CN105218422A - A kind of preparation method of isocyanic ester - Google Patents
A kind of preparation method of isocyanic ester Download PDFInfo
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- CN105218422A CN105218422A CN201510672466.0A CN201510672466A CN105218422A CN 105218422 A CN105218422 A CN 105218422A CN 201510672466 A CN201510672466 A CN 201510672466A CN 105218422 A CN105218422 A CN 105218422A
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- reaction
- decollator
- hourglass shape
- cylindrical shell
- slurry
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- 150000002148 esters Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 202
- 239000002002 slurry Substances 0.000 claims abstract description 165
- 239000007788 liquid Substances 0.000 claims abstract description 128
- 150000001412 amines Chemical class 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 154
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 63
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 63
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 28
- -1 dimethyl terephthalate ester Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 61
- 239000002245 particle Substances 0.000 description 50
- 239000000047 product Substances 0.000 description 31
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 8
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 239000007792 gaseous phase Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 125000000266 alpha-aminoacyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of method preparing isocyanic ester based on salify light phosgenation, the salt-forming reaction of the method is divided into two steps, the first step adopts conventional reactor to carry out preliminary salt-forming reaction, second step adds a certain proportion of Semi-polarity organic solvent and carries out salify slaking reaction in the reactor of the liquid slurry decollator with hourglass shape, and hourglass shape decollator cylindrical shell is arranged with star shape discharge port.Can guarantee that raw material is amino through salify slaking reaction process can be converted into amine hydrochlorate high conversion, can the acquisition isocyanate products of high yield through follow-up photochmeical reaction.
Description
Technical field
The present invention relates to a kind of preparation method of isocyanic ester, prepare the method for isocyanic ester more particularly by salify light phosgenation, belong to light phosgenation and prepare isocyanic ester field.
Background technology
Isocyanic ester is the speciality chemical that a class has-N=C=O functional group, and the high reaction activity of-N=C=O functional group makes it be widely used as the fine chemical product such as agricultural chemicals, medicine synthetic intermediate and polyurethane material synthesis material.The polyurethane material taking isocyanic ester as basic raw material is more various in style with it, flexible and changeable, the feature of different properties and be applied to national economy and the national defense construction every field such as building, vehicle, household electrical appliance, space flight and aviation, electromechanics, boats and ships, chemical industry, metallurgical mining, light industry, weaving, health care.
Fat (ring) race isocyanic ester (ADI) is the special isocyanate products that in molecular structure ,-N=C=O functional group is connected with fatty (ring) race group, ADI and polyether glycol or polyester polyol polyurethane products obtained through reactive polymeric, there is the application performance that non yellowing etc. is good, be widely used as industry and automobile polyurethane coating, get the attention in recent years.
A product more special in ADI is xylylene diisocyanate (XDI), and molecular formula is C
10h
8n
2o
2, molecular weight is 188.19, and its major industrialized product has m-xylylene diisocyanate (m-XDI), terephthalylidene vulcabond (p-XDI), and structural formula is respectively:
XDI vapour pressure is lower, and reactive behavior is higher, because NCO functional group in its molecular structure does not have directly to be connected with phenyl ring, and by methylene radical (-CH
2-) be separated by, prevent between phenyl ring and NCO group and resonate, XDI and polyurethane product thereof are stablized light, non yellowing.Can be used for high-grade polyurethane coating, elastomerics, leather, sizing agent, ophthalmic lens etc.
At present, the preparation technology about ADI reports a lot, and disclosed mainstream technology is that organic amine and phosgene reaction prepare isocyanic ester.In addition, some other method is also disclosed.Under the clear 52-46042 of Japanese Laid-Open Patent is disclosed in the existence of copper class catalyzer, the method that the aromatic compound of band chloromethyl and alkaline cyanate react; Under US Patent No. 4207251 is disclosed in catalytic metal existence, the vapor phase process technology that the methane amide that N-replaces is oxidized by oxygen-containing gas; Chinese patent CN103351313A, CN101805271A, CN102827035A, CN102659632A all disclose the synthesis technique that triphosgene prepares ADI, use triphosgene under catalytic condition, to carry out reaction with fat (ring) race's diamines or its hydrochloride and prepare ADI.
Above non-phosgene metallization processes is all because yield is low, operational path is complicated and economy problems fails suitability for industrialized production, and existing phosgenation technology is mainly divided into gas phase phosgenation technology and liquid phase phosgenation technology.
Gas phase phosgenation technology to need amine heat to gas phase state, and need that amine boiling point is low, gasifiable, amine can stable existence under gas phase state, operate in addition and carry out all at high temperature under high pressure, technological difficulty is larger.
Liquid phase phosgenation technology is divided into direct light phosgenation and salify light phosgenation, direct light phosgenation is for obtain corresponding isocyanic ester by primary amine and phosgene direct reaction, there is a drawback in direct light phosgenation, when the reactive behavior height of amine, isocyanic ester meeting and the reaction of free amino of generation generate ureas by product.Salify light phosgenation; first amine and sour gas such as hydrogenchloride, carbon dioxide reaction is needed to obtain hydrochloride of corresponding amines or carbonate; then this amine salt and phosgene reaction are prepared isocyanic ester; when preparing aliphatics, alicyclic isocyanate, usually can select first amine to be prepared into corresponding hydrochloride and carbonate carries out photochmeical reaction again.
English Patent GB1162155A discloses and generates hydrochloride at-10-50 DEG C of amine and hydrogen chloride gas salt-forming reaction, the ratio 30:1-18:1 of solvent and amine, carries out photochmeical reaction at 120-160 DEG C.English Patent GB1086782A discloses, and generates hydrochloride, carries out photochmeical reaction at 120-128 DEG C, the ratio 30:1-18:1 of solvent and amine at 0-60 DEG C of amine and hydrogen chloride gas salt-forming reaction.Though above-mentioned two kinds of methods are by improving, reduce the generation of photochmeical reaction byproduct in process thing, but because using solvent ratios excessive in its reaction process, during aftertreatment, solvent evaporation needs lot of energy, and too low concentration needs the equipment size such as reactor to increase, cause volumetric efficiency and economic benefit bad.
English Patent GB1146664A discloses the amine of 7wt% at 25 DEG C by film reactor and hydrogenchloride salify, then first at 160 DEG C of phosgenation reactions, and then at 190 DEG C phosgene reaction.Utilize film reactor salify, if liquid film thinner Spatial-temporal Transformation rate is low; If liquid film is thicker, within a short period of time, hydrogenchloride can not enter liquid film depths, and the hydrochloride that top layer produces stops hydrogenchloride to enter liquid film inside further, and salify is incomplete, industrially cannot realize.
Chinese patent CN101203488A discloses and is greater than normal atmosphere 0.01MPa at pressure, salify at temperature 120 DEG C, the viscosity of hydrochloride can be reduced, thus improve salt-forming conversions rate and space-time yield, the transformation efficiency that amine is converted into hydrochloride can reach 99.8mol%, and the yield of the isocyanic ester obtained after phosgenation reaction can reach 98.10%.Although this patent relies on high temperature to solve the problem of salify viscosity, but due under high temperature fat (ring) race's amine and hydrogen chloride gas precursor reactant very fast, amine is seriously coated, salify is incomplete, final phosgenation liquid has a large amount of ureogenesis, and easily generate chloro by product, being separated to the later stage increases difficulty.
Chinese patent CN1045578A discloses and makes solvent with ester, wherein the amount of solvent controls weight ratio at solvent and amine or its hydrochloride from 8:1-16:1, at 30 DEG C or lower than at 30 DEG C of temperature, amine and phosgene or hydrogenchloride carry out cold reaction or salt-forming reaction, carry out thermal response at 120-170 DEG C with phosgene and prepare isocyanic ester, productive rate about 91wt%.Although this technology decreases the generation of chloro by product to a certain extent, reduce isocyanic ester separating-purifying difficulty, use ester class more traditional benzene series solvent on the high side, economic benefit is bad, is difficult to realization of industrialization.
Chinese patent CN102070491A discloses at 25-35 DEG C, phenylenedimethylidyne diamines and hydrogen chloride gas salt-forming reaction generate hydrochloride, hydrochloride concentration 4-6wt% in salt-forming reaction still, after gained hydrochloride centrifugal concentrating to hydrochloride concentration 20-30wt% after high pressure, low pressure two step are photochemical the obtained reaction solution containing xylylene diisocyanate.Then this patent elder generation salify in dilute solution concentrates, and carries out thermo-optical reaction, thus reduce the reaction times after concentrated, improve Spatial-temporal Transformation rate, but hydrochloride viscosity increases after it is concentrated, be unfavorable for being uniformly mixed of conveying in pipeline and thermo-optical step of reaction, industrialization be difficult to realize.
Mainly there are two class by products in isocyanate production processes, wherein a class by product be aminocompound, the hydrochloride that formed of amino acyl chlorides and hydrogenchloride, another kind of by product is the oligopolymer that amino acyl chlorides, diamino compounds and isocyanic ester form urea.If mix uneven in salify hybrid reaction process, very easily cause the high local concentrations of aminocompound, thus cause the generation of by product.Above-mentioned by product is insoluble in Conventional solvents usually, not only reduces reaction yield, and simultaneously owing to being solid-state under normal temperature, very easily blocking pipe, therefore, reduce the generation of side reaction, be the emphasis of phosgenation reactor mend gene always.EP0699657B1 discloses a kind of coaxial injector; CA2258194A1 discloses a kind of microstructure formula nozzle; EP1275639B1 discloses a kind of Venturi; W003045900A1 disclose a kind of in establish the plate-type reactor of porous sparger; EP1319655B1 discloses a kind of distribution mode of small hole injection gas; CN1310875C discloses a kind of plate-type reactor operated under middle pressure; US2005113601A1 discloses a kind of tubular reactor with central nozzle and vortex generator.GB1165831A discloses a kind of tubular reactor with stirring; CN101372463A discloses a kind of jet injection reactor; W02008055898A1 discloses a kind of tubular reactor with nozzle; CN101357316A discloses a kind of three pipe cocurrent flow type reactors.Have reactor or need dissipate significant energy, or complex structure, or cause partial concn inconsistent.CN101623615A discloses a kind of telescopic sparger, proposes the mixing on whole flow area, but enters because material is divided into several strands, adds control and operation difficulty.
The innovation of the technologic optimization of above-mentioned salt-forming reaction and reactor mixed form aspect all can not realize conversion completely that is amino and hcl reaction.Amino is that acid-base neutralisation reacts with the salt-forming reaction process nature of hydrogenchloride, and be mainly mass transport limitation, its raw material mixed effect directly determines reaction effect.Especially fatty amine activity is higher, in cold reaction or salt-forming reaction process, comparatively fast easily cause amine salt coated, cause the transformation efficiency of amine lower, the unconverted amine be wrapped by generates the by products such as substituted urea in the meeting of phosgenation thermal response stage and product isocyanate reaction, causes ultimate yield to reduce and quality product decline.
In order to overcome existing isocyanic ester salify photochemical process in amine hydrochlorate lower concentration situation photochmeical reaction Spatial-temporal Transformation rate low, under high density, amide hydrochloride viscosity is excessive, and cause amine salify incomplete, side reaction is many, and the not easily problem such as conveying, need to improve prior art.
Summary of the invention
The object of the present invention is to provide a kind of method preparing isocyanic ester, based on salify phosgenation reaction, when not being lowered into reactant salt amine hydrochlorate concentration, traditional salt-forming reactor is adopted to carry out preliminary salt-forming reaction, salify slaking reaction is carried out subsequently in salify slaking reaction device, a certain proportion of lower molecular weight ketone or nitrile solvents is added in hydrochloride slurry, improve hydrochloride slurry in traditional halogenated aryl hydrocarbon class inert solvent, disperse uneven situation, hydrochloride slurry micro-scale is distributed more even, obtain transformation efficiency high, the hydrochloride slurry of even particle size distribution, and then the shortening heat photochmeical reaction time, reduce the generation of by product in photochemical process, improve the finished product isocyanic ester yield and product quality.
In order to realize above goal of the invention, the technical solution adopted in the present invention is as follows:
Prepare a method for isocyanic ester, comprise the steps:
(a) preliminary salt-forming reaction: amine obtains amine hydrochlorate slurry with the preliminary salt-forming reaction of hydrogenchloride after inert organic solvents dilution;
(b) salify slaking reaction: the amine hydrochlorate slurry of step (a) gained is imported in salify slaking reaction device, add Semi-polarity organic solvent simultaneously, pass into hydrogenchloride and cure into reactant salt, obtain slaking amine hydrochlorate slurry;
(c) pressurization phosgenation reaction: step (b) gained slaking amine hydrochlorate slurry and phosgene are carried out pressurization phosgenation reaction, obtains the reaction solution containing isocyanic ester;
(d) product purification: step (c) gained is obtained isocyanate products containing the reaction solution of isocyanic ester is refining.
Isocyanic ester prepared by the present invention has general formula (I):
R(NCO)
n(I)，
Wherein, n is 2 or 3; R represents aromatic group, aliphatic or alicyclic hydrocarbon radical, preferred aliphat or alicyclic alkyl, and more preferably carbonatoms is the aliphatic or alicyclic hydrocarbon radical of 4-15; Described R is hexa-methylene, mphenylenedimethylim-, terephthalylidene or anti-form-1 more preferably, 4-cyclohexyl; More preferably mphenylenedimethylim-or terephthalylidene again; Most preferably be mphenylenedimethylim-;
Described isocyanic ester is preferably m-xylylene diisocyanate and/or terephthalylidene vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, anti-form-1,4-cyclohexylene diisocyanate; Be more preferably m-xylylene diisocyanate or terephthalylidene vulcabond, more preferably m-xylylene diisocyanate.
In the described preliminary salt-forming reaction of step (a) of the present invention:
Described amine has general formula (II):
R(NH
2)
n(II)，
Wherein, the definition of R and n is as previously mentioned, identical with R with n in isocyanic ester general formula prepared by the present invention; N is 2 or 3; R represents aromatic group, aliphatic or alicyclic hydrocarbon radical, preferred aliphat or alicyclic alkyl, and more preferably carbonatoms is the aliphatic or alicyclic hydrocarbon radical of 4-15; Described R is hexa-methylene, mphenylenedimethylim-, terephthalylidene, anti-form-1 more preferably, 4-cyclohexyl; More preferably mphenylenedimethylim-or terephthalylidene again; Most preferably be mphenylenedimethylim-.
In the present invention, described amine is preferably meta-xylylenediamine and/or terephthalylidene diamines, isophorone diamine, hexamethylene-diamine, anti-form-1,4-cyclohexanediamine; Be more preferably meta-xylylenediamine.
Described in the preliminary salt-forming reaction of step (a) of the present invention, inert organic solvents is the stability being conducive to described salt-forming reaction, and being conducive to the inert solvent reacting each components dissolved degree, described inert organic solvents includes but not limited to the one or two or more in benzene, toluene, chlorobenzene, orthodichlorobenzene (ODCB), santochlor, a chlordiphenyl, dimethyl terephthalate ester and diethyl phthalate; Described inert organic solvents is preferably orthodichlorobenzene (ODCB).
During amine salt-forming reaction of the present invention, consider from salify angle, amine generates amine hydrochlorate with hcl reaction in inert organic solvents.
Hydrogenchloride of the present invention is pure hydrogen chloride gas, and described hydrogenchloride is 1.0-2.5:1 with the molar equivalent ratio of the amino of described amine, is preferably 1.2-2.0:1.In step (a) of the present invention, keep hydrogenchloride to be more than 1.2 with amino equivalence ratio, then can keep the high conversion of amine, equivalence ratio controls below 2.0 simultaneously, from the viewpoint of economy, industrially advantageously.
Consider industrial production efficiency, in the preliminary salt-forming reaction of step (a) of the present invention, based on the total mass of amine and inert organic solvents, the input concentration of described amine is 5-30wt%, preferably 10-20wt%.In the present invention rapid (a), the concentration controlling charging amine is more than 5wt%, can realize high efficiency; Control charging amine concentration is below 30wt% simultaneously, effectively can suppress the problem such as the side reaction of phosgenation urea and muriate increase in phosgenation reaction.
Step (a) of the present invention can adopt reactor, the various published reactor such as the reactor with microstructure formula nozzle or the reactor with Venturi with coaxial injector.
The preliminary salt-forming reaction residence time of step (a) of the present invention is 100ms-15s, preferred 1-5s.
The temperature of the described preliminary salt-forming reaction of step (a) of the present invention is 0-30 DEG C.When temperature is higher than 30 DEG C, the too fast amine easily caused of salt-forming reaction coated, causes the increase of chlorinated impurities; When temperature is 30 DEG C or lower than 30 DEG C, the reaction result that even can obtain near 0 DEG C; Although also can amine hydrochlorate be obtained at lower temperatures, disadvantageously, because need a large amount of cooling, and salt-forming reaction speed can be corresponding slack-off.Consider the miniaturization of hydrochloride particle diameter, the viscosity of hydrochloride, and follow-up with thermal equilibrium during phosgene reaction etc. factor, therefore, in the present invention, the temperature of the preliminary salt-forming reaction of step (a) is preferably 20-25 DEG C.
The concentration of the amine hydrochlorate slurry that step (a) of the present invention obtains is 10-30wt%.
The described salify slaking reaction of step (b) of the present invention:
Transformation efficiency due to amine formation hydrochloride directly affects the effect of follow-up photochmeical reaction, amino conversion not exclusively, free amino can react with the NCO group generated by products such as generating substituted urea, reduce yield and affect product quality, therefore, the present invention proposes this salify curing step especially, to guarantee the high conversion of amine.
The present invention proposes salify slaking reaction first, this step of reaction in published salify light phosgenation patent from not mentioned.A certain proportion of Semi-polarity organic solvent is added in the amine hydrochlorate slurry obtained to step (a) in step (b) in the present invention, effectively can improve the solubleness of amine hydrochlorate in inert organic solvents, improve the situation of amine hydrochlorate skewness in traditional halogenated aryl hydrocarbon class inert solvent, the amine hydrochlorate particulate fraction of coated free amine group is dissolved broken, inner free amine group is discharged, generation amine hydrochlorate is reacted further with hydrogen chloride gas, cure into reactant salt, ensure that free amino is converted into hydrochloride to greatest extent.
Semi-polarity organic solvent described in step (b) of the present invention should be inertia relative to reaction system, and the boiling point of selected Semi-polarity organic solvent should lower than the boiling point of salt-forming reaction inert solvent used.
Semi-polarity organic solvent described in step (b) of the present invention is one or more in lower molecular weight ketone or nitrile solvents, preferred boiling point is one or more in the ketone of 50-100 DEG C or nitrile solvents, is more preferably one or both or three kinds in acetone, methylethylketone and acetonitrile.
In the present invention, the consumption that step (b) adds described Semi-polarity organic solvent in hydrochloride slurry is the 5-20wt% of the amine hydrochlorate slurry total mass obtained based on step (a), preferred 10-15wt%.When the consumption of described Semi-polarity organic solvent is lower than 5wt%, not obvious to the polarization state improvement result of original dispersion system, cannot realize improving hydrochloride particle solubleness in a solvent, do not have the effect promoting salify slaking, when the consumption of Semi-polarity organic solvent is higher than 20wt%, hydrochloride particle solubleness has in a solvent no longer included obvious improvement, and crosses the interpolation of solvent at high proportion, will certainly increase and causes later separation difficulty and increase separating energy consumption.
Step (b) reaction time of the present invention is 1-15min, preferred 5-10min; Passing into the amount of hydrogenchloride with the molar equivalent ratio of the amino of amine hydrochlorate is 0.6-1.0:1.
In the present invention, the reactor of step (b) salify slaking reaction is tank reactor, and the internal core parts of described tank reactor are the liquid slurry decollator of hourglass shape.
In the present invention, the stirring rake of described tank reactor is positioned at the axle center place of tank reactor, this stirring rake is radial flow is main stirring rake, the radial flow of high-shear and systemic circulation ability can be able to be provided to be main stirring rake form for six straight leaf open turbine oars, four oblique leaf open turbine oars or straight leaf disc vane wheel oar etc.; Described stirring rake can be one group, also can be many groups; Described stirring rake is via stir shaft high speed rotating under outside driven by motor, and rotating speed 500-1000rpm, guarantee that in decollator, hydrochloride slurry is high speed turbulence state, hydrochloride slurry gets rid of to hourglass shape liquid slurry decollator by the radial turbine that stirring rake brings.
In the present invention, the liquid slurry decollator main body of described hourglass shape is the cylindrical shell of hourglass shape with bottom, the area equation of the upper and lower end face of hourglass shape cylindrical shell or not etc.; The hourglass shape liquid slurry decollator of preferred upper and lower end face area equation; The height of described hourglass shape liquid slurry decollator is the 1/4-1/2 of tank reactor height, preferred 1/3-1/2; The distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is the 1/6-1/5 of tank reactor height; The stirring rake of described tank reactor is positioned at hourglass shape liquid slurry decollator axle center place, and stirrer paddle and hourglass shape liquid slurry decollator lower surface distance are the 1/4-1/3 of liquid slurry decollator height; The cross section smallest circle diameter of described hourglass shape liquid slurry decollator is the 1/3-2/3 of hourglass shape liquid slurry decollator lower surface circular diameter; Stirring rake radical length is the 2/3-5/6 that hourglass shape liquid slurry decollator lower surface circular diameter is; Hourglass shape cylindrical shell upper surface diameter is the 3/4-5/4 of lower surface; Hourglass shape cylindrical shell lower surface diameter is the 2/5-3/5 of reactor diameter.
In the present invention, described hourglass shape liquid slurry decollator adopts outer coils to heat, and outer coils can adopt electrically heated, also can adopt circulator bath or circulation oil bath heating.Maintain slurry temperature 60-90 DEG C in described hourglass shape liquid slurry decollator, at this temperature, described amine hydrochlorate slurry can maintain low viscosity, keep good mobility, heat-processed can impel the hydrochloride of coated free ammonia broken in thermal stresses effect lower part simultaneously, is partly discharged by coated free ammonia; Then hydrochloride slurry viscosity is comparatively large lower than 60 DEG C for temperature, poor fluidity; Temperature can cause hydrochloride unstable higher than 90 DEG C in addition, easily condenses, and is formed and is difficult to broken bulk particle, affect thermal reaction rate.
In the present invention, the cylindrical shell of the liquid slurry decollator of hourglass shape described in step (b) is porous cylindrical shell, and cylindrical shell is arranged with star shape discharge port.The outer corners angle of described star shape is less than or equal to 60 degree for being more than or equal to 15 degree, ensure that liquid slurry can be subject to the shearing action of discharge port edges and corners when discharge port sprays, discharge port star shape includes but not limited to as the one or two or more in triangle star, corner star, pentagram, hexagram, heptangle star and anistree star etc.When described liquid outlet opening corner angle angle be greater than 60 degree then slurry by time shearing action deficiency cause shear effect poor, then slurry can be caused to not easily pass through edges and corners because circulating face is narrow when corner angle angle is less than 15 degree, easily form material dead band.
In the present invention, along with axial direction due height is different, described hourglass shape liquid slurry decollator cross-sectional area is also different, and its cylindrical shell top discharge mouth percentage of open area, perforate size and hole shape etc. are also not identical.The overall percentage of open area of cylindrical shell described in step (b) is 50-75%; Preferably, based on whole cylindrical shell height, the cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 55-70%, based on whole cylindrical shell height; The percentage of open area of the cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 50-60%, based on whole cylindrical shell height; Cylindrical shell lower surface to distance lower surface 1/3 apart from cylindrical shell percentage of open area be 60-75%, based on whole cylindrical shell height.The overall percentage of open area of described cylindrical shell can cause liquid slurry outflow outlet area inadequate lower than 50%, can not ensure that in liquid slurry decollator, slurry flows out smoothly, percentage of open area can cause slurry outflow discharge area excessive higher than 75%, and slurry is suffered shears deficiency, reduces gas-liquid mixed effect.
In the present invention, for laterally zygomorphic hourglass shape liquid slurry decollator: the amine hydrochlorate slurry that step (a) obtains imports in the internal core part liquid pulp stock disperser of tank reactor by liquid inlet opening, when the design of hourglass shape can ensure liquid slurry turbulence therein, under centrifugal force and self gravitation dual function, the hydrochloride particle of large-size is more easily distributed in hourglass bottom, secondly the hydrochloride particle that size is placed in the middle is mainly distributed in upper and lower both sides, hourglass axial centre place, and the hydrochloride pulp particle size being in hourglass top is minimum.
Because of the special shape of described hourglass shape liquid slurry decollator in the present invention, in hydrochloride slurry, the hydrochloride particle of different scale has specific distribution on axially different height, therefore, the size of hourglass shape liquid slurry decollator liquid outlet opening star shape also should corresponding adjustment.Based on whole cylindrical shell height, the size of the star shape of the star discharge port between upper surface to distance upper surface 1/3 is measured with its circumscribed circle, and its external circular diameter is 150-300 μm; Material within the scope of this is the hydrochloride slurry that grain graininess is less, and therefore liquid outlet opening can arrange size comparatively greatly, is convenient to increase streams flux, improves the throughput of equipment.Based on whole cylindrical shell height, the size of the star shape of the star discharge port between cylindrical shell lower surface to distance lower surface 1/3 is measured with its circumscribed circle, and its circumscribed circle diameter is 50-150 μm; Within the scope of this, material particles degree is comparatively large, then this position discharge port size is set should be less, be subject to enough shearings when can guarantee hydrochloride slurry flows, the fragmentation of hydrochloride particle size reduced, the free amine group coated by hydrochloride is discharged completely simultaneously.Based on whole cylindrical shell height, the size of the star shape of the star discharge port between distance upper surface 1/3 to distance lower surface 1/3 is measured with its circumscribed circle, and its circumscribed circle diameter is 80-200 μm; Material within the scope of this is the moderate hydrochloride slurry of grain graininess.
In the present invention, based on whole cylindrical shell height, the star discharge port between cylindrical shell lower surface to distance lower surface 1/4 is triangle star or corner star; Discharge port within the scope of this, except completing the shearing of hydrochloride particle, also should ensure that the material namely entered in this liquid slurry decollator all can leave this decollator and enter salify slaking reaction still lower end without dead band in hourglass shape liquid slurry decollator.
The present invention, described dry hydrogen chloride gas is introduced bottom salify slaking reaction still through gas-phase feed pipe, enter salify slaking reaction still by a porous gas distributing disc, react with the free amine group coated by hydrochloride discharged and generate amine hydrochlorate, complete the slaking of salification process.It is inner that described porous gas distributing disc is positioned at slaking reaction still, diameter is the 3/5-4/5 of reactor diameter, its distance hourglass shape liquid slurry decollator lower surface, upper surface distance is the 1/12-1/10 of reactor height, the diameter dimension of the miniature circular hole of described porous gas distributing disc is 5mm-2cm, and percentage of open area is 60-80%.Percentage of open area can cause pneumatic outlet position very few lower than 60%, and gas dispersion is in bad order, and percentage of open area can cause pneumatic outlet sectional area excessive higher than 80%, and under identical air flow, gas flow rate is lower, reduces gas-liquid mixed effect.
Internal core parts in the inventive method are adopted to be that the tank reactor of the liquid slurry decollator of hourglass shape carries out salify slaking reaction, when the amine hydrochlorate slurry concentration obtained in step (a) is 10wt%, the slaking amine hydrochlorate slurry obtained after slaking in step (b) salify slaking reaction still, the viscosity at 30 DEG C is below 1500mPa.s.And adopting traditional salifying method, amide hydrochloride concentration is when 10wt%, and the viscosity of hydrochloride slurry rises to 8000-20000mPa.s at 30 DEG C.According to general knowledge, when hydrochloride slurry viscosity is higher than 5000mPa.s, very easily cause pipeline to block in production process, the hydrochloride slurry prepared by method provided by the invention not easily causes pipeline to block in process of production, and production equipment operation stability obtains larger raising.
In addition, in the conditions of the invention, the particle diameter of hydrochloride particle in hydrochloride slurry can be suppressed to increase, and when amide hydrochloride concentration in salt-forming reaction still remains 10wt%, the number average bead diameter of hydrochloride particle is 5-20 μm; Adopt traditional salifying method, when amide hydrochloride concentration reaches 10wt% in a kettle., in solution, the median size of particle is 80-150 μm, larger size of particles is disadvantageous carrying out in the phosgenation reaction described in step (c), the conference of hydrochloride size of particles causes the hydrochloride particle surface of the amount of same substance to amass little, be unfavorable for the contact reacts of hydrochloride and phosgene, the hydrochloride particle diameter prepared by method provided by the invention is little, the hydrochloride particle surface of the amount of same substance is long-pending large, is conducive to hydrochloride and phosgene contact reacts.
In pressurization phosgenation reaction described in step (c) of the present invention:
In the present invention, described pressurization phosgenation reaction, also referred to as high pressure phosgenation reaction, at 0.1-1.5MPa, operates under the absolute pressure of preferred 0.2-0.6MPa.Pressure is comparatively slow lower than phosgenation reaction speed during 0.2MPa, and higher than during 0.6MPa to equipment and operational requirement higher.
Due to the characteristic of the phosgenation reaction of amine hydrochlorate, according to generally accepted viewpoint, the phosgenation of amine hydrochlorate slowly and reaction be divided into two steps to carry out:
The first step, amine hydrochlorate and phosgene reaction generate urea chloride;
Second step, urea chloride decomposes generation isocyanic ester and releases hydrogenchloride simultaneously.
Preferably, two steps of the pressurization phosgenation reaction of the amine hydrochlorate described in the present invention are carried out under the following conditions:
The first step, carry out under relatively high pressure condition, the absolute pressure of reaction is preferably 0.4-0.6MPa;
Second step, carries out under relatively low pressure condition, and the absolute pressure of reaction is preferably 0.2-0.4MPa.
Urea chloride is dissociated into isocyanic ester and hydrogenchloride, is the balanced reaction of pressure dependence type.The present invention can make this reaction offset to product isocyanic ester side by the pressure suitably reducing compressive reaction.Because urea chloride decomposes do not require any phosgene, a small amount of hydrochloride remaining in solution also only needs a small amount of phosgene, and the feature of low pressure causes phosgene hold-up in phosgenation operation low, and this is also favourable viewed from security standpoint.
In the present invention, the temperature of reaction of the described pressurization phosgenation reaction of step (c) is 120-170 DEG C, and preferred temperature is 140-150 DEG C.When temperature of reaction is lower than 120 DEG C, photochmeical reaction overlong time, then too much can cause yield to decline because of side reaction higher than 170 DEG C.In the present invention, the heating embodiment of the reactor of described pressurization phosgenation reaction need pass into according to phosgene and temperature caused by phosgenation reaction reduces and regulates.
In the present invention, the type of reactor of the described pressurization phosgenation reaction of step (c) can select tubular reactor, stirred vessel and miscellaneous equipment.
In the present invention, the mean residence time of the described pressurization phosgenation reaction of step (c) is 1-600 minute, preferred mean residence time 30-300 minute, more preferably 60-180 minute.
Mol ratio amino in the phosgene that the described pressurization phosgenation of step (c) passes into and amine hydrochlorate is 1.2:1-10:1, preferred 1.5-8:1.
In the present invention, the phosgene of step (c) described pressurization phosgenation reaction passes into the form of pure phosgene or phosgene solution, and the solvent of described phosgene solution is selected from the one or two or more in benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, dimethyl terephthalate ester and diethyl phthalate.Phosgene in phosgene solution accounts for the 10-30wt% of solvent quality.
Product purification described in step (d) of the present invention:
Product purification of the present invention need remove unreacted phosgene, hydrogenchloride, steam desolventize, tar etc.
In the present invention, product purification needs one or more rectifying tower as the equipment of separation and purification of products, and product purification comprises the removing of hydrogen chloride gas and phosgene in reaction solution, the removing of inert organic solvents, reacts removing of heavy constituent by product (being commonly called as tar) and removing of boiling point and the close light constituent impurity of product.
The isocyanate products purity prepared in the present invention reaches 99.90wt%-99.95wt%, and product look number can reach 0-5Hazen, and the hydrolyzable chloride content in product is 0-10ppm, and chloride content is 0-100ppm.
In the present invention, the transformation efficiency of amine can reach 99.0-99.9mol%.And in traditional salify photochemical process, when amide hydrochloride concentration reaches 1Owt% in a kettle., the salt-forming conversions rate of amine is 95.0-97.0mol%, and when in reactor, amide hydrochloride concentration reaches 15wt%, the salt-forming conversions rate of amine is only 90.0-94.5mol%.The yield of the high then isocyanic ester of salt-forming conversions rate of amine is high, and can suppress the generation of by product.
Beneficial effect of the present invention is:
Employing internal core parts are the reactor of tank reactor as salify slaking of the liquid slurry decollator of hourglass shape first, the shearing action of the star discharge port that the cylindrical shell by hourglass shape liquid slurry decollator distributes, what promote hydrochloride pulverizes the effect reaching and reduce hydrochloride particle diameter and viscosity again.
Add appropriate Semi-polarity organic solvent in salify maturing process and effectively improve hydrochloride particle solubleness in a solvent, play the effect promoting salify slaking.
The advantages such as it is high that the isocyanate products that the present invention prepares has purity, and look is number low, and hydrolysis chlorine, chloride content are low.
Accompanying drawing illustrates:
The salify slaking reaction still schematic diagram of Fig. 1 to be internal core parts be laterally zygomorphic hourglass shape liquid slurry decollator
1 gas-phase feed pipe
2 first liquid phase feeding pipes
3 second liquid phase feed-pipes
4 gaseous phase outlets
5 hourglass shape liquid slurry decollators
6 stirring rakes
7 porous gas distributing discs
8 leakage fluid drams
Fig. 2 is embodiment 2 laterally zygomorphic hourglass shape liquid slurry decollator center Longitudinal cross section schematic
The outer coil pipe of 9 electrically heated
10 star liquid slurry discharge ports
Embodiment
The following examples will be further described method provided by the present invention, but the invention is not restricted to listed embodiment, also should be included in other any known change in interest field of the presently claimed invention.
Purity test instrument and condition: Shimadzu GC-2010, pillar: DB-530 × 0.25mm × 0.25 μm sample size: 1 μ L, vaporizer temperature: 260 DEG C, post flow: 1mL/min, splitting ratio: 50:1, column temperature: 50 DEG C, keeps 2min, with 5 DEG C/min ramp to 80 DEG C, keep 5min, with 20 DEG C/min ramp to 280 DEG C, keep 10min, detector temperature: 300 DEG C
Particle diameter testing standard and INSTRUMENT MODEL: Rise-2002 type wet method laser diffraction formula particle-size analyzer measures the particle diameter of hydrochloride particle in acetonitrile solution
Look number test: LovibondNessleriser2250 type look instrument
Viscosity test: BrookfieldR/S rheometer
Chloride content testing standard: GB12009.1-89
Hydrolysis chlorine testing standard: GB12009.2-89
As shown in Figure 1: the hydrochloride slurry obtained through preliminary salt-forming reaction is incorporated in hourglass shape liquid slurry decollator 5 by salify slaking reaction still first liquid phase feeding pipe 2, Semi-polarity solvent is introduced in hourglass shape liquid slurry decollator 5 by second liquid phase feed-pipe 3, hydrogen chloride gas is introduced in gas distribution dish 7 through gas-phase feed pipe 1, hydrochloride slurry leaves hourglass shape liquid slurry decollator 5 after again being sheared by liquid slurry decollator star discharge port after stirring rake 6 high speed shear advances, hydrochloride slurry after slaking reaction completes squeezes into pressurization phosgenation reaction still by leakage fluid dram 8, in whole process, excessive gas is discharged through gaseous phase outlet 4.
Embodiment 1
The autoclave that use has injection reactor, phosgene is blown into pipe and stir is as the conversion unit of step a, and volume is 10 liters.817g (6mol) MXDP is dropped into and 7354g orthodichlorobenzene (the total amine concentration of charging is 10wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 8L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min, preliminary salt-forming reaction is carried out in the stirring of simultaneously opening reactor simultaneously.
The present embodiment use salify slaking reaction still to adopt the hourglass shape liquid slurry decollator of upper and lower end face area equation, the height of described hourglass shape liquid slurry decollator is 1/4 of tank reactor height, the distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is 1/5 of tank reactor height, stirring rake and hourglass shape liquid slurry decollator lower surface distance are 1/4 of liquid slurry decollator height, the cross section smallest circle diameter of described hourglass shape liquid slurry decollator is 1/3 of hourglass shape liquid slurry decollator lower surface circular diameter, stirring rake radical length is 2/3 of hourglass shape liquid slurry decollator lower surface circular diameter, hourglass shape cylindrical shell lower surface diameter is 2/5 of reactor diameter.Based on whole cylindrical shell height, the cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 55%; The percentage of open area of the cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 50%; Cylindrical shell lower surface to distance lower surface 1/3 apart from cylindrical shell percentage of open area be 60%.Described star shape outer corners angle is 15 degree, and described outlet star shape is triangle star.
The hydrochloride slurry that initial reactor obtains is introduced in liquid slurry decollator 5 by salify slaking reaction still first liquid phase feeding pipe 2, slurry feed rate is 100g/min, acetone is introduced in liquid slurry decollator 5 by second liquid phase feed-pipe 3, input speed is 10g/min, liquid slurry decollator 5 adopts outer coil pipe electrical tracing, maintaining hydrochloride slurry temperature is 70 DEG C, hydrochloride slurry enters salify slaking reaction still after being sheared by the star discharge port on liquid slurry decollator surface after stirring rake 6 high speed shear advances, hydrogen chloride gas is introduced in Gas distribution dish 7 through gas-phase feed pipe 1 simultaneously, hydrogen chloride gas enters salify slaking reaction still through Gas distribution panel surface aperture, it is 4L/min that hydrogenchloride passes into speed, stop reaction 10min, MXDP hydrochloride slurry is squeezed into pressurization phosgenation reaction still by relief outlet 8, in whole process, excessive gas is discharged through gaseous phase outlet 4.
Wherein in preliminary salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1, sample from salify slaking still relief outlet after salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 15um after measured.Then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 35g/min, reaction absolute pressure remains on 0.5MPa, reaction 1.5h, then reaction absolute pressure is down to 0.1Mpa, the speed that passes into of phosgene changes 5g/min, reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1128g (yield is 99.9mol%) xylylene diisocyanate, and product data refer to table 1.
Embodiment 2
Use the tank reactor identical with embodiment 1.817g (6mol) MXDP is dropped into and 7354g orthodichlorobenzene (the total amine concentration of charging is 10wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 8L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min, preliminary salt-forming reaction is carried out in the stirring of simultaneously opening reactor simultaneously.
The present embodiment use salify slaking reaction still to adopt the hourglass shape liquid slurry decollator of upper and lower end face area equation, the height of described hourglass shape liquid slurry decollator is 1/3 of tank reactor height, the distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is 1/6 of tank reactor height, stirring rake and hourglass shape liquid slurry decollator lower surface distance are 1/3 of liquid slurry decollator height, the cross section smallest circle diameter of described hourglass shape liquid slurry decollator is 1/2 of hourglass shape liquid slurry decollator lower surface circular diameter, stirring rake radical length is 5/6 of hourglass shape liquid slurry decollator lower surface circular diameter, hourglass shape cylindrical shell lower surface diameter is 3/5 of reactor diameter.Based on whole cylindrical shell height, the cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 65%; The percentage of open area of the cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 55%; Cylindrical shell lower surface to distance lower surface 1/3 apart from cylindrical shell percentage of open area be 70%.Described star shape outer corners angle is 40 degree, and described outlet star shape is corner star.
The hydrochloride slurry that initial reactor obtains is introduced in liquid slurry decollator 5 by salify slaking reaction still first liquid phase feeding pipe 2, slurry feed rate is 100g/min, acetonitrile is introduced in liquid slurry decollator 5 by second liquid phase feed-pipe 3, input speed is 10g/min, liquid slurry decollator 5 adopts outer coil pipe electrical tracing, maintaining hydrochloride slurry temperature is 70 DEG C, hydrochloride slurry enters salify slaking reaction still after being sheared by the star discharge port on liquid slurry decollator surface after stirring rake 6 high speed shear advances, hydrogen chloride gas is introduced in Gas distribution dish 7 through gas-phase feed pipe 1 simultaneously, hydrogen chloride gas enters salify slaking reaction still through Gas distribution panel surface aperture, it is 4L/min that hydrogenchloride passes into speed, stop reaction 10min, MXDP hydrochloride slurry is squeezed into pressurization phosgenation reaction still by relief outlet 8, in whole process, excessive gas is discharged through gaseous phase outlet 4.
Wherein in preliminary salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1, sample from salify slaking still relief outlet after salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 18um after measured.Then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 35g/min, reaction absolute pressure remains on 0.5MPa, reaction 1.5h, then reaction absolute pressure is down to 0.1Mpa, the speed that passes into of phosgene changes 5g/min, reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1127g (yield is 99.8mol%) xylylene diisocyanate, and product data refer to table 1.
Embodiment 3
Use the tank reactor identical with embodiment 1.1225g (9mol) MXDP is dropped into and 6946g orthodichlorobenzene (the total amine concentration of charging is 15wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 12L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min, preliminary salt-forming reaction is carried out in the stirring of simultaneously opening reactor simultaneously.
The present embodiment uses salify slaking reaction still to adopt upper and lower end face area unequal hourglass shape liquid slurry decollator, the height of described hourglass shape liquid slurry decollator is 1/3 of tank reactor height, the distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is 1/6 of tank reactor height, stirring rake and hourglass shape liquid slurry decollator lower surface distance are 1/3 of liquid slurry decollator height, the cross section smallest circle diameter of described hourglass shape liquid slurry decollator is 1/2 of hourglass shape liquid slurry decollator lower surface circular diameter, stirring rake radical length is 5/6 of hourglass shape liquid slurry decollator lower surface circular diameter, hourglass shape cylindrical shell upper surface diameter is 3/4 of lower surface diameter, hourglass shape cylindrical shell lower surface diameter is 3/5 of reactor diameter.Based on whole cylindrical shell height, the cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 65%; The percentage of open area of the cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 55%; Cylindrical shell lower surface to distance lower surface 1/3 apart from cylindrical shell percentage of open area be 70%.Described star shape outer corners angle is 40 degree, and described outlet star shape is corner star.
The hydrochloride slurry that initial reactor obtains is introduced in liquid slurry decollator 5 by salify slaking reaction still first liquid phase feeding pipe 2, slurry feed rate is 100g/min, methylethylketone is introduced in liquid slurry decollator 5 by second liquid phase feed-pipe 3, input speed is 10g/min, liquid slurry decollator 5 adopts outer coil pipe electrical tracing, maintaining hydrochloride slurry temperature is 80 DEG C, hydrochloride slurry enters salify slaking reaction still after being sheared by the star discharge port on liquid slurry decollator surface after stirring rake 6 high speed shear advances, hydrogen chloride gas is introduced in Gas distribution dish 7 through gas-phase feed pipe 1 simultaneously, hydrogen chloride gas enters salify slaking reaction still through Gas distribution panel surface aperture, it is 6L/min that hydrogenchloride passes into speed, stop reaction 10min, MXDP hydrochloride slurry is squeezed into pressurization phosgenation reaction still by relief outlet 8, in whole process, excessive gas is discharged through gaseous phase outlet 4.
Wherein in preliminary salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1, sample from salify slaking still relief outlet after salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 20um after measured.Then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 53g/min, reaction absolute pressure remains on 0.5MPa, react 1.5 hours, then reaction absolute pressure is down to 0.1Mpa, the speed that passes into of phosgene changes 7.5g/min, reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1685g (yield is 99.6mol%) xylylene diisocyanate, and product data refer to table 1.
Embodiment 4
Use the tank reactor identical with embodiment 1.1225g (9mol) MXDP is dropped into and 6946g orthodichlorobenzene (the total amine concentration of charging is 15wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 12L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min, preliminary salt-forming reaction is carried out in the stirring of simultaneously opening reactor simultaneously.
The present embodiment uses salify slaking reaction still to adopt upper and lower end face area unequal hourglass shape liquid slurry decollator, the height of described hourglass shape liquid slurry decollator is 1/2 of tank reactor height, the distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is 1/6 of tank reactor height, stirring rake and hourglass shape liquid slurry decollator lower surface distance are 1/3 of liquid slurry decollator height, the cross section smallest circle diameter of described hourglass shape liquid slurry decollator is 1/2 of hourglass shape liquid slurry decollator lower surface circular diameter, stirring rake radical length is 5/6 of hourglass shape liquid slurry decollator lower surface circular diameter, hourglass shape cylindrical shell upper surface diameter is 5/4 of lower surface diameter, hourglass shape cylindrical shell lower surface diameter is 3/5 of reactor diameter.The cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 70%, based on whole cylindrical shell height; The percentage of open area of the cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 60%, based on whole cylindrical shell height; Cylindrical shell lower surface to distance lower surface 1/3 apart from cylindrical shell percentage of open area be 75%, based on whole cylindrical shell height.Described star shape outer corners angle is 60 degree, and described outlet star shape is anistree star.
The hydrochloride slurry that initial reactor obtains is introduced in liquid slurry decollator 5 by salify slaking reaction still first liquid phase feeding pipe 2, and slurry feed rate is 100g/min, acetone, acetonitrile, methylethylketone mol ratio 1, 1:1 mixed solution is introduced in liquid slurry decollator 5 by second liquid phase feed-pipe 3, input speed is 10g/min, liquid slurry decollator 5 adopts outer coil pipe electrical tracing, maintaining hydrochloride slurry temperature is 80 DEG C, hydrochloride slurry enters salify slaking reaction still after being sheared by the star discharge port on liquid slurry decollator surface after stirring rake 6 high speed shear advances, hydrogen chloride gas is introduced in Gas distribution dish 7 through gas-phase feed pipe 1 simultaneously, hydrogen chloride gas enters salify slaking reaction still through Gas distribution panel surface aperture, it is 6L/min that hydrogenchloride passes into speed, stop reaction 10min, MXDP hydrochloride slurry is squeezed into pressurization phosgenation reaction still by relief outlet 8, in whole process, excessive gas is discharged through gaseous phase outlet 4.
Wherein in preliminary salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1, sample from salify slaking still relief outlet after salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 22um after measured.Then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 53g/min, reaction absolute pressure remains on 0.5MPa, react 1.5 hours, then reaction absolute pressure is down to 0.1Mpa, the speed that passes into of phosgene changes 7.5g/min, reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1683g (yield is 99.5mol%) xylylene diisocyanate, and product data refer to table 1.
Comparative example 1
The autoclave that use has injection reactor, phosgene is blown into pipe and stir is as conversion unit, and volume is 10 liters.817g (6mol) MXDP is dropped into and 7354g orthodichlorobenzene (the total amine concentration of charging is 10wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 8L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min simultaneously, open the stirring of reactor, wherein in salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1 simultaneously.After salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 60um after measured, then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 35g/min, reaction absolute pressure remains on 0.5MPa, react 1.5 hours, then reaction is carried out under absolute pressure 0.1Mpa, the speed that passes into of phosgene is 5g/min, and reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1106g (yield is 95.0mol%) m-xylylene diisocyanate, and product data refer to table 1.
Comparative example 2
The autoclave that use has injection reactor, phosgene is blown into pipe and stir is as conversion unit, and volume is 10 liters.1225g (9mol) MXDP is dropped into and 6946g orthodichlorobenzene (the total amine concentration of charging is 15wt%) forms MXDP solution (or being called reaction solution) in raw material tank.External cooling method is adopted to keep reacting liquid temperature to be 20 DEG C.By high-pressure pump, hydrogen chloride gas is passed in the nozzle of injection reactor, hydrogenchloride pass into speed 12L/min, enter MXDP solution by the nozzle ejection that feedstock pump begins through injection reactor with the speed of 158g/min simultaneously, open the stirring of reactor, wherein in salt-forming reaction operation, the equivalence ratio of hydrogen chloride gas and phenylenedimethylidyne diamines amino is 1.5:1 simultaneously.After salify terminates, use laser diffraction formula particle size analyzer in acetonitrile solution, measure the particle diameter of hydrochloride particle, the number average bead diameter of hydrochloride particle is 100um after measured, then phosgenation reaction still is warming up to 145 DEG C, enter pipe with light air-blowing and be blown into phosgene with 53g/min, reaction absolute pressure remains on 0.5MPa, reaction 1.5h, then reaction is carried out under absolute pressure 0.1Mpa, the speed that passes into of phosgene is 7.5g/min, and reaction 2h, after reaction terminates, by being blown into nitrogen in system, remove unreacted phosgene and hydrogen chloride gas thus.The phosgenation liquid of gained is carried out desolventizing, and rectifying obtains 1573g (yield is 93.0mol%) m-xylylene diisocyanate, and product data refer to table 1.
Table 1 product performance test data table
Claims (10)
1. prepare a method for isocyanic ester, comprise the steps:
(a) preliminary salt-forming reaction: amine obtains amine hydrochlorate slurry with the preliminary salt-forming reaction of hydrogenchloride after inert organic solvents dilution;
(b) salify slaking reaction: the amine hydrochlorate slurry of step (a) gained is imported in reactor, adds Semi-polarity organic solvent simultaneously, pass into hydrogenchloride and cure into reactant salt, obtain slaking amine hydrochlorate slurry;
(c) pressurization phosgenation reaction: step (b) gained slaking amine hydrochlorate slurry and phosgene are carried out pressurization phosgenation reaction, obtains the reaction solution containing isocyanic ester;
(d) product purification: step (c) gained is obtained isocyanate products containing the reaction solution of isocyanic ester is refining.
2. the method for claim 1, it is characterized in that, the tank reactor of step (b) described salify slaking reaction device to be internal core parts the be liquid slurry decollator of hourglass shape, the liquid slurry decollator of described hourglass shape is the cylindrical shell of hourglass shape with bottom, hourglass shape cylindrical shell upper and lower end face area equation or not etc., the hourglass shape liquid slurry decollator of preferred upper and lower end face area equation.
3. method as claimed in claim 2, it is characterized in that, the height of described hourglass shape liquid slurry decollator is the 1/4-1/2 of tank reactor height, preferred 1/3-1/2; The distance of described hourglass shape liquid slurry decollator lower surface and tank reactor bottom surface is the 1/6-1/5 of tank reactor height; The stirring rake of tank reactor is positioned at the liquid slurry decollator axle center place of hourglass shape, and stirrer paddle and hourglass shape liquid slurry decollator lower surface distance are the 1/4-1/3 of liquid slurry decollator height; The cross section smallest circle diameter of described hourglass shape liquid slurry decollator is the 1/3-2/3 of hourglass shape liquid slurry decollator lower surface circular diameter; Stirrer paddle radical length is the 2/3-5/6 of hourglass shape liquid slurry decollator lower surface circular diameter; Hourglass shape cylindrical shell upper surface diameter is the 3/4-5/4 of lower surface diameter; Hourglass shape cylindrical shell lower surface diameter is the 2/5-3/5 of reactor diameter.
4. method as claimed in claim 2 or claim 3, it is characterized in that, the cylindrical shell of the liquid slurry decollator of hourglass shape described in step (b) is the porous cylindrical shell being arranged with star shape discharge port, and the overall percentage of open area of described cylindrical shell is 50-75%; Preferably, based on whole cylindrical shell height, the cylindrical shell upper surface of the liquid slurry decollator of described hourglass shape to distance upper surface 1/3 apart from cylindrical shell percentage of open area be 55-70%, the percentage of open area of cylindrical shell between distance upper surface 1/3 to distance lower surface 1/3 is 50-60%, cylindrical shell lower surface to apart from lower surface 1/3 apart from cylindrical shell percentage of open area be 60-75%.
5. method as claimed in claim 4, it is characterized in that, described star shape outer corners angle is more than or equal to 15 degree and is less than or equal to 60 degree; Described star shape is the one or two or more in triangle star, corner star, pentagram, hexagram, heptangle star and anistree star.
6. the method according to any one of claim 1-5, it is characterized in that, the described Semi-polarity organic solvent of step (b) is one or more in lower molecular weight ketone and nitrile, one or more in the ketone of preferred boiling point 50-100 DEG C and nitrile, are more preferably one or both or three kinds in acetone, methylethylketone and acetonitrile; The consumption of described Semi-polarity organic solvent is the 5-20wt% of the amine hydrochlorate slurry total mass obtained based on step (a), preferred 10-15wt%.
7. the method for claim 1, it is characterized in that, the described inert organic solvents of step (a) is selected from the one or two or more in benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, dimethyl terephthalate ester and diethyl phthalate, is preferably orthodichlorobenzene.
8. the method according to any one of claim 1-7, is characterized in that, the pressurization phosgenation reaction described in step (c), at 0.1-1.5MPa, operates under the absolute pressure of preferred 0.2-0.6MPa; Temperature of reaction is 120-170 DEG C, preferred 140-150 DEG C; Mean residence time is 1-600 minute, preferred 30-300 minute, more preferably 60-180 minute.
9. the method as described in claim 1 or 8, it is characterized in that, the described phosgene of step (c) passes into the form of pure phosgene or phosgene solution, and the solvent of described phosgene solution is selected from the one or two or more in benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, dimethyl terephthalate ester and diethyl phthalate; Phosgene in described phosgene solution accounts for the 10-30wt% of solvent quality
10. method as claimed in any one of claims 1-9 wherein, it is characterized in that, described isocyanic ester has general formula (I):
R(NCO)
n(I)，
Described amine has general formula (II):
R(NH
2)
n(II)，
Wherein, n is 2 or 3; R represents aromatic group, aliphatic or alicyclic hydrocarbon radical, preferred aliphat or alicyclic alkyl, and more preferably carbonatoms is the aliphatic or alicyclic hydrocarbon radical of 4-15; Described R more preferably hexa-methylene, mphenylenedimethylim-, terephthalylidene, anti-form-1,4-cyclohexyl; More preferably mphenylenedimethylim-or terephthalylidene again; Most preferably be mphenylenedimethylim-.
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| CN107200691A (en) * | 2017-06-07 | 2017-09-26 | 江苏蓝丰生物化工股份有限公司 | Replace the preparation method of class para-phenylene diamine dihydrochloride |
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| CN111217975B (en) * | 2018-11-27 | 2022-01-07 | 万华化学集团股份有限公司 | Method for producing resin for optical material |
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| CN110183356A (en) * | 2019-05-20 | 2019-08-30 | 江苏蓝丰生物化工股份有限公司 | Replace the application of the preparation method and non-nitrile polar organic solvent of class paraphenylene diisocyanate in its preparation |
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Denomination of invention: A preparation method of isocyanate Effective date of registration: 20211123 Granted publication date: 20170322 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20170322 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |