CN101200436A - Method for continuously preparing 1,6-hexamethyl diisocyanate - Google Patents
Method for continuously preparing 1,6-hexamethyl diisocyanate Download PDFInfo
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- CN101200436A CN101200436A CNA2007103062391A CN200710306239A CN101200436A CN 101200436 A CN101200436 A CN 101200436A CN A2007103062391 A CNA2007103062391 A CN A2007103062391A CN 200710306239 A CN200710306239 A CN 200710306239A CN 101200436 A CN101200436 A CN 101200436A
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- hexamethylene diisocyanate
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 125000005442 diisocyanate group Chemical group 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011552 falling film Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012442 inert solvent Substances 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 13
- 239000006200 vaporizer Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 5
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010504 bond cleavage reaction Methods 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical group CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical group CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000011437 continuous method Methods 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 abstract 2
- DXZCANUBKZARPR-UHFFFAOYSA-N methyl n-[6-(methoxycarbonylamino)hexyl]carbamate Chemical compound COC(=O)NCCCCCCNC(=O)OC DXZCANUBKZARPR-UHFFFAOYSA-N 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 10
- -1 aliphatic isocyanates Chemical class 0.000 description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000005494 condensation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000001149 thermolysis Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUPZNXVZUKYOFY-UHFFFAOYSA-N C(=O)OC(N)N Chemical compound C(=O)OC(N)N JUPZNXVZUKYOFY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 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
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Abstract
The invention relates to a method for the consecutive preparation of 1, 6-methylene diisocyanate. The solution dissolved with dimethylhexane-1, 6-dicarbamate is continuously injected into a scraper falling-film evaporator to form falling film, and thermal cracking reaction starts; the temperature of the inner wall of the evaporator is controlled at 220-245 DEG C, and the reaction pressure is controlled at 0.2-0.6MPa. The alcohol generated in the reaction is evaporated from the top part of the evaporator following a small proportion of solvent, and 1, 6-methylene diisocyanate product, along with the majority of the solvent, is collected from the bottom of the evaporator, and the yield is greater than 90 percent.
Description
Technical field
The present invention relates to a kind of continuous preparation 1, the method for 6-hexamethylene diisocyanate.
Background technology
1,6-hexamethylene diisocyanate (HDI) is the aliphatic isocyanates that has the call in the present polyurethane industrial, and become the bigger isocyanic ester kind of demand after tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), poly-methyl polyphenyl isocyanic ester (PAPI), be mainly used in and produce high-grade polyurethane coating, elastomerics, tackiness agent, textile finshing agent etc.Two isocyano group activity of HDI are similar, and the urethane of deriving has that density is little, intensity is high, machine-shaping is simple, nontoxic, adiabatic heat-proof quality is good, the flame-proof heat-resistant performance is better than characteristics such as other types plastics.Compare with aromatic isocyanates such as PAPI with MDI, TDI, the HDI distinctive saturability of urethane of deriving makes it have not yellowing, protects look, protects advantages such as light, anti-efflorescence, oil resistant, wear resisting property, has at aspects such as aerospace, car and boat, weaving, plastics, coating, rubber industries comparatively widely and uses.
Phosgenation is the major industry route of preparation HDI at present, but has problems in process of production: because phosgene is hypertoxic gas, series of engineering technical problems such as the safety of production process, environmental protection are difficult to thorough solution; Handle imperfection if absorb, have a large amount of byproduct hydrogen chlorides to leak in phosgenation, cause environmental pollution and byproduct hydrogen chloride serious to the equipment corrosion of production process, therefore to the requirement height of equipment material, corresponding investment is bigger; Contain hydrolysis chlorine in the HDI product that phosgenation makes, influence the application performance of product.So non-phosgene route synthesizing isocyanate becomes the developing direction of technology.The process for cleanly preparing of exploitation HDI has vast market prospect and sound social environment benefit.
Isocyanic ester non-phosgene synthetic route mainly contains oil of mirbane and carbon monoxide synthesis method; The synthesis method of amine and carbon monoxide and alcohol; Amine, carbonic acid gas, alkali and dewatering agent synthesis method; The carbamate thermolysis process.Wherein carbamate thermolysis process synthesizing isocyanate have that process cleaning, reaction conditions relatively easily realize, quality product height, characteristics such as environment-friendly.The typical patent report of known carbamate thermolysis synthesizing isocyanate has:
A kind of preparation diphenylmethanediisocyanate method has been described in CN1850792A, to carry out heat scission reaction in ditan diamino-methyl formate and the carrier adding flask, with vacuum means separating by-products methyl alcohol, reaction solution obtains diphenylmethanediisocyanate and carrier, the carrier recycle after separating.The process transformation efficiency is near 100%, and selectivity is up to 93.8%.This invention has only realized carbamate intermittent fever cracked process, does not finish serialization.
A kind of preparation method who organic multiple-amino ester formate is resolved into organic multiple isocyanate and alcohol has been described in CN1406224A, it is characterized in that have or solvent-free situation under with organic multiple-amino ester formate heat fused, pure and mild at least a portion vulcabond that forms simultaneously when decompression is decomposed or isocyano unification carbamate, perhaps both remove during decomposing.This method especially is fit to the preparation aromatic polyisocyanate.Process productive rate 90% more than.This invention also belongs to intermittent fever cracked process, does not realize serialization.
JP02212465 adopts two-step approach to realize thermal decomposition process, and the first step is that by-product alcohol is removed in carbamate and solvent cracking under boiling state, and reaction soln forms film then, continues to finish pyrolysis.
US4547322 is dissolved in carbamate in the solvent and flows downward from reactor top, and fully contact with the upstream carrier vapor of another strand, the alcohols of by-product is brought to the reactor upper end, collects as vapour condensation with carrier, and reactor lower part obtains isocyanate solution.
Among the US5731458, the carbamate cracking generates corresponding isocyanate and alcohol, and this process is to carry out in the stripping section of a reactive distillation post, and control condition makes reaction away from rectifying column reboiler zone.Used high boiling solvent to play shock absorption.
The general boiling point of the employed solvent of foregoing invention is higher, and difficulty is bigger when separating with isocyanate products.
Summary of the invention
The present invention adopts 1,6-hexa-methylene diamino manthanoate Continuous Heat decomposition technique replaces traditional phosgene route one-step synthesis 1, the 6-hexamethylene diisocyanate, various problems such as raw material severe toxicity, seriously corroded, the process of having avoided the use phosgene to bring is dangerous, environmental pollution, it is simple to have flow process, and reaction efficiency height, mild condition, reaction times weak point, product are easy to separate and quality height, by product and characteristics such as solvent cycle use, process environment close friend.
The reaction process that the present invention relates to is as follows:
1,6-hexa-methylene carbamate pyrolysis is reversible reaction, is having under the situation of catalyst-free, the generation cracking of being heated of each carbamate groups respectively loses a part alcohols, and the carbon nitrogen-atoms forms two keys afterwards, obtain 1, the 6-hexamethylene diisocyanate.ROH in the reaction formula is easy to the alcohols under the cracking under reaction conditions, comprises methyl alcohol, trichlorine methyl alcohol, ethanol, trichloro-ethyl alcohol, phenol, the single replacement and polysubstituted halogenated phenol.Wherein methyl alcohol, ethanol, phenol etc. are specially adapted to the present invention.The generation that can the alcohol that generate in the reaction process in time separate isocyanic ester with reaction system has fundamental influence.
1,6-hexa-methylene carbamate pyrolysis at high temperature carries out usually, because isocyano has very high reactive behavior, significant thermo-sensitivity is especially at high temperature arranged, side reaction takes place easily, the inhibition side reaction of therefore must adopting an effective measure, use inert solvent diluting reaction raw material among the present invention, can reduce isocyano concentration, and promote the system thermally equivalent, prevent local temperature runaway.Simultaneously in conjunction with the lower inert solvent of another kind of boiling point as carrier, quicken to remove the alcohols that dereaction generates, improve transformation efficiency.
This reaction needs to carry out in inert solvent, and inert solvent is meant under reaction conditions can dissolve 1 well, 6-hexa-methylene diamino manthanoate, and not with 1, the interactional any solvent of 6-hexamethylene diisocyanate or alcohols.1 of pyrolysis generation, the 6-hexamethylene diisocyanate also can play the effect of reaction solvent.
For reducing inert solvent and the isolating technical difficulty of isocyanate products, need satisfying the boiling-point difference that as far as possible widens solvent and product under the situation of reaction conditions, so the boiling point of inert solvent is unsuitable too high.Spendable inert solvent comprises N, accelerine, N, N-Diethyl Aniline, N, the N-first and second basic aniline, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethylformamide, N, N-diethyl acetamide, adjacent methyl chlorobenzene, PARA NITRO CHLOROBENZENE (PNCB), santochlor, diethyl phthalate, methyl phenyl ketone etc.Can select the mixture of a kind of solvent or two or more these kind solvents during use.
Can also use above-mentioned at least a solvent, and use in conjunction with the lower inert solvent of another kind of boiling point.The inert solvent that boiling point is lower gasifies than being easier under reaction conditions, and not with 1,6-hexamethylene diisocyanate or alcohols react, and can be used as vector gas physics and removes the alcohols that dereaction generates, and accelerates separation of by-products speed, improves transformation efficiency.
The inert solvent that this class boiling point is lower comprises benzene, toluene, 1,1-ethylene dichloride, tetracol phenixin, dme, methyl ethyl ether, ether, dimethyl sulfoxide (DMSO) etc.
For reducing inert solvent and 1, the technical difficulty of 6-hexamethylene diisocyanate product separation, the above-mentioned two class inert solvent boiling points and 1 that the present invention uses, the 6-hexamethylene diisocyanate is compared all relatively low, and its mid-boiling point higher relatively solvent and part by weight of boiling point relatively low solvent in this two classes inert solvent in this two classes inert solvent are 0.1～10.
Among the present invention, 1, the concentration range of 6-hexa-methylene carbamate solution is at 1～40wt%, and suitable temperature of reaction is at 150～300 ℃.For reaching best temperature of reaction, reaction pressure is generally greater than atmospheric pressure, and its scope changes to some extent according to the difference of inert solvent or solvent composite type, generally at 0.1～1.0MPa, preferably at 0.4～0.7MPa.Among the present invention, the mean residence time of material in reactor be with 1, the difference of 6-hexa-methylene carbamate type, concentration and temperature of reaction and changing to some extent, and mean residence time is 10～60 minutes.
The present invention can realize with totally continuous method, also can realize with batch intermittence or semicontinuous method.Because advantages such as the work of treatment before and after the reactions such as reactor is little, operational stability good, no heating and cooling that full continuation method has, constant product quality are so full continuation method relatively is fit to industrialization promotion.Promptly under certain temperature and pressure condition, having under the condition of catalyst-free, reaction mass is after feed preheater V101 preheating, in pump P101 input is furnished with/carry out heat scission reaction among the continuous scraped falling-film evaporator R101 of high speed scraping blade.Material keeps certain residence time in reactor, and the alcohol of by-product through the continuous extraction reaction system of the pipeline of falling-film evaporator, is collected in light constituent storage tank V103 by aforesaid vector gas after the E101 condensation.1 of generation, 6-hexamethylene diisocyanate product are collected in the heavy constituent storage tank V102 of band condensation chuck with the inert solvent outflow reactor.Detailed process is seen accompanying drawing of the present invention.
Filtering catalyst (if present) and adopt known separate inert solvent as methods such as underpressure distillation after, obtain having highly purified 1,6-hexamethylene diisocyanate product.Extra high if desired product purity, can be further with known as purification process processing reaction products such as recrystallization, molecular distillation, extractions.
1 of the present invention's production, 6-hexamethylene diisocyanate productive rate can reach more than 90%, can reach 97%.
Illustrate the present invention by the following example, but the invention is not restricted to the following example.
Description of drawings
Fig. 1 is preparation 1 continuously, 6-hexamethylene diisocyanate process flow sheet
Embodiment
Embodiment one
At first use nitrogen replacement reaction system air, scraped falling-film evaporator chuck heated oil temperature rise to 280 ℃.With the N that is preheating to 120 ℃, accelerine and toluene mixture liquid (blank inert solvent, weight ratio is 1: 1) with formation falling liquid film and vaporization in the flow feeding single tube scraped falling-film evaporator of 100g/h, the scraper plate rotating speed remains on 120rpm, the vaporizer inner wall temperature is controlled at 235～245 ℃, and system pressure is stabilized in 0.5～0.6MPa.After system is stable, with be preheating to 120 ℃ 1,6-hexa-methylene diamino-methyl formate solution (the above-mentioned mixed solution of 10g hexa-methylene diamino-methyl formate/100g) switches above-mentioned barren inert solvent, flow with 110g/h feeds formation falling liquid film and vaporization in the scraped falling-film evaporator, begin reaction, switch the gathering system of the upper and lower outlet of vaporizer simultaneously.Control vaporizer inner wall temperature is 235～245 ℃, and reaction pressure is stabilized in 0.5～0.6MPa.Reaction solution is 15min at the mean residence time of scraped falling-film evaporator.
The average discharge such as the table 1 of vaporizer overhead fraction component:
The average discharge of table 1. vaporizer overhead fraction component
| The component title | Flow g/h |
| Toluene N, accelerine methyl alcohol | 41.8 17.3 2.8 |
Base of evaporator extraction material average discharge such as a mistake! The bookmark self reference is invalid.：
Table 2 base of evaporator extraction material average discharge
| The component title | Flow g/h |
| Toluene N, accelerine hexamethylene diisocyanate hexa-methylene diamino-methyl formate | 7.5 31.6 6.5 0.4 |
1,6-hexamethylene diisocyanate productive rate is 94.7%, does not find its trimer product.Can be with methods such as known rectification under vacuum, extractions with 1, the 6-hexamethylene diisocyanate with raw material and separated from solvent, the latter recycles.
Embodiment two
Operation is with embodiment one, solvent uses with embodiment one, with 1, the 6-hexa-methylene diamino-methyl formate replaces to 1,6-hexa-methylene diamino ethyl formate, reaction raw materials liquid concentration are 15g/100g (mixed solvent), and the reaction solution flow is 115g/h, the vaporizer inner wall temperature is controlled at 220～230 ℃, and system pressure is stabilized in 0.45～0.6MPa.All the other operational conditions are constant.
The average discharge such as the table 3 of vaporizer overhead fraction component:
The average discharge of table 3. vaporizer overhead fraction component
| The component title | Flow g/h |
| Toluene N, accelerine ethanol | 39.2 15.8 5.8 |
Base of evaporator extraction material average discharge such as table 4:
Table 4. base of evaporator extraction material average discharge
| The component title | Flow g/h |
| Toluene N, accelerine hexamethylene diisocyanate hexa-methylene diamino ethyl formate | 9.9 33.4 8.8 0.3 |
1,6-hexamethylene diisocyanate productive rate is 97.2%, does not find its trimer product.Can be with methods such as known rectification under vacuum, extractions with 1, the 6-hexamethylene diisocyanate with raw material and separated from solvent, the latter recycles.
Embodiment three
Operation is with embodiment one, and with 1, the 6-hexa-methylene diamino-methyl formate replaces to 1,6-hexa-methylene diamino ethyl formate, and solvent replacing is N, N-Diethyl Aniline and toluene is 3: 2 mixed solution by weight.Reaction raw materials liquid concentration is 15g/100g (mixed solvent), and the reaction solution flow is 115g/h.The vaporizer inner wall temperature is controlled at 220～230 ℃, and system pressure is stabilized in 0.20～0.3MPa.All the other operational conditions are constant.
The average discharge such as the table 5 of vaporizer overhead fraction component:
The average discharge of table 5. vaporizer overhead fraction component
| The component title | Flow g/h |
| Toluene N, N-Diethyl Aniline ethanol | 31.1 17.7 5.9 |
Base of evaporator extraction material average discharge such as table 6:
Table 6. base of evaporator extraction material average discharge
| The component title | Flow g/h |
| Toluene N, N-Diethyl Aniline hexamethylene diisocyanate hexa-methylene diamino ethyl formate | 8.3 41.0 8.7 0.4 |
1,6-hexamethylene diisocyanate productive rate is 96.1%, does not find its trimer product.Can be with methods such as known rectification under vacuum, extractions with 1, the 6-hexamethylene diisocyanate with raw material and separated from solvent, the latter recycles.
Claims (7)
1. prepare 1 continuously, the method for 6-hexamethylene diisocyanate is characterized in that 1, and 6-hexa-methylene carbamate is thermo-cracking preparation 1 continuously in falling film reactor, the 6-hexamethylene diisocyanate.
2. according to the method for claim 1, prepare 1 continuously, the concrete steps of 6-hexamethylene diisocyanate are: with 1 of preheating, 6-hexa-methylene diamino manthanoate solution feeds and forms falling liquid film and vaporization in the scraped falling-film evaporator, the beginning heat scission reaction; The alcohols that reaction generates with most of low boiling point solvent from the extraction of vaporizer top, the hexamethylene diisocyanate product with most of high boiling solvent from the base of evaporator extraction.
3. according to the method for claim 2,1, the concentration range of 6-hexa-methylene carbamate solution is at 1～40wt%, and the scraped falling-film evaporator inner wall temperature is at 150～300 ℃, reaction pressure is at 0.1～1.0MPa, and the mean residence time of material in scraped falling-film evaporator is 10～60 minutes.
4. according to the method for claim 2, the boiling point of the employed kind solvent of process is higher relatively, not with 1, the material that 6-hexamethylene diisocyanate or alcohols are had an effect, comprise N, accelerine, N, N-Diethyl Aniline, N, the N-first and second basic aniline, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethylformamide, N, a kind of solvent in N-diethyl acetamide, adjacent methyl chlorobenzene, PARA NITRO CHLOROBENZENE (PNCB), santochlor, diethyl phthalate, the methyl phenyl ketone or two or more mixtures.
5. according to the method for claim 2, the employed another kind of solvent of process is the lower vector gas of boiling point, is mainly used in the alcohols of taking by-product out of, promotes that heat scission reaction carries out.This class inert solvent comprises benzene, toluene, 1,1-ethylene dichloride, tetracol phenixin, dme, methyl ethyl ether, ether, dimethyl sulfoxide (DMSO).
6. according to claim 4,5 method, the part by weight of relative higher-class inert solvent of boiling point and the relatively low class inert solvent of boiling point is 0.1～10.
7. according to the method for claim 1, the present invention can realize with totally continuous method, also can realize with batch intermittence or semicontinuous method.
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| CNA2007103062391A CN101200436A (en) | 2006-12-31 | 2007-12-30 | Method for continuously preparing 1,6-hexamethyl diisocyanate |
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| CN200610172181.1 | 2006-12-31 | ||
| CNA2007103062391A CN101200436A (en) | 2006-12-31 | 2007-12-30 | Method for continuously preparing 1,6-hexamethyl diisocyanate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102712580A (en) * | 2010-01-19 | 2012-10-03 | 巴斯夫欧洲公司 | Method for producing isocyanates by thermally splitting carbamates |
| CN102992969A (en) * | 2012-12-24 | 2013-03-27 | 上海三爱富新材料股份有限公司 | Method and device for producing fluorine-containing vinyl ether by acyl fluoride |
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| CN113651719A (en) * | 2021-09-16 | 2021-11-16 | 宁夏瑞泰科技股份有限公司 | Refining method of hexamethylene diisocyanate photochemical liquid |
| CN114768708A (en) * | 2022-03-29 | 2022-07-22 | 中国科学院过程工程研究所 | Device and method for preparing m-xylylene diisocyanate |
| CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
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- 2007-12-30 CN CNA2007103062391A patent/CN101200436A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712580A (en) * | 2010-01-19 | 2012-10-03 | 巴斯夫欧洲公司 | Method for producing isocyanates by thermally splitting carbamates |
| CN102712580B (en) * | 2010-01-19 | 2014-11-26 | 巴斯夫欧洲公司 | Method for producing isocyanates by thermally splitting carbamates |
| CN102992969A (en) * | 2012-12-24 | 2013-03-27 | 上海三爱富新材料股份有限公司 | Method and device for producing fluorine-containing vinyl ether by acyl fluoride |
| CN109369457A (en) * | 2018-12-13 | 2019-02-22 | 湖南海利常德农药化工有限公司 | A kind of preparation method of m-xylylene diisocyanate |
| CN113651719A (en) * | 2021-09-16 | 2021-11-16 | 宁夏瑞泰科技股份有限公司 | Refining method of hexamethylene diisocyanate photochemical liquid |
| CN113651719B (en) * | 2021-09-16 | 2023-08-04 | 宁夏瑞泰科技股份有限公司 | Refining method of hexamethylene diisocyanate photochemical liquid |
| CN114768708A (en) * | 2022-03-29 | 2022-07-22 | 中国科学院过程工程研究所 | Device and method for preparing m-xylylene diisocyanate |
| CN115572245A (en) * | 2022-09-29 | 2023-01-06 | 四川元理材料科技有限公司 | Industrial method for producing IPDI (isophorone diisocyanate) by thermal cracking of n-butyl isophorone dicarbamate |
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