A sulfonyl isocyanate composition with improved stability and preparation method thereof

Abstract

The present invention relates to a sulfonyl isocyanate composition with improved stability and a preparation method thereof. The sulfonyl isocyanate composition comprises 10-8000 ppm of an isomeric component and / or 0.05-5% of a sulfonamide component. The sulfonyl isocyanate composition of the present invention has improved stability. After storage at 50°C for 6 months, the weight percentage of the isocyanate monomer changes by ≤2% compared to the initial value. This solves the problems of decreased product purity and unstable color during storage, and eliminates the need for the addition of additional stabilizers.

Description

Technical Field

[0001] The invention belongs to the technical field of isocyanates, and particularly relates to a sulfonyl isocyanate composition with improved stability and a preparation method thereof. Background Art

[0002] Sulfonyl isocyanate is very active due to the presence of sulfonyl group. It is often used as a coating dehydrating agent. In addition, it is also used as an additive for lithium battery electrolyte to inhibit the decomposition of the electrolyte and extend the service life.

[0003] It can be seen that people need to utilize the active properties of sulfonyl isocyanates, but their active reactivity also leads to poor storage stability. The isocyanate groups are easily reactive, resulting in a decline in product quality. Furthermore, sulfonyl isocyanates react violently with water and release carbon dioxide, which can easily lead to dangerous situations such as drum bulging and pressure buildup during storage. Furthermore, in addition to poor storage stability, the introduction of air or moisture from the environment during use can accelerate its degradation and pose safety risks.

[0004] Typically, sulfonyl isocyanate stability can be improved by adding external stabilizers. However, this approach can impact downstream applications. For example, battery-grade additives require very high purity, and even trace amounts of stabilizers can significantly impact electrolyte performance. To address this issue, attempts have been made to improve product quality through secondary distillation, but this process incurs significant processing costs and consumes a lot of energy.

[0005] Therefore, it is necessary to study and improve the stability of sulfonyl isocyanate without adding external stabilizers or catalysts, and adopt a simple and easy method to inhibit the degradation of product quality during storage. Summary of the Invention

[0006] To address the problems of the prior art, the inventors of the present application surprisingly discovered that controlling the content of sulfonylamine and the content of isomers in sulfonyl isocyanate to a certain level can improve the stability of sulfonyl isocyanate and maintain excellent product quality after long-term storage, thereby completing the present invention.

[0007] An object of the present invention is to provide a sulfonyl isocyanate composition with improved stability, wherein the composition achieves better storage stability by controlling the content of sulfonylamine and the content of sulfonyl isocyanate isomers.

[0008] Another object of the present invention is to provide a method for preparing the sulfonyl isocyanate composition with improved stability.

[0009] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0010] A sulfonyl isocyanate composition comprises a sulfonyl isocyanate and an isomer of the sulfonyl isocyanate or a sulfonamide component, wherein the isomer content of the sulfonyl isocyanate is 10 ppm to 8000 ppm, and the sulfonamide content is 0.05 to 5%, based on the total mass of the composition.

[0011] In a preferred embodiment, the sulfonyl isocyanate composition comprises sulfonyl isocyanate, isomers of sulfonyl isocyanate and a sulfonamide component, wherein the isomer content of the sulfonyl isocyanate is 10 ppm to 8000 ppm, and the sulfonamide content is 0.05 to 5%, based on the total mass of the composition.

[0012] In a specific embodiment, the isomer content of the sulfonyl isocyanate is 10 ppm-8000 ppm, preferably 100-3000 ppm, and the sulfonamide content is 0.05-5%, preferably 0.1-4%, based on the total mass of the composition.

[0013] In a specific embodiment, the general structural formula of the sulfonyl isocyanate is formula (I):

[0014]

[0015] Wherein, n=1, 2, 3, 4; R is selected from C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom, a halogen atom, a group containing at least one selected from oxygen, sulfur, and nitrogen atom; preferably, it is phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom.

[0016] In a specific embodiment, the isomer of the sulfonyl isocyanate is an isomer of the sulfonyl isocyanate.

[0017] In a specific embodiment, the general structural formula of the sulfonamide is formula (II):

[0018]

[0019] Wherein, n=1, 2, 3, 4; R is selected from C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom, a halogen atom, a group containing at least one selected from oxygen, sulfur, and nitrogen atom; preferably, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom.

[0020] In a specific embodiment, after the sulfonyl isocyanate composition is stored at 50° C. for 6 months, the mass percentage change rate of the sulfonyl isocyanate component is ≤2%, and the color number change rate of the sulfonyl isocyanate composition is less than 20%.

[0021] On the other hand, the preparation method of the aforementioned sulfonyl isocyanate composition comprises the following steps:

[0022] S1: mixing the raw material sulfonamide with the catalyst for reaction;

[0023] S2: continuing to react the mixed solution obtained in S1 with phosgene until the raw material amine content is less than 10%, wherein the phosgene feeding position is preferably below the liquid level of the reactor;

[0024] S3: Separate and purify the reaction solution obtained in S2 to obtain a sulfonyl isocyanate composition.

[0025] In a specific embodiment, the catalyst contains at least one isocyanate group, preferably one or more of an aliphatic isocyanate, an aromatic isocyanate, or a derivative thereof; more preferably one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, meta-xylylene diisocyanate, 1,3-diisocyanatomethylcyclohexane, pentamethylene diisocyanate, silane isocyanate, cyclohexyl isocyanate, butyl isocyanate, propyl isocyanate, ethyl isocyanate, methyl isocyanate, or a derivative thereof.

[0026] In a specific embodiment, the isomer content in the sulfonamide is 10-8500 ppm and / or the water content in the sulfonamide is 20-2000 ppm.

[0027] Wherein, the general structural formula of the sulfonamide is shown as formula (II):

[0028]

[0029] Wherein, n=1, 2, 3, 4; R is selected from C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom, a halogen atom, a group containing at least one selected from oxygen, sulfur, and nitrogen atom; preferably, it is phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom.

[0030] Compared with the prior art, the present invention has the following positive effects:

[0031] (1) The sulfonyl isocyanate composition of the present invention is storage-stable. After storage at 50° C. for 6 months, the mass percentage of the isocyanate monomer changes by ≤2% compared with the initial value, thereby solving the problem of decreased product purity during storage and avoiding dangerous conditions such as drum bulging that are prone to occur during use.

[0032] (2) The sulfonyl isocyanate of the present invention has a stable color during storage, which effectively avoids the problem of color introduction in downstream applications.

[0033] (3) The sulfonyl isocyanate composition of the present invention does not require an external stabilizer, and the preparation method is simple and easy. DETAILED DESCRIPTION

[0034] In order to better understand the technical solution of the present invention, the following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0035] In one embodiment of the present invention, a sulfonyl isocyanate composition is provided, comprising a sulfonyl isocyanate and a sulfonyl isocyanate isomer component, wherein the sulfonyl isocyanate isomer content is 10 ppm-8000 ppm, for example, including but not limited to 10 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 500 ppm, 800 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, 5000 ppm, 5500 ppm, 6000 ppm, 6500 ppm, 7000 ppm, 7500 ppm, 8000 ppm, preferably 100-3000 ppm, based on the total mass of the composition.

[0036] In another embodiment, a sulfonyl isocyanate composition comprises a sulfonyl isocyanate and a sulfonamide component, wherein the sulfonamide content is 0.05-5%, for example, including but not limited to 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, preferably 0.1-4%, based on the total weight of the composition.

[0037] In another embodiment, a sulfonyl isocyanate composition comprises a sulfonyl isocyanate, an isomer of a sulfonyl isocyanate, and a sulfonamide component, wherein the isomer content of the sulfonyl isocyanate is 10 ppm to 8000 ppm, and the sulfonamide content is 0.05 to 5%, based on the total mass of the composition.

[0038] Wherein, the general structural formula of the sulfonyl isocyanate is shown in formula (I):

[0039]

[0040] Wherein, n=1, 2, 3, 4; R is selected from C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom, a halogen atom, a group containing at least one selected from oxygen, sulfur, and nitrogen atom; preferably, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom.

[0041] Correspondingly, the sulfonyl isocyanate isomers are isomers of sulfonyl isocyanate that do not contain the aforementioned sulfonyl isocyanate, i.e., all other isomers that do not contain the main structure of the sulfonyl isocyanate. For example, p-toluenesulfonyl isocyanate may have isomers of o-toluenesulfonyl isocyanate and / or m-toluenesulfonyl isocyanate.

[0042] Wherein, the general structural formula of the sulfonamide component is shown as formula (II):

[0043]

[0044] Wherein, n=1, 2, 3, 4; R is selected from C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom, a halogen atom, a group containing at least one selected from oxygen, sulfur, and nitrogen atom; preferably, it is phenyl, substituted phenyl, a five-membered or six-membered heterocyclic aromatic group containing at least one selected from oxygen, sulfur, and nitrogen atom.

[0045] In the present invention, by controlling the content of the isomers and / or sulfonamide of the sulfonyl isocyanate in the sulfonyl isocyanate composition, the sulfonyl isocyanate composition is ultimately stored at 50° C. for 6 months, wherein the change rate of the mass percentage of the sulfonyl isocyanate compared with the initial value is ≤2%, and the color number change rate is less than 20%, thereby significantly improving the storage stability.

[0046] The above-mentioned sulfonyl isocyanate composition with improved stability is prepared by the following preparation method, which comprises the following steps:

[0047] S1: mixing the raw material sulfonamide with part or all of the catalyst for reaction;

[0048] S2: continuing to react the mixed solution obtained in S1 with phosgene until the raw material amine content is less than 10%, wherein the phosgene feeding position is preferably below the liquid level of the reactor;

[0049] S3: Separate and purify the reaction solution obtained in S2 to obtain a sulfonyl isocyanate composition.

[0050] In the present invention, the catalyst contains at least one isocyanate group, including but not limited to one or more of aliphatic isocyanates, aromatic isocyanates, or derivatives thereof, specifically including but not limited to one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, meta-xylylene diisocyanate (XDI), 1,3-diisocyanatomethylcyclohexane (HXDI), pentamethylene diisocyanate, silane isocyanate, cyclohexyl isocyanate, butyl isocyanate, propyl isocyanate, ethyl isocyanate, and methyl isocyanate.

[0051] In the present invention, the raw material sulfonamide includes but is not limited to one or more of aliphatic amines, aromatic amines, heterocyclic substituted amines, amines containing oxygen, sulfur, or nitrogen substituents, or halogenated amines containing a sulfonyl group. The sulfonylamine isomer component in the raw material sulfonamide leads to the production of isomers in the isocyanate. Therefore, the isomer content in the raw material amine can be adjusted by collecting different fractions through distillation. The temperature and the fraction collected are selected according to the boiling point. For sulfonamide, distillation can be performed and the latter fraction is collected for purification.

[0052] In the present invention, moisture in the raw sulfonamide degrades the catalyst activity, thereby affecting the sulfonamide conversion rate during the reaction, and further leading to an increase in the sulfonamide content in the product. The water content in the sulfonamide can be controlled by drying. Preferably, the isomer content in the raw sulfonamide is controlled to be 10-8500 ppm and / or the water content in the sulfonamide is controlled to be 20-2000 ppm.

[0053] The present invention is further described below with reference to the embodiments, but the present invention is not limited thereto.

[0054] The reagent information used in the present invention is shown in Table 1 below:

[0055] Table 1 Main raw material information

[0056] Reagent name factory purity p-Toluenesulfonamide Inokai ＞99.0％ p-Chlorobenzenesulfonamide Inokai ＞99.0％ chlorobenzene Inokai ＞99.0％ n-Butyl isocyanate Inokai ＞99.0％ Cyclohexyl isocyanate Inokai ＞99.0％

[0057] The gas phase analysis of the present invention was tested using an Agilent 7890B: chromatographic column: Agilent 19091J-413HP-5, column oven gradient temperature, maximum column oven temperature 325°C, covering the maximum column temperature of 350°C; 30m x 320μm x 0.25μm; carrier gas: purified and dried high-purity N2; combustion gas: H2 (purity above 99.999%), supporting gas: purified and dried air, tail gas: N2, its flow rate 40mL / min; column flow rate: 1.3mL / min, column oven temperature: 40°C (1min) 10 ℃ / min320℃(5min); injection port temperature: 300℃; detector temperature: 320℃.

[0058] Example 1

[0059] Preparation of p-toluenesulfonamide with different isomer contents by distillation.

[0060] In a four-necked flask, 2000 g of p-toluenesulfonamide was added and distillation separation was carried out under a pressure of 5 mmHg. The fraction was heated to 200° C. and fraction collection began. The temperature was raised to 210° C. at a rate of 1° C. per 10 min until no more fraction was distilled at 210° C. During the heating process, fraction 1, fraction 2, fraction 3, fraction 4, fraction 5, and fraction 6 were collected in sequence. Fractions 1-6 were weighed respectively, and the isomer contents in fractions 1-6 were determined by the above-mentioned gas phase method. The results are shown in Table 2 below.

[0061] Table 2 p-Toluenesulfonamide fraction collection

[0062] fractions 1# 2# 3# 4# 5# 6# Mass / g 150 175 165 150 160 200 Isomer content / ppm 10000 8500 6000 1000 50 10

[0063] Example 2

[0064] 20 parts of fraction 2 (p-toluenesulfonamide with an isomer content of 8500 ppm) were added to 79 parts of chlorobenzene, and 1 part of n-butyl isocyanate was added thereto. The temperature was raised to 60°C and maintained at 60°C for 30 minutes. Subsequently, phosgene was introduced at a rate of 50 L / h to below the reaction liquid surface. The temperature was raised to 120°C and maintained at this temperature for 3 hours. The p-toluenesulfonamide content in the reaction liquid was measured by gas phase analysis to be 7%. Nitrogen was introduced to drive out unreacted phosgene, and the solvent was removed to obtain a crude p-toluenesulfonamide product. The crude product was subjected to rectification and separation to obtain a composition 1 with an isomer content of 8000 ppm. The p-toluenesulfonamide content in the reaction liquid and the isomer content in the composition were determined by gas phase analysis.

[0065] Example 3

[0066] A p-toluenesulfonyl isocyanate composition was prepared in the same manner as in Example 2, except that fraction 3 (p-toluenesulfonamide having an isomer content of 6000 ppm) was used instead of p-toluenesulfonamide in Example 2. After distillation and separation, Composition 2 having an isomer content of 5700 ppm was obtained. The p-toluenesulfonamide content in the reaction solution and the isomer content in the composition were determined by gas phase analysis.

[0067] Example 4

[0068] Using the same method as in Example 1, p-chlorobenzenesulfonamide with an isomer content of 1000 ppm was distilled. A p-chlorobenzenesulfonyl isocyanate composition was prepared in exactly the same manner as in Example 2, except that p-chlorobenzenesulfonamide with an isomer content of 1000 ppm was used instead of p-toluenesulfonamide in Example 2. After distillation and separation, Composition 3 with an isomer content of 950 ppm was obtained. The p-chlorobenzenesulfonamide content in the reaction solution and the isomer content in the composition were determined by gas phase analysis.

[0069] Example 5

[0070] A p-toluenesulfonyl isocyanate composition was prepared in the same manner as in Example 2, except that fraction 5 (p-toluenesulfonamide having an isomer content of 50 ppm) was used instead of the p-toluenesulfonamide in Example 2. After distillation and separation, composition 4 having an isomer content of 10 ppm was obtained. The p-toluenesulfonamide content in the reaction solution and the isomer content in the composition were determined by gas phase analysis.

[0071] Comparative Example 1

[0072] A p-toluenesulfonyl isocyanate composition was prepared in the same manner as in Example 2, except that fraction 1 (p-toluenesulfonamide having an isomer content of 10,000 ppm) was used instead of the p-toluenesulfonamide in Example 2. After distillation and separation, a composition 5 having an isomer content of 9,500 ppm was obtained. The p-toluenesulfonamide content in the reaction solution and the isomer content in the composition were determined by gas phase analysis.

[0073] Comparative Example 2

[0074] A p-toluenesulfonyl isocyanate composition was prepared in the same manner as in Example 2, except that fraction 6 (p-toluenesulfonamide having an isomer content of 10 ppm) was used instead of the p-toluenesulfonamide in Example 2. After distillation and separation, composition 6 having an isomer content of 5 ppm was obtained. The p-toluenesulfonamide content in the reaction solution and the isomer content in the composition were determined by gas phase analysis.

[0075] Example 8

[0076] The color stability of sulfonyl isocyanate compositions with different isomer contents during storage was evaluated.

[0077] Color number testing of the compositions (compositions 1-6) was performed according to the method of GB / T3143-1982. The sulfonyl isocyanate compositions (compositions 1-6) were placed in transparent glass bottles, filled with nitrogen, and sealed. The different sulfonyl isocyanate compositions (compositions 1-6) were then stored at 50°C for 6 months. The stored compositions were designated as composition 1a, composition 2a, composition 3a, composition 4a, composition 5a, and composition 6a, respectively. Color number testing of compositions 1a-6a was performed according to the method of GB / T3143-1982, and component content of compositions 1a-6a was tested according to the vapor phase method. The results are shown in Table 3 below.

[0078] Table 3 Stability of compositions 1a-6a

[0079]

[0080] As demonstrated in Table 3 above, the sulfonyl isocyanate compositions (Compositions 1-4) having an isomer content in the range of 10-8000 ppm showed minimal color change after 6 months of storage. The compositions exhibited excellent color stability and did not introduce color into downstream applications. Furthermore, the monomer content changed by less than 2% during storage, demonstrating stable quality.

[0081] The sulfonyl isocyanate compositions with an isomer content of less than 10 ppm or greater than 8000 ppm (compositions 5 and 6) showed a significant increase in color after storage for 6 months, becoming yellowish and exhibiting poor color stability. The monomer content decreased by 3% during storage, resulting in turbidity, which affected downstream use.

[0082] Example 9

[0083] Preparation of p-toluenesulfonamide with different water contents

[0084] Paratoluenesulfonamide with an initial water content of 5000 ppm was placed in a vacuum oven at 50° C. for vacuum drying. Part of the sample was taken out at regular intervals and the water content was measured according to GB / T6284. The results are shown in Table 2 below.

[0085] Table 4 p-Toluenesulfonamide fraction collection

[0086] Drying time / h 1 2 5 10 24 30 Water content / ppm 2500 2001 1030 493 21 10

[0087] Example 10

[0088] 20 parts of p-toluenesulfonamide (water content 21 ppm) were added to 79 parts of chlorobenzene, and 1 part of n-butyl isocyanate was added thereto. The temperature was raised to 60° C. and maintained at 60° C. for 30 minutes. Phosgene was then introduced at a rate of 50 L / h to below the reaction liquid level. The temperature was raised to 120° C. and maintained at this temperature for 3 hours. Nitrogen was introduced to drive out unreacted phosgene, and the solvent was removed to obtain a crude p-toluenesulfonamide product. The p-toluenesulfonamide content in the crude product was measured by gas phase analysis to be 0.06%. The crude product was distilled to remove heavy components to obtain a composition 7 with a p-toluenesulfonamide content of 0.05%. The p-toluenesulfonamide content in the crude product and the p-toluenesulfonamide content in the composition were determined by gas phase analysis.

[0089] Example 11

[0090] The p-toluenesulfonyl isocyanate composition 8 was prepared in the same manner as in Example 10 except that p-toluenesulfonamide with a water content of 493 ppm was used. The p-toluenesulfonamide content in the crude product was 1.5%, and the p-toluenesulfonamide content in the composition 8 was 1.3%.

[0091] Example 12

[0092] Para-chlorobenzenesulfonamide having a water content of 1030 ppm was prepared by the same method as in Example 9. Para-chlorobenzenesulfonyl isocyanate composition 9 was prepared in the same manner as in Example 10, except that para-chlorobenzenesulfonamide having a water content of 1030 ppm was used. Analysis of the crude product revealed a para-chlorobenzenesulfonamide content of 3.1%, while the para-chlorobenzenesulfonamide content in composition 9 was 2.7%.

[0093] Example 13

[0094] The p-toluenesulfonyl isocyanate composition 10 was prepared in the same manner as in Example 10 except that p-toluenesulfonamide with a water content of 2001 ppm was used. The p-toluenesulfonamide content in the crude product was 6.9% and the p-toluenesulfonamide content in the composition 10 was 5.0%.

[0095] Comparative Example 3

[0096] The p-toluenesulfonyl isocyanate composition 11 was prepared in the same manner as in Example 10, except that p-toluenesulfonamide with a water content of 10 ppm was used. Analysis showed that the p-toluenesulfonamide content in the crude product was 0.03%, and the p-toluenesulfonamide content in the composition 11 was 0.02%.

[0097] Comparative Example 4

[0098] The p-toluenesulfonyl isocyanate composition 12 was prepared in the same manner as in Example 10 except that p-toluenesulfonamide with a water content of 2500 ppm was used. The p-toluenesulfonamide content in the crude product was 11% and the p-toluenesulfonamide content in the composition 12 was 8.3%.

[0099] Example 14

[0100] The storage stability of sulfonyl isocyanate compositions with different sulfonamide contents was evaluated.

[0101] The component content of the compositions (compositions 7-12) was tested according to a gas phase method. The sulfonyl isocyanate compositions (compositions 7-12) were placed in transparent glass bottles, which were filled with nitrogen and sealed. Then, different sulfonyl isocyanate compositions (compositions 7-12) were stored at 50° C. for 6 months. The stored compositions were respectively recorded as composition 7a, composition 8a, composition 9a, composition 10a, composition 11a, and composition 12a. The component content of compositions 7a-12a was tested according to a gas phase method. The color number of compositions 7a-12a was tested according to GB / T3143-1982. The results are shown in Table 5 below.

[0102] Table 5 Composition stability

[0103]

[0104] From the above data, it can be seen that after storing a composition with a sulfonamide content within 0.05-5% at 50° C. for 6 months, the monomer component content in the composition decreases by less than 2%, and the color number change rate is less than 20%.

[0105] For compositions with a sulfonamide content of less than 0.05% or greater than 5%, after storage at 50°C for 6 months, the content of the monomer component in the composition decreases significantly, the sample becomes turbid, and the color turns significantly yellow, affecting its use in downstream fields.

[0106] Example 15

[0107] 20 parts of p-toluenesulfonamide (water content 205 ppm, isomer content 1000 ppm) were added to 79 parts of chlorobenzene, and 1 part of n-butyl isocyanate was added thereto. The temperature was raised to 60°C and kept at 60°C for 30 minutes. Subsequently, phosgene was introduced at a rate of 50 L / h to below the reaction liquid level. The temperature was raised to 120°C and maintained at this temperature for 3 hours. Nitrogen was introduced to drive out the unreacted phosgene. After removing the solvent, a crude p-toluenesulfonamide product was obtained. The p-toluenesulfonamide content in the crude product was measured to be 1.3% by gas phase analysis. The crude product was distilled to remove heavy components to obtain a composition 13 with a p-toluenesulfonamide content of 0.7% and an isomer content of 930 ppm. The p-toluenesulfonamide content in the crude product and the p-toluenesulfonamide content in the composition were determined by gas phase analysis.

[0108] The component content of composition 13 was tested using a vapor phase method. Sulfonyl isocyanate composition 13 was placed in a transparent glass bottle, filled with nitrogen, and sealed. The bottle was then stored at 50°C for 6 months. The stored composition was recorded as composition 13a. The component content of composition 13a was tested using a vapor phase method. The color number of composition 13a was tested using the method of GB / T3143-1982. The results are shown in the following table.

[0109] Table 6 Stability of Composition 13

[0110]

[0111] The above data show that after storage at 50°C for 6 months, the monomer component content of the composition with a sulfonamide content within 0.05-5% and an isomer content within 10-8000 ppm decreases by less than 2%, the color number change rate is less than 20%, and the product quality is stable.

[0112] In summary, the sulfonyl isocyanate composition having an isomer content of 10-8000 ppm and / or a sulfonamide content of 0.05-5% has improved storage stability during storage and can still be used or sold normally after storage.

[0113] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. Those skilled in the art will appreciate that, based on the teachings of this specification, modifications or adjustments may be made to the present invention. Such modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A sulfonyl isocyanate composition, characterized in that The sulfonyl isocyanate composition comprises a sulfonyl isocyanate, and an isomer or a sulfonamide component of the sulfonyl isocyanate, wherein the isomer content of the sulfonyl isocyanate is 10 ppm to 8000 ppm, or the sulfonamide content is 0.05 to 5%, based on the total mass of the composition; The general structural formula of the sulfonyl isocyanate is formula (I): Wherein, n=1, 2, 3, 4; R is selected from phenyl and substituted phenyl; The sulfonyl isocyanate is p-toluenesulfonyl isocyanate or p-chlorobenzenesulfonyl isocyanate.

2. The sulfonyl isocyanate composition according to claim 1, wherein The sulfonyl isocyanate composition comprises sulfonyl isocyanate, isomers of sulfonyl isocyanate and sulfonamide components, wherein the isomer content of the sulfonyl isocyanate is 10ppm-8000ppm, and the sulfonamide content is 0.05-5%, based on the total mass of the composition.

3. The sulfonyl isocyanate composition according to claim 2, characterized in that The isomer content of the sulfonyl isocyanate is 100-3000 ppm, and the sulfonamide content is 0.1-4%, based on the total mass of the composition.

4. The sulfonyl isocyanate composition according to claim 1, characterized in that R is selected from substituted phenyl groups.

5. The sulfonyl isocyanate composition according to any one of claims 1 to 4, characterized in that The isomers of the sulfonyl isocyanate are isomers of the sulfonyl isocyanate.

6. The sulfonyl isocyanate composition according to any one of claims 1 to 4, characterized in that The general structural formula of the sulfonamide is formula (II): Wherein, n=1, 2, 3, 4; R is selected from phenyl and substituted phenyl.

7. The sulfonyl isocyanate composition according to any one of claims 1 to 4, characterized in that After the sulfonyl isocyanate composition is stored at 50° C. for 6 months, the mass percentage change rate of the sulfonyl isocyanate component is ≤2%, and the color number change rate of the sulfonyl isocyanate composition is less than 20%.

8. The method for preparing the sulfonyl isocyanate composition according to any one of claims 1 to 7, characterized in that: The following steps are included: S1: mixing the raw material sulfonamide with the catalyst for reaction; S2: continuing to react the mixed solution obtained in S1 with phosgene until the raw material amine content is less than 10%; S3: Separate and purify the reaction solution obtained in S2 to obtain a sulfonyl isocyanate composition.

9. The preparation method according to claim 8, characterized in that In step S2, the phosgene feed position is below the liquid level of the reactor.

10. The preparation method according to claim 8, characterized in that The catalyst contains at least one isocyanate group.

11. The preparation method according to claim 10, characterized in that: The catalyst is one or more of aliphatic isocyanate, aromatic isocyanate, or derivatives thereof.

12. The preparation method according to claim 11, characterized in that The catalyst is one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, 1,3-diisocyanatomethylcyclohexane, pentamethylene diisocyanate, silane isocyanate, cyclohexyl isocyanate, butyl isocyanate, propyl isocyanate, ethyl isocyanate, methyl isocyanate or derivatives thereof.

13. The preparation method according to any one of claims 8 to 12, characterized in that: The isomer content in the sulfonamide is 10-8500 ppm and / or the water content in the sulfonamide is 20-2000 ppm.

Images