CN114768708A - Device and method for preparing m-xylylene diisocyanate - Google Patents
Device and method for preparing m-xylylene diisocyanate Download PDFInfo
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- CN114768708A CN114768708A CN202210479689.5A CN202210479689A CN114768708A CN 114768708 A CN114768708 A CN 114768708A CN 202210479689 A CN202210479689 A CN 202210479689A CN 114768708 A CN114768708 A CN 114768708A
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- thermal decomposition
- xylylene
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- decomposition reaction
- xylylene diisocyanate
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- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- FSPRIMKLIVYESK-UHFFFAOYSA-N [3-(carbamoyloxymethyl)phenyl]methyl carbamate Chemical compound NC(=O)OCC1=CC=CC(COC(N)=O)=C1 FSPRIMKLIVYESK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000007790 scraping Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- ZYURHZPYMFLWSH-UHFFFAOYSA-N octacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 9
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 9
- 229940032094 squalane Drugs 0.000 claims description 9
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- JXNCWJJAQLTWKR-UHFFFAOYSA-N zinc;methanolate Chemical compound [Zn+2].[O-]C.[O-]C JXNCWJJAQLTWKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 229940112669 cuprous oxide Drugs 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 21
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- -1 m-xylylene diamine phosgene salt Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000013341 scale-up Methods 0.000 description 3
- HOPNITFHNCUXTG-UHFFFAOYSA-N 3-ethoxycarbonylbenzoic acid Chemical compound CCOC(=O)C1=CC=CC(C(O)=O)=C1 HOPNITFHNCUXTG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 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
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
Abstract
The present invention relates to an apparatus for preparing m-xylylene diisocyanate, comprising: the raw material conveying unit, the melting unit, the thermal decomposition unit and the collection unit are connected in sequence; and a mechanical film scraping device is arranged in the reactor of the thermal decomposition unit. The method comprises the following steps: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate; wherein, a mechanical film scraping device is arranged in the reactor. The scheme provided by the invention realizes the simple, easy, green and environment-friendly preparation of m-xylylene diisocyanate with low cost, can realize the amplification production, and simultaneously the product prepared by the method has high yield and high purity and is prepared without byproducts.
Description
The present application claims the priority of patent application No. 202210324955.7 (prior application filed on 3/29/2022 entitled apparatus and process for the preparation of m-xylylene diisocyanate).
Technical Field
The invention relates to the field of organic matter synthesis, in particular to a device and a method for preparing m-xylylene diisocyanate.
Background
Currently, isocyanates are special chemicals with isocyanate (N ═ C ═ O) functional groups and are important raw materials for the production of polyurethane products. The m-xylylene diisocyanate belongs to aliphatic diisocyanate, and due to the introduction of methylene between a benzene ring and an isocyanate group, the influence of the conjugation effect of macromolecules of the benzene ring on an-NCO group is prevented, so that the isocyanate group of the m-xylylene diisocyanate is more stable, and the m-xylylene diisocyanate is used as various anti-yellowing coatings, the field of high-grade polyurethane spectacle lenses, the high-end fields of m-xylylene diisocyanate type polymer photochemical materials and the like.
At present, the industrial production process of m-xylylene diisocyanate is a m-xylylene diamine phosgene salt formation method. The phosgene method uses virulent phosgene in production, generates more hydrogen chloride byproducts in the production process, has higher requirements on high temperature resistance, temperature control, corrosion resistance and the like of equipment, and has large safety risk. Therefore, the development of a novel m-xylylene diisocyanate green synthetic route is a problem to be solved urgently.
Green synthetic isocyanates have gained increasing attention in recent years. Among green isocyanate synthesis methods, thermal decomposition of carbamate has been one of the hot research points for non-phosgene synthesis of isocyanate. The method has the advantages of relatively low temperature, mild reaction and easy operation and control. The carbamate pyrolysis method is that carbamate firstly removes one molecule of alkyl alcohol to generate intermediate monocarbamate, then monocarbamate is thermally decomposed to remove another molecule of alkyl alcohol to generate diisocyanate, and the removed alkyl alcohol can be recycled.
Arco company develops a process for preparing MDI by carbonylating nitrobenzene and CO, Asahi develops a process for synthesizing MDI by oxidizing and carbonylating aniline, ethanol and CO, but the processes are not industrially produced, and Enani company develops a new method for producing toluene diisocyanate, but the method still has the problems of catalyst separation and recovery, product concentration, low selectivity and the like.
U.S. Pat. No. 4, 5043471A discloses a process for preparing MDI by thermal decomposition of MDU, which comprises using dibutyl tin dilaurate as catalyst, and feeding 50% of sulfolane solution containing MDU into a thin-layer evaporator at a flow rate of 100g/h for reaction at a temperature of 270 deg.C and a reaction pressure of 4kPa, wherein the single-pass yield of MDI is 54.1%.
CN1721060A discloses a method for preparing MDI through thermal decomposition of a kettle reactor, which comprises the steps of adding raw materials, a solvent and a catalyst into a flask by adopting a one-pot method, and thermally decomposing for 40min under the nitrogen atmosphere, wherein the yield of MDI is 63%. US4307029 thermally decomposes MDC to give MDI in 44.1% yield. The maximum yield of MDI after 24h of reaction at 195 ℃ in US4294774 is 46%.
CN105143177A discloses a method for producing xylylene diisocyanate, in which xylylene diisocyanate as a product is separated from alcohols and solvents, and the solvents are directly taken out and mixed with fresh xylylene diaminocarbonate for recycling, so that the xylylene diisocyanate remaining in the solvents is polymerized and accumulated in the solvents, which causes the solvents to easily deteriorate and cannot be normally used, and the yield of the products is not high.
Therefore, there is a need to develop a method for preparing m-xylylene diisocyanate, which can overcome the above disadvantages in the prior art, is simple and easy to implement, is environmentally friendly, has low cost, can realize large-scale production, and can obtain a product with high yield, high purity and rapid separation.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a device and a method for preparing m-xylylene diisocyanate, which solve the problems of low recovery rate and complex process in the existing m-xylylene diisocyanate preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an apparatus for preparing m-xylylene diisocyanate, the apparatus comprising: the raw material conveying unit, the melting unit, the thermal decomposition unit and the collection unit are connected in sequence;
and a mechanical film scraping device is arranged in the reactor of the thermal decomposition unit.
The device for preparing m-xylylene diisocyanate provided by the invention can realize simple, easy, green and environment-friendly preparation of m-xylylene diisocyanate with low cost and can realize scale-up production, and meanwhile, the product prepared by the method has high yield and high purity, and the preparation without byproducts is realized.
As a preferred technical scheme of the invention, the material feeding mode in the thermal decomposition unit is overflow feeding.
Preferably, a heavy component collecting device and a cold trap cooling device are arranged in the thermal decomposition unit in a matched manner.
In the invention, the heavy component collecting device is used for collecting the high-boiling-point solvent and a small part of polymerized products; the cold trap cools the device to achieve primary condensation of the thermally decomposed product.
Preferably, the collection unit comprises a condensation collection device and an alcohol collection device.
Preferably, the alcohol collecting device comprises an alcohol collecting tank and a vacuum pump which are arranged in sequence. To achieve collection of the byproduct alcohol.
In a second aspect, the present invention provides a process for preparing m-xylylene diisocyanate, which comprises: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein, a mechanical film scraping device is arranged in the reactor.
In a preferred embodiment of the present invention, the m-xylylene dicarbamate includes m-xylylene dicarbamate and/or m-xylylene dicarbamate.
As a preferred embodiment of the present invention, the solvent comprises 1 or a combination of at least 2 of n-octacosane, diphenyl ether, sulfolane, naphthenic oil or squalane, preferably 1 or a combination of at least 2 of naphthenic oil, sulfolane or squalane.
In the present invention, the combination of solvents may be a combination of n-octacosane and diphenyl ether, a combination of sulfolane and naphthenic oil, a combination of sulfolane and squalane, and the like, but is not limited to the enumerated combinations, and other combinations not enumerated within this range are also applicable.
In the invention, the organic solvents belong to high boiling point solvents in a vacuum state, and on one hand, the dispersibility and the heat transfer effect of the solvents are good; on the other hand, the boiling point of the solvent is far higher than that of the product m-xylylene diisocyanate, the intermediate product and the reactant m-xylylene dicarbamate, so that the product m-xylylene diisocyanate can be quickly distilled out under corresponding pressure, and side reactions are reduced.
As a preferred technical scheme of the invention, the catalyst comprises a basic metal catalyst and/or a transition metal catalyst;
preferably, the catalyst comprises 1 or a combination of at least 2 of basic zinc carbonate, zinc chloride, manganese oxide, cuprous oxide, nickel oxide, cobalt oxide, molybdenum oxide, dibutyl tin oxide, or zinc methoxide.
In the present invention, the combination of the catalysts may be a combination of basic zinc carbonate and zinc chloride, a combination of manganese oxide and cuprous oxide, a combination of nickel oxide and cobalt oxide, a combination of molybdenum oxide and dibutyltin oxide, a combination of dibutyltin oxide and zinc methoxide, etc., but the combinations are not limited to the listed combinations, and other combinations not listed are also applicable within the scope of the present invention.
According to the invention, the catalyst comprises a heterogeneous catalyst and a homogeneous catalyst, so that the target product is not polluted, the yield of the target product is improved, and the catalyst is low in cost, low in toxicity, green and environment-friendly.
In a preferred embodiment of the present invention, the mass of the catalyst in the mixture is 1 to 30% of the mass of the m-xylylene dicarbamate, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%, but is not limited to the above-mentioned values, and other values not listed in the range are also applicable.
In the present invention, the amount of the primer in the mixture is 3 to 8% by mass of the solvent, and may be, for example, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, or 8%, and the like, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In a preferred embodiment of the present invention, the pressure of the thermal decomposition reaction is 0.1 to 1MPa, and may be, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa or 1MPa, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the pressure of the thermal decomposition reaction can be specifically selected in the range of 0.5 to 0.9MPa, because unreacted ethyl isophthalate, intermediates and the product m-xylylenediisocyanate are distilled off when the pressure is less than 1000 Pa; when the pressure is larger than the range value of 0.5MPa, the saturated vapor pressure of the m-xylylene diisocyanate does not reach, the m-xylylene diisocyanate is remained in the reaction kettle for continuous reaction, and the loss rate is high.
Preferably, the thermal decomposition reaction temperature is 120-.
In the invention, the temperature for carrying out the thermal decomposition reaction is specifically selected within the range of 120-300 ℃, if the temperature exceeds the range, the reaction time can be greatly shortened by overhigh temperature, but reactants and a solvent can be quickly boiled and evaporated; if the temperature is less than the range, the product cannot reach the temperature corresponding to the saturated vapor pressure and cannot be distilled out.
As a preferable technical scheme of the invention, the flow rate of reaction materials in the thermal decomposition reaction is 1-500g/h, for example, the concentration may be 1g/h, 2g/h, 3g/h, 4g/h, 5g/h, 6g/h, 7g/h, 8g/h, 9g/h, 10g/h, 20g/h, 30g/h, 40g/h, 50g/h, 60g/h, 70g/h, 80g/h, 90g/h, 100g/h, 150g/h, 200g/h, 250g/h, 300g/h, 350g/h, 400g/h, 450g/h, or 500g/h, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the invention, the flow rate of the reaction materials in the thermal decomposition reaction needs a specific range, if the flow rate exceeds the range, although the conversion rate of the m-xylylene dicarbamate is very high, the yield of the m-xylylene diisocyanate is very low, and the m-xylylene diisocyanate is very unstable and is easy to self-polymerize, so that the consumption cost of the raw materials is very high; if the ratio is less than this range, the energy consumption in the reaction process is high although the conversion of ethyl isophthalate and the yield of m-xylylene diisocyanate are high.
Preferably, stirring is performed during the thermal decomposition reaction.
As a preferred technical solution of the present invention, the method comprises: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate comprises m-xylylene dicarbamate methyl and/or m-xylylene dicarbamate ethyl; the solvent comprises 1 or a combination of at least 2 of n-octacosane, diphenyl ether, sulfolane, naphthenic oil or squalane; the catalyst comprises a basic metal catalyst and/or a transition metal catalyst; the catalyst comprises 1 or the combination of at least 2 of basic zinc carbonate, zinc chloride, manganese oxide, cuprous oxide, nickel oxide, cobalt oxide, molybdenum oxide, dibutyl tin oxide or zinc methoxide; the mass of the catalyst in the mixture is 1-30% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 0.1-1 MPa; the temperature of the thermal decomposition reaction is 120-300 ℃; the flow rate of the reaction materials in the thermal decomposition reaction is 1-500 g/h.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the device and the method for preparing m-xylylene diisocyanate provided by the invention have the characteristics of simplicity, easiness in implementation, environmental protection, lower cost, capability of realizing large-scale production and easiness in industrialization and automation.
(2) The m-xylylene diisocyanate prepared by the method has high yield and high purity, and does not need to be separated and purified; the high-boiling-point organic solvent used in the method is cheap and easy to obtain and is easy to separate from the product, the conversion rate of the m-xylylene diamino ethyl formate is more than or equal to 87 percent, the selectivity of the m-xylylene diisocyanate is more than 98 percent, and the purity is more than or equal to 99.5 percent.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing m-xylylene diisocyanate according to example 1 of the present invention;
in the figure: 1-raw material pump, 2-melting unit, 3-overflow falling film, 4-temperature control equipment, 5-mechanical film scraping device, 6-heat preservation equipment, 7-heavy component collecting device, 8-cold trap cooling device, 9-sampling port, 10-condensation collecting device, 11-alcohol collecting tank and 12-vacuum pump.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This example provides an apparatus for preparing m-xylylene diisocyanate, as shown in fig. 1, comprising: the raw material conveying unit, the melting unit 2, the thermal decomposition unit and the collection unit are connected in sequence;
in the embodiment, the raw material conveying unit can be used for mixing the reaction materials and then feeding the mixture into the melting unit 2 through the raw material pump 1 for heating so that the raw materials are in a uniform phase;
a mechanical film scraping device 5 is arranged in the reactor of the thermal decomposition unit.
The material feeding mode in the thermal decomposition unit is overflow feeding, such as the overflow feeding of the reaction raw materials is realized by adopting an overflow falling film 3 mode in the embodiment;
a heavy component collecting device 7 and a cold trap cooling device 8 are arranged in the thermal decomposition unit in a matched manner; in this embodiment, the thermal decomposition unit is further provided with a temperature control device 4 and a heat preservation device 6, which are needed, in a matching manner, so as to realize efficient control of the reaction temperature.
The collecting unit comprises a condensation collecting device 10 and an alcohol collecting device; in this embodiment, the condensation and collection device 10 rapidly vaporizes the m-xylylene diisocyanate generated by thermal decomposition in the reactor under vacuum state, and pumps the vaporized m-xylylene diisocyanate into a condensation device for condensation, so as to realize condensation and collection of m-xylylene diisocyanate products; in addition, the condensation collection equipment is also provided with a sampling port 9 so as to realize the detection of the obtained m-xylylene diisocyanate product.
The alcohol collecting device comprises an alcohol collecting tank 11 and a vacuum pump 12 which are arranged in sequence.
The m-xylylene diisocyanate prepared by the equipment has high yield and high purity, and does not need to be separated and purified; the high boiling point organic solvent used in the method is cheap and easy to obtain and is easy to separate from the product.
Application example 1
The present application example provides a method for preparing m-xylylene diisocyanate, the method comprising: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate is m-xylylene dicarbamate; the solvent is naphthenic oil; the catalyst is molybdenum oxide; the mass of the catalyst in the mixture is 20% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 0.4 MPa; the temperature of the thermal decomposition reaction is 200 ℃; the flow rate of the reaction materials in the thermal decomposition reaction is 200 g/h.
The m-xylylene diisocyanate prepared by the method has high yield and high purity, and does not need to be separated and purified; the high boiling point organic solvent used in the method is cheap and easy to obtain and is easy to separate from the product. The indices of the obtained material are detailed in table 1.
Application example 2
The present application example provides a method of preparing m-xylylene diisocyanate, the method comprising: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate is m-xylylene dicarbamate ethyl; the solvent is a combination of sulfolane and naphthenic oil in a mass ratio of 1: 1; the catalyst comprises zinc chloride and manganese oxide in a mass ratio of 1: 1; the mass of the catalyst in the mixture is 5% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 1 MPa; the temperature of the thermal decomposition reaction is 300 ℃; the flow rate of the reaction materials in the thermal decomposition reaction is 20 g/h.
The m-xylylene diisocyanate prepared by the method has high yield and high purity, and does not need to be separated and purified; the high boiling point organic solvent used in the method is cheap and easy to obtain and is easy to separate from the product. The indexes of the obtained materials are detailed in table 1.
Application example 3
The preparation of m-xylylene diisocyanate was carried out using the apparatus of example 1, and the specific procedure was as follows: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst which passes through a melting unit into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate is m-xylylene dicarbamate methyl ester; the solvent is sulfolane; the catalyst is basic zinc carbonate; the mass of the catalyst in the mixture is 30% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 0.1 MPa; the temperature of the thermal decomposition reaction is 180 ℃; the flow rate of the reaction materials in the thermal decomposition reaction is 500 g/h.
According to the results of the application examples, the device and the method for preparing m-xylylene diisocyanate have the characteristics of simplicity, easiness in implementation, environmental friendliness, lower cost, capability of realizing scale-up production and easiness in industrialization and automation. The indexes of the obtained materials are detailed in table 1.
Application example 4
The preparation of m-xylylene diisocyanate was carried out using the apparatus of example 1, and the procedure was as follows: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst which passes through a melting unit into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate is m-xylylene dicarbamate and m-xylylene dicarbamate in a mass ratio of 1: 1; the solvent is naphthenic oil and squalane; the catalyst is a combination of dibutyltin oxide and zinc methoxide with the mass ratio of 1: 3; the mass of the catalyst in the mixture is 10% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 0.8 MPa; the temperature of the thermal decomposition reaction is 230 ℃; the flow rate of the reaction material in the thermal decomposition reaction is 370 g/h.
The indexes of the obtained materials are detailed in table 1.
Application example 5
The difference from application example 3 is only that no mechanical film scraping device is arranged in the reactor. The indexes of the obtained materials are detailed in table 1.
Application example 6
The only difference from application example 3 was that m-xylylene dicarbamate in the reactor was in a solid state. The indexes of the obtained materials are detailed in table 1.
Application example 7
The only difference from application example 3 is that no solvent was added to the contents of the reactor. The indices of the obtained material are detailed in table 1.
Application example 8
The difference from the application example 3 is only that the m-xylylene dicarbamate is replaced by equal amount of 1, 4-cyclohexyl dicarbamate, and the corresponding catalyst is replaced by ZnSAPO-34, which is the shape of a framework of a silicoaluminophosphate molecular sieve SAPO-34 introduced by Zn metal element. The indices of the obtained material are detailed in table 1.
TABLE 1
According to the results of the application examples, the device and the method for preparing m-xylylene diisocyanate have the characteristics of simplicity, easiness in implementation, environmental friendliness, lower cost, capability of realizing scale-up production and easiness in industrialization and automation.
It is to be noted that the present invention is described by the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (10)
1. An apparatus for preparing m-xylylene diisocyanate, comprising: the raw material conveying unit, the melting unit, the thermal decomposition unit and the collection unit are connected in sequence;
and a mechanical film scraping device is arranged in the reactor of the thermal decomposition unit.
2. The apparatus according to claim 1, wherein the feeding of the material in the thermal decomposition unit is by overflow feeding;
preferably, a heavy component collecting device and a cold trap cooling device are arranged in the thermal decomposition unit in a matched manner;
preferably, the collection unit comprises a condensation collection device and an alcohol collection device;
preferably, the alcohol collection apparatus comprises an alcohol collection tank and a vacuum pump arranged in this order.
3. A process for preparing m-xylylene diisocyanate, comprising: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor.
4. The method of claim 3, wherein the m-xylylene dicarbamate comprises m-xylylene dicarbamate and/or m-xylylene dicarbamate.
5. The method of claim 3 or 4, wherein the solvent comprises 1 or a combination of at least 2 of n-octacosane, diphenyl ether, sulfolane, naphthenic oil, or squalane, preferably a combination of 1 or at least 2 of naphthenic oil, sulfolane, or squalane.
6. The method of any of claims 3-5, wherein the catalyst comprises a basic metal catalyst and/or a transition metal catalyst;
preferably, the catalyst comprises 1 or a combination of at least 2 of basic zinc carbonate, zinc chloride, manganese oxide, cuprous oxide, nickel oxide, cobalt oxide, molybdenum oxide, dibutyl tin oxide, or zinc methoxide.
7. The process according to any one of claims 3 to 6, wherein the mass of catalyst in the mixture is 1 to 30% of the mass of the m-xylylene dicarbamate.
8. The process according to any one of claims 3 to 7, wherein the pressure of the thermal decomposition reaction is from 0.1 to 1 MPa;
preferably, the temperature of the thermal decomposition reaction is 120-300 ℃.
9. The process according to any one of claims 3 to 8, wherein the flow rate of the reaction mass in the thermal decomposition reaction is from 1 to 500 g/h;
preferably, stirring is performed during the thermal decomposition reaction.
10. The method of any one of claims 3-9, wherein the method comprises: introducing a mixture containing molten m-xylylene dicarbamate, a solvent and a catalyst into a reactor for thermal decomposition reaction to obtain m-xylylene diisocyanate;
wherein a mechanical film scraping device is arranged in the reactor;
the m-xylylene dicarbamate comprises m-xylylene dicarbamate and/or m-xylylene dicarbamate; the solvent comprises 1 or a combination of at least 2 of n-octacosane, diphenyl ether, sulfolane, naphthenic oil or squalane, preferably 1 or a combination of at least 2 of naphthenic oil, sulfolane or squalane; the catalyst comprises a basic metal catalyst and/or a transition metal catalyst; the catalyst comprises 1 or the combination of at least 2 of basic zinc carbonate, zinc chloride, manganese oxide, cuprous oxide, nickel oxide, cobalt oxide, molybdenum oxide, dibutyl tin oxide or zinc methoxide; the mass of the catalyst in the mixture is 1-30% of the mass of the m-xylylene dicarbamate;
the pressure of the thermal decomposition reaction is 0.1-1 MPa; the temperature of the thermal decomposition reaction is 120-300 ℃; the flow rate of the reaction materials in the thermal decomposition reaction is 1-500 g/h.
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