CN1827593A - Process for preparing polyisocyanate by solid phosgene - Google Patents
Process for preparing polyisocyanate by solid phosgene Download PDFInfo
- Publication number
- CN1827593A CN1827593A CN 200510008982 CN200510008982A CN1827593A CN 1827593 A CN1827593 A CN 1827593A CN 200510008982 CN200510008982 CN 200510008982 CN 200510008982 A CN200510008982 A CN 200510008982A CN 1827593 A CN1827593 A CN 1827593A
- Authority
- CN
- China
- Prior art keywords
- solid phosgene
- polyamines
- salt
- polyisocyanates
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims description 46
- 239000007787 solid Substances 0.000 title claims description 35
- 239000005056 polyisocyanate Substances 0.000 title claims description 16
- 229920001228 polyisocyanate Polymers 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229920000768 polyamine Polymers 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 13
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 8
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical group C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 6
- 229940024606 amino acid Drugs 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 229930182817 methionine Natural products 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 4
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- XUYPXLNMDZIRQH-LURJTMIESA-N N-acetyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(C)=O XUYPXLNMDZIRQH-LURJTMIESA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- JUTSLNNVUDLPLD-UHFFFAOYSA-N 2-[2-(aminomethyl)phenyl]ethanamine Chemical compound NCCC1=CC=CC=C1CN JUTSLNNVUDLPLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006035 Tryptophane Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229960004799 tryptophan Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract 2
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000000640 hydroxylating effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 12
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229960005337 lysine hydrochloride Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012852 risk material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparation of 1, 2-dialkoxy-3-fluorobenzene by an intermediate of 2-fluorin-6-halogenated phenol. The said method consists of selecting 2-fluorophenol as its stock, and obtaining the intermediate of 2-fluorin-6-halogenated phenol; afterwards, performing multiple steps such as etherifing the said intermediate and etherifing again by introducing the hydroxyl group, alternatively, hydroxylating and etherifing the said intermediate; finally, obtaining the said 1, 2-dialkoxy-3-fluorobenzene. The method is of low cost, high yield rate, so it is suitable for the industrial production.
Description
Technical field
The present invention relates to a kind of method of utilizing solid phosgene and polyamines or its salt to prepare polyisocyanates.
Background technology
Isocyanic ester is generally used for preparing urethane resin, coating and tackiness agent.As everyone knows, urethane has been widely used at aspects such as optical material, automobile and structure material, sealing material, daily necessities owing to have the favorable mechanical performance.In addition, with amino acid, for example Methionin is the polyisocyanates and the urethane resin of feedstock production, owing to have excellent biological compatibility, can be used as biomedical uses.
The method for preparing at present isocyanic ester is normally utilized the reaction of phosgene and amine.At patent US5,136,086, US4,419,295, among JP2002-003462, JP06-234722, CN1125718A, CN1197793A, CN1516688A and the EP424836, all be to utilize phosgene that amine is carried out phosgenation reaction to prepare isocyanic ester.But have a lot of problems because having used phosgene in this method, for example phosgene severe toxicity, explosive belongs to the high-risk material, uses to be subjected to a lot of restrictions; And be difficult to transportation, preserve complicated operating process.In addition, because phosgene is gas at normal temperatures and pressures, solubleness in solvent is limited, therefore for fully carrying out of guaranteeing to react, reaction times needs very long, so just increase the consumption of phosgene in the reaction greatly, increased difficulty and environmental protection pressure that tail gas absorbs, made production cost improve and production security decline simultaneously.Therefore this method is unsuitable for the scale operation isocyanic ester.
In patent CN1436772A, utilize trichloromethylchloroformate (superpalite) and Armeen, primary aromatic amine and aromatic diamine to prepare polyisocyanates, productive rate reaches 80-96%.Though it is the toxicity of trichloromethylchloroformate is lower than phosgene,, therefore also not obvious to the improvement effect of phosgenation reaction because the preparation process of trichloromethylchloroformate is used phosgene.And, in storage and use, also there are some obstacles because trichloromethylchloroformate is a liquid.
Because these shortcomings and restriction that phosgene and trichloromethylchloroformate exist in application, solid phosgene (triphosgene, two-(trichloromethyl) carbonic ether) becomes the ideal substitute.It is similar with trichloromethylchloroformate to phosgene that solid phosgene prepares the reaction principle of isocyanic ester, all is to slough HCl with the amine condensation earlier, sloughs HCl then under heating condition again, obtains isocyanic ester.But solid phosgene is safe in utilization, easy to operate, has very big advantage aspect industrial applications.
Abundant national expenditures solid phosgene of Deng Yong and clock and β-phenylethylamine reaction obtains β-styroyl isocyanic ester, in the reaction phenylethylamine drips of solution is added in the ice bath refrigerative solid phosgene solution, then in reflux temperature reaction (West China pharmaceutical journal, 2000,15 (4), 289).Human solid phosgene and gamma-amino propyl-siloxane prepared in reaction γ-isocyanic ester propyl-siloxanes such as Bai Zhengwu, the drips of solution with solid phosgene in the reaction be added to-amine aqueous solution of 5-0 ℃ in, subsequently in 50 ℃ of reactions (chemistry and biotechnology, 2004 (2), 16).Utilize solid phosgene to 1 among the patent CN 1394851, the 5-diaminonaphthalene carries out phosgenation, with 1, and reaction at high temperature again after 5-diaminonaphthalene solution joins in the solid phosgene at low temperatures.This several method all be by reinforced at low temperatures with the process of control amine with the condensation reaction of solid phosgene, and then heating carries out elimination reaction, needs cool off earlier reheat during reaction, process is more loaded down with trivial details.And phosgenation reaction carries out under pressurized conditions in patent CN1394851, and to having relatively high expectations of conversion unit, the HCl that forms in the reaction can not discharge simultaneously, makes that HCl content increases in the finished product.In addition, 1, the speed that 5-diaminonaphthalene solution joins in the solid phosgene solution is very fast, may cause local superheating, makes side reaction increase, and might form a large amount of tarring products.The increase of by product quantity in the finished product makes that the aftertreatment purification process of reaction is more complicated, greatly reduces the purity of product.These isocyanic ester that all can cause obtaining can not satisfy service requirements at aspects such as color and luster, mechanical propertys when preparation urethane.
More than several methods of utilizing solid phosgene to prepare isocyanic ester all only limit to primary amine and diamines, the phosgenation reaction of the salt that forms for the polyamines more than the triamine and amine and acid is not all discussed.Because the phosgenation reaction of the above polyamines of triamine is more difficult, reaction needs higher temperature usually, and in the longer reaction times, the by product kind that may form in the reaction is more, and therefore condition and the control in the reaction process for reaction requires higher.In addition, because the acid molecule in the amine salt can dissociate out in the phosgenation reaction process, contain the formation that a large amount of acid can suppress isocyanic ester in the reaction system, so the phosgenation reaction of amine salt is also comparatively difficult, is preferably in and constantly discharges the acid that forms in the reaction process.The present invention is primarily aimed at these problems and has invented a kind of polyamines and its salt phosgenation reaction of being applicable to and prepare the method for isocyanic ester.
The present invention is when utilizing solid phosgene and polyamines prepared in reaction isocyanic ester, by in reactor, dripping the method for polyamines and its salts solution and solid phosgene solution, each process that adds a small amount of reactant with the control reaction, reach the purpose that reduces by product, and avoid the formation of tarring product as far as possible.Just at high temperature carry out, and remain synthesis under normal pressure when the phosgenation reaction among the present invention is initial, do not have particular requirement for equipment like this, and help the effusion of HCl.Method of the present invention more is applicable to the suitability for industrialized production polyisocyanates, and the tarring product that forms in the reaction process is less, and HCl content is low in the product, and the polyisocyanates product that obtains can be used to prepare the polyurethane material that color, purity etc. is had relatively high expectations.
Summary of the invention
The present invention substitutes phosgene with solid phosgene, prepares polyisocyanates with polyamines or its reactant salt.Described polyamines contains two or more amino, and described polyamines can be fat polyamine by described polyamines, and aliphatic chain can be straight or branched, quadrol, 1 for example, 6-hexanediamine, 1,4-butanediamine, 1,4-pentamethylene diamine, 1,2,6-hexanediamine, 1,3,6-heptamethylene diamine etc.; Also can be for not being with or having substituent cyclic aliphatic polyamines or an aralkyl polyamines, for example 1,4-diamino-cyclohexane, 1,3-diamino-cyclohexane, adjacent dibenzylamine, a dibenzylamine, to dibenzylamine, 2-(beta-aminoethyl) benzylamine etc.; Also can be for containing the aromatic multi-amine of two or more amino, for example 2,4-tolylene diamine, 2,5-tolylene diamine, 1,2,4-benzene triamine etc.; Can also be the polyamines for preparing by the amino acid esterification, for example the diamines or the triamine that obtain of amino acid such as Methionin, glycine, L-glutamic acid, tryptophane, Gelucystine and thanomin reaction.Described salt can preferably use hydrochloride for hydrochloride, vitriol, nitrate or the phosphoric acid salt etc. of above various amine.Can use single amine or its salt in the reaction, also can use mixed amine or/and its salt.
The mol ratio of amine and solid phosgene is 1 among the present invention: 1-1: 20, preferred 1: 2-1: 5.
Solvent with solid phosgene reaction among the present invention is to phosgenation reaction inert solvent, and arene for example is as benzene,toluene,xylene etc.; Or the halogenated aryl hydrocarbon class, as chlorobenzene, orthodichlorobenzene etc.; Or the benzene nitrile, as cyanobenzene; Or aliphatics and aromatic ester class, pentyl acetate for example, ethyl benzoate etc.The preferred orthodichlorobenzene of solvent.Solvent load is 1-10 a times of reaction raw materials gross weight.Solvent is used further to this reaction after recyclable after the reaction.
When reaction is reinforced among the present invention, amine and solid phosgene are dissolved in respectively in the solvent, are added drop-wise in the reactor.Control the condensation reaction of amine and solid phosgene by the mode that only adds a small amount of reaction raw materials at every turn.
The drips of solution of polyamines and solid phosgene is added to when in the reactor condensation reaction taking place among the present invention, and HCl is sloughed in the intermediate product heating, obtains polyisocyanates.Two-step reaction carries out simultaneously, and temperature is at 100-200 ℃, and preferred 140-150 ℃, reaction times 5-15 hour, preferred 8-10 hour.
After the polyamines of predetermined amount and solid phosgene solution splashed into reactor and uniform mixing fully among the present invention, at 100-200 ℃, preferred 140-150 ℃ was continued slaking 1-5 hour, preferred 2-3 hour down.
Can reach more than 85% through productive rate behind the vacuum fractionation, the content of NCO can reach more than 95% of theoretical value in the product.
Following examples describe the present invention in detail, but the present invention is not limited thereto.
Embodiment 1:
Lysine triisocyanate (LTI):
Add 449.6g (4.31mol) 35%HCl solution in the 1L four-hole boiling flask and in 30 minutes, drip 167.2g (2.74mol) thanomin, dropwise the back and add 250.0g (1.37mol) lysine hydrochloride, and 45 ℃ of following stirring reactions 10 minutes.Temperature is risen to 110 ℃, be decompressed to 4KPa, boil off the moisture content in the reaction system.Recover to feed HCl gas reaction 3 hours behind the normal pressure, again pressure reducing and steaming moisture content wherein.This process repeats for several times, and lysine hydrochloride runs out of the back stopped reaction, adds orthodichlorobenzene (ODCB) and methanol crystallization, and crystal obtains Methionin amino ethyl ester tri hydrochloride (LAET) for several times with the ODCB washing.
The 2500ml reactor is joined mechanical stirring and two cover droppers.In reactor, add 100ml orthodichlorobenzene (ODCB); respectively 298.5 (1mol) Methionin amino ethyl ester tri hydrochloride (LAET) is dissolved in 500ml ODCB; 594g (2mol) is two-and (trichloromethyl) carbonic ether (solid phosgene) is dissolved among the 1000ml ODCB, under nitrogen protection these two kinds of solution joined in the Dropping feeder.Temperature of reaction kettle remains on 145 ℃, drips the ODCB solution of LAET and solid phosgene in 10 hours.Dropwise the back and be incubated 2 hours under this temperature, the mixing solutions that obtains adds gac and stirs decolouring, suction filtration after the cooling.Filtrate decompression boils off rectifying behind the solvent, collects the cut of 80-85 ℃/60mmHg.Product by analysis, LTI content 91.5% (HPLC), NCO content 46.23wt% (theoretical value 47.2wt%), HCl content 0.2wt%, ODCB content 0.08wt%.
Embodiment 2:
Lysine triisocyanate (LTI):
Except that two-(trichloromethyl) carbonic ether changes into the 445.5g (1.5mol), other reaction conditionss obtain LTI content 68.6% (HPLC) in the product, NCO content 40.3wt% (theoretical value 47.2wt%) with embodiment 1, HCl content 0.70wt%, ODCB content 0.81wt%.
Embodiment 3:
Lysine triisocyanate (LTI):
Except that two-(trichloromethyl) carbonic ether changes into the 891g (3mol), other reaction conditionss obtain LTI content 86.3% (HPLC) in the product, NCO content 43.6wt% (theoretical value 47.2wt%) with embodiment 1, HCl content 0.35wt%, ODCB content 0.31wt%.
Embodiment 4:
Hexamethylene diisocyanate:
116g (1mol) 1, the 300ml toluene solution of 6-hexanediamine, 386g (1.3mol) be two-and the 600ml toluene solution of (trichloromethyl) carbonic ether is added drop-wise in the 100ml toluene by the method among the embodiment 1, add insulation 2 hours under uniform temp afterwards in following 8 hours at 120 ℃.50-60 ℃/60mmHg cut is collected in aftertreatment and rectifying.Hexamethylene diisocyanate content 89% (HPLC) wherein, NCO content 41.5wt% (theoretical value 50wt%), HCl content 0.67wt%, toluene level 0.22wt%.
Embodiment 5:
Hexamethylene diisocyanate:
Except that temperature of reaction changes into 140 ℃, other reaction conditionss are with embodiment 4.Obtain hexamethylene diisocyanate content 95% (HPLC) in the product, NCO content 48.8wt% (theoretical value 50wt%), HCl content 0.17wt%, toluene level 0.06wt%.
Embodiment 6:
1,2,4-benzene triisocyanate:
232.5g (1mol) 1,2,400ml cyanobenzene solution, the 594g (2mol) of 4-benzene three amine hydrochlorates be two-and the 1000ml cyanobenzene solution of (trichloromethyl) carbonic ether is added drop-wise in the 100ml cyanobenzene by the method among the embodiment 1,160 ℃ add in following 8 hours, insulation 3 hours under uniform temp afterwards.110-120 ℃/2mmHg cut is collected in aftertreatment and rectifying.Wherein 1,2,4-benzene triisocyanate content 83.2% (HPLC), NCO content 49.3wt% (theoretical value 62.7wt%), HCl content 0.84wt%, cyanobenzene content 1.2wt%.
Embodiment 7:
1,2,4-benzene triisocyanate:
Except that the dropping time changes 10 hours into, dropwise the back soaking time and change into outside 2 hours, other reaction conditionss are with embodiment 6.Obtain in the product 1,2,4-benzene content 85% (HPLC), NCO content 52.4wt% (theoretical value 62.7wt%), HCl content 0.81wt%, cyanobenzene content 1.3wt%.
Claims (5)
1. one kind prepares the method for polyisocyanates with solid phosgene, and it is characterized in that: with solid phosgene and polyamines and/or its reactant salt, make polyisocyanates, its step is as follows:
(1) be dissolved in solid phosgene and polyamines or its salt in the inert solvent respectively;
(2) under about 100-200 ℃, solid phosgene solution and polyamines drips of solution are added in the reactor, react;
(3) vacuum fractionation obtains polyisocyanates.
2. as claimed in claim 1ly prepare the method for polyisocyanates, it is characterized in that: polyamines and/or its salt that described polyamines and/or its salt are selected from fat polyamine and/or its salt, aromatic multi-amine and/or its salt, are obtained by the amino acid esterification with solid phosgene.
3. as each described method for preparing polyisocyanates with solid phosgene among the claim 1-2, it is characterized in that: described polyamines is selected from: quadrol, 1, the 6-hexanediamine, 1, the 4-butanediamine, 1, the 4-pentamethylene diamine, 1,2, the 6-hexanediamine, 1,3, the 6-heptamethylene diamine, 1, the 4-diamino-cyclohexane, 1, the 3-diamino-cyclohexane, adjacent dibenzylamine, between dibenzylamine, to dibenzylamine, 2-(beta-aminoethyl) benzylamine, 2, the 4-tolylene diamine, 2, the 5-tolylene diamine, 1,2,4-benzene triamine, or Methionin, glycine, L-glutamic acid, tryptophane, diamines or triamine that amino acid such as Gelucystine and thanomin reaction obtain, or the hydrochloric acid of above-mentioned amine, sulfuric acid, phosphoric acid or nitrate.
4. as each describedly prepares the method for polyisocyanates with solid phosgene among the claim 1-3, it is characterized in that: described inert solvent is aromatic hydrocarbon, halogenated aryl hydrocarbon, benzene nitrile, aliphatic ester or aromatic ester class.
5. as each describedly prepares the method for polyisocyanates with solid phosgene among the claim 1-4, it is characterized in that: the mol ratio of described polyamines and/or its salt and solid phosgene is about 1: 1-1: 20.
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