CN114507161A - Method for synthesizing isophorone diisocyanate - Google Patents
Method for synthesizing isophorone diisocyanate Download PDFInfo
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- CN114507161A CN114507161A CN202011287433.1A CN202011287433A CN114507161A CN 114507161 A CN114507161 A CN 114507161A CN 202011287433 A CN202011287433 A CN 202011287433A CN 114507161 A CN114507161 A CN 114507161A
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- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/06—Preparation of derivatives of isocyanic acid from or via ureas
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Abstract
The invention provides a method for synthesizing isophorone diisocyanate, which comprises the following steps: (1) mixing isophorone diamine, a carbonylation agent, a first solvent and a catalyst to carry out carbonylation reaction, carrying out solid-liquid separation and carrying out purification treatment to obtain isophorone dicarbamate; (2) mixing the isophorone dicarbamate and a second solvent for a pyrolysis reaction, and purifying a product to obtain the isophorone diisocyanate. The method has simple process, no pollution and potential safety hazard, and the yield and the purity of the intermediate product isophorone dicarbamate and the final product isophorone diisocyanate are high.
Description
Technical Field
The invention belongs to the field of isocyanate synthesis, relates to a method for synthesizing (cyclo) aliphatic diisocyanate, and particularly relates to a method for synthesizing isophorone diisocyanate.
Background
Isophorone diisocyanate (IPDI) is a non-yellowing (cyclo) aliphatic diisocyanate. IPDI contains two different isocyanate groups: one aliphatic, one cycloaliphatic, and the reactivity is different. Because of the unique chemical structure, IPDI can be almost compatible with various paint resins, has excellent compatibility with a plurality of solvents, and has the advantages of large molecular weight, small toxicity, good weather resistance, long service life, proper price, excellent heat resistance and the like, so that IPDI becomes diisocyanate with the most universality. IPDI is used as a cross-linking agent, a coupling agent and a hydroxylation stabilizer in the polyester removal industry and is generally used for manufacturing high-grade polyurethane adhesives; is the core raw material of rocket propellant.
The IPDI production mainly adopts a phosgenation method, although the process is mature, the phosgene used is extremely toxic, and potential accident potential exists; the byproduct hydrogen chloride is easy to corrode equipment, so that the production device is expensive in cost; the product contains a small amount of hydrolytic chlorine, which affects the applicability of the product.
Therefore, the preparation of isocyanate without phosgene has become a focus of attention of scientific research institutions and chemical enterprises in various countries around the world. In recent years, the research and production of non-phosgenation IPDI synthetic routes have been advanced. Among them, the preparation of corresponding isocyanate by thermal cracking of carbamate is a non-phosgene route which is studied more deeply and reported more recently, and is considered as a route with a better practical application prospect. The aminolysis reaction of dimethyl carbonate has developed recently to be a non-phosgene method for synthesizing carbamate, but dimethyl carbonate is relatively expensive, reaction selectivity is not high, azeotrope is easy to form with methanol to cause separation difficulty, and the catalyst is mainly homogeneous catalyst, which limits large-scale application. The non-phosgene route for producing IPDI by a urea method has the total yield of more than 90 percent, is a promising process for producing IPDI by the non-phosgene method, has certain competitive capacity in the market, but has high requirements on equipment, complex flow, difficult operation, high boiling point of by-products, difficult separation and recovery, and easy corrosion to equipment or difficult separation of subsequent catalysts due to the use of metal salt catalysts or homogeneous catalysts.
The prior art method has certain defects, such as high raw material toxicity, high potential safety hazard, high raw material cost, complex process and the like. Therefore, the development of a non-phosgene preparation method which is green and safe, has simple process and high IPDI product yield is of great significance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for synthesizing isophorone diisocyanate, which has the advantages of simple process, no pollution and potential safety hazard, and high yield and purity of isophorone dicarbamate as an intermediate product and isophorone diisocyanate as a final product.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides a method for synthesizing isophorone diisocyanate, which comprises the following steps:
(1) mixing isophorone diamine, a carbonylation agent, a first solvent and a catalyst to carry out carbonylation reaction, carrying out solid-liquid separation and carrying out purification treatment to obtain isophorone dicarbamate;
(2) mixing the isophorone dicarbamate and a second solvent for a pyrolysis reaction, and purifying a product to obtain the isophorone diisocyanate.
Compared with the phosgene route, the synthetic route of the synthetic method has the advantages that the use of virulent phosgene is avoided, and the method belongs to a safe, nontoxic and harmless green production process; compared with other non-phosgene routes, the method has the advantages of simple operation and high yield and purity of IPDI.
As a preferred embodiment of the present invention, the carbonylation agent in step (1) comprises any one or a combination of at least two of urea, methyl carbamate, ethyl carbamate, n-propyl carbamate, isopropyl carbamate, n-butyl carbamate, isobutyl carbamate, sec-butyl carbamate, or tert-butyl carbamate, and typical but non-limiting examples of the combination are: combinations of urea and methyl carbamate, methyl carbamate and ethyl carbamate, ethyl carbamate and n-propyl carbamate, n-propyl carbamate and isopropyl carbamate, isopropyl carbamate and n-butyl carbamate, n-butyl carbamate and isobutyl carbamate, isobutyl carbamate and sec-butyl carbamate, sec-butyl carbamate and tert-butyl carbamate, or urea, methyl carbamate and ethyl carbamate, and the like.
Preferably, the molar ratio of the carbonylating agent to the isophorone diamine in step (1) is (2-20):1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1 or 19:1, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
As a preferred embodiment of the present invention, the first solvent in step (1) comprises any one or a combination of at least two of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, and the combination is typically but not limited to: a combination of methanol and ethanol, a combination of ethanol and n-propanol, a combination of n-propanol and isopropanol, a combination of isopropanol and n-butanol, a combination of n-butanol and isobutanol, a combination of isobutanol and sec-butanol, a combination of sec-butanol and tert-butanol, a combination of tert-butanol and methanol, or a combination of methanol, ethanol and isopropanol, and the like.
Preferably, the molar ratio of the first solvent to the isophorone diamine in step (1) is (3-100):1, such as 5:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, or 90:1, but is not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferred embodiment of the present invention, the catalyst comprises any one or a combination of at least two of calcium oxide, magnesium oxide, aluminum oxide, silicon oxide, scandium oxide, titanium dioxide, manganese dioxide, ferric oxide, ferroferric oxide, cobaltous oxide, nickel oxide, copper oxide, molybdenum trioxide, yttrium oxide, zirconium dioxide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, tungsten trioxide, silver oxide, cerium oxide, lanthanum oxide, praseodymium oxide, or neodymium oxide, and the combination is typically but not limited to: combinations of calcium oxide and magnesium oxide, magnesium oxide and aluminum oxide, aluminum oxide and silicon oxide, silicon oxide and scandium oxide, scandium oxide and titanium dioxide, titanium dioxide and manganese dioxide, manganese dioxide and ferric oxide, ferric oxide and ferroferric oxide, ferroferric oxide and cobaltous oxide, cobaltous oxide and nickel oxide, nickel oxide and copper oxide, copper oxide and molybdenum trioxide, molybdenum oxide and yttrium oxide, yttrium oxide and zirconium dioxide, zirconium dioxide and niobium monoxide, niobium monoxide and niobium dioxide, niobium dioxide and niobium trioxide, niobium trioxide and niobium pentoxide, niobium pentoxide and tungsten pentoxide, tungsten trioxide and silver oxide, silver oxide and cerium oxide, A combination of cerium oxide and lanthanum oxide, a combination of lanthanum oxide and praseodymium oxide, a combination of praseodymium oxide and neodymium oxide, a combination of calcium oxide, magnesium oxide and aluminum oxide, and the like.
Preferably, the amount of the catalyst added in step (1) is 0.01 to 30% by mass of the isophorone diamine, such as 0.02%, 0.1%, 0.5%, 1%, 2%, 5%, 10%, or 20%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred embodiment of the present invention, the temperature of the carbonylation reaction in the step (1) is 120 to 260 ℃, for example, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the carbonylation reaction time in step (1) is 1-12 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the purification treatment in the step (1) comprises the steps of carrying out deamination treatment, first solvent removal treatment and decarbonylation agent treatment on the filtrate obtained by the solid-liquid separation.
In the invention, the deamination treatment is carried out in a deamination tower, the first solvent removal treatment is carried out in a first solvent removal tower, and the decarbonylating agent treatment is carried out in a decarbonylating agent tower.
Preferably, the first solvent, the carbonylation agent and the heavy component polymer obtained by the purification treatment are returned to the step (1) for carbonylation reaction.
As a preferred embodiment of the present invention, the second solvent in step (2) comprises any one or a combination of at least two of p-xylene, m-xylene, o-xylene, chlorobenzene, bromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, 1-phenyl-2-methylpropane, mesitylene, hemimellitene or 1,2, 4-trimethylbenzene, and the combination is typically, but not limited to, as follows: a combination of para-xylene and meta-xylene, a combination of meta-xylene and ortho-xylene, a combination of ortho-xylene and chlorobenzene, a combination of chlorobenzene and bromobenzene, a combination of bromobenzene and ortho-chlorotoluene, a combination of ortho-chlorotoluene and meta-chlorotoluene, a combination of meta-chlorotoluene and para-chlorotoluene, a combination of ortho-dichlorobenzene and meta-dichlorobenzene, a combination of meta-dichlorobenzene and para-dichlorobenzene, a combination of para-dichlorobenzene and ethylbenzene, a combination of ethylbenzene and n-propylbenzene, a combination of n-propylbenzene and isopropylbenzene, a combination of isopropylbenzene and n-butylbenzene, a combination of n-butylbenzene and sec-butylbenzene, a combination of sec-butylbenzene and tert-butylbenzene, a combination of tert-butylbenzene and 1-phenyl-2-methylpropane, a combination of 1-phenyl-2-methylpropane and mesitylene, a combination of mesitylene and hemimellitene, hemimellitene and 1, combinations of 2, 4-trimethylbenzene, combinations of o-xylene, chlorobenzene, and mesitylene, and the like.
Preferably, the isophorone dicarbamate is 0.1 to 50% by mass of the second solvent, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, or 45%, etc., but is not limited to the recited values, and other values not recited within this range are also applicable.
Preferably, the pyrolysis reaction of step (2) is carried out under catalysis of a catalyst.
In the invention, the pyrolysis reaction in the step (2) can be directly carried out, and the addition of the catalyst can accelerate the reaction rate, shorten the reaction time and reduce the generation of byproducts.
Preferably, the catalyst is a metal catalyst.
Preferably, the metal catalyst comprises any one or a combination of at least two of aluminum, scandium, titanium, vanadium, chromium, manganese, iron, nickel, cobalt, copper, zinc, molybdenum, tin, gallium, zirconium, silver or tungsten, such as a combination of aluminum and scandium, scandium and titanium, titanium and vanadium, vanadium and chromium, chromium and manganese, manganese and iron, iron and nickel, nickel and cobalt, cobalt and copper, copper and zinc, zinc and molybdenum, molybdenum and tin, tin and gallium, gallium and zirconium, zirconium and silver, silver and none, or aluminum, scandium and titanium, and the like.
Preferably, the amount of the catalyst added in step (2) is 0.01-30% by mass of the isophorone dicarbamate, such as 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, or 25%, but not limited to the recited values, and other values not recited in the recited values are also applicable.
In a preferred embodiment of the present invention, the temperature of the pyrolysis reaction in the step (2) is 160 to 320 ℃, for example, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃ or 310 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the pyrolysis reaction in step (2) is performed at a pressure of 0 to 5.0MPa, such as 0MPa, 0.02MPa, 0.05MPa, 0.1MPa, 0.2MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa or 4.5MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pyrolysis reaction time in step (2) is 0.5 to 8 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, and the like, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the purification treatment in step (2) includes a second solvent removal treatment of the reaction solution after the pyrolysis reaction.
In the invention, the second solvent removing treatment is carried out in a second solvent removing tower.
Preferably, the second solvent and the isophorone dicarbamate obtained by the purification treatment are returned to the step (2) for pyrolysis reaction.
As a preferred embodiment of the present invention, the method for synthesizing isophorone diisocyanate comprises the following steps:
(1) mixing isophorone diamine, a carbonylation agent, a first solvent and a catalyst, carrying out carbonylation reaction for 1-12 h at 120-260 ℃, carrying out solid-liquid separation, and carrying out purification treatment to obtain isophorone dicarbamate;
the molar ratio of the carbonylation agent to the isophorone diamine is (2-20):1, the molar ratio of the first solvent to the isophorone diamine is (3-100):1, and the addition amount of the catalyst is 0.01-30% of the mass of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, first solvent removal treatment and decarbonylation agent treatment on the filtrate obtained by the solid-liquid separation; the first solvent, the carbonylation agent and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, a catalyst and a second solvent at 160-320 ℃ and under 0-5.0 MPa to perform pyrolysis reaction for 0.5-8 h, and purifying a product to obtain isophorone diisocyanate;
the mass of the isophorone dicarbamate is 0.1-50% of that of the second solvent, and the addition amount of the catalyst is 0.01-30% of that of the isophorone dicarbamate;
and the purification treatment comprises the step of removing a second solvent from the reaction liquid after the pyrolysis reaction, and the second solvent obtained by the purification treatment and the isophorone dicarbamate are returned to carry out the pyrolysis reaction.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a method for synthesizing isophorone diisocyanate, which adopts a non-phosgene route, and has the advantages of mild reaction conditions, simple operation, no pollution and small potential safety hazard; the invention adopts high-efficiency heterogeneous catalyst, can promote heavy component polymer by-products to be continuously converted into IPDC, the yield of the synthesized IPDC can reach more than 99.0 percent, the purity can reach more than 99.5 percent, the yield of IPDI can reach more than 99.0 percent, and the purity of IPDI can reach more than 99.5 percent. Has good industrial application prospect.
Drawings
FIG. 1 is a system diagram of the synthesis of isophorone diisocyanate according to an embodiment of the present invention;
in the figure: the method comprises the following steps of 1-carbonylation reactor, 2-deamination tower, 3-first solvent removing tower, 4-decarbonylating agent removing tower, 5-IPDC refining tower, 6-pyrolysis reactor, 7-second solvent removing tower and 8-IPDI refining tower.
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
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
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 a method for synthesizing isophorone diisocyanate, which uses a synthesis system as shown in fig. 1, and comprises the following steps:
(1) mixing isophorone diamine, urea, ethanol and an iron oxide catalyst, performing carbonylation reaction for 5 hours at 190 ℃, performing solid-liquid separation, and performing purification treatment to obtain isophorone dicarbamate;
the molar ratio of the urea to the isophorone diamine is 2.1:1, the molar ratio of the ethanol to the isophorone diamine is 20:1, and the mass of the iron oxide catalyst is 10% of that of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, ethanol removal treatment and urea removal treatment on the filtrate obtained by the solid-liquid separation; the ethanol, the urea and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, a copper catalyst and chlorobenzene at 250 ℃ and 1.4 MPa for carrying out pyrolysis reaction for 3h, and purifying a product to obtain isophorone diisocyanate;
the isophorone dicarbamate is 5% of the chlorobenzene, and the addition amount of the copper catalyst is 10% of the mass of the isophorone dicarbamate;
and the purification treatment comprises dechlorinating benzene treatment on the reaction liquid after the pyrolysis reaction, and the chlorobenzene and isophorone dicarbamate obtained by the purification treatment are returned to carry out the pyrolysis reaction.
The reaction result is detected and analyzed by gas chromatography, the IPDA conversion rate is 100%, the IPDC yield is 99.3%, the IPDC product purity is 99.5%, the IPDI yield is 99.0%, and the IPDI purity is 99.5%.
Example 2
This example provides a method for synthesizing isophorone diisocyanate, which comprises the steps of:
(1) mixing isophorone diamine, n-propyl carbamate, n-propanol and a titanium dioxide catalyst, carrying out carbonylation reaction for 5 hours at 200 ℃, carrying out solid-liquid separation, and carrying out purification treatment to obtain isophorone dicarbamate;
the molar ratio of the n-propyl carbamate to the isophorone diamine is 15:1, the molar ratio of the n-propanol to the isophorone diamine is 20:1, and the mass of the titanium oxide catalyst is 10% of that of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, n-propanol removal treatment and n-propyl deaminated formate treatment on the filtrate obtained by the solid-liquid separation; the n-propanol, the deaminated n-propyl formate and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, the copper and zinc catalysts and p-xylene, performing pyrolysis reaction for 3h at 250 ℃ and 1.0MPa, and purifying the product to obtain isophorone diisocyanate;
the mass of the isophorone dicarbamate is 5% of that of the p-xylene, and the addition amount of the copper and zinc catalysts is 5% of that of the isophorone dicarbamate;
and the purification treatment comprises the step of carrying out paraxylene removal treatment on the reaction liquid after the pyrolysis reaction, and returning paraxylene and isophorone dicarbamate obtained by the purification treatment to carry out the pyrolysis reaction.
The reaction result is detected and analyzed by gas chromatography, the IPDA conversion rate is 100%, the IPDC yield is 99.5%, the IPDC product purity is 99.5%, the IPDI yield is 99.3%, and the IPDI purity is 99.5%.
Example 3
This example provides a method for synthesizing isophorone diisocyanate, which comprises the steps of:
(1) mixing isophorone diamine, methyl carbamate, methanol, zirconium oxide and cobaltous oxide catalyst, performing carbonylation reaction for 5 hours at 210 ℃, performing solid-liquid separation, and performing purification treatment to obtain isophorone dicarbamate;
the molar ratio of the methyl carbamate to the isophorone diamine is 5:1, the molar ratio of the methanol to the isophorone diamine is 50:1, the mass of the cobaltous oxide catalyst is 5% of the mass of the isophorone diamine, and the mass of the zirconia catalyst is 5% of the mass of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, methanol removal treatment and methyl deamination formate treatment on the filtrate obtained by the solid-liquid separation; the methanol, the deamination methyl formate and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate with o-chlorotoluene at 250 ℃ and under 0.75MPa to perform pyrolysis reaction for 3h, and purifying a product to obtain isophorone diisocyanate;
the isophorone dicarbamate is 20% of the mass of the o-chlorotoluene;
and the purification treatment comprises the step of removing o-chlorotoluene from the reaction liquid after the pyrolysis reaction, and the o-chlorotoluene and isophorone dicarbamate obtained by the purification treatment are returned to carry out the pyrolysis reaction.
The reaction result is detected and analyzed by gas chromatography, the IPDA conversion rate is 100%, the IPDC yield is 99.6%, the IPDC product purity is 99.6%, the IPDI yield is 99.2%, and the IPDI purity is 99.5%.
Example 4
This example provides a method for synthesizing isophorone diisocyanate, which comprises the steps of:
(1) mixing isophorone diamine, n-butyl carbamate, n-butyl alcohol and a niobium trioxide catalyst, carrying out carbonylation reaction for 12 hours at 120 ℃, carrying out solid-liquid separation, and carrying out purification treatment to obtain isophorone dicarbamate;
the molar ratio of n-butyl carbamate to isophorone diamine is 2:1, the molar ratio of n-butyl alcohol to isophorone diamine is 3:1, and the addition amount of the niobium trioxide catalyst is 0.01% of the mass of isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, n-butanol removal treatment and n-butyl carbamate deamination treatment on the filtrate obtained by the solid-liquid separation; the n-butanol, n-butyl carbamate and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, the vanadium catalyst and n-butylbenzene, performing pyrolysis reaction for 8 hours at 160 ℃ and 1.0MPa, and purifying a product to obtain isophorone diisocyanate;
the mass of the isophorone carbamic acid ester is 0.1% of that of the n-butylbenzene, and the adding amount of the vanadium catalyst is 0.01% of that of the isophorone carbamic acid ester;
and the purification treatment comprises the step of removing n-butylbenzene from the reaction liquid after the pyrolysis reaction, and the n-butylbenzene and isophorone dicarbamate obtained by the purification treatment are returned to carry out the pyrolysis reaction.
The reaction result is detected and analyzed by gas chromatography, the IPDA conversion rate is 99.0%, the IPDC yield is 95.0%, the IPDC product purity is 99.5%, the IPDI yield is 92.0%, and the IPDI purity is 99.5%.
Example 5
This example provides a method for synthesizing isophorone diisocyanate, which comprises the following steps:
(1) mixing isophorone diamine, sec-butyl carbamate, sec-butyl alcohol and a cerium dioxide catalyst, carrying out carbonylation reaction for 1h at 260 ℃, carrying out solid-liquid separation, and carrying out purification treatment to obtain isophorone dicarbamate;
the molar ratio of the sec-butyl carbamate to the isophorone diamine is 20:1, the molar ratio of the sec-butyl alcohol to the isophorone diamine is 100:1, and the addition amount of the cerium dioxide catalyst is 30% of the mass of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, sec-butyl alcohol removal treatment and sec-butyl carbamate deamination treatment on the filtrate obtained by the solid-liquid separation; the sec-butyl alcohol, the sec-butyl carbamate and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, the manganese catalyst and sec-butylbenzene, performing pyrolysis reaction for 0.5h at 320 ℃ and 5.0MPa, and purifying a product to obtain isophorone diisocyanate;
the mass of the isophorone dicarbamate is 50% of that of the sec-butylbenzene, and the addition amount of the manganese catalyst is 30% of that of the isophorone dicarbamate;
and the purification treatment comprises the step of carrying out sec-butylbenzene removal treatment on the reaction liquid after the pyrolysis reaction, and returning the sec-butylbenzene and the isophorone dicarbamate obtained through the purification treatment to carry out the pyrolysis reaction.
The reaction result is detected and analyzed by gas chromatography, the IPDA conversion rate is 100%, the IPDC yield is 96.0%, the IPDC product purity is 99.5%, the IPDI yield is 94.2%, and the IPDI purity is 99.5%.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above 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 within the protective 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 is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for synthesizing isophorone diisocyanate, which is characterized by comprising the following steps:
(1) mixing isophorone diamine, a carbonylation agent, a first solvent and a catalyst for carbonylation reaction, performing solid-liquid separation and purifying to obtain isophorone dicarbamate;
(2) mixing the isophorone dicarbamate and a second solvent for a pyrolysis reaction, and purifying a product to obtain the isophorone diisocyanate.
2. The process of claim 1, wherein the carbonylation agent of step (1) comprises any one or a combination of at least two of urea, methyl carbamate, ethyl carbamate, n-propyl carbamate, isopropyl carbamate, n-butyl carbamate, isobutyl carbamate, sec-butyl carbamate, or tert-butyl carbamate;
preferably, the molar ratio of the carbonylation agent to the isophorone diamine in step (1) is (2-20): 1.
3. The method according to claim 1 or 2, wherein the first solvent of step (1) comprises any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or a combination of at least two thereof;
preferably, the molar ratio of the first solvent to the isophorone diamine in step (1) is (3-100): 1.
4. The method according to any one of claims 1 to 3, wherein the catalyst in step (1) comprises any one or a combination of at least two of calcium oxide, magnesium oxide, aluminum oxide, silicon oxide, scandium oxide, titanium dioxide, manganese dioxide, ferric oxide, ferroferric oxide, cobaltous oxide, nickel oxide, copper oxide, molybdenum trioxide, yttrium oxide, zirconium dioxide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, tungsten trioxide, silver oxide, cerium oxide, lanthanum oxide, praseodymium oxide, and neodymium trioxide;
preferably, the adding amount of the catalyst in the step (1) is 0.01-30% of the mass of the isophorone diamine.
5. The process according to any one of claims 1 to 4, wherein the temperature of the carbonylation reaction in step (1) is 120 to 260 ℃;
preferably, the carbonylation reaction time in the step (1) is 1-12 h.
6. The method according to any one of claims 1 to 5, wherein the purification treatment of step (1) comprises a deamination treatment, a first solvent removal treatment and a decarbonylation agent treatment of the filtrate obtained by the solid-liquid separation;
preferably, the first solvent, the carbonylation agent and the heavy component polymer obtained by the purification treatment are returned to the step (1) for carbonylation reaction.
7. The method according to any one of claims 1 to 6, wherein the second solvent of step (2) comprises any one of p-xylene, m-xylene, o-xylene, chlorobenzene, bromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, 1-phenyl-2-methylpropane, mesitylene, hemimellitene, 1,2, 4-trimethylbenzene or a combination of at least two thereof;
preferably, the isophorone dicarbamate is 0.1-50% of the mass of the second solvent;
preferably, the pyrolysis reaction of step (2) is carried out under catalysis of a catalyst;
preferably, the catalyst is a metal catalyst;
preferably, the metal catalyst comprises any one or a combination of at least two of aluminum, scandium, titanium, vanadium, chromium, manganese, iron, nickel, cobalt, copper, zinc, molybdenum, tin, gallium, zirconium, molybdenum, silver or tungsten;
preferably, the adding amount of the catalyst in the step (2) is 0.01-30% of the mass of the isophorone dicarbamate.
8. The method according to any one of claims 1 to 7, wherein the temperature of the pyrolysis reaction in the step (2) is 160 to 320 ℃;
preferably, the pressure of the pyrolysis reaction in the step (2) is 0-5.0 MPa;
preferably, the time of the pyrolysis reaction in the step (2) is 0.5-8 h.
9. The method according to any one of claims 1 to 8, wherein the purification treatment of step (2) comprises subjecting the reaction solution after the pyrolysis reaction to a second solvent removal treatment;
preferably, the second solvent and the isophorone dicarbamate obtained by the purification treatment are returned to the step (2) for pyrolysis reaction.
10. The method according to any one of claims 1 to 9, wherein the reaction comprises the steps of:
(1) mixing isophorone diamine, a carbonylation agent, a first solvent and a catalyst, carrying out carbonylation reaction for 1-12 h at 120-260 ℃, carrying out solid-liquid separation, and carrying out purification treatment to obtain isophorone dicarbamate;
the molar ratio of the carbonylation agent to the isophorone diamine is (2-20):1, the molar ratio of the first solvent to the isophorone diamine is (3-100):1, and the addition amount of the catalyst is 0.01-30% of the mass of the isophorone diamine;
the purification treatment comprises the steps of carrying out deamination treatment, first solvent removal treatment and decarbonylation agent treatment on the filtrate obtained by the solid-liquid separation; the first solvent, the carbonylation agent and the heavy component polymer obtained by the purification treatment are returned to carry out carbonylation reaction;
(2) mixing the isophorone dicarbamate, a catalyst and a second solvent at 160-320 ℃ and under 0-5.0 MPa to perform pyrolysis reaction for 0.5-8 h, and purifying a product to obtain isophorone diisocyanate;
the mass of the isophorone dicarbamate is 0.1-50% of that of the second solvent, and the addition amount of the catalyst is 0.01-30% of that of the isophorone dicarbamate;
and the purification treatment comprises the step of removing a second solvent from the reaction liquid after the pyrolysis reaction, and the second solvent obtained by the purification treatment and the isophorone dicarbamate are returned to carry out the pyrolysis reaction.
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| CN115433106A (en) * | 2022-09-30 | 2022-12-06 | 四川元理材料科技有限公司 | Industrialized synthesis process of isophorone diamino n-butyl formate |
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| CN116474761A (en) * | 2023-06-20 | 2023-07-25 | 中国科学院过程工程研究所 | Catalyst for synthesizing glutarimide, preparation method and application thereof |
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| WO2024103323A1 (en) * | 2022-11-17 | 2024-05-23 | 万华化学集团股份有限公司 | Isocyanate composition, and preparation method therefor and use thereof |
| CN116474761A (en) * | 2023-06-20 | 2023-07-25 | 中国科学院过程工程研究所 | Catalyst for synthesizing glutarimide, preparation method and application thereof |
| CN116474761B (en) * | 2023-06-20 | 2023-09-22 | 中国科学院过程工程研究所 | Catalyst for synthesizing glutarimide, preparation method and application thereof |
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