CN101805304A - Method for preparing aliphatic polyisocyanurate by using microreactor - Google Patents
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Abstract
The invention discloses a method for preparing aliphatic polyisocyanurate by using a microreactor, which comprises the following steps: adding isocyanurate and a catalyst compound system formed by quaternary ammonium salt and inert alcohol solvent to enable the isocyanurate to generate a polymerization reaction; then feeding a formed material flow into a dynamic reactor for continuously carrying out a polymerization reaction; and enabling reaction solution obtained by the reaction to pass through a second-stage evaporator to obtain a polyisocyanurate product. The method can well control the reactivity of the catalyst, so that a trimerization reaction of the isocyanurate is finished under a mild condition to obtain a tripolymer product with excessively-high quality.
Description
Technical field
The present invention relates to a kind of aliphatic isocyanates trimer preparation method, specifically, is a kind of method for preparing aliphatic polyisocyanurate by microreactor.
Background technology
Microreactor is a kind of fluid flowing passage made from micro-processing technology; be the chemical reactor of characteristic dimension in hundreds of microns; early 1980s; Tuckerman and Pease have proposed the notion of " microchannel heat sink " first, have successfully solved " thermal boundary " problem that unicircuit is extensive and ultra-largeization faced.Early 1990s, microreactor begins to use in chemical field, because its good application characteristic, little chemical industry technology conception just causes chemical field expert's great interest and concern rapidly.The use of microreactor in chemical field says it is a kind of pipeline reactor of continuous flow in essence, and it comprises mixing tank, interchanger, reactor, controller etc.Because microreactor has good operability and safety coefficient, be particularly suitable in the reaction of heat release fast, using.
Before more than 100 years, German famous scientist's Huffman has been found that three isocyanate group are reacted and can have been generated isocyanuric acid ester.The sixties in last century, the industrialization of the isocyanuric acid ester of Beyer Co., Ltd, its HDI tripolymer is owing to have stable isocyanuric acid ester heterocycle structure in the molecule, thereby volatility is low, toxicity is little, stability in storage is good, compare with biuret, have excellent more weathering resistance, thermotolerance, light stability, viscosity is low, therefore goods hardness height is widely used in the polyurethane material.
The HDI isocyanuric acid ester can be used for preparing polyurethane coating, has good weather resisteant, chemical stability and long working life.The trimerical stability in storage of HDI especially is better than biuret.Simultaneously, the anti-yellowing property of tripolymer in product is placed is significantly better than biuret and other class adducts product, but in preparation tripolymer process, have following problem: catalyzer is remaining easily, influences the later stage application; Obtain the easy flavescence of adducts, influence the later stage product properties; It is bigger to obtain trimerical product viscosity, influences workability.Therefore, the trimerical development of high-performance is significant for the development in the raising of HDI product performance and market.
USP4324879 disclosed adopt molecular weight at the quaternary amine alkali of 121-300 as catalyzer, temperature of reaction 20-80 ℃, solvent is selected to depend primarily on catalyzer, with catalyst dissolution, can be toluene, dimethyl formamide, dimethyl sulfoxide (DMSO) and composition thereof.According to catalyst type, temperature is risen to 70 ℃ of-120 ℃ of termination reactions, catalyzer at high temperature decomposes.If adding terminator, its consumption are the 5-20% of theoretical amount.Its shortcoming is that temperature of reaction is higher, can cause the aggravation of tripolymer level of response, and polymer increases, cause the finished product viscosity to increase, and because temperature of reaction is higher, the easy flavescence of tripolymer, and the solvent of solvent that adopts and later stage product configuration is inconsistent, influences trimerical application performance.
USP5905151 has disclosed a kind of trimeric catalyzer, selects hot active substance for use, the lithium salts of the hydroxyl of aliphatics or aromatic carboxylic acid and contain the organism of a hydroxyl at least.Temperature of reaction 125-250 ℃, reaction times 2-120min, catalyst levels: lithium salts 0.001-0.01%, hydroxy-containing compounds 0.05-4.0%.Suitable lithium salts comprises single lithium salts and two lithium salts of aliphatics or aromatic carboxylic acid, and the hydroxyl organism is preferably 1, ammediol, 1,3 butylene glycol.The shortcoming of this patent is that temperature of reaction is too high, and viscosity is excessive, the possible flavescence of the final product color that obtains, and have metal ion, in the product application process, influence product performance.
CN1280588A relates to the purposes of cationic supercarbonate as the cyclotrimerization catalyzer of isocyanic ester, also relate to the method for preparing polyisocyanates by the catalysis cyclotrimerization of isocyanic ester, wherein employed catalyst system, comprise as catalyzer based on the ring catalyst for trimerization of quaternary ammonium salt with as the imidazoles or derivatives thereof of promotor.
The catalyzer that USP5070137 adopted is the N-2-hydroxyalkyl quaternary ammonium salt of uncle's aliphatic carboxylic acid, and the tripolymer color and luster that obtains is low, and quality is good; Catalyst levels 20-200ppm, catalyzer can be used solvent cut, can add alcohol as synergistic catalyst, as 1, ammediol, temperature of reaction 30-120 ℃, the formation speed of isocyanuric acid ester can be measured by the refractive index of assaying reaction system, and the trimerization reaction transformation efficiency is controlled between the 10-45%.Come decaying catalyst with Mono Chloro Acetic Acid, Benzoyl chloride.
By above-mentioned domestic and international patent analyses as can be seen, the trimerical research of aliphatic isocyanates mainly is to carry out aspect the selection of the selection of release, related solvents at new trimerization catalysts and terminator.The problem that trimerization reaction mainly exists is that exothermic heat of reaction is excessive, difficult with the control reaction process, and the catalyzer and the auxiliary agent that append are on the high side, the particularly use of dibasic alcohol, easily and isocyanic ester generation polycondensation, the by product of not expecting is arranged in the product of generation, and in last handling process, can not eliminate these micro-components, thereby influence final trimerical application performance.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing aliphatic polyisocyanurate by microreactor.
Provided by the present invention to prepare the method for aliphatic polyisocyanurate by microreactor as follows: with in isocyanic ester and the catalyst composite system adding microreactor that is formed by quaternary ammonium salt and inert alcoholic solvent, make the isocyanic ester polymerization reaction take place, formed reactant flow is sent in the dynamic response device proceeded polyreaction then; Reaction solution process secondary evaporimeter by above-mentioned reaction obtains obtains the polyisocyanurate product.
Reaction raw materials of the present invention is aliphatic series and/or alicyclic two or polyisocyanates, promptly have at least 2, preferred 2-4, (aliphatic series NCO) and/or alicyclic polyisocyanates, described polyisocyanates can use separately or mix use with another kind for preferred especially 2 or 3 isocyanate groups.Suitable vulcabond is preferably the vulcabond with 4-20 carbon atom, tetramethylene-1 for example, 4-vulcabond, pentamethylene-1,5-vulcabond, hexa-methylene-1,6-vulcabond (HDI), lysinediisocyanate, isophorone diisocyanate (IPDI) and dicyclohexyl methane diisocyanate (H
12MDI).This type of vulcabond can use separately or mix use with another kind.Especially preferably use HDI, IPDI.
In the method for the invention, the preparation method of the isocyanate material of use is inessential for the enforcement of the inventive method, and the preparation of this isocyanic ester raw material is adopted phosgenation or non-phosgene relation not quite.
Catalyst composite of the present invention is is the compound system of quaternary ammonium salt and inert alcohol kind solvent, and this type of catalyst system can be good at impelling the aliphatic isocyanates trimerization reaction to obtain suitable tripolymer isocyanuric acid ester product; Can comparatively gentlely impel the aliphatic isocyanates reaction to generate three dimerization products.
In catalyst composite of the present invention was, main catalyzer was the quaternary ammonium salt of mentioning in existing literature and the patent.This type of catalyzer can be good at impelling the aliphatic isocyanates trimerization reaction to obtain tripolymer isocyanuric acid ester product, but this type of activity of such catalysts is higher, makes the trimerization reaction excessive velocities, can cause runaway reaction., according to method of the present invention, preferably, the substituting group on the ammonium ion of described quaternary ammonium salt is selected, its substituting group is mainly alkyl chain C for this reason
nH
2n+1, wherein n represents 1-15.Obtain easily having: methyl quaternary ammonium, ethyl quaternary ammonium salt, butyl quaternary ammonium salt, hexyl quaternary ammonium salt, octyl group quaternary ammonium salt with the main structure type of operable quaternary ammonium salt catalyst, preferred long hexyl quaternary ammonium salt and the octyl group quaternary ammonium salt of carbochain, most preferably octyl group quaternary ammonium salt.
Quaternary ammonium salt catalyst is as salt, though it has amphiphatic characteristics, but the solvability in isocyanic ester is very low, it exists with solid form in isocyanic ester, it is poor to cause reacting discrete form like this, finally cause the polyreaction weak effect, therefore in the use of catalyzer, need complex solvent to use.Study according to dissolubility test, in order to reach solvability and preferable reaction effect preferably, have the certain proportion scope between quaternary ammonium salt and the solvent, the mass percent that preferred described quaternary ammonium salt catalyst accounts for described catalyst composite system is 20-60%, preferred 30-50%.
Mention in above-mentioned document, the solvent that they adopt mostly is dibasic alcohol or toluene kind solvent.Wherein, dibasic alcohol can make vulcabond and dibasic alcohol polymerization reaction take place, generates the high polymer of not expecting.And toluene, dimethyl formamide, dimethyl sulfoxide (DMSO) and composition thereof is as solvent, and its solvability is not good, makes reaction generate some solid ureas materials of not expecting.Find after deliberation that now the inertia alcohols that can adopt low molecule simple function group is as the dissolution with solvents catalyzer.Dissolve the reactive behavior that the catalyzer that obtains can be good at control catalyst by the inertia alcohols, the trimerization reaction of isocyanic ester is finished under the condition of gentleness, obtain the very high tripolymer product of quality.The inertia alcohols of described low molecule simple function group has primary alconol, secondary alcohol and the tertiary alcohol.Since alcohols as the compound that contains the hydroxyl activity group can with isocyanic ester under certain condition, reaction generates carbamate groups, therefore will select existing very strong solvability, and the alcohols of very weak reactive behavior is arranged again.In conjunction with the characteristics of two aspects, the preferred in the present invention secondary alcohol and the tertiary alcohol; From the structure steric hindrance of molecule, in conjunction with the advantage of two aspects, the tertiary alcohol most preferably, its basic structure is:
R1-C(R2)(R3)-OH
Wherein R1, R2 have represented identical or different groups with R3, and this group has been represented and contained alkyl, alkylene or the aryl group of 15 carbon atoms at the most.Representational tertiary alcohols is the trimethyl carbinol, tertiary amyl alcohol, uncle's hexanol and uncle's nonyl alcohol etc., and it can be separately as solvent or mixes use with another kind in the present invention.From common property, being easy to get property and operability, more preferably adopt the trimethyl carbinol.In order to reach solvability preferably, preferable reaction effect and the side reaction of minimum controllable, there is the certain proportion scope between quaternary ammonium salt and the solvent, the mass percent that described inert solvent accounts for described catalyst composite system is 40-80%, preferred 50-70%.In this scope, composite catalyst system can well be controlled reaction process.
This type of catalyst system belongs to compound system, can comparatively gentlely impel the aliphatic isocyanates reaction to generate three dimerization products, this system is as the catalyzer that promotes reaction process, use the certain scope that exists, excessive usage quantity can cause the rapid reaction of isocyanic ester equally, moment causes a large amount of heat to discharge, and causes the excessive polymerization of whole system; But when catalyst levels was very few, polymerization that can not initiator system made the catalyzed reaction failure.Therefore, based on the weight of reaction raw materials isocyanic ester, the consumption of this type of catalyst composite system is 10-3000ppm, is preferably 100-500ppm.In this scope, composite catalyst system can well be controlled the trimerization reaction process.
Mention that in the application's background technology part the problem that trimerization reaction mainly exists is that exothermic heat of reaction is excessive, difficult with the control reaction process, cause the finished product molecular weight distribution not good, quality product is lower, and in the technology amplification process, causes technology to amplify failure.Method provided by the present invention adopts second reactor to prepare polyisocyanates, in catalyst compounded adding microreactor, make the isocyanic ester rapid reaction, then resulting reactant flow is sent into and carried out further polyreaction in the dynamic response device and obtained the higher tripolymer product of quality.This operational path, adopt microreactor that isocyanic ester and trace catalyst are reacted efficiently, reduced the usage quantity of catalyzer, make the catalytic trimerization reaction obtain good control, delayed the polyreaction of isocyanic ester simultaneously, its heat in reaction process is under control, has finally obtained the higher tripolymer product of quality; And the trimerization reaction release of heat can provide heat for partial dynamic response device, has reduced the heat in the technology like this for amount.
Microreactor (micro passage reaction) is a kind of fluid flowing passage made from micro-processing technology, is the chemical reactor of characteristic dimension in hundreds of microns.Early 1990s, microreactor begins to use in chemical field, has good application characteristic.Say that in essence microreactor is a kind of pipeline reactor of continuous flow, it comprises mixing tank, interchanger, reactor, controller etc.Its internal structure can be the structure of various ways, because the characteristic of microreactor size, microreactor has good operability and safety coefficient, is particularly suitable for using in the reaction of heat release fast.Microreactor is applied in the poly-acid cyanamide ester and sets forth to some extent in the literature, and this mainly is a well blend effect of having utilized microreactor; Microreactor is applied in the reaction process of strong heat release, also sets forth to some extent.Yet, do not seeing relevant report aspect the isocyanate trimerization prepared in reaction isocyanuric acid ester so far as yet.The heat that the present invention adopts microreactor obviously to disperse the isocyanic ester polyreaction to discharge, reaction system can be well controlled, and finally obtains suitable product.
The present invention has adopted microreactor as first step reactor, its dispersion effect is very good, reaction is highly susceptible to control, because the trimerization reaction of isocyanic ester under the quaternary ammonium salt catalyst condition, need intensive to mix, so that snap-out release goes out heat, because the reaction times is very of short duration, therefore selected microreactor as first step reactor, the preferred 10-60 of the temperature of microreactor ℃, most preferably 20-40 ℃, under this temperature of reaction, catalyzer is added in the microreactor, because activity of such catalysts is very high, under the mixing condition efficiently of microreactor, its dispersion effect is very good, therefore isocyanic ester can generate polyisocyanates in the tubular reactor rapid reaction, and it stops the reaction times is 1-10 minute, preferred 3-7 minute, in at this moment, by miniature hybrid reaction system, the temperature of reaction of the hierarchy of control that can be stable obtains tripolymer, dimer, carbodiimide occupies most polyisocyanates; If be lower than this time, because the time is shorter, catalyzer is not enough in the dispersion of isocyanic ester, generates a large amount of solids easily, and causes excessively polymerization of part, generates excessive superpolymer; If the reaction times is long, the reaction times of isocyanic ester and catalyst mix is longer, may produce a large amount of heats, can not effectively discharge, and causes excessive polymerization, and causing reaction product equally is not the product of expectation; Therefore, when selecting microreactor, should select to mix better relatively, and suitable microreactor of the residence time.The reaction solution that obtains through microreactor enters second stage reactive system, finally obtains suitable tripolymer product.
The material of microreactor of the present invention is generally chosen stainless steel, glass, pottery, alloy or enamel, preferred stainless steel and stupalith, most preferably stupalith.The form of microreactor is mainly circle, ellipse, trilateral, square and hexagon etc., and circular microreactor, the microchannel number of described microreactor are 20-500, is preferably 200-300; The diameter of described circular microreactor is generally 0.01-2mm, is preferably 0.07-0.15mm.The mobile needs certain power of liquid in microreactor, at this pressure of selecting 0.1-1bar as power.
The HDI tripolymer is the polyisocyanate curing agent that autohemagglutination forms under catalyst action, its theoretical functionality is 3, usually the trimer product that obtains is the mixture of a plurality of components, functionality has tripolymer, dimer, carbodiimide, linear polymer and ring-type polymer etc. greater than 3 in the autohemagglutination product of HDI.Because the required functionality of HDI tripolymer is greater than 3, therefore the reaction product that obtains from first step reactor needs further in-depth reaction, and the functionality that obtains is higher than 3 polymeric articles.The present invention preferably adopts tank reactor as second stage reactor.In this second stage reactor, the further polymerization of reaction solution has obtained final (monomer content is certain) trimerical product.
The second stage reactor that the present invention mentions is the dynamic response device, preferred conventional tank reactor.In this tank reactor, the tripolymer solution of complete reaction does not react and slaking the tripolymer product that finally obtains through further under certain insulation measure.In this process, second stage reactor has absorbed the heat that first step reactor is discharged, only need the trace heat or need not heat.In the reactor of the second stage, only need intensive to disperse promptly can obtain good reaction effect.Because the dispersion effect of microreactor is very good, and the tripolymer product that obtains is very good, thus the reaction times of tank reactor reduce relative with temperature.From tripolymer reaction, the preferred 20-60 of its temperature of reaction ℃, most preferably 30-50 ℃; From final quality product and application performance, its reaction time of trimerization reaction and slaking preferred 0-5 hour, most preferably 1-2 hour.Through reaction and the maturation process of short period of time, make the tripolymer steady quality of the finished product, in separation and put procedure, its tripolymer and polymeric ratio remain unchanged.In this process, if the reaction times is too short, the reaction product extent of polymerization deficiency that it obtains, following monomer remove with the product last handling process in, its component changes easily, and product changes in put procedure easily, influences the performance of product at last; If the reaction times is long, may cause the excessive polymerization of product, the product of not expected, and with the prolongation in reaction times causes product to produce not desired color easily and deepens phenomenon.
In the technical process of most adducts demonomerization, adopted secondary evaporimeter to carry out monomer and removed, the present invention adopts this area secondary evaporimeter commonly used equally, separates obtaining the lower tripolymer product of monomer content.
Embodiment
To give further instruction to method provided by the present invention by following examples, but therefore the present invention is not subjected to any restriction.
Embodiment 1
With nitrogen the HDI monomer is removed a spot of air and steam, it is that 0.1mm, length are in 10 centimetres the microreactor that the HDI monomer of the catalyzer (mass ratio of the DABCOTMR and the trimethyl carbinol is 4: 6) of 0.01g/min and 100g/min is joined the default internal diameter of being made by ten thousand magnificent urethane companies to 40 ℃, the microchannel number is 250, reaction pressure is 0.2bar, reaction raw materials residence time in reactor is about 3 minutes, stop successive catalyzer and monomer feed after 30 minutes, detect NCO and viscosity at the sampling spot that is provided with; Reaction solution enters in one 5 liters the reactor that disposes agitator, nitrogen inlet, automatic temperature control system subsequently, temperature of reaction kettle is promoted to 30 ℃ in advance, the exothermic heat of reaction that depends in the microreactor is increased to 50 ℃ with the temperature of reaction of second reactor, reaction is 1 hour in second reactor, obtain corresponding tripolymer product, analyze by viscosity and NCO, determine the terminal point of reaction process.Through the secondary separation system, obtain corresponding tripolymer product, obtain corresponding product through NCO and viscosity test, its NCO content is 22.96%, viscosity is 2209mPas.
Embodiment 2
With nitrogen the HDI monomer is removed a spot of air and steam, it is that 0.1mm, length are in 15 centimetres the microreactor that the HDI monomer of the catalyzer (mass ratio of the DABCOTMR and the trimethyl carbinol is 1: 1) of 0.01g/min and 100g/min is joined the default internal diameter of being made by ten thousand magnificent urethane companies to 40 ℃, the microchannel number is 250, reaction pressure is 0.2bar, reaction raw materials residence time in microreactor is about 5 minutes, stop successive catalyzer and monomer feed after 30 minutes, detect NCO and viscosity at the sampling spot that is provided with; Reaction solution enters in one 5 liters the reactor that disposes agitator, nitrogen inlet, automatic temperature control system subsequently, temperature of reaction kettle is promoted to 30 ℃ in advance, the exothermic heat of reaction that depends in the microreactor is increased to 50 ℃ with the temperature of reaction of second reactor, reaction is 0.5 hour in second reactor, obtain corresponding tripolymer product, analyze by viscosity and NCO, determine the terminal point of reaction process.Through the secondary separation system, obtain corresponding tripolymer product, obtain corresponding product through NCO and viscosity test, its NCO content is 22.93%, viscosity is 2218mPas.
Comparative Examples 1
With nitrogen the HDI monomer is removed a spot of air and steam, the monomer HDI of 3000g joined in one 5 liters the reactor that disposes agitator, nitrogen inlet, automatic temperature control system, temperature of reaction kettle is promoted to 50 ℃ in advance, drip 0.3g catalyzer (mass ratio of the DABCO TMR and the trimethyl carbinol is 4: 6), reaction is 4 hours in reactor, obtain corresponding tripolymer product, analyze, determine the terminal point of reaction process by viscosity and NCO.Through the secondary separation system, obtain corresponding tripolymer product, obtain corresponding product through NCO and viscosity test, its NCO content is 21.92%, viscosity is 2530mPas.In the reaction process, temperature rises very fast, and a large amount of solid particulates is arranged in the reactor, and the viscosity of resulting the finished product is big.
Comparative Examples 2
Comparative catalyst's experimental study, wherein catalyzer adopts commercial catalysts DABCO TMR, no composite tertiary alcohol solvent cut, test according to step substantially the same manner as Example 1, the reaction product viscosity that obtains is big, wherein contains a large amount of solid precipitations, and reaction is difficult to control, the NCO content of the finished product is 21.12%, and viscosity is 3530mPas.
Claims (14)
1. method for preparing aliphatic polyisocyanurate by microreactor, may further comprise the steps: isocyanic ester is added in the microreactor with the catalyst composite system that is formed by quaternary ammonium salt and inert alcohol kind solvent, make the isocyanic ester polymerization reaction take place, formed reactant flow is sent in the dynamic response device proceeded polyreaction then; Reaction solution process secondary evaporimeter by above-mentioned reaction obtains obtains the polyisocyanurate product.
2. method according to claim 1 is characterized in that, described isocyanic ester is aliphatic series and/or alicyclic two or polyisocyanates; Preferred described isocyanic ester is the vulcabond with 4-20 carbon atom.
3. method according to claim 2, it is characterized in that, described vulcabond is selected from: tetramethylene-1,4-vulcabond, pentamethylene-1,5-vulcabond, hexa-methylene-1, the mixture of one or more in 6-vulcabond, lysinediisocyanate, isophorone diisocyanate and the dicyclohexyl methane diisocyanate; Preferably, described vulcabond is a hexa-methylene-1,6-vulcabond, isophorone diisocyanate.
4. according to claim 1 or 3 described methods, it is characterized in that the substituting group on the ammonium ion of described quaternary ammonium salt is alkyl chain C
nH
2n+1, wherein n represents 1-15.
5. method according to claim 4 is characterized in that, described quaternary ammonium salt is selected from: methyl quaternary ammonium, ethyl quaternary ammonium salt, butyl quaternary ammonium salt, hexyl quaternary ammonium salt and octyl group quaternary ammonium salt; Wherein, preferred hexyl and octyl group ammonium salt; More preferably octyl group quaternary ammonium salt.
6. method according to claim 5 is characterized in that, described quaternary ammonium salt accounts for the 20-60% that described catalyst composite is, preferred 30-50%.
7. according to claim 1 or 6 described methods, it is characterized in that the described inert alcohol kind solvent that constitutes catalyst composite system is primary alconol, secondary alcohol or the tertiary alcohol; Wherein, the preferred secondary alcohol or the tertiary alcohol; The tertiary alcohol that more preferably has following structure:
R1-C(R2)(R3)-OH
Wherein, R1, R2 and the identical or different group of R3 representative, described group is to contain alkyl, alkylene or the aryl group of 15 carbon atoms at the most.
8. method according to claim 7 is characterized in that, described inert alcohol kind solvent is selected from: the mixture of one or more in the trimethyl carbinol, tertiary amyl alcohol, uncle's hexanol and the uncle's nonyl alcohol; Wherein, preferred tertiary butanols.
9. method according to claim 8 is characterized in that, described inert alcohol kind solvent accounts for the 40-80 quality % that described catalyst composite is, preferred 50-70 quality %.
10. according to claim 1 or 9 described methods, it is characterized in that the consumption that described catalyst composite is is 10-3000ppm, preferred 100-500ppm.
11. method according to claim 10 is characterized in that, the temperature of reaction in the described microreactor is 10-60 ℃, further preferred 20-40 ℃; The stop reaction times that isocyanic ester and described catalyst composite tie up in the microreactor is 1-10 minute, preferred 3-7 minute.
12., it is characterized in that the material of described microreactor is selected from: stainless steel, glass, pottery, alloy or enamel according to claim 1 or 11 described methods; Preferred stainless steel or stupalith, most preferably stupalith.
13. method according to claim 12 is characterized in that, the form of described microreactor is circle, ellipse, trilateral, square or hexagon; Be preferably circular microreactor, and the microchannel number of circular microreactor is 20-500, preferred 200-300; The diameter of circular microreactor is 0.01-2mm, and preferred diameter is 0.07-0.15mm.
14., it is characterized in that described dynamic response device is a tank reactor according to claim 1 or 13 described methods; The temperature of reaction of tank reactor is 20-60 ℃, preferred 30-50 ℃; The residence time of reactant flow in tank reactor is 0-5 hour, preferred 1-2 hour.
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| WO2013060614A1 (en) | 2011-10-28 | 2013-05-02 | Basf Se | Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| WO2013060809A2 (en) | 2011-10-28 | 2013-05-02 | Basf Se | Method for producing polyisocyanates, which are flocculation-stable in solvents, from (cyclo)aliphatic diisocyanates |
| CN105111109A (en) * | 2015-09-17 | 2015-12-02 | 杭州海虹精细化工有限公司 | Method for preparing nitrourea by utilizing microchannel reactor |
| US9617402B2 (en) | 2011-10-28 | 2017-04-11 | Basf Se | Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates |
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| EP3336117A1 (en) | 2017-09-20 | 2018-06-20 | Basf Se | Method for the preparation of flocculation stable polyisocyanates of (cyclo)aliphatic diisocyanates in solvents |
| EP3336118A1 (en) | 2017-09-20 | 2018-06-20 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
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| WO2022128925A1 (en) | 2020-12-18 | 2022-06-23 | Basf Se | Color-stable curing agent compositions comprising polyisocyanates of (cyclo)aliphatic diisocyanates |
| CN116813878A (en) * | 2023-08-29 | 2023-09-29 | 吉林中科优锐科技有限公司 | Method for continuously preparing 1,5 naphthalene diisocyanate prepolymer |
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