CN117586128A - Salt forming method of m-xylylene diisocyanate - Google Patents
Salt forming method of m-xylylene diisocyanate Download PDFInfo
- Publication number
- CN117586128A CN117586128A CN202311589683.4A CN202311589683A CN117586128A CN 117586128 A CN117586128 A CN 117586128A CN 202311589683 A CN202311589683 A CN 202311589683A CN 117586128 A CN117586128 A CN 117586128A
- Authority
- CN
- China
- Prior art keywords
- reaction
- controlling
- mass ratio
- reaction kettle
- hcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 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 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 12
- -1 amine hydrochloride Chemical class 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003507 refrigerant Substances 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a salt forming method of m-xylylene diisocyanate, which comprises the following steps: a. adding m-xylylenediamine and a solvent into a stirred reaction kettle according to the mass ratio of 1:10-1:20, and controlling the stirring rotating speed to be 300-450 r/min; b. a refrigerant system of the reaction kettle is operated, so that the reflux temperature of the refrigerant is between-10 and 10 ℃; c. introducing HCl into the reaction kettle, wherein the mass ratio of the flow rate of the HCl to the mass ratio of the M-XDA is (1-3): 1, controlling the reaction temperature to be 10-30 ℃, and controlling the salification reaction time to be within 120 min; d. after the reaction is finished, amine hydrochloride is obtained, and the ammonia concentration is sampled and tested. By optimizing the process parameters, controlling the reaction temperature, the stirring rotation speed, the hydrogen chloride flow, the reaction time and the like, the generation of byproducts is effectively reduced, the salt formation conversion rate is improved, and the method plays an important role in improving the yield of the subsequent phosgenation reaction products.
Description
Technical Field
The invention relates to a synthetic method of aromatic diisocyanate, in particular to a salt forming method of m-xylylene diisocyanate.
Background
M-xylylene diisocyanate (M-XDI), which is a novel aromatic diisocyanate, and its products and related derivatives have excellent properties. Amine coating is easily caused in the case of poor reaction control during M-XDI synthesis, while urea byproducts are produced during the subsequent thermal-pho-todization. The salifying method is adopted to change the amine into amine salt, so that the generation of urea which is a byproduct in the photochemical process can be effectively inhibited, the control of the salifying process becomes particularly important, the index of hydrochloride or carbonate of the amine becomes an important control standard, the content of chlorinated impurities in isocyanate obtained by subsequent photochemical reaction is influenced, and the chlorinated impurities tend to cause unexpected chromaticity change in downstream products, so that the application of the products in the high-end field is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a salt forming method of m-xylylene diisocyanate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a salt forming method of m-xylylene diisocyanate is characterized in that: the method comprises the following steps:
a. adding m-xylylenediamine and a solvent into a reaction kettle with stirring according to the mass ratio of 1:10-1:20, wherein the stirring speed is controlled at 300-450 r/min, the reaction kettle is provided with a jacket, and a refrigerant is introduced into the jacket;
b. the coolant system of the reaction kettle is operated to control the coolant reflux temperature to be between-10 and 10 ℃;
c. introducing HCl into the reaction kettle, wherein the mass ratio of the flow rate of the HCl to the mass ratio of the M-XDA is (1-3): 1, controlling the reaction temperature to be 10-30 ℃, and controlling the salification reaction time to be within 120 min;
d. after the reaction, amine hydrochloride with the concentration below 7wt% is obtained, and the sample is taken to test the ammonia concentration.
The solvent is any one of o-dichlorobenzene, chlorobenzene and toluene.
The principle of the invention is as follows:
(i) Reaction temperature: the salt forming reaction process is exothermic, and the higher the system temperature, the more white smoke generated by the reaction indicates the more byproducts. In order to control the reaction temperature to 10-30 ℃, a reaction kettle with a refrigerant jacket is adopted.
(ii) Stirring rotation speed: the stirring rotation speed affects the salt particle size, the particle size is too large, the amine coating is easily caused, the later photochemical byproducts tend to be increased, the amine conversion rate is reduced due to the existence of the amine hydrochloride coating phenomenon in the salifying reaction, urea byproducts are generated in the subsequent phosgenation reaction, and meanwhile, the amine hydrochloride particles are different and are unevenly dispersed, so that the photochemical reaction time is prolonged, and the rotation speed is controlled to be 300-450 r/min;
(iii) Solvent ratio: the proportion of the amine and the solvent is controlled, so that amine hydrochloride generated by the reaction of M-XDA and HCl can be uniformly dispersed, and the salt formation conversion rate is improved. The proportion of the amine and the solvent is controlled to be 1:10-1:20, so that the concentration of the amine hydrochloride is below 7wt%, and if the concentration of the amine hydrochloride is above 7%, the viscosity of the slurry of the obtained hydrochloride is increased, the fluidity of the slurry is reduced, and the industrial production is not facilitated. Although the problem of salt formation viscosity can be solved by adopting a mode of increasing the temperature, the amine reacts with HCl quickly at high temperature, so that the amine is coated by the hydrochloride, and incomplete salt formation can be caused;
(iv) Hydrogen chloride flow rate: the larger the flow of the hydrogen chloride is, the more severe the reaction is, the more obvious the foaming is, the diamine is influenced by the coating of the foam to react with the hydrogen chloride, so that the conversion rate is reduced, and the mass ratio of the HCl flow to the M-XDA is controlled to be (1-3): 1;
(v) Reaction time: the salification reaction time is controlled to be completed within 120 min. After the salification reaction is finished, the retention time of the salification reaction liquid in a stirring-free state is less than 60min, so that the content of chlorinated products in the reaction liquid or the products can be effectively reduced.
The beneficial effects of the invention are as follows: by optimizing the process parameters, controlling the key factors such as reaction temperature, stirring rotation speed, hydrogen chloride flow, reaction time and the like, the generation of byproducts is effectively reduced, the salt formation conversion rate is improved, and the obtained amine hydrochloride with the concentration below 7wt% has an important effect on the improvement of the yield of the subsequent phosgenation reaction product.
Detailed Description
The following examples serve to further illustrate the process of the invention. The spirit and scope of the invention disclosed above is not limited by these examples.
Example 1:
a salt forming method of m-xylylene diisocyanate is characterized in that: the method comprises the following steps:
a. adding M-XDA and o-dichlorobenzene into a reaction kettle according to the mass ratio of 1:16, stopping adding when the liquid level reaches 70%, starting stirring, and controlling the stirring rotating speed at 300r/min;
b. a refrigerant system is operated to control the reflux temperature of the refrigerant to be between-10 and 10 ℃;
c. introducing hydrogen chloride, controlling the mass ratio of the hydrogen chloride flow to the M-XDA to be 1.5:1, and stopping the reaction after the reaction is carried out for 10min at the reaction temperature of 20 ℃ without generating a large amount of white smoke;
d. after the reaction, amine hydrochloride was obtained, and the ammonia concentration was measured by sampling and the conversion was 95.63%.
Example 2:
the salt forming method is the same as in example 1, and the process conditions are shown in the following table:
| reaction time (min) | Stirring rotation speed (r/min) | HCl/M-XDA | chlorobenzene/M-XDA | Reaction temperature (. Degree. C.) | Conversion (%) |
| 40 | 350 | 1.5 | 12 | 10 | 100 |
Example 3:
the salt forming method is the same as in example 1, and the process conditions are shown in the following table:
| reaction time (min) | Stirring rotation speed (r/min) | HCl/M-XDA | toluene/M-XDA | Reaction temperature (. Degree. C.) | Conversion (%) |
| 50 | 400 | 2 | 15 | 25 | 100 |
Although the invention has been described in detail in the foregoing description, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (3)
1. A salt forming method of m-xylylene diisocyanate is characterized in that: the method comprises the following steps:
a. adding m-xylylenediamine and a solvent into a stirred reaction kettle according to the mass ratio of 1:10-1:20, and controlling the stirring rotating speed to be 300-450 r/min;
b. the coolant system of the reaction kettle is operated to control the coolant reflux temperature to be between-10 and 10 ℃;
c. introducing HCl into the reaction kettle, wherein the mass ratio of the flow rate of the HCl to the mass ratio of the M-XDA is (1-3): 1, controlling the reaction temperature to be 10-30 ℃, and controlling the salification reaction time to be within 120 min;
d. after the reaction, amine hydrochloride with the concentration below 7wt% is obtained, and the sample is taken to test the ammonia concentration.
2. A process for salifying isophthalylene diisocyanate as claimed in claim 1, wherein: the solvent is any one of o-dichlorobenzene, chlorobenzene and toluene.
3. A process for salifying isophthalylene diisocyanate as claimed in claim 1, wherein: the reaction kettle is provided with a jacket, and a refrigerant is introduced into the jacket.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311589683.4A CN117586128A (en) | 2023-11-27 | 2023-11-27 | Salt forming method of m-xylylene diisocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311589683.4A CN117586128A (en) | 2023-11-27 | 2023-11-27 | Salt forming method of m-xylylene diisocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117586128A true CN117586128A (en) | 2024-02-23 |
Family
ID=89916308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311589683.4A Pending CN117586128A (en) | 2023-11-27 | 2023-11-27 | Salt forming method of m-xylylene diisocyanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117586128A (en) |
-
2023
- 2023-11-27 CN CN202311589683.4A patent/CN117586128A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114507160A (en) | Method for synthesizing 1, 5-pentamethylene diisocyanate by salifying phosgenation method | |
| CN111718282B (en) | Method for preparing isocyanate with low chlorinated impurity content based on salification phosgenation | |
| HU210256B (en) | Production of polyarylamine crosslinked with methylene | |
| CN104945283A (en) | Method for preparing isocyanate monomer | |
| CN112358419B (en) | Synthesis process of 3, 4-dichlorophenyl isocyanate | |
| CN111269145A (en) | Preparation method of acetamidine hydrochloride | |
| CN114044745A (en) | Method for synthesizing 1, 5-pentamethylene diisocyanate by gas phase phosgenation method | |
| CN110294844B (en) | Method for synthesizing high molecular weight polyphenylene sulfide by controlling water content | |
| CN117586128A (en) | Salt forming method of m-xylylene diisocyanate | |
| CN102675509A (en) | Preparation method of nonionic polyacrylamide (NPAM) | |
| CN101899020A (en) | DZ synthesized by mixing mother solution | |
| CN114751869B (en) | Preparation method of high-dispersion melamine cyanurate flame retardant | |
| CN114195981B (en) | Biphenyl epoxy resin and synthetic method and application thereof | |
| CN111662178B (en) | Method for synthesizing allyl chloroformate by phosgene method | |
| CN101343229A (en) | Technique for preparing mix dinitrobenzene with continuous nitrification of nitrobenzene | |
| CN101265198B (en) | Method for preparing tri-isopropanolamine | |
| CN112824376B (en) | Method for preparing isocyanate with low hydrolytic chlorine content by gas phase method | |
| CN1313444C (en) | Semicontinuous method of preparing DSD acid by iron powder reducing DNS sodium salt | |
| CN104726528B (en) | The technique that a kind of method through prepares ampicillin | |
| CN112358420A (en) | Method for synthesizing m-xylylene diisocyanate by low-temperature salt formation method | |
| CN112441951A (en) | Method for synthesizing diisocyanate containing ether bond by salifying phosgenation method | |
| CN113087631A (en) | Preparation method of 4, 4' -diaminodiphenyl ether | |
| CN109369915B (en) | Method for synthesizing polyimide | |
| CN112321730A (en) | Preparation method of high-viscosity carboxymethyl cellulose ammonium | |
| CN114369024B (en) | PTA and BDO esterification process for PBAT production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |