CN101805304B - Method for preparing aliphatic polyisocyanurate through microreactor - Google Patents
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- CN101805304B CN101805304B CN 201010149678 CN201010149678A CN101805304B CN 101805304 B CN101805304 B CN 101805304B CN 201010149678 CN201010149678 CN 201010149678 CN 201010149678 A CN201010149678 A CN 201010149678A CN 101805304 B CN101805304 B CN 101805304B
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- ammonium salt
- isocyanic ester
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 11
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 10
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims description 28
- -1 ethyl quaternary ammonium salt Chemical class 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 12
- 239000012948 isocyanate Substances 0.000 abstract description 11
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 239000013638 trimer Substances 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006006 cyclotrimerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing aliphatic polyisocyanurate by means of a microreactor comprising the steps of: adding isocyanate and a catalyst composite system formed by quaternary ammonium salt and inert alcohol solvent into a microreactor to enable isocyanate to generate polymerization reaction, and then sending the formed reactant flow into a dynamic reactor to continue the polymerization reaction; and (3) passing the reaction liquid obtained by the reaction through a secondary evaporator to obtain a polyisocyanurate product. The method can well control the reaction activity of the catalyst, so that the trimerization reaction of the isocyanate is completed under mild conditions, and a trimer product with very high quality is obtained.
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 through microreactor.
Background technology
Microreactor is a kind of fluid flowing passage made from micro-processing technology; Be the reaction apparatus 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 drum, unit etc.Because microreactor has good operability and SF, 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 NCOs react and can have been generated isocyanuric acid ester.The sixties in last century, the industriallization 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; Hardness is high, therefore is widely used in the polyurethane material.
The HDI isocyanuric acid ester can be used for preparing polyurethane coating, has good weather resisteant, chemicalstability 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 obviously is better than biuret and other type 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, N, DMSO 99.8MIN. 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 metals 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 POLYMETHYLENE POLYPHENYLISOCYANATE by the catalysis cyclotrimerization of isocyanic ester; Wherein employed catalystsystem, 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 through 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 99min..
Can find out that through above-mentioned domestic and international patent analyses the trimerical research of aliphatic isocyanates mainly is to carry out aspect the selection of selection and terminator of release, related solvents at new trimerization catalysts.The problem that trimerization reaction mainly exists is that exothermic heat of reaction is excessive, and is difficult with the control reaction process, and the catalyzer that appends and auxiliary agent are on the high side; The particularly use of divalent alcohol; Be prone to 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 through microreactor.
Provided by the present invention to prepare the method for aliphatic polyisocyanurate through microreactor following: with isocyanic ester and the catalyst composite that is formed by quaternary ammonium salt and inert alcoholic solvent is in the adding microreactor; 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 through above-mentioned reaction obtains obtains the polyisocyanurate product.
The reaction raw materials that the present invention adopted is aliphatic series and/or alicyclic two or POLYMETHYLENE POLYPHENYLISOCYANATE; Promptly have at least 2; Preferred 2-4; (aliphatic series NCO) and/or alicyclic polyisocyanates, said POLYMETHYLENE POLYPHENYLISOCYANATE 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), LDI, 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.
The catalyst composite system that the present invention adopted 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 the catalyst composite system that the present invention adopted, main catalyzer is 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 said 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, the solvability in isocyanic ester is very low, and 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 said quaternary ammonium salt catalyst accounts for said catalyst composite system is 20-60%, preferred 30-50%.
In above-mentioned document, mention, mostly the solvent that they adopt is divalent alcohol or toluene kind solvent.Wherein, divalent alcohol can make vulcabond and divalent alcohol polymerization reaction take place, generates the high polymer of not expecting.And toluene, N, DMSO 99.8MIN. and composition thereof is as solvent, and its solvability is not good, makes reaction generate some solid ureas materials of not expecting.Existing discovery after deliberation, 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 through the inertia alcohols, the trimerization reaction of isocyanic ester is accomplished under the condition of gentleness, obtain the very high tripolymer product of quality.The inertia alcohols of said 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; See from the structure steric hindrance of molecule, in conjunction with the advantage of two aspects, the tertiary alcohol most preferably, its substruction is:
R1-C(R2)(R3)-OH
Wherein R1, R2 and R3 have represented identical or different groups, 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 said inert solvent accounts for said 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 used the certain scope that exists as the catalyzer that promotes reaction process, and 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 MWD 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 POLYMETHYLENE POLYPHENYLISOCYANATE; 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; Reduce the usage quantity of catalyzer, made 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 confession amount in the technology like this.
Microreactor (micro passage reaction) is a kind of fluid flowing passage made from micro-processing technology, is the reaction apparatus 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 drum, unit etc.Its internal structure can be the structure of various ways, because the characteristic of microreactor size, microreactor has good operability and SF, is particularly suitable in the reaction of heat release fast, using.Microreactor is applied in to gather in the acid cyanamide ester and in document, sets forth to some extent, 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 drum, and its dispersion effect is very good, and 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 drum, 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, so isocyanic ester can generate POLYMETHYLENE POLYPHENYLISOCYANATE in the tubular reactor rapid reaction; It stops reaction times is 1-10 minute, preferred 3-7 minute, at this moment between in; Through miniature hybrid reaction system, the temperature of reaction of the hierarchy of control that can be stable obtains tripolymer, dimer, carbodiimide and occupies most POLYMETHYLENE POLYPHENYLISOCYANATE; 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, possibly produce great amount of heat, 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 gets into second stage reactive system, finally obtains suitable tripolymer product.
The material of microreactor according to the 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 said microreactor are 20-500, is preferably 200-300; The diameter of said 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, the reaction product that therefore obtains from first step reactor drum 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 drum.In this second stage reactor drum, the further polymerization of reaction solution has obtained final (monomer content is certain) trimerical product.
The second stage reactor drum 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 drum has absorbed the heat that first step reactor drum is discharged, and only needs the heat of trace perhaps need not heat.In the reactor drum 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, so the reaction times of tank reactor and temperature reduce relatively.See from the tripolymer reaction, the preferred 20-60 of its temperature of reaction ℃, most preferably 30-50 ℃; See its reaction time of trimerization reaction and slaking preferred 0-5 hour, most preferably 1-2 hour from final quality product and application performance.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 that it obtains is not enough; Following monomer remove with the product last handling process in; Its component changes easily, and product changes in put procedure easily, influences performance of products at last; If the reaction times is long, possibly 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 further explain method provided by the present invention through following examples, but therefore the present invention does not receive 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 preset internal diameter by ten thousand magnificent urethane manufactured to 40 ℃; The microchannel number is 250; Reaction pressure is 0.2bar; Reaction raw materials residence time in reactor drum is about 3 minutes, stops successive catalyzer and monomer after 30 minutes, detects NCO and viscosity at the sampling spot that is provided with; Reaction solution gets in one 5 liters the reaction kettle that disposes whisking appliance, nitrogen inlet, automatic temperature control system subsequently; In advance temperature of reaction kettle is promoted to 30 ℃; The exothermic heat of reaction that depends in the microreactor is increased to 50 ℃ with the temperature of reaction of second reactor drum, and reaction is 1 hour in second reactor drum, obtains corresponding tripolymer product; Analyze through viscosity and NCO, confirm 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 preset internal diameter by ten thousand magnificent urethane manufactured to 40 ℃; The microchannel number is 250; Reaction pressure is 0.2bar; Reaction raw materials residence time in microreactor is about 5 minutes, stops successive catalyzer and monomer after 30 minutes, detects NCO and viscosity at the sampling spot that is provided with; Reaction solution gets in one 5 liters the reaction kettle that disposes whisking appliance, nitrogen inlet, automatic temperature control system subsequently; In advance temperature of reaction kettle is promoted to 30 ℃; The exothermic heat of reaction that depends in the microreactor is increased to 50 ℃ with the temperature of reaction of second reactor drum, and reaction is 0.5 hour in second reactor drum, obtains corresponding tripolymer product; Analyze through viscosity and NCO, confirm 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 reaction kettle that disposes whisking appliance, nitrogen inlet, automatic temperature control system, in advance temperature of reaction kettle is promoted to 50 ℃, drip 0.3g catalyzer (mass ratio of the DABCO TMR and the trimethyl carbinol is 4: 6); Reaction is 4 hours in reactor drum; Obtain corresponding tripolymer product, analyze, confirm the terminal point of reaction process through 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 reaction kettle, 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; According to making an experiment with embodiment 1 essentially identical step; 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 (21)
1. method for preparing aliphatic polyisocyanurate through 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 through above-mentioned reaction obtains obtains the polyisocyanurate product; Wherein, said inert alcohol kind solvent is primary alconol, secondary alcohol or the tertiary alcohol, and said quaternary ammonium salt accounts for the 20-60 quality % that said catalyst composite is.
2. method according to claim 1 is characterized in that, said isocyanic ester is aliphatic series and/or alicyclic two or POLYMETHYLENE POLYPHENYLISOCYANATE.
3. method according to claim 2 is characterized in that, said isocyanic ester is the vulcabond with 4-20 carbon atom.
4. method according to claim 2; It is characterized in that; Said vulcabond is selected from: tetramethylene-1; 4-vulcabond, pentamethylene-1,5-vulcabond, hexa-methylene-1, the mixture of one or more in 6-vulcabond, LDI, isophorone diisocyanate and the dicyclohexyl methane diisocyanate.
5. according to claim 1 or 4 described methods, it is characterized in that the substituting group on the ammonium ion of said quaternary ammonium salt is alkyl chain C
nH
2n+1, wherein n represents 1-15.
6. method according to claim 5 is characterized in that, said 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.
7. method according to claim 5 is characterized in that, said quaternary ammonium salt accounts for the 30-50 quality % that said catalyst composite is.
8. according to claim 1 or 7 described methods, it is characterized in that said inert alcohol kind solvent is the tertiary alcohol with following structure:
R1-C(R2)(R3)-OH
Wherein, R1, R2 and the identical or different group of R3 representative, said group is to contain alkyl, alkylene or the aryl group of 15 carbon atoms at the most.
9. method according to claim 8 is characterized in that, said 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.
10. method according to claim 9 is characterized in that, said inert alcohol kind solvent accounts for the 40-80 quality % that said catalyst composite is.
11. method according to claim 10 is characterized in that, said inert alcohol kind solvent accounts for the 50-70 quality % that said catalyst composite is.
12., it is characterized in that based on the weight of said isocyanic ester, the consumption that said catalyst composite is is 10-3000ppm according to claim 1 or 10 described methods.
13. method according to claim 12 is characterized in that, based on the weight of said isocyanic ester, the consumption that said catalyst composite is is 100-500ppm.
14. method according to claim 12 is characterized in that, the temperature of reaction in the said microreactor is 10-60 ℃; The stop reaction times that isocyanic ester and said catalyst composite tie up in the microreactor is 1-10 minute.
15. method according to claim 14 is characterized in that, the temperature of reaction in the said microreactor is 20-40 ℃; The stop reaction times that isocyanic ester and said catalyst composite tie up in the microreactor is 3-7 minute.
16. method according to claim 1 is characterized in that, the material of said microreactor is selected from: stainless steel, glass, pottery, alloy or enamel.
17. method according to claim 16 is characterized in that, the form of said microreactor is circle, ellipse, trilateral, square or hexagon.
18. method according to claim 17 is characterized in that, said microreactor is circular microreactor, and the microchannel number of circular microreactor is 20-500; The diameter of circular microreactor is 0.01-2mm.
19. method according to claim 18 is characterized in that, the microchannel number of said circular microreactor is 200-300; The diameter of circular microreactor is 0.07-0.15mm.
20., it is characterized in that said dynamic response device is a tank reactor according to claim 1 or 17 described methods; The temperature of reaction of tank reactor is 20-60 ℃; The residence time of reactant flow in tank reactor is 0-5 hour.
21. method according to claim 20 is characterized in that, the temperature of reaction of said tank reactor is 30-50 ℃; The residence time of reactant flow in tank reactor is 1-2 hour.
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| US9617402B2 (en) | 2011-10-28 | 2017-04-11 | Basf Se | Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates |
| JP6080857B2 (en) | 2011-10-28 | 2017-02-15 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing polyisocyanates of (cyclo) aliphatic diisocyanates that are stable in aggregation in solvents |
| CN107815087B (en) | 2011-10-28 | 2023-02-28 | 巴斯夫欧洲公司 | Color-stable curing compositions of polyisocyanates containing (cyclo) aliphatic diisocyanates |
| CA2982261C (en) * | 2015-04-21 | 2023-09-26 | Covestro Deutschland Ag | Solids based on polyisocyanurate polymers produced under adiabatic conditions |
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| EP3305824A1 (en) | 2016-10-07 | 2018-04-11 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3305863A1 (en) | 2016-10-07 | 2018-04-11 | Basf Se | Method for the preparation of flocculation stable polyisocyanates of (cyclo)aliphatic diisocyanates in solvents |
| CN106588798B (en) * | 2016-10-19 | 2019-02-05 | 万华化学集团股份有限公司 | A kind of preparation method of low turbidity oligomeric isocyanates |
| EP3431521A1 (en) | 2017-07-20 | 2019-01-23 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3336118A1 (en) | 2017-09-20 | 2018-06-20 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3336117A1 (en) | 2017-09-20 | 2018-06-20 | Basf Se | Method for the preparation of flocculation stable polyisocyanates of (cyclo)aliphatic diisocyanates in solvents |
| CN111349020A (en) * | 2020-05-06 | 2020-06-30 | 江苏快达农化股份有限公司 | Synthetic method for preparing 3, 3-dimethyl-4, 4-biphenyl diisocyanate by phosgene continuous method |
| CN112079979B (en) * | 2020-09-07 | 2022-08-09 | 中海油常州涂料化工研究院有限公司 | Bio-based pentamethylene diisocyanate curing agent and preparation method and application thereof |
| WO2022128925A1 (en) | 2020-12-18 | 2022-06-23 | Basf Se | Color-stable curing agent compositions comprising polyisocyanates of (cyclo)aliphatic diisocyanates |
| CN117946019A (en) * | 2022-10-28 | 2024-04-30 | 万华化学集团股份有限公司 | Preparation method of low-color-number low-odor polyisocyanate curing agent |
| CN116813878B (en) * | 2023-08-29 | 2023-11-10 | 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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