CN115716906B - Hexamethylene diisocyanate composition and preparation method and application thereof - Google Patents
Hexamethylene diisocyanate composition and preparation method and application thereof Download PDFInfo
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- CN115716906B CN115716906B CN202211565041.6A CN202211565041A CN115716906B CN 115716906 B CN115716906 B CN 115716906B CN 202211565041 A CN202211565041 A CN 202211565041A CN 115716906 B CN115716906 B CN 115716906B
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- hexamethylene diisocyanate
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- phosgene
- diisocyanate composition
- hexamethylenediamine
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000005057 Hexamethylene diisocyanate Substances 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 25
- 230000008859 change Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 65
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 60
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000005056 polyisocyanate Substances 0.000 abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 abstract description 14
- 239000000047 product Substances 0.000 description 26
- 239000012043 crude product Substances 0.000 description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012264 purified product Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- -1 aliphatic isocyanate Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-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
- 230000006872 improvement Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WSLLZVOGCXKCIP-UHFFFAOYSA-N 1,1-dichloro-6-isocyanatohexane Chemical compound ClC(Cl)CCCCCN=C=O WSLLZVOGCXKCIP-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ODZCMRWKICFGTO-UHFFFAOYSA-N C(C1=CC=CC=C1)C(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Cl Chemical compound C(C1=CC=CC=C1)C(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Cl ODZCMRWKICFGTO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XNWSMNKRGNKRKP-UHFFFAOYSA-M propanoate;tetramethylazanium Chemical compound CCC([O-])=O.C[N+](C)(C)C XNWSMNKRGNKRKP-UHFFFAOYSA-M 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种六亚甲基二异氰酸酯组合物及其制备方法和应用，所述六亚甲基二异氰酸酯组合物包含六亚甲基二异氰酸酯和0.2‑500 ppm的环状化合物，在140℃热处理4h的色度变化率在8以下。本发明提供的六亚甲基二异氰酸酯组合物制备得到的聚异氰酸酯具有优异的低色度相对稳定性。The present invention relates to a hexamethylene diisocyanate composition and a preparation method and application thereof. The hexamethylene diisocyanate composition comprises hexamethylene diisocyanate and 0.2-500 ppm of a cyclic compound, and the chromaticity change rate after heat treatment at 140°C for 4 hours is less than 8. The polyisocyanate prepared by the hexamethylene diisocyanate composition provided by the present invention has excellent low chromaticity relative stability.
Description
Technical Field
The invention relates to the technical field of isocyanate, in particular to a hexamethylene diisocyanate composition with low chromaticity and relatively stability, and a preparation method and application thereof.
Background
Hexamethylene diisocyanate, which is an aliphatic isocyanate, has excellent yellowing resistance compared to aromatic isocyanates, is generally obtained industrially by reacting hexamethylenediamine with phosgene, and is particularly advantageously carried out in the gas phase. However, it is frequently the case that, for whatever reason, the commercial isocyanate products are coloured or that there is an adverse effect on the colour of the polyisocyanates, such as trimers or biurets or uretdiones, in the modification step downstream thereof.
Patent CN113072512a discloses a method for improving the turbidity change of polyisocyanates during storage by controlling the content of dichlorohexyl isocyanate in 1, 6-hexamethylene diisocyanate, but does not teach improvement of the chromaticity of the product nor the influence of other impurities on chromaticity.
Patent CN106946741B discloses a method for preparing dicyclohexylmethane diisocyanate excellent in storage yellowing resistance, by purifying raw material dicyclohexylmethane diamine, controlling aromatic monoamine compound therein to be below 0.1wt%, and phosgenating the raw material to obtain dicyclohexylmethane diisocyanate excellent in yellowing resistance, but no guiding effect is provided for color number improvement of hexamethylene diisocyanate and prepolymer thereof.
Patent CN110982045B provides a method for preparing low color number isocyanate curing agent, controlling the double bond content in long chain alcohol to be less than or equal to 10ppm and peroxide content to be less than or equal to 500ppm, but no teaching is given about the quality of isocyanate.
Patent CN112250835B discloses a reduction in colour achieved by adjusting the pH of the solution of the catalyst for the preparation of the polyisocyanate to 5-7, nor does it teach the quality of the isocyanate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hexamethylene diisocyanate composition with low chromaticity and relatively stability, a preparation method and application thereof, and polyisocyanate obtained by taking the hexamethylene diisocyanate composition as a raw material has the characteristic of low chromaticity and relatively stability.
To achieve the purpose, the invention adopts the following technical scheme:
a hexamethylene diisocyanate composition comprising hexamethylene diisocyanate and from 0.2 to 500ppm of a cyclic compound.
The hexamethylene diisocyanate composition of the present invention is a substantially single compound containing 99% by weight or more of hexamethylene diisocyanate as a main component (i.e., hexamethylene diisocyanate), but is defined as a hexamethylene diisocyanate composition because it contains the above-mentioned cyclic compound as a subcomponent.
The hexamethylene diisocyanate composition, the cyclic compound comprises any one or at least two of the following compounds:
Wherein X is CH 3 or H or Cl or Br.
The impurities are derived from products obtained by reacting the impurities in the feed amine with phosgene (or bromine-containing phosgene), wherein one part of the impurities in the amine is directly derived from the feed amine, and the other part of the impurities in the amine is the feed amine or a byproduct of the impurities in the feed amine after being heated at high temperature.
In the studies of the present inventors, it was found that when the above cyclic compound is contained in an amount of 0.2 to 500ppm in the hexamethylene diisocyanate composition, the isocyanate and the polyisocyanate obtained therefrom have excellent low-color relative stability, and the low-color relative stability is deteriorated when the content is less than 0.2ppm or more than 500 ppm.
Preferably, the hexamethylene diisocyanate composition has a cyclic compound content of 0.4 to 200ppm, more preferably 0.8 to 100ppm.
The content of the cyclic compound described in the present invention may be carried out by, but not limited to, controlling the reaction conditions, or the separation conditions, or additionally adding so that the content of the cyclic compound is controlled within the range.
In addition, the color change rate of the product obtained by heat treatment of the hexamethylene diisocyanate composition at 140 ℃ for 4 hours can be controlled to be below 8 by controlling the content of the cyclic compound.
The chroma change rate of the isocyanate composition was tested as follows:
1) The initial chromaticity of the hexamethylene diisocyanate composition is tested by using a German BYK LCS IV liquid color difference meter, and the initial value is recorded as H 1;
2) Adding a certain mass of hexamethylene diisocyanate composition into a 20ml glass bottle, and sealing with nitrogen;
3) Preheating an oven to 140 ℃, putting a sample of the hexamethylene diisocyanate composition glass bottle after nitrogen sealing, and heating for 4 hours;
4) After the heating was completed, the sample was taken out of the oven, cooled to room temperature and the test chromaticity was recorded as H 2.
The chromaticity change rate was (H 2-H1)/H1 x 100%).
The hexamethylene diisocyanate composition has a product color change rate of 5 or less, preferably 3 or less, when heat-treated at 140 ℃ for 4 hours.
As is well known to those skilled in the art, the hexamethylene diisocyanate compositions may be prepared by phosgenation of hexamethylene diamine compositions. As the phosgenation reaction, specifically, a liquid-phase phosgenation method in which a hexamethylenediamine composition is reacted with phosgene in a liquid phase or a gas-phase phosgenation method in which a hexamethylenediamine composition is reacted with phosgene in a gas phase can be employed, and the hexamethylenediamine composition obtained by gas-phase phosgenation is preferable in the present invention.
Firstly, gasifying hexamethylene diamine after preheating or without inert gas, reacting with phosgene after preheating and gasifying to obtain hexamethylene diisocyanate composition reaction liquid, then carrying out dephosgene, dehydrochlorination and desolventizing treatment on the reaction liquid obtained in the steps to obtain hexamethylene diisocyanate crude product, and finally carrying out impurity removal refining on the obtained hexamethylene diisocyanate crude product to obtain the hexamethylene diisocyanate composition product.
The stream comprising hexamethylenediamine is preheated to a temperature above 200 ℃, preferably 200-510 ℃ before the phosgenation reaction is carried out, and the stream comprising phosgene is preheated to a temperature above 200 ℃, preferably 200-510 ℃. The stream comprising hexamethylenediamine in the present invention comprises hexamethylenediamine and/or inert gases such as nitrogen, argon, helium, etc., and the stream comprising phosgene comprises fresh phosgene, which means phosgene which has not undergone any reaction involving phosgene after synthesis of phosgene from chlorine and carbon monoxide, and/or recycled phosgene, which means phosgene which has not undergone reaction after phosgenation and which can continue to participate in the phosgenation after separation and purification, and optionally inert gases such as nitrogen, argon, helium, etc.
In the present invention, the reaction of phosgene and hexamethylenediamine is carried out at an absolute pressure of 0.01 to 0.5MPa, preferably 0.1 to 0.4MPa. The reaction temperature is 200-600 ℃, preferably 300-550 ℃;
the high-temperature residence time of the amine and the phosgene in the reaction zone in the invention is too long, which easily leads to the decomposition or polymerization of the amine, the phosgene and the target isocyanate, and the occurrence of undesired side reactions, and too short residence time leads to the insufficient reaction time of the phosgene and the amine, incomplete reaction and serious influence on the reaction yield, so that the reaction residence time of the amine and the phosgene in the reaction zone in the invention is 0.02-20s, preferably 0.05-10s.
The higher molar ratio of phosgene to amino is favorable for converting amine into isocyanate, but can cause higher phosgene stock of a system and increase safety risk, and simultaneously can increase cost caused by phosgene preheating, condensation and the like, and the excessively low molar ratio of phosgene to amino can cause poor reaction effect and influence reaction yield and stable operation of the device, so that the molar ratio of phosgene to amino is 2-15:1, preferably 4-8:1.
The gas phase target isocyanate product passing through the reaction zone is typically at a temperature above 200 ℃, typically absorbed by a gas phase capture liquid comprising an inert solvent, and the reaction product is quenched to obtain a liquid stream containing isocyanate, which is transferred from the gas phase to the liquid phase, while part of the hydrogen chloride, unreacted phosgene and by-products are also distributed in the reaction absorption liquid.
The reactive gas phase trapping liquid of the present invention comprises a solvent. The inert solvent includes one or more of toluene, xylene, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, methyl benzoate, ethyl benzoate, butyl benzoate, propyl benzoate, chlorobenzene, o-dichlorobenzene, p-chlorotoluene, bromobenzene, and the like, but is not limited thereto. These solvents may be used alone or in combination in any ratio.
In the invention, the reaction product obtained in the reaction process can be subjected to the operations of dephosgene, dehydrochlorination and desolventizing to obtain the hexamethylene diisocyanate crude product. After absorption and purification, the phosgene can be used as circulating phosgene to enter the reaction system again. Part or all of the solvent after being purified can be used as the capturing liquid for recycling.
According to the invention, the impurity removal and refining process is carried out on the obtained hexamethylene diisocyanate crude product by adopting a rectification and purification process, and finally the hexamethylene diisocyanate composition product is obtained.
When rectification and purification are carried out, continuous rectification or batch rectification can be adopted, the rectification towers can be plate towers or packed towers, and the number of the rectification towers can be one tower or two towers or more than two towers so as to achieve the rectification effect, and the method is not particularly limited.
According to a preferred embodiment of the process of the invention, the content of the abovementioned cyclic compounds in the hexamethylene diisocyanate composition is controlled by means of continuous rectification. Specifically, the theoretical plate number of the rectifying column is preferably 15 to 40, more preferably 25 to 35. The reflux ratio of the rectifying column is preferably 2-13:1, more preferably 2-6:1. The pressure at the top of the rectification column is preferably from 0.3 to 10kpa, more preferably from 0.7 to 5kpa. The bottom temperature of the rectification column is preferably 120 to 190 ℃, more preferably 130 to 145 ℃. The withdrawal amount from the top of the rectification column is preferably 2 to 9% by weight, more preferably 3 to 7% by weight.
Polyisocyanates prepared from the hexamethylene diisocyanate compositions having the above-mentioned cyclic compound contents, such as polyisocyanates containing any one or a combination of at least two of (a) isocyanurate groups, (b) uretdione groups, (c) biuret groups, (d) urethane groups, (e) ureido groups, (f) iminooxadiazinedione groups, (g) allophanate groups, (h) uretonimine groups or (i) carbodiimide groups, have the advantage of being relatively stable in low color.
Finally, the present invention provides a polyisocyanate composition including, but not limited to, an isocyanurate group-containing polyisocyanate composition prepared by starting from a hexamethylene diisocyanate composition, conducting a trimerization reaction in the presence of a catalyst, stopping the reaction by adding a terminator after reaching the end of the reaction, and then separating to obtain an isocyanurate group-containing polyisocyanate composition.
The catalyst can be a composition of at least one of a) quaternary ammonium salt, quaternary ammonium base and quaternary phosphonium salt and one or more of a five-membered or six-membered heterocyclic organic compound containing nitrogen atom, phosphorus atom, oxygen atom or sulfur atom.
The compound a is preferably one or more of tetrabutylammonium acetate, tetramethylammonium propionate, tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide and benzyltriphenylphosphine chloride, and the compound b is preferably one or more of pyrazole, pyridine, imidazole, pyrrole, thiophene, furan and pyridazine.
The terminator is an acid compound including, but not limited to, at least one of di-n-butyl phosphate, hydrochloric acid, phosphoric acid, dimethyl phosphate, diethyl phosphate, p-toluenesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, acetyl chloride, benzoyl chloride.
The temperature of the trimerization reaction is 60-90 ℃;
The mass ratio of the hexamethylene diisocyanate to the catalyst is 200-100000:1, and the use amount of the terminator is not particularly limited, and preferably, the mass ratio of the hexamethylene diisocyanate to the terminator is 1000-10000:1.
The invention has the beneficial effects that:
according to the method provided by the invention, the hexamethylene diisocyanate composition with the cyclic compound content of 0.2-500ppm can be obtained, the chromaticity change rate of heat treatment at 140 ℃ for 4 hours is below 8, and the polyisocyanate product prepared by using the hexamethylene diisocyanate composition as the raw material has excellent low chromaticity and relatively stable characteristics compared with the existing product.
Detailed Description
The invention is further illustrated below in connection with the examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claimed invention.
Raw materials and sources:
Hexamethylenediamine is an industrial grade product of Inward/Vicat (Shanghai), phosgene is self-produced by Wanhua chemical group Co., ltd., dichlorobenzene, allatin with a purity of 99.5%, tetrabutylammonium acetate, altin with a purity of 99.5%, pyrazole, allatin with a purity of 99%, absolute ethyl alcohol, merck chemistry, a purity of 99.5%, di-n-butyl phosphate, altin with a purity of 98.5%, cyclohexylaminoacyl chloride, chemenu and a purity of 95%.
The test of the cyclic compounds in the hexamethylene diisocyanate compositions in the following examples and comparative examples was carried out by gas chromatography. Firstly, determining different retention times of the cyclic compound components in gas chromatography by gas chromatography, wherein the contents are obtained by adopting an area normalization method, and the testing method comprises the following steps:
The analytical instrument was Agilent 7890B, the column model was DB-5 (30 m. Times.0.25 mm. Times.0.25 um), the detector was a FID detector, the sample inlet temperature was 260 ℃ and the detector temperature was 300 ℃, the temperature program was 10 ℃ to 90 ℃ at 10 ℃ per minute, 2min at 15 ℃ to 180 ℃ at 15 ℃ per minute, 2min at 20 ℃ per minute to 280 ℃ for 15min, and the sample injection amount was 0.2ul.
The product chromaticity test adopts a German BYK LCS IV liquid color difference meter.
Examples 1 to 5, comparative examples 1 to 2 were prepared by phosgene method to obtain hexamethylene diisocyanate compositions, and prepolymer was prepared by using the hexamethylene diisocyanate compositions obtained in examples 1 to 5 and comparative examples 1 to 2, respectively, as raw materials.
Example 1
The inlet temperature of hexamethylenediamine into the reactor is 378 ℃, the inlet temperature of phosgene into the reactor is 382 ℃, the reaction pressure is 0.15MPa, the reaction temperature is 473 ℃, the reaction time is 16s, and the molar ratio of phosgene to hexamethylenediamine is 5.3:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 28, the pressure at the top of the rectifying tower is 0.5kpa, the temperature at the bottom of the rectifying tower is 133 ℃, the reflux ratio is 4:1, the extraction amount at the top of the rectifying tower is 5wt%, the hexamethylene diisocyanate crude product is fed from the 4 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between 20 th and 21 th theoretical plates, the content of the cyclic compound in the product is 94ppm, and the chromaticity change rate is 2.5 after heat treatment for 4 hours at 140 ℃.
Example 2
The inlet temperature of hexamethylenediamine into the reactor is 315 ℃, the inlet temperature of phosgene into the reactor is 291 ℃, the reaction pressure is 0.02MPa, the reaction temperature is 374 ℃, the reaction time is 0.03s, and the molar ratio of phosgene to hexamethylenediamine is 8:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 33, the pressure at the top of the rectifying tower is 1.2kpa, the temperature at the bottom of the rectifying tower is 141 ℃, the reflux ratio is 5:1, the extraction amount at the top of the rectifying tower is 9wt%, the hexamethylene diisocyanate crude product is fed from the 5 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between the 22 th theoretical plate and the 23 rd theoretical plate, the content of the cyclic compound in the product is 0.7ppm, and the chromaticity change rate is 1.2 after heat treatment for 4 hours at 140 ℃.
Example 3
The inlet temperature of hexamethylenediamine into the reactor is 492 ℃, the inlet temperature of phosgene into the reactor is 507 ℃, the reaction pressure is 0.37MPa, the reaction temperature is 542 ℃, the reaction time is 9.2s, and the molar ratio of phosgene to hexamethylenediamine is 3:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 17, the pressure at the top of the rectifying tower is 4.7kpa, the temperature at the bottom of the rectifying tower is 183 ℃, the reflux ratio is 3:1, the extraction amount at the top of the rectifying tower is 2.5wt%, the hexamethylene diisocyanate crude product is fed from the 6 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between the 14 th theoretical plate and the 15 th theoretical plate, the content of the cyclic compound in the product is 231ppm, and the chromaticity change rate is 7.2 after heat treatment for 4 hours at 140 ℃.
Example 4
The inlet temperature of hexamethylenediamine entering a reactor is 274 ℃, the inlet temperature of phosgene entering the reactor is 251 ℃, the reaction pressure is 0.015MPa, the reaction temperature is 331 ℃, the reaction time is 1.4s, and the molar ratio of phosgene to hexamethylenediamine is 14:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 38, the pressure at the top of the rectifying tower is 9.3kpa, the temperature at the bottom of the rectifying tower is 124 ℃, the reflux ratio is 12:1, the extraction amount at the top of the rectifying tower is 7wt%, the hexamethylene diisocyanate crude product is fed from the 6 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between the 30 th theoretical plate and the 31 th theoretical plate, the content of the cyclic compound in the product is 0.3ppm, and the chromaticity change rate is 4.8 after heat treatment for 4 hours at 140 ℃.
Example 5
Using the product obtained in example 3, cyclohexylaminoacyl chloride was added thereto to adjust the content of the cyclic compound to 52ppm.
Comparative example 1
The inlet temperature of hexamethylenediamine into a reactor is 527 ℃, the inlet temperature of phosgene into the reactor is 536 ℃, the reaction pressure is 0.6MPa, the reaction temperature is 608 ℃, the reaction time is 23s, and the molar ratio of phosgene to hexamethylenediamine is 1:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 12, the pressure at the top of the rectifying tower is 12.3kpa, the temperature at the bottom of the rectifying tower is 251 ℃, the reflux ratio is 1:1, the extraction amount at the top of the rectifying tower is 1.8wt%, the hexamethylene diisocyanate crude product is fed from the 7 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between the 10 th and 11 th theoretical plates, the content of the cyclic compound in the product is 562ppm, and the chromaticity change rate is 11.2 after heat treatment for 4 hours at 140 ℃.
Comparative example 2
The inlet temperature of hexamethylenediamine entering a reactor is 194 ℃, the inlet temperature of phosgene entering the reactor is 197 ℃, the reaction pressure is 0.003MPa, the reaction temperature is 279 ℃, the reaction time is 0.01s, and the molar ratio of phosgene to hexamethylenediamine is 18:1. After the reaction product leaves the reaction zone, chlorobenzene is adopted for spraying and sucking to obtain a hexamethylene diisocyanate composition reaction solution, the reaction solution is subjected to subsequent dephosgene and desolventizing to obtain a hexamethylene diisocyanate composition crude product, and the final product is obtained through refining.
The product refining is carried out by adopting a continuous rectification mode, and the control parameters are as follows:
The theoretical plate number of the rectifying tower is 47, the pressure at the top of the rectifying tower is 0.02kpa, the temperature at the bottom of the rectifying tower is 111 ℃, the reflux ratio is 16:1, the extraction amount at the top of the rectifying tower is 15wt%, the hexamethylene diisocyanate crude product is fed from the 7 th theoretical plate, the purified product is extracted from the side line of the rectifying tower, the extraction position is between the 24 th theoretical plate and the 25 th theoretical plate, the content of the cyclic compound in the product is 0.13ppm, and the chromaticity change rate is 9.4 after heat treatment for 4 hours at 140 ℃.
The hexamethylene diisocyanate compositions obtained in examples 1 to 5 and comparative examples 1 to 2 were used to prepare prepolymers, respectively. The prepolymer preparation was carried out in the manner of example 1 in patent CN 112250835B.
Preparation example
5G of a mixture of tetrabutylammonium acetate and pyrazole at a mass ratio of 1:0.8 was dissolved in 20g of absolute ethanol to prepare a catalyst composition having a mass concentration of 20%. Under nitrogen protection, 2kg of the hexamethylene diisocyanate composition obtained in examples and comparative examples was heated in a water bath at 60℃for 1 hour, then a catalyst composition having a monomer content of 150ppm (dry weight: 0.3 g) relative to hexamethylene diisocyanate was added, the reaction was continued at 70℃until the NCO content in the reaction liquid reached 39.3%, di-n-butyl phosphate (0.24 g) having a monomer content of 120ppm relative to hexamethylene diisocyanate was added to terminate the reaction, and then, the reaction was distilled 2 times under conditions of 150℃and 0.2Torr using a thin film evaporator to prepare a polyisocyanate composition. The product was stored at 35 ℃ and the colorimetric data were measured periodically, see in particular table 1.
In summary, by controlling the cyclic compound in the hexamethylene diisocyanate composition to 0.1 to 500ppm, the color change rate after heat treatment at 140 ℃ for 4 hours is less than 8, and the polyisocyanate obtained from this as a raw material has excellent low color relative stability.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made by those skilled in the art without departing from the invention, which modifications and additions are also to be considered as within the scope of the invention.
Claims (14)
1. A hexamethylene diisocyanate composition comprising hexamethylene diisocyanate and from 0.2 to 500ppm of a cyclic compound comprising any one or a combination of at least two of the following compounds:
Wherein X is CH 3 or H or Cl or Br.
2. The hexamethylene diisocyanate composition according to claim 1, wherein the hexamethylene diisocyanate composition has a cyclic compound content of 0.4 to 200ppm.
3. The hexamethylene diisocyanate composition according to claim 1, wherein the hexamethylene diisocyanate composition has a cyclic compound content of 0.8 to 100ppm.
4. The hexamethylene diisocyanate composition according to any of claims 1-3, wherein the hexamethylene diisocyanate composition has a product color change rate of 8 or less after heat treatment at 140 ℃ for 4 hours;
the chroma change rate of the isocyanate composition was tested as follows:
1) The initial chromaticity of the hexamethylene diisocyanate composition is tested by using a German BYK LCS IV liquid color difference meter, and the initial value is recorded as H 1;
2) Adding a certain mass of hexamethylene diisocyanate composition into a 20ml glass bottle, and sealing with nitrogen;
3) Preheating an oven to 140 ℃, putting a sample of the hexamethylene diisocyanate composition glass bottle after nitrogen sealing, and heating for 4 hours;
4) Taking out the sample from the oven after heating, cooling to room temperature, and recording the test chromaticity as H 2;
The chromaticity change rate was (H 2-H1)/H1 x 100%).
5. The method for producing a hexamethylene diisocyanate composition according to any one of claims 1 to 4, comprising the steps of allowing hexamethylene diamine to react with phosgene after the preheating and gasifying in the presence or absence of an inert gas to obtain a reaction solution of the hexamethylene diisocyanate composition, subjecting the reaction solution obtained in the above steps to a dephosgene, dehydrochlorination and desolventizing treatment to obtain a crude hexamethylene diisocyanate product, and finally subjecting the crude hexamethylene diisocyanate product obtained as described above to impurity removal and purification to obtain the hexamethylene diisocyanate composition product.
6. The process of claim 5, wherein the stream comprising hexamethylenediamine is preheated to a temperature above 200℃and the stream comprising phosgene is preheated to a temperature above 200℃before the phosgenation reaction.
7. The process of claim 5, wherein the stream comprising hexamethylenediamine is preheated to 200-510℃and the stream comprising phosgene is preheated to 200-510℃before the phosgenation reaction.
8. The method of any one of claims 5-7, wherein the inert gas is one or more of nitrogen, argon, helium.
9. The process according to claim 5 to 7, wherein the reaction of phosgene and hexamethylenediamine is carried out at an absolute pressure of 0.01 to 0.5MPa, a reaction temperature of 200 to 600℃and a reaction residence time of amine and phosgene in the reaction zone of 0.02 to 20s.
10. The process according to claim 5 to 7, wherein the reaction of phosgene and hexamethylenediamine is carried out at an absolute pressure of 0.1 to 0.4MPa, a reaction temperature of 300 to 550℃and a reaction residence time of amine and phosgene in the reaction zone of 0.05 to 10s.
11. The process according to any one of claims 5 to 7, wherein the molar ratio of phosgene to amino groups in hexamethylenediamine is in the range of 2 to 15:1.
12. The process according to any one of claims 5 to 7, wherein the molar ratio of phosgene to amino groups in hexamethylenediamine is in the range of 4 to 8:1.
13. The method according to any one of claims 5 to 7, wherein the impurity removal refining is performed in a rectifying column having a theoretical plate number of 15 to 40 and a reflux ratio of 2 to 13:1;
and/or the pressure at the top of the rectification column is 0.3-10kpa, and/or the temperature at the bottom of the rectification column is 120-190 ℃;
and/or the extraction amount of the top of the rectifying tower is 2-9wt%.
14. The method according to any one of claims 5 to 7, wherein the impurity removal refining is performed in a rectifying column having a theoretical plate number of 25 to 35 and a reflux ratio of 2 to 6:1;
And/or the pressure at the top of the rectifying tower is 0.7-5kpa, and/or the temperature at the bottom of the rectifying tower is 130-145 ℃;
and/or the extraction amount of the top of the rectifying tower is 3-7wt%.
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