based on Pt, Pd, Rh, Ru, Cu, Ag, Au-and/or Ir.
15. the method according to one of claim 9～14 is characterized in that, with the reaction-ure mixture that contains catalyzer this multicomponent reactor (5) is carried out pre-condition and handles.
16. the method according to one of claim 9～15 is characterized in that, this is reflected in the multicomponent reactor (5) in temperature is that 90～180 ℃ and pressure are 15～35bar operation definitely down.
17. the method according to one of claim 9～16 is characterized in that, this is reflected at mean residence time is to carry out under 1 minute～10 minutes.
18. the method according to one of claim 9～17 is characterized in that, this ratio that is reflected at reactor surface and reactor volume (A/V) is 20～50 000m
2/ m
3Under carry out.
19. the method according to one of claim 9～18 is characterized in that, is metered into reactant composition A, B and C continuously, and mix, next the reaction-ure mixture that will determine volume flow adds in the multicomponent reactor (5), reacts, and the product mixtures to gained carries out aftertreatment subsequently.
20. the method according to one of claim 9～19 is characterized in that, uses the reaction-ure mixture based on composition A, B and C, this mixture contains at least a activator as other composition.
21. method according to one of claim 9～20, it is characterized in that, after the working time that the device operation is determined, to choose accumulation wantonly has at least one pre-reactor (5.1) of filler (5.1.3) and the Packed new pre-reactor of optional outfit to change, continue at least one another pre-reactor (5.1) of operation during this time, to carry out continuation method.
22. the method according to one of claim 9～21 is characterized in that, the velocity of flow in the pre-reactor (5.1) is less than the velocity of flow in the latter linked reactor unit.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006037406 | 2006-08-10 | ||
| DE102006037406.1 | 2006-08-10 | ||
| DE102007023762.8 | 2007-05-22 |
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| Publication Number | Publication Date |
|---|---|
| CN101362774A true CN101362774A (en) | 2009-02-11 |
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ID=40389399
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101701672A Pending CN101362774A (en) | 2006-08-10 | 2007-08-09 | System and process for continuous industrial preparation of 3-glycidyl-oxypropylalkoxysilanes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408581A (en) * | 2013-08-28 | 2013-11-27 | 淄博市临淄齐泉工贸有限公司 | Continuous production reaction device and continuous production reaction method for N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane |
| CN113248536A (en) * | 2021-05-31 | 2021-08-13 | 南京林业大学 | Preparation method of gamma-glycidyl ether oxypropyl trialkoxysilane |
-
2007
- 2007-08-09 CN CNA2007101701672A patent/CN101362774A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408581A (en) * | 2013-08-28 | 2013-11-27 | 淄博市临淄齐泉工贸有限公司 | Continuous production reaction device and continuous production reaction method for N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane |
| CN103408581B (en) * | 2013-08-28 | 2016-06-29 | 淄博市临淄齐泉工贸有限公司 | N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane produces reaction unit and method continuously |
| CN113248536A (en) * | 2021-05-31 | 2021-08-13 | 南京林业大学 | Preparation method of gamma-glycidyl ether oxypropyl trialkoxysilane |
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Application publication date: 20090211 |