CN101121727A - System, reactor and process for continuous industrial preparation of 3-methacryloyloxypropylalkoxysilanes - Google Patents
System, reactor and process for continuous industrial preparation of 3-methacryloyloxypropylalkoxysilanes Download PDFInfo
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Abstract
The present invention relates to a device, a reactor and a method for implementing continuously the industrial reaction as follows, to make the methacrylic acid allyl ester A and HSi-compound B under the state of existing activator C and optional adjuvant. The device is based on at least that as follows: a material feeding chief pipe (3) for component A (1) and B (2), at least one multi-element reactor (5) which comprises at least one replaceable front reactor (5.1) and at least one other connecting to at least two reactor units of a reactor unit (5.3) locating the downstream of the front reactor, and a outcome rear processing (8).
Description
Technical field
The present invention relates to be used for the novel reactor of continuous industrial preparation of 3-methacryloyloxypropylalkoxysilanes and new device and associated method, the production of described 3-methacryloxypropyl organoalkoxysilane is by allowing allyl methacrylate [CH
2=C (CH
3) C (O) O-CH
2CH=CH
2] carry out with the reaction of HSi-compound.
Background technology
Organosilane, vinyl chlorosilane and vinyl alkoxy silane (EP 0 456 901 A1 for example, EP 0 806 427 A2), (DE-AS 28 15 316 for the chlorine alkyl chlorosilane, EP 0 519 181 A1, DE195 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 0 838 467 A1, DE103 01 997 A1), (DE-OS 27 53 124, EP 0 709 391 A2 for the aminoalkyl group organoalkoxysilane, 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 (EP0 387 689 A2) etc. has high technology and industry attractiveness.The method and apparatus for preparing them is known just for a long time.These products are the few relatively products of tonnage, and produce with a batch method (Batchverfahren) in most cases.Usually, people use multiduty device for this reason, and the highland makes full use of a batch device (Batch-Anlage) to reach as far as possible.Yet, when product is changed, need the purification and the flushing process of expensive batch device.In addition, in the intensive batch device of large volume, costliness and personnel, usually need the long reaction mixture residence time, to reach enough yields.In addition, described reaction is accompanied by the heat release of 100-180kJ/mol reaction heat usually.Therefore, unfavorable side reaction also can cause remarkable influence to selectivity and yield in reaction.When described reaction related to hydrosilylation reactions, the segregation of possible hydrogen had proposed considerable requirement to safety technique.In addition, in half batch of mode, usually place charging thing and catalyzer together in advance and add other charging thing to metering wherein.In addition, batch or the medium and small fluctuation of technological process of half batch of device caused the considerable variation of yield and product quality between the different batches.If wish to be transformed into a batch scale (technological process is amplified (scale-up)), also run into many difficulties from laboratory scale and pilot scale.
Micro-structured reactor itself is known, for example is used for continuous production Aethoxy Sklerol (DE 10 2,004,013 551 A1) or especially synthetic ammonia, methyl alcohol, MTBE (WO 03/078052).Also known the microreactor (WO 01/54807) that is used for catalyzed reaction.But, still lack the microreactor technology that is used for the industrial production organosilane so far, perhaps be to realize at least.The trend of organoalkoxysilane and chlorosilane hydrolysis (when small amount of moisture just exist) and correspondingly stick to and also be regarded as permanent problem in the organosilane production equipment undoubtedly.
Summary of the invention
Therefore there is such task, for industrial production 3-methacryloxypropyl organoalkoxysilane provides other possibility.Particularly there is such requirement, the other possibility of this class organosilane of continuous production promptly is provided, make every effort to wherein make that above-mentioned defective minimizes.
According to the present invention, being proposed of task is solved by the content of listing in claims.
Under situation of the present invention, be surprisingly found out that, can be under the situation that has catalyzer C, in simple and economical mode, commercial scale continuous ground in based on the device of multicomponent reactor (5), advantageously to use allyl methacrylate (component A) hydrosilylation to contain the B component of HSi, particularly hydrogen organoalkoxysilane, wherein especially, described multicomponent reactor (5) contains at least two reactor units that form is interchangeable lead reactor (5.1) and the reactor unit that is connected described lead reactor downstream (5.3) that at least one is other.
Therefore, can be in the present embodiment advantageously by using multicomponent reactor (5) to help operate continuously method of the present invention, this is can still on purpose, alternately change lead reactor with new lead reactor under operational condition because this multicomponent reactor (5) makes, has deposited the hydrolysate of significant quantity in described lead reactor after one period operating time.
Can use lead reactor in particularly advantageous mode thus; this lead reactor is equipped with weighting material; can realize thus on purpose and separate hydrolysate and or hydrolysis particle and reducing thus effectively because precipitation and adhere to the device that causes in the reactor and block trend and stop time.
Different with batch charging, in the present invention, the charging thing can also can carry out cold mixing thus in the continuous premix in the tight front of multicomponent reactor, then in the multicomponent reactor heating and at this hard objectives ground arranged and react continuously.Also can add catalyzer to this charging thing mixture.Then, the aftertreatment continuously of described product is for example in evaporation, rectifying and/or carry out aftertreatment (only mentioning some possibilities) in short path or thin layer evaporator.The reaction heat of emitting when reaction can be advantageously through deriving through heating agent with high surface area and (if existence) of the proportional reactor wall of reactor volume in the multicomponent reactor.In addition, under the situation of using this multicomponent reactor, can significantly improve the space time yield of quick heat release (w rmet nend) reaction.This is the higher average charging substrate concentration level (also promptly not being subjected to the restriction of charging thing dilution) of comparing by parallel feeding thing more quickly, with batch method, and/or temperature raise (the extra acceleration that this can induce reaction usually).In addition, the invention enables and to guarantee process safety in simple and economical relatively mode.Therefore, can reach high technology under situation of the present invention improves, has particularly realized that by higher transformation efficiency and selectivity the yield until 10% improves.Preferably, of the present invention being reflected in the stainless steel multicomponent reactor carried out.Thus, can avoid using exotic materials in mode advantageously in order to carry out described reaction.In addition, when pressurization is carried out under the response situation being undertaken by continuous mode, can guarantee longer work-ing life by the reactor of metal preparation, this is because compare with a batch method, and material obviously is subjected to tired invasion and attack more lentamente.In addition, compare with the comparable experiment of carrying out when batch method, reproducibility is able to remarkable improvement.In addition, provide the technological process when the result of laboratory scale and pilot scale transforms to amplify risk by the inventive method.Especially, in utilizing the continuation method of the present invention of apparatus of the present invention, can realize the not lugs working time of wonderful length, wherein said parking causes that owing to adhering to and/or depositing the multicomponent reactor advantageously comprises at least one lead reactor interchangeable, that preferably fill with weighting material in apparatus of the present invention.In addition, find that the particularly advantageous part of the inventive method is, before essence reaction beginning, with reaction mixture (particularly when this reaction mixture contains homogeneous catalyst) flushing (also regulating in advance) multicomponent reactor in wonderful mode.By this measure, can unexpectedly apace the constant processing condition be adjusted to high level.
Therefore, theme of the present invention is to be used for the industrial device that reacts continuously, wherein, under the situation of other auxiliary agent that has catalyzer C and choose wantonly, make the reaction of allyl methacrylate A and HSi-compd B, this installs at least based on following: at the charging thing common excretory duct (Eduktzusammenf ü hrung) (3) of component A (1) and B (2); At least one multicomponent reactor (5), it comprises form and is at least two reactor units at least one interchangeable lead reactor (5.1) and reactor unit (5.3) form that is connected this lead reactor system downstream that at least one is other with regard to it; And product postprocessing (8).
In addition, theme of the present invention also is to be used to transform hydrolyzable silane, particularly contains unitary those the multicomponent reactor (5) of H-Si, comprises at least two reactor units of form at least one interchangeable lead reactor (5.1) and the reaction member (5.3) that is connected this lead reactor system downstream that at least one is other with regard to it.
Wherein preferably, the lead reactor (5.1) of filling with weighting material.To this suitable weighting material is (but and nonexcludability) structural weighting material for example, also promptly have identical or different size, preferably have so average (durchschnittlich) particle size, rule or irregular particle, described average particle size particle size be preferably each reactor unit (5.1) cross-sectional area free cross section≤1/3, preferred especially 1/5 to 1/100, and the average grain cross-sectional area is preferably 100-10
-6Mm
2For example has circle or near the chip of circle or rectangular cross section, fiber/fine hair, spherolite, fragment, bar, spiral-line, cylinder, pipe, thin slice, saddle type, honeycomb, plate, grid, fabric, porous sponge, irregularly shaped or cavity body, (structure) packing that is equipped with by the said structure system or bundle etc., by metal, metal oxide, pottery, the spheroid of glass or synthetic materials preparation, wherein said weighting material for example, but nonexcludability ground is by steel, stainless steel, titanium, copper, aluminium, titanium oxide, aluminum oxide, silicon carbide, silicon oxide, quartzy, silicate, clay, zeolite, alkali glass (Alkaliglas), boron glass, silica glass, porous ceramics, the vitrifying pottery, special ceramics, SiC, Si
3N
4, BN, SiBNC form.
Description of drawings
Fig. 1-6 shows the device of the preferred embodiments of the invention and the schema of device part.
Like this, Fig. 1 shows a preferred continuous apparatus, wherein charging thing component A and B one Rise and flow into unit (3), supply to the unit (5) that wherein contains embedded catalyst, herein React and post processing product in unit (8).
Fig. 2 shows another preferred embodiment of continuous apparatus of the present invention, wherein to component B introduces catalyst C, particularly homogeneous catalyst. But, also this catalyst can be supplied to In the unit (3), perhaps, as shown in Figure 3, short before multicomponent reactor unit (5) entrance Distance is interior adds catalyst C metering in the mixture of component A and B to.
In addition, can add other optional auxiliary agent to each above-mentioned materials flow.
Wherein, reactor unit refers to the element of multicomponent reactor (5), wherein each element table Show district or reative cell for above-mentioned reaction, referring to (5.1) among Fig. 4 for example (with preposition anti-Answer the reactor unit of device form) and Fig. 5 in (5.5) [whole block reactor (Blockreaktor) (5.3.1) reactor unit] and (5.10) [microtubule fasolculus formula heat exchange reaction The reactor unit of device (5.9)]. Also namely, within the scope of the present invention, multicomponent reactor (5) Reactor unit particularly stainless steel capillary or quartz glass capillary, stainless steel tube and/or The stainless steel reactor that may customize is in for example microtubule fasolculus formula heat exchange reactor [for example (5.9)] Lead reactor (5.1), pipe (5.10) and whole block reactor [for example (5.3.1)] shape Formula around the part (5.5). Wherein the inwall of reactor elements can be coated, for example uses pottery Layer, metal oxide layer apply, and described metal oxide for example is Al2O
3、TiO
2、SiO
2、ZrO
2, Zeolite, silicate only mention certain some here, but also can use organic polymer apply, Particularly use fluoropolymer, for example the Teflon applies.
Like this, device of the present invention comprises one or more multicomponent reactors (5), with regard to this multicomponent reaction device based at least 2 to 1000000 (comprising all natural numbers therebetween) reactor units, preferred 3-10000, especially preferred 4-1000, reactor unit
Wherein the reactor chamber of at least one reactor unit or reative cell preferably have perpendicular to stream The semicircle of moving direction, half elliptic, circle, ellipse, triangle, square, rectangle or Person's trapezoidal cross-section.
Preferably, this cross section has 75 μ m2-75cm
2Cross-sectional area. Particularly preferred 0.7-120mm2Cross-sectional area (comprising the numerical value that all are therebetween). Transversal in circle In the situation of face, diameter is preferably 〉=30 μ m to＜15mm, particularly 150 μ m to 10mm. Many Angular cross section preferably has 〉=and 30 μ m are to＜15mm, preferred 0.1 to 12mm the length of side. At root Can there be cross section with different moulding in the multicomponent reactor (5) according to apparatus of the present invention Reactor unit.
In addition, (the also i.e. reacting material flow from reactor unit of the structure length in the reactor unit And/or the entrance of product stream [referring to for example (5.1 and 5.1.1) or (5.5 and 5.5.1)] To outlet [referring to (5.1.2) or (5.5.2)]) be preferably 5cm-500m and (comprise that all are positioned at Numerical value during this time), especially preferably 〉=15cm to 100m, the most preferred 20cm-50m, particularly 25cm-30m.
Especially preferred such reactor unit in device of the present invention, in all cases, its Reaction volume (being also referred to as reactor volume, also is the product of cross-sectional area and structure length) Be 0.01ml to 100l (comprising all numerical value during being positioned at). Particularly preferably, the present invention The reactor volume of the reactor unit of device is 0.05ml to 10l, the most preferred 1ml to 5 L, the most preferred 3ml to 2l, particularly 5ml to 500ml.
In addition, apparatus of the present invention can be based on one or more multicomponent reactors (5), and are described many Element reactor (5) preferably is connected in parallel. But, also can be with above-mentioned multicomponent reactor (5) Be connected in series, enter rear one so that the product of being discharged by previous multicomponent reactor can guide The multicomponent reactor.
Existing multicomponent reactor (5) can advantageously carry out feed with charging thing component materials flow (4) and/or (5.2), and described charging thing component materials flow (4) and/or (5.2) are assigned in each tributary (Teilstr m) suitably referring to (5.4) and (5.11) among Fig. 6 among Fig. 5 for example.Can be after reaction with product materials flow interflow, referring to (5.7), (5.12) and (7) among Fig. 6 among Fig. 5 for example, advantageously in post-processing unit (8), carry out aftertreatment then.This post-processing unit (8) can at first have enriching stage or evaporation stage, then is one or more distillation stages.
In addition, the multicomponent reactor (5) of device of the present invention based at least one, preferred at least two stainless steel capillaries that are connected in parallel, perhaps based at least two quartz glass capillaries that are connected in parallel, perhaps at least one bundled tube heat exchange reactor (5.9) or at least one whole block reactor (5.3.1).
Wherein people use particularly stainless steel capillary, reactor or lead reactor, and they advantageously are made up of high strength, high temperature resistant and rustless stainless steel; But exemplary nonexcludability ground, lead reactor, kapillary, block reactor, bundled tube heat exchange reactor etc. are made of 1.4571 or 1.4462 shaped steel, referring to particularly according to the steel of DIN 17007.In addition, can have polymer layer around the stainless steel capillary or the multicomponent reactor surface of this reaction chamber, for example fluorine-containing layer, especially the Teflon perhaps has ceramic layer, preferably porous SiO optionally
2, TiO
2Perhaps Al
2O
3Layer is especially for adsorptive catalyst.
Particularly advantageously, can use whole block reactor, for example but as the block reactor of attemperation, it constitutes (hereinafter being also referred to as flat board) by specific structurized metal sheet, by http://www.heatric.com/pche-construction.html as can be known.
Described structurizing metal sheet or dull and stereotyped preparation can for example be undertaken by the technology of burn into turning, shearing, milling, punching press, roll-in, galvanic corrosion, laser processing, plasma technique or the known working method of its itself, and structurizing metal sheet or flat board can be prepared the block reactor thus.Like this, with the structure that extra high tolerance range will well limit and have purpose to be orientated, for example groove and seam are incorporated on the side of metal sheet (the particularly metal sheet that is prepared by stainless steel).Thus, each groove and/or seam be in its front that begins to locate to be positioned at metal sheet, runs through and end at the front that this metal sheet is oppositely arranged usually.
Like this, Fig. 5 shows the whole block reactor (5.3.1) with a plurality of reactor units or element (5.5).Wherein these dull and stereotyped are made of metal substrate and metallic walls (5.6) disposed thereon usually, they and the wrapper plate that is made of metal and the unit (6.5,6.6) that is used for attemperation, preferably another flat board or structural metal plate, limited reaction chamber (5.5) together.In addition, described unit (5.3.1) comprise be used for receiving and distribute reactor elements (5.5) charging thing mixture (5.2) zone (5.4) and be used for the product materials flow of autoreaction zone (5.5) in the future and the zone (5.7) at the ejecta interflow of product materials flow (7).In addition, in whole block reactor (5.3.1) framework, a plurality of so above-mentioned flat boards can also be bonded to each other.Described combination can for example be undertaken by (diffusion) welding or soldering; Here is adaptable processing technology also referring to www.imm-mainz.de/seiten/de/u-050527115034_2679.php? PHPSESSID=75a 6285eb0433122b9cecaca3092dadb.In addition, this whole block reactor (5.3.1) is advantageously centered on by temperature adjustment unit (6.5,6.6), and described temperature adjustment unit makes it possible to heating or cools off this block reactor (5.3.1), also is autotelic temperature regulation.For this reason, medium (D) (for example Marlotherm or Mediatherm) can carry out temperature adjustment by heat exchanger (6.7), flow into conduit (6.1) and through (6.6) and (6.2) outflow, and flow in the heat exchanger unit (6.7) through the conduit (6.8) of pump (6.9) and temperature adjustment unit (6.5).The reaction heat that discharges in whole block reactor (5.3.1) can be controlled at shortest path best, can avoid influencing unfriendly the temperature spikes of required reaction process thus.But whole block reactor (5.3.1) and relevant temperature adjustment unit (6.5,6.6) can be set so also, also promptly between two reactor elements planes, be provided with the temperature adjustment plane, make the directional transmissions of the medium temperature between zone (6.1,6.6) and (6.6,6.2) become possibility.
In apparatus of the present invention, particularly preferably be such multicomponent reactor (5), this multicomponent reactor (5) comprises at least one lead reactor (5.1) and reactor unit (5.3) (for example stainless steel capillary) that at least one is other, perhaps lead reactor (5.1) and at least one whole block reactor (5.3.1), perhaps lead reactor (5.1) and at least one microtubule fasolculus formula heat exchange reactor (5.9) are referring to Fig. 4.In addition, make described lead reactor (5.1) temperature adjustment suitably, also can cool off and/or can heat by (D, 6.3,6.4).
Usually, the water of trace has just caused the hydrolysis of organoalkoxysilane charging thing or chlorosilane feed thing, and causes deposition and adhesion thus.The special advantage of this embodiment of lead reactor (5.1) in multicomponent reactor (5) framework (especially for silane reaction) is: except carrying out successive reaction, by on purpose separating and drainage water hydrolysis products and/or particle can be advantageously will be reduced to stop time outside the plan and fault-time minimum.Like this, can be in lead reactor constructed according to the invention (5.1) upstream and/or the downstream connect the extra strainer that is used for particle separation.
Usually, the device that is used for industrial continuous enforcement reaction of the present invention is based on following: at charging thing common excretory duct (3), at least one above-mentioned multicomponent reactor (5) and the product postprocessing (8) of component A and B, referring to Fig. 1,2 and 3, wherein said multicomponent reactor (5) comprises at least two reactor units that form is interchangeable lead reactor (5.1) (it is preferably filled with weighting material) and the reactor unit (5.3) that is connected described lead reactor system downstream that at least one is other.
All can be by pump and randomly on purpose collaborate continuously in the zone (3) by the heavy system of difference (Differenzw gesystem) from the unitary charging thing of storage tank component A and B.Usually, component A and B preferably mix 10-40 ℃ of metering interpolation with in zone (3) in envrionment temperature.But also can heat at least a component, two kinds of components or additive or corresponding mixture in advance.Therefore, can carry out climatic regulation (klimatieren) and/or reservoir container is designed to can be thermoregulated in described storage tank unit.In addition, described charging thing component can be collaborated under pressure.Can supply with charging thing mixture to multicomponent reactor (5) continuously by conduit (4).
Described multicomponent reactor (5) preferably reaches by temperature control medium D (6.1,6.2) or remains on the ideal service temperature, make and advantageously to avoid unfavorable temperature spikes and temperature fluctuation or reduction or it to be reduced to enough low that and temperature spikes and temperature fluctuation are known by batch device according to device of the present invention.
Product materials flow or crude product stream (7) can supply to product postprocessing (8) continuously, rectification cell for example, wherein, for example can through cat head (10) extract low-boiling products F (for example with excessive use with best callable silane) out and at the bottom of tower (9) extract high boiling point product E continuously out.But, also can (8) extract flow measurement out from the unit as product.
If require the reaction of component A and B component under the condition that has catalyzer C, to carry out, can add by metering in an advantageous manner so homogeneous catalyst is added in the feed material stream.Add the suspended catalyst that feed material flows to but also can using is measured.Wherein the largest particle diameter of suspended catalyst advantageously should be less than 1/3 of the size (Ausdehnung) of the minimum free cross section of the reactor unit of multicomponent reactor (5).
As shown in Figure 2, collaborated them in zone (3) with component A before, described catalyzer C is advantageously measured to be added in the B component.
Referring to Fig. 3,, the mixture that homogeneous catalyst C or suspended catalyst C are made up of A and B is in addition supplied to conduit (4) nearby preferably through conduit (2.2) in multicomponent reactor inlet front.
Under the situation of homogeneous catalyst, can also be to charging thing component A and B auxiliary agent that add other, that mainly be in a liquid state, for example but nonexcludability, activator, initiator, stablizer, inhibitor, solvent or thinner etc.
But, also can select to be equipped with the multicomponent reactor (5) of embedded catalyzer C, referring to Fig. 1.Catalyzer C wherein, for example but nonexcludability be preset on the reaction chamber surface of each reactor elements.
Usually, of the present invention be used for industrial continuous enforcement randomly at the device of the reaction that has described compd A under catalyzer C and other auxiliary agent condition and compd B based on following: at least one charging thing common excretory duct (3); At least one multicomponent reactor (5) comprises at least two according to reactor unit of the present invention (5.1 and 5.3) with regard to it; And product postprocessing (8).Suitably, prepare the charging thing in the storage tank unit that is used for reacting or use raw material, and supply with on request or the metering interpolation.In addition, device according to the present invention is equipped with that in the prior art conventional measurement, metering are added, close, transport, carried, monitoring, regulon, and waste gas and waste treatment device.In addition, this according to device of the present invention can advantageously be installed in can transport and stackable container in, and flexible operating.Like this, device of the present invention can for example use required in all cases charging thing source and energy derive fast and neatly.People can utilize device of the present invention and all advantages to prepare product continuously and for example by the further processed products of client or further use.
The continuous industry that is used for of the present invention is implemented α, the other outstanding especially advantage of the device of the reaction of β-unsaturated compound A and HSi compd B is: such possibility is provided now, also promptly with simple and economical mode continuously and production and sales amount neatly 000 ton of annual 5kg-50, a small amount of special outcome that preferred annual 10kg-10 is 000 ton.Unnecessary stop time be can advantageously avoid thus, yield, optionally temperature spikes and temperature fluctuation and the long residence time and the unfavorable side reaction that causes thus influenced.Especially, can utilize these devices to prepare above-mentioned silane from economics, ecology, the best mode in the friendly degree of client aspect.
Therefore, another theme of the present invention is the method for the 3-methacryloxypropyl organoalkoxysilane of industrial continuous preparation general formula (I):
Y-Si(R‘)
m(OR)
3-m (I)，
Wherein Y represents the 3-methacryloxypropyl, and R ' and R represent C independently
1-C
4Alkyl, and m=0 or 1,
In the method, implement the reaction of charging thing component A and B in multicomponent reactor (5) under the condition that has catalyzer C and optional other component, it is based at least two reactor units of form at least one interchangeable lead reactor (5.1) and the reactor unit (5.3) that is connected this lead reactor system downstream that at least one is other with regard to multicomponent reactor (5).
Preferably, described being reflected at least one multicomponent reactor (5) carried out, its reactor unit is made up of stainless steel or silica glass, perhaps its reaction chamber is by stainless steel or silica glass restriction, wherein the surface of reactor unit can for example apply or cover with the Teflon through applying or being capped.
In addition, in the method for the invention, preferably use its each cross section to be semicircle, half elliptic, circle, ellipse, trilateral, square, rectangle or trapezoid reactor unit.
Wherein, advantageously using its each cross-sectional area is 75 μ m
2-75cm
2Reactor unit.
In addition, preferably use such reactor unit, it has 5cm-200m, preferred especially 10cm-120m, and the most preferred 15cm-80m, the scantling length of more special 18cm-30m comprises that the institute between above-mentioned scope might numerical value.
Use suitable reactor unit in the methods of the invention, its each reaction volume is 0.01ml-100l (comprising all numerical value during being positioned at), preferred 0.1ml-50l, preferred especially 1ml-20l, the most preferred 2ml-10l, particularly 5ml-5l.
In the method according to the invention, described reaction can advantageously be carried out in the device with such multicomponent reactor (5) equally, described multicomponent reactor (5) is based on following: (i) lead reactor of at least two parallel connections (5.1) and at least one are connected the stainless steel capillary in described lead reactor downstream, perhaps (ii) the lead reactor of at least two parallel connections (5.1) and at least one are connected the quartz glass capillary in described lead reactor downstream, the perhaps (iii) lead reactor of at least two parallel connections (5.1) and at least one whole block reactor (5.3.1), the perhaps (iv) lead reactor of at least two parallel connections (5.1) and at least one bundled tube heat exchange reactor (5.9).
Particularly advantageous is such multicomponent reactor (5), it comprises at least two according to replaceable lead reactor of the present invention (5.1), is provided with the weighting material for example mentioned above of the hydrolysate that is used to separate used hydrolyzable silane in this lead reactor (5.1).Particularly advantageously, method of the present invention is carried out in the reactor unit of stainless steel preparation.
In addition, preferably, in the method for the invention with the reactor unit surface of the contacted multicomponent reactor of charging thing/product mixtures by catalyst-coated.
In case in the inventive method scope, component A and B react under the situation that has homogeneous catalyst C, so just be surprisingly found out that, particularly advantageously be, by with the mixture of homogeneous catalyst C and B component or by the mixture of homogeneous catalyst C and component A and B, perhaps the short period of time is moved this device (for example reaching 10-120 minute) and randomly once or repeatedly washes with the greater catalytic agent concentration, regulates this multicomponent reactor in advance.
The material that is used for regulating in advance this multicomponent reactor can be received and then at least in proportion metering add feed material stream to, perhaps be delivered directly to the product postprocessing process and carry out aftertreatment.
By the above-mentioned multicomponent of adjusting in advance reactor (particularly constituting), can be implemented in steady state operation under the highest yield quickly in beat all and favourable mode by stainless steel.
In the methods of the invention, can in gas phase and/or liquid phase, carry out described reaction.Wherein, reaction mixture or product mixtures can exist with single-phase, two-phase or three-phase.Preferably, in the methods of the invention, described reaction with single-phase, particularly carry out with liquid phase.
The method according to this invention is advantageously being used under the multicomponent reactor condition, carries out under 10-250 ℃ and 0.1-500 crust absolute pressure.Preferably, the reaction of component A and B, hydrosilylation reactions particularly, in the multicomponent reactor in 50-200 ℃ of temperature, preferred 60-180 ℃ of temperature, special 70-90 ℃ temperature, under 0.5-300 crust absolute pressure, under the preferred 1-200 crust absolute pressure, particularly preferably in carrying out under the 2-50 crust absolute pressure.
Usually, the pressure difference in apparatus of the present invention also is the pressure difference between charging thing common excretory duct (3) and the product postprocessing (8), is 1-10 crust absolute pressure.Advantageously, particularly when using Trimethoxy silane (TMOS), device of the present invention can be equipped with constant pressure regulating valve.Preferably, described constant pressure regulating valve is regulated 1-100 crust absolute pressure, preferably until 70 crust absolute pressures, especially preferably until 40 crust absolute pressures, the particularly value of 10-35 crust absolute pressure.
According to the present invention, described reaction can be at 1-110
4h
-1I.N. carry out under the linear velocity (LV).The flow velocity of materials flow is preferably 0.0001-1m/s i.N. in the reactor unit, preferred especially 0.0005-0.7m/s, particularly 0.05-0.3m/s, and all are positioned at the possible numerical value of above-mentioned scope.If touch upon reactor surface area (A) and reactor volume (V) ratio as a rule in reaction, so preferred 20-5000m according to the present invention
2/ m
3The A/V ratio, comprise that all are positioned at the possible numerical value of described scope, advantageously to carry out method of the present invention.This A/V is than being measuring at thermal conduction and the influence of possible out-phase (wall).
Therefore, in the methods of the invention, reaction advantageously 10 seconds-60 minutes, preferred 1-30 minute, preferred 2-20 minute especially, particularly carry out under 3-10 minute the mean residence time condition.Equally, all disclosed possibility numerical value in above-mentioned scope are all verified individually is favourable.
In the method according to the invention, can preferably use 3-methacryloxy 1-propylene (being called allyl methacrylate or allyl methacrylate(AMA)) as component A.
What be suitable as B component in the methods of the invention is the silane of general formula (II):
HSi(R‘)
m(OR)
3-m (II)，
Wherein R ' represents C independently with R
1-C
4Alkyl, and m=0 or 1, preferred R ' expression methyl and as radicals R preferable methyl or ethyl.
Therefore, according to the present invention, preferably use Trimethoxy silane (TMOS), triethoxyl silane (TEOS), methyl dimethoxysilane or methyldiethoxysilane.
In the methods of the invention, component A and B are preferably with 1: 5-100: 1, preferred especially 1: 4-5: 1, the most preferred 1: 2-2: 1, particularly 1.0: 1.5-1.5: 1.0 A uses the mol ratio of B, comprise all possible numerical value within described scope, for example but nonexcludability ground, 1: 1.2-0.8.
The inventive method is preferably carried out under the condition that has homogeneous catalyst C.But the inventive method also can be carried out under the condition of not adding catalyzer, wherein can expect the obvious decline of yield usually.
Especially, the inventive method is used to implement to be used for the hydrosilylation reactions of production according to the organosilane of formula (I), wherein particularly be selected from following homogeneous catalyst: the platinum group complex catalyst, those of Karstedt type for example, as the Pt in toluene (0) divinyl tetramethyl disiloxane, PtCl
4, H
2[PtCl
6] or H
2[PtCl
6] 6H
2O, preferred " Speyer-catalyzer ", cis (Ph
3P)
2PtCl
2, the complex catalyst of Pd, Rh, Ru, Cu, Ag, Au, Ir or other transition metal and precious metal those.Wherein, known complex catalyst itself can be dissolved in organic solvent, the preferred polar solvent, exemplary but nonexcludability ground, ether, as THF, ketone, as acetone, alcohol, as Virahol, aliphatic series or aromatic hydrocarbon are as toluene, dimethylbenzene.
In addition, can add activator to described homogeneous catalyst or homogeneous catalyst solution, for example with organic or mineral acid form, for example HCl, H
2SO
4, H
3PO
4, monocarboxylic acid or dicarboxylic acid, HCOOH, H
3C-COOH, propionic acid, oxalic acid, succsinic acid, citric acid, phenylformic acid, phthalic acid are only mentioned here.
In addition, add organic or mineral acid can be realized the function that other is favourable, for example as the inhibitor of the impurity of stablizer and trace scope to reaction mixture.
As long as use homogeneous catalyst or suspended catalyst in the methods of the invention, so based on the metal meter, olefin component A is preferably 2 000 000 to the mol ratio of catalyzer: 1 to 1 000: 1, preferred especially 1 000 000: 1 to 4 000: 1, particularly 500 000: 1 to 10 000: 1 and the institute within above-mentioned scope might numerical value.
But,, also can use the embedded catalyst or the heterogeneous catalyst that are selected from transition metal or precious metal or corresponding multielement catalyzer in order to carry out hydrosilylation reactions.Therefore, for example (but nonexcludability ground) uses precious metal cavernous body or the precious metal on gac.But, also can in multicomponent reactor scope, be provided for receiving the fixed bed of heterogeneous catalyst.Therefore, also can be for example (but nonexcludability ground) will be at carrier (for example especially by SiO
2, TiO
2, Al
2O
3, ZrO
2The spheroid that constitutes, bar, pill, right cylinder, stirrer etc.) on other heterogeneous catalyst be applied in the conversion zone of reactor unit.
Example with catalyst fixed bed whole block reactor is referring to following http://www.heatric.com/iqs/sid.0833095090382426307150/mab_react ors.html
In addition, can use solvent or thinner as auxiliary agent, for example alcohol, aliphatic series and aromatic hydrocarbon, ether, ester, ketone, CKW, FCKW only enumerate.These auxiliary agents can for example be removed from product in product postprocessing.
In the methods of the invention, equally can the known inhibitor of use itself, polymerization inhibitor for example, perhaps corresponding mixture is as extra auxiliary agent.
Usually, the method according to this invention is carried out in the following way:
Usually, at first charging thing component A, B and C optionally and other preparation are optionally added in metering, and with its mixing.Wherein strive reaching tolerance range≤± 20%, the homogeneous catalyst of preferred≤± 10%.Under special circumstances, can before the inlet of multicomponent reactor, short distance just add homogeneous catalyst and other optional auxiliary agent to the mixture metering of component A and B.Then, can supply with charging thing mixture and under temperature control condition, make described component reaction to described multicomponent reactor.Suitably, of the present invention being reflected under the condition that has at least a stablizer carried out, thereby avoids " forming the flower-shaped thing of rice krispies (Popcorn-Bildung) ".This stablizer and uses thereof itself is known, and is for example known by EP 0707009A1 or EP 0708081A2.Like this, for example can use the 2,6 di t butyl phenol of 0.05-3mol% (based on the amount of charging thing component A and B) as polymerization inhibitor.In addition, also can before reaching the temperature of reacting, wash or regulate in advance the multicomponent reactor with charging thing that contains catalyzer or charging thing mixture earlier.The preconditioning of multicomponent reactor also can be carried out under the temperature that raises a little.Product materials flow (crude product) that collaborate in the multicomponent reactor then, or that obtain can be with the suitable manner aftertreatment in the product postprocessing of apparatus of the present invention.In addition, can allow described product stand extra purification, for example but nonexcludability ground, purify using under short-path evaporator or the thin layer evaporator condition.The preferred operate continuously of described method.
Therefore, method of the present invention can used under the condition of device of the present invention in an advantageous manner with the product output operate continuously in 000 ton of every year of 5kg-50 and for example but nonexcludability ground advantageously produces the 3-methacryloxypropyl trimethoxy silane.
Embodiment
The present invention further sets forth by following embodiment, but does not limit theme of the present invention.
Embodiment
The preparation of 3-methacryloxypropyl trimethoxy silane
Be used for continuous production 3-methacryloxypropyl trimethoxy silane (Dynasylan
MEMO) used device is basically by stainless steel lead reactor (diameter is the stainless steel bead of 10mm, long 50mm, diameter average out to 1.5mm as weighting material) charging thing storage vessel, HPLC pump, regulon, measuring unit and metering adding device, T type mixing tank, four parallel connections, replaceable and that fill with weighting material, stainless steel integrated block reactor (to this referring to Fig. 5), thermoswitch, constant pressure regulating valve, has the N of using
2The short-path evaporator that the downstream of the stripping tower of operation connects and in device, being used to supply with the charging thing in said apparatus part and product outlet, reclaim the compound conduit between outlet and the waste gas outlet.In addition, be provided with about the temperature regulation of heating systems at lead reactor and block reactor with the cooling system.
At first, at room temperature, with allyl methacrylate (Degussa/R hm), [53g chloroplatinic acid-hexahydrate adds to 1dm with acetone to platinum (IV) catalyzer
3] and stabiliser system (N, N-phenylbenzene-P-pHENYLENE dI AMINE, DPPD and 2, the 6-di-tert-butyl-4-methy phenol, ionol) with mol ratio allyl methacrylate: Pt=16300: 1 and allyl methacrylate: DPPD: ionol=mix at 225: 1: 1, metering is added, and in T type mixing tank with Trimethoxy silane (TMOS, Degussa AG) with allyl methacrylate: TMOS=1: 1 mol ratio is mixed, and supplies in the reactor assembly continuously.Wherein pressure is 25 ± 10 crust.When device starts, should guarantee not contain as far as possible H
2O and O
2Unit state.Therefore, described device uses the charging thing mixture of allyl methacrylate-catalyzer-stablizer to wash in reactor system 1 hour before the temperature rising, then metering interpolation TMOS.The temperature of temperature adjustment being bathed with the continuous throughput of 90g/h altogether raises, with the temperature regulation to 75 in the reactor system ℃, and operate continuously 28 days.From crude product stream timing extraction sample, and measure by GC-WLD and to study.Based on the TMOS meter, transformation efficiency surpasses 99%, based target product meter, and selectivity is about 80%.The product materials flow of gained is by continuous stripping.Overhead product is fed into the calorifics afterfire, and bottom product is fed in the purification distillation of being undertaken by thin layer evaporator or short-path evaporator.
Claims (22)
1. device that is used for the following reaction of industrial continuous enforcement, wherein under the condition of other auxiliary agent that has catalyzer C and choose wantonly, make allyl methacrylate A and the reaction of HSi-compd B, described device is at least based on as follows: at the charging thing common excretory duct (3) of component A (1) and B (2), at least one multicomponent reactor (5), it comprises form and is other at least two reactor units of the reactor unit (5.3) that is connected described lead reactor system downstream of at least one interchangeable lead reactor (5.1) and at least one with regard to this multicomponent reactor (5), and product postprocessing (8).
2. the device of claim 1 is characterized in that reactor unit (5.3), comprises 1-100000 reactor unit with regard to this reactor unit (5.3).
3. claim 1 or 2 device is characterized in that reactor unit, and wherein lead reactor (5.1) has the free responding volume of 5ml-10l, and reactor unit (5.3) has the free responding volume of 1ml-100l altogether.
4. the device of one of claim 1-3, it is characterized in that at least one multicomponent reactor (5), described multicomponent reactor (5) is based on following: (i) lead reactor of at least two parallel connections (5.1) and at least one are connected the stainless steel capillary in described lead reactor downstream, perhaps (ii) the lead reactor of at least two parallel connections (5.1) and at least one are connected the quartz glass capillary in described lead reactor downstream, the perhaps (iii) lead reactor of at least two parallel connections (5.1) and at least one whole block reactor (5.3.1), the perhaps (iv) lead reactor of at least two parallel connections (5.1) and at least one microtubule fasolculus formula heat exchange reactor (5.9).
5. the device of one of claim 1-4 is characterized in that at least two lead reactor (5.1), and described lead reactor (5.1) is equipped with weighting material.
6. the device of one of claim 1-5, it is characterized in that multicomponent reactor (5), described multicomponent reactor (5) comprises 4-8 lead reactor (5.1) in parallel and that fill with weighting material and the whole block reactor (5.3.1) that is connected described lead reactor downstream, should comprise 10-4000 reactor unit (5.5) by whole block reactor.
7. be used to transform the multicomponent reactor (5) of hydrolyzable silane, it comprises form and is other at least two reactor units of the reactor unit that is connected described lead reactor downstream (5.3) form of at least one interchangeable lead reactor (5.1) and at least one with regard to this multicomponent reactor (5).
8. the multicomponent reactor of the device of one of claim 1-6 or claim 7 is characterized in that lead reactor (5.1), and described lead reactor (5.1) is filled with structure weighting material (5.1.3).
9. the method that is used for the 3-methacryloxypropyl organoalkoxysilane of industrial continuous production general formula (I):
Y-Si(R‘)
m(OR)
3-m (I)，
Wherein Y represents the 3-methacryloxypropyl, and R ' and R represent C independently
1-C
4Alkyl, and m=0 or 1,
In the method, implement the reaction of charging thing component A and B in multicomponent reactor (5) under the condition that has catalyzer C and optional other component, it is based at least two reactor units of form at least one interchangeable lead reactor (5.1) and the reactor unit (5.3) that is connected this lead reactor system downstream that at least one is other with regard to this multicomponent reactor (5).
10. the method for claim 9 is characterized in that, described being reflected at least one multicomponent reactor (5) carried out, and wherein said reactor unit is constructed with stainless steel, and is equipped with at least two lead reactor (5.1) with weighting material (5.1.3).
11. the method for claim 9 or 10 is characterized in that, makes allyl methacrylate [CH
2=C (CH
3) C (O) O-CH
2CH=CH
2] as component A and silane reaction as the general formula (II) of B component,
HSi(R‘)
mOR
3-m (II)，
R ' represents C independently with R in the general formula (II)
1-C
4Alkyl, and m=0 or 1.
12. the method for one of claim 9-11 is characterized in that, with 0.8-1.2: 1 mol ratio is used B component, also is hydrosilanes, and A, also is alkene.
13. the method for one of claim 9-12 is characterized in that, uses homogeneous catalyst C, and it is with 1-10: 60000 the mol ratio to component A is used, based on the precious metal meter.
14. the method for one of claim 9-13 is characterized in that, describedly is reflected at existence based on PtCl
4Perhaps H
2PtCl
6Perhaps H
2PtCl
66H
2Carry out under the condition of the catalyzer C of O.
15. the method for one of claim 9-14 is characterized in that, with the charging thing mixture preconditioning multicomponent reactor (5) that contains catalyzer.
16. the method for one of claim 9-15 is characterized in that, is reflected at the pressure operation of 60-90 ℃ of temperature and 15-35 crust absolute pressure in multicomponent reactor (5).
17. the method for one of claim 9-16 is characterized in that, described reaction is carried out with 1 minute-10 minutes mean residence time.
18. the method for one of claim 9-17 is characterized in that, described reaction is with 20-50000m
2/ m
3Reactor surface the ratio A/V of reactor volume is carried out.
19. the method for one of claim 9-18, it is characterized in that continuous measurement adds and parallel feeding thing component A, B and C, the charging thing mixture with the defined volume flow supplies in the multicomponent reactor (5) then, reaction, and the thus obtained product mixtures of aftertreatment subsequently.
20. the method for one of claim 9-19 is characterized in that, uses the charging thing mixture based on component A, B and C, it contains as at least a stablizer of other component and at least a activator optionally.
21. the method for one of claim 9-20, it is characterized in that, after limiting the operating time, change at least one lead reactor (5.1) that randomly is filled with weighting material (5.1.3) with the new optional lead reactor of weighting material that is equipped with, the lead reactor (5.1) of manipulate at least one other is with this continuation method of further enforcement.
22. the method for one of claim 9-21 is characterized in that, the velocity of flow in lead reactor (5.1) is lower than the velocity of flow of the reactor unit that connects in the downstream.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006037403.7 | 2006-08-10 | ||
| DE102006037403 | 2006-08-10 | ||
| DE102007023760.1 | 2007-05-22 |
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| Publication Number | Publication Date |
|---|---|
| CN101121727A true CN101121727A (en) | 2008-02-13 |
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ID=39084247
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101407246A Pending CN101121727A (en) | 2006-08-10 | 2007-08-09 | System, reactor and process for continuous industrial preparation of 3-methacryloyloxypropylalkoxysilanes |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115948721A (en) * | 2023-03-15 | 2023-04-11 | 杭州幄肯新材料科技有限公司 | Method for preparing tantalum carbide coating by CVD (chemical vapor deposition) method |
-
2007
- 2007-08-09 CN CNA2007101407246A patent/CN101121727A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115948721A (en) * | 2023-03-15 | 2023-04-11 | 杭州幄肯新材料科技有限公司 | Method for preparing tantalum carbide coating by CVD (chemical vapor deposition) method |
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