CN116768760A - Method for synthesizing m-xylylene diisocyanate - Google Patents
Method for synthesizing m-xylylene diisocyanate Download PDFInfo
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- CN116768760A CN116768760A CN202310751426.XA CN202310751426A CN116768760A CN 116768760 A CN116768760 A CN 116768760A CN 202310751426 A CN202310751426 A CN 202310751426A CN 116768760 A CN116768760 A CN 116768760A
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- Prior art keywords
- dicarbamate
- xylylene
- heterogeneous catalyst
- combination
- isophthalylene
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 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 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- 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 22
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 9
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 claims description 8
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052680 mordenite Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 4
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000013341 scale-up Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- -1 hydroxyl compound Chemical class 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFRMYGQGQDWVNG-UHFFFAOYSA-N [3-(formyloxymethyl)phenyl]methyl formate Chemical compound O=COCC1=CC=CC(COC=O)=C1 OFRMYGQGQDWVNG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 239000002608 ionic liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
Abstract
The application provides a method for synthesizing m-xylylene diisocyanate, which comprises the following steps: and carrying out pyrolysis reaction on the m-xylylene dicarbamate and the heterogeneous catalyst under normal pressure or negative pressure, and simultaneously carrying out on-line alcohol separation to obtain the m-xylylene diisocyanate. The method has the advantages of high yield of the m-xylylene diisocyanate, few byproducts, simple process, environmental protection, low solvent cost, easy separation from products, easy recycling of heterogeneous catalyst and easy scale-up production.
Description
Technical Field
The application belongs to the field of isocyanate synthesis, and particularly relates to a method for synthesizing m-xylylene diisocyanate.
Background
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 (XDI) belongs to aliphatic polyisocyanates, and due to the fact that methylene is introduced between benzene rings and isocyanate groups, the XDI prevents the influence of the conjugation effect of benzene ring macromolecules on-NCO groups, so that the m-xylylene diisocyanate has excellent weather resistance, superior productivity, cohesiveness and color stability, is more favorable in toxicity than other isocyanates, and is mainly applied to yellowing-resistant coatings, high-grade polyurethane elastomers, high-grade polyurethane spectacle lenses and the like.
Currently, the industrial process for XDI is the phosgene process. The phosgene method uses highly toxic phosgene in production, generates more hydrogen chloride byproducts in the production process, has harsh production conditions, high equipment cost and high safety risk. Thus, there is a need to develop a non-phosgene XDI green synthetic route.
Among the green methods for synthesizing isocyanates, the urethane pyrolysis method is a method recognized by many researchers that the non-phosgene method for preparing isocyanates is most expected to be industrialized. The method has the advantages of relatively low temperature, mild reaction and easy operation and control. The carbamate pyrolysis method is that the carbamate firstly removes one molecule of alkyl alcohol to produce intermediate monocarbamate, then the monocarbamate is thermally decomposed to remove another molecule of alkyl alcohol to produce diisocyanate, and the removed alkyl alcohol can be recycled, so the process is a green chemical process. For example, EP 1512682A1 describes a multistage process for the production of cycloaliphatic diisocyanates. In the first stage, a dicarbamate is formed from the reaction of a diamine, a carbonic acid derivative, and a hydroxy compound. The hydroxyl compound is an alcohol having a boiling point of less than 190 ℃ at normal pressure, and preferably it is 1-butanol. After purifying the obtained dicarbamate, it is thermally cracked in a second stage to obtain the alicyclic diisocyanate and the hydroxy compound.
In order to inhibit the recombination of hydroxyl compounds with isocyanates, a high quantitative separation of the thermally cracked products is necessary. To achieve this, US 5386053 describes the use of hydroxyl compounds having a boiling point sufficiently far from the boiling point of the diisocyanate. Thus, aliphatic hydroxyl compounds are preferred, and n-butanol and/or isobutanol are particularly preferred, having boiling points well below that of industrially relevant diisocyanates. However, in the case of using such a low boiling hydroxyl compound, when the crude product is refined in the distillation step, the hydroxyl compound will be obtained as a distillate, and the isocyanate will be a bottom product. Thus, the isocyanate will still contain high boiling impurities such as carbamates. In addition, the use of catalysts for the pyrolysis cracking reaction in such an arrangement becomes difficult because the catalyst will be entrained in the isocyanate, promoting the reaction of the isocyanate groups and shortening the shelf life of the product. If, after removal of the hydroxyl compounds, the bottom product is distilled again in a downstream process step, the isocyanate is located in the distillate fraction. However, it will be difficult to achieve high purity because the high boiling impurities can cleave and release low boiling hydroxyl compounds which again become part of the distillate and recombine with the diisocyanate.
CN 103965079a discloses a method for continuously preparing aliphatic or cycloaliphatic diisocyanate, the raw materials are continuously pyrolyzed in a scraped film falling film pyrolysis evaporator, the product is subjected to primary and secondary condensation through a rectifying column, and diisocyanate and ethanol are respectively recovered. The method can rapidly separate intermediates, products and byproducts generated in the pyrolysis process. However, ethanol is inevitably reacted with isocyanate or monoisocyanate again to form carbamate in the condensation process, and the reaction temperature is high, so that the side reaction of isocyanate polymerization is aggravated, and the separation efficiency and the yield are reduced due to the factors. CN 105143177a discloses a process for the production of xylylene diisocyanate, which also involves similar problems with a similar secondary condensation process.
EP 2679575A1 and EP 2088137B1 both describe transesterification steps for converting an alkyl or aralkyl dicarbamate to an aryl dicarbamate. The main purpose of transesterification is to form aryl dicarbamates, which allow pyrolysis reaction to diisocyanates under milder conditions and have fewer byproducts than alkyl dicarbamates or aralkyl dicarbamates, higher boiling alcohols allowing better purification of the isocyanate are not described.
CN 111108094a discloses a multi-step process for preparing diisocyanates by cleavage of the corresponding dicarbamates into the diisocyanate and the hydroxyl compound, separation of the diisocyanate from the hydroxyl compound by distillation, wherein the diisocyanate is obtained as distillate. In the method, the hydroxyl compound is aromatic hydroxyl compound or higher fatty alcohol, the boiling point of the hydroxyl compound is higher than that of diisocyanate, the hydroxyl compound has large molecular weight and higher boiling point, the hydroxyl compound is difficult to separate from a system in the pyrolysis reaction, the separation energy consumption and the transportation cost in the process are increased, and the reaction efficiency is also unfavorable.
In the above-mentioned publication, the catalyst used for pyrolysis is mainly a homogeneous catalyst, and the difficulty of subsequent separation and reuse is large, which is not beneficial to industrialization. US 4613466 discloses a pyrolysis catalyst for copper, zinc or zinc-nickel, zinc-copper alloy, which decomposes HDU (n-butyl 1, 6-hexamethylene dicarbamate) at 370 ℃ to obtain high yield of HDI (1, 6-hexamethylene diisocyanate), but the application has higher reaction temperature and the catalyst used is not easy to recycle. CN 101195590A discloses a method for pyrolyzing HDU (1, 6-hexamethylene dicarbamate) with an ionic liquid as a reaction medium and a supported metal oxide as a catalyst, wherein the yield of HDI is 69-88%, but the reaction medium is expensive, the cost of the product is greatly increased, and the yield of the product is still to be improved. CN 101386585a pyrolyzes HDU (1, 6-hexamethylene dicarbamate) with a combination of metallic zinc, metallic nickel and metallic copper as catalysts, the highest yield of HDI reaches 57%, and the yield remains to be improved.
Therefore, there is a need to develop a method for preparing m-xylylene diisocyanate in high yield and high efficiency, which overcomes the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for synthesizing isophthalene diisocyanate, which has the advantages of high yield of isophthalene diisocyanate, few byproducts, simple process, environment friendliness, low solvent cost, easy separation from products, easy recycling of heterogeneous catalyst and easy scale-up production.
In order to achieve the technical effects, the application adopts the following technical scheme:
the application provides a method for synthesizing m-xylylene diisocyanate, which comprises the following steps:
and carrying out pyrolysis reaction on the m-xylylene dicarbamate and the heterogeneous catalyst under normal pressure or negative pressure, and simultaneously carrying out on-line alcohol separation to obtain the m-xylylene diisocyanate.
According to the application, through the catalysis of the heterogeneous catalyst with excellent performance, during the pyrolysis reaction under normal pressure or negative pressure, the alcohol is smoothly discharged, and the m-xylylene dicarbamate can be rapidly pyrolyzed at a lower temperature, so that the XDI polymerization reaction is greatly inhibited, and the yield is improved.
In the present application, the reaction is carried out under a protective atmosphere, that is, the air in the reaction apparatus is replaced with a protective gas, and the reaction is restarted. The protective atmosphere can be nitrogen, argon or helium and the like.
In a preferred embodiment of the present application, the m-xylylene dicarbamate includes any one of m-xylylene dicarbamate, n-propyl m-xylylene dicarbamate, isopropyl m-xylylene dicarbamate, n-butyl m-xylylene dicarbamate, isobutyl m-xylylene dicarbamate, and tert-butyl m-xylylene dicarbamate.
As a preferred embodiment of the present application, the heterogeneous catalyst comprises a support and an active component supported on the support.
Preferably, the active component comprises Ni, co, cu, fe, zn, znO, niO, ni 2 O 3 、CuO、FeO、Fe 2 O 3 、Fe 3 O 4 、CoO、Co 2 O 3 、Co 3 O 4 Or Al 2 O 3 Any one or a combination of at least two, typical but non-limiting examples of which are: a combination of Ni and Co, a combination of Co and Cu, a combination of Cu and Fe, a combination of Fe and Zn, a combination of Zn and ZnO, a combination of ZnO and NiO, niO and Ni 2 O 3 Is a combination of Ni 2 O 3 And CuO, cuO and FeO, feO and Fe 2 O 3 Combination of (2), fe 2 O 3 And Fe (Fe) 3 O 4 Combination of (2), fe 3 O 4 And CoO, coO and Co 2 O 3 Is a combination of (C), co 2 O 3 And Co 3 O 4 Is a combination of (C), co 3 O 4 And Al 2 O 3 Is a combination of (1), al 2 O 3 And Ni or Ni, niO and Fe 2 O 3 Combinations of (a) and the like.
As a preferred embodiment of the present application, the pyrolysis reaction is carried out under the condition of a solvent including any one or a combination of at least two of dibutyl sebacate, dioctyl sebacate, dihexyl phthalate, dioctyl terephthalate, liquid paraffin or naphthenic oil, typical but non-limiting examples of which are: a combination of dibutyl sebacate and dioctyl sebacate, a combination of dioctyl sebacate and dihexyl phthalate, a combination of dihexyl phthalate and dioctyl phthalate, a combination of dioctyl phthalate and dioctyl terephthalate, a combination of dioctyl terephthalate and liquid paraffin, a combination of liquid paraffin and naphthenic oil, or a combination of naphthenic oil and dibutyl sebacate, and the like.
Preferably, the support comprises any one or a combination of at least two of mordenite, ZSM-5 molecular sieve, or Y-type molecular sieve, such as a combination of mordenite and ZSM-5 molecular sieve, a combination of ZSM-5 molecular sieve and Y-type molecular sieve, a combination of Y-type molecular sieve and mordenite, or a combination of mordenite, ZSM-5 molecular sieve and Y-type molecular sieve, or the like.
Preferably, the mass of the active component is 5-50% of the total mass of the heterogeneous catalyst, such as 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present application, the mass fraction of the isophthalenedicarbamate in the solvent is 0.5 to 30%, such as 1%, 2%, 5%, 10%, 15%, 20% or 25%, etc., but the present application is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
As a preferred technical scheme of the application, the mass ratio of the m-xylylene dicarbamate to the heterogeneous catalyst is (0.3-100) 0.1, such as 0.5:0.1, 1:0.1, 2:0.1, 5:0.1, 10:0.1, 15:0.1, 20:0.1, 25:0.1, 30:0.1, 40:0.1, 50:0.1, 60:0.1, 70:0.1, 80:0.1 or 90:0.1, etc., but the application is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
In a preferred embodiment of the present application, the vacuum degree of the pyrolysis reaction is 0.001 to 0.1MPa, for example, 0.002MPa, 0.005MPa, 0.01MPa, 0.015MPa, 0.02MPa, 0.03MPa, 0.05MPa or 0.08MPa, etc., but the vacuum degree is not limited to the values recited above, and other values not recited in the numerical range are similarly applicable.
In the present application, the pressure of the pyrolysis reaction may be expressed in terms of gauge pressure, absolute pressure, or the like, in addition to the vacuum degree.
In the application, the proper pressure is selected to only distill out the pyrolysis byproduct alcohol, and not distill out unreacted m-xylylene diformate, monoisocyanate intermediate and m-xylylene diisocyanate product. When the pressure is too low, the m-xylylene diisocyanate or solvent and the like may be distilled out, and the reaction efficiency is reduced; too high pressure affects the discharge of alcohol out of the system and also reduces the reaction efficiency.
In a preferred embodiment of the present application, the pyrolysis reaction temperature is 120 to 260 ℃, such as 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, etc., but is not limited to the values listed, and other values not listed in the range are applicable, preferably 150 to 220 ℃.
In a preferred embodiment of the present application, the pyrolysis reaction time is 0.2 to 10 hours, such as 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or 9 hours, etc., but the present application is not limited to the listed values, and other non-listed values within the range are equally applicable, preferably 0.5 to 5 hours.
As a preferred technical scheme of the application, the method for synthesizing the m-xylylene diisocyanate comprises the following steps:
carrying out pyrolysis reaction on m-xylylene dicarbamate, a solvent and a heterogeneous catalyst for 0.5-5 hours under the conditions of vacuum degree of 0.001-0.1 MPa and temperature of 120-260 ℃, and simultaneously carrying out on-line separation of alcohol to obtain the m-xylylene diisocyanate;
the mass fraction of the m-xylylene dicarbamate in the solvent is 0.5-30%, and the mass ratio of the m-xylylene dicarbamate to the heterogeneous catalyst is (0.3-100): 0.1;
the heterogeneous catalyst comprises a carrier and an active component supported on the carrier, wherein the mass of the active component accounts for 5-50% of the total mass of the heterogeneous catalyst;
the active component comprises Ni, co, ni, cu, fe, zn, znO, niO, ni 2 O 3 、CuO、FeO、Fe 2 O 3 、Fe 3 O 4 、CoO、Co 2 O 3 、Co 3 O 4 Or Al 2 O 3 Any one or a combination of at least two of the following;
the carrier comprises any one or a combination of at least two of mordenite, ZSM-5 molecular sieve or Y-type molecular sieve.
Compared with the prior art, the application has at least the following beneficial effects:
the application provides a method for synthesizing m-xylylene diisocyanate, which has the advantages of high yield of 98.5%, few byproducts, simple process, environment friendliness, low solvent cost, easy separation from products, easy recycling of heterogeneous catalyst and easy mass production.
Detailed Description
To facilitate understanding of the present application, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a method for synthesizing isophthalene diisocyanate, comprising:
weighing 10% Co 3 O 4 30g of m-xylylene dicarbamate and 570g of solvent naphthenic oil, putting the mixture into a 1L stainless steel autoclave, after nitrogen is used for replacing air in the autoclave, starting stirring, controlling the reaction temperature to 200 ℃, controlling the absolute pressure of the reaction to be 0.005MPa, after 2 hours of reaction, stopping the reaction, sampling and analyzing, wherein the conversion rate of the m-xylylene dicarbamate is 100%, and the XDI yield is 98.5%. (ZSM-5 molecular sieve has a silica-alumina ratio of 25).
Example 2
The present embodiment provides a method for synthesizing isophthalene diisocyanate, comprising:
weighing 10% Co 3 O 4 1% Co/ZSM-5 2g, 30g of m-xylylene dicarbamate, 570g of solvent dioctyl sebacate, putting into a 1L stainless steel autoclave, after nitrogen replaces air in the autoclave, starting stirring, controlling the reaction temperature to 240 ℃, controlling the absolute pressure of the reaction to 0.05MPa, after reacting for 1h, stopping the reaction, sampling and analyzing, wherein the m-xylylene dicarbamate conversion rate is 100%, and the XDI yield is 96.5%. (ZSM-5 molecular sieve has a silica-alumina ratio of 25).
Example 3
The present embodiment provides a method for synthesizing isophthalene diisocyanate, comprising:
weighing 10% Co-5% Cu/HY 2g, 30g of m-xylylene dicarbamate, 570g of solvent dioctyl sebacate, putting into a 1L stainless steel autoclave, after nitrogen replaces air in the autoclave, starting stirring, controlling the reaction temperature to 180 ℃, controlling the absolute pressure of the reaction to be 0.01MPa, after reacting for 5 hours, stopping the reaction, sampling and analyzing, wherein the conversion rate of m-xylylene dicarbamate is 100%, and the XDI yield is 98.1%. (HY molecular sieve silicon-aluminum ratio is 9-12).
Example 4
The present embodiment provides a method for synthesizing isophthalene diisocyanate, comprising:
weighing 10% Co 3 O 4 1% Co/ZSM-5.1 g, m-xylylene dicarbamate 3g, solvent dioctyl sebacate 600g, putting into a 1L stainless steel autoclave, after nitrogen replaces air in the autoclave, starting stirring, controlling the reaction temperature to 120 ℃, controlling the absolute pressure of the reaction to 0.1MPa, after reacting for 5 hours, stopping the reaction, and sampling and analyzing (ZSM-5 molecular sieve silicon-aluminum ratio is 25).
Example 5
The present embodiment provides a method for synthesizing isophthalene diisocyanate, comprising:
weighing 10% Co 3 O 4 0.3g of 1% Co/ZSM-5, 300g of m-xylylene dicarbamate and 1000g of dioctyl sebacate as a solvent are put into a 2L stainless steel autoclave, after the air in the autoclave is replaced by nitrogen, stirring is started, the reaction temperature is controlled to 260 ℃, the absolute pressure of the reaction is 0.001MPa, after the reaction is carried out for 0.2h, the reaction is stopped, sampling analysis is carried out, and the (ZSM-5 molecular sieve silicon-aluminum ratio is 25).
The applicant states that the detailed process equipment and process flows of the present application are described by the above examples, but the present application is not limited to, i.e., does not mean that the present application must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present application, equivalent substitution of raw materials for the product of the present application, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present application and the scope of disclosure.
Claims (10)
1. A method of synthesizing isophthalylene diisocyanate, the method comprising:
and carrying out pyrolysis reaction on the m-xylylene dicarbamate and the heterogeneous catalyst under normal pressure or negative pressure, and simultaneously carrying out on-line alcohol separation to obtain the m-xylylene diisocyanate.
2. The method of claim 1, wherein the isophthalylene dicarbamate comprises any one of m-xylylene dicarbamate, m-xylylene dicarbamate ethyl ester, n-propyl isophthalylene dicarbamate, isopropyl isophthalylene dicarbamate, n-butyl isophthalylene dicarbamate, isobutyl isophthalylene dicarbamate, or tert-butyl isophthalylene dicarbamate.
3. The method according to claim 1 or 2, wherein the heterogeneous catalyst comprises a support and an active component supported on the support;
preferably, the active component comprises Ni, co, cu, fe, zn, znO, niO, ni 2 O 3 、CuO、FeO、Fe 2 O 3 、Fe 3 O 4 、CoO、Co 2 O 3 、Co 3 O 4 Or Al 2 O 3 Any one or a combination of at least two of the following;
preferably, the carrier comprises any one or a combination of at least two of mordenite, ZSM-5 molecular sieve or Y-type molecular sieve;
preferably, the mass of the active component accounts for 5-50% of the total mass of the heterogeneous catalyst.
4. A process according to any one of claims 1 to 3, wherein the pyrolysis reaction is carried out under solvent conditions, the solvent comprising any one or a combination of at least two of dibutyl sebacate, dioctyl sebacate, dihexyl phthalate, dioctyl terephthalate, liquid paraffin or naphthenic oil.
5. The method according to any one of claims 1 to 4, wherein the mass fraction of the isophthalenedimethylene dicarbamate in the solvent is 0.5 to 30%.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the isophthalenedimethylene dicarbamate to the heterogeneous catalyst is (0.3 to 100): 0.1.
7. The method according to any one of claims 1 to 6, wherein the vacuum degree of the pyrolysis reaction is 0.001 to 0.1MPa.
8. The method according to any one of claims 1-7, wherein the temperature of the pyrolysis reaction is 120-260 ℃, preferably 150-220 ℃.
9. The method according to any one of claims 1-8, wherein the pyrolysis reaction time is 0.2-10 hours, preferably 0.5-5 hours.
10. The method according to any one of claims 1-9, characterized in that the method comprises:
carrying out pyrolysis reaction on m-xylylene dicarbamate, a solvent and a heterogeneous catalyst for 0.5-5 hours under the conditions of vacuum degree of 0.001-0.1 MPa and temperature of 120-260 ℃, and simultaneously carrying out on-line separation of alcohol to obtain the m-xylylene diisocyanate;
the mass fraction of the m-xylylene dicarbamate in the solvent is 0.5-30%, and the mass ratio of the m-xylylene dicarbamate to the heterogeneous catalyst is (0.3-100): 0.1;
the heterogeneous catalyst comprises a carrier and an active component supported on the carrier, wherein the mass of the active component accounts for 5-50% of the total mass of the heterogeneous catalyst;
the active component comprises Ni, co, ni, cu, fe, zn, znO, niO, ni 2 O 3 、CuO、FeO、Fe 2 O 3 、Fe 3 O 4 、CoO、Co 2 O 3 、Co 3 O 4 Or Al 2 O 3 Any one or a combination of at least two of the following;
the carrier comprises any one or a combination of at least two of mordenite, ZSM-5 molecular sieve or Y-type molecular sieve.
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| CN202310751426.XA CN116768760A (en) | 2023-06-25 | 2023-06-25 | Method for synthesizing m-xylylene diisocyanate |
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