CN117865904A - Preparation method of tris (hydroxyethyl) isocyanurate - Google Patents
Preparation method of tris (hydroxyethyl) isocyanurate Download PDFInfo
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- CN117865904A CN117865904A CN202311753641.XA CN202311753641A CN117865904A CN 117865904 A CN117865904 A CN 117865904A CN 202311753641 A CN202311753641 A CN 202311753641A CN 117865904 A CN117865904 A CN 117865904A
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- hydroxyethyl
- isocyanurate
- tris
- ethylene carbonate
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- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 179
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 47
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 tri-hydroxyethyl isocyanurate Chemical compound 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 238000006266 etherification reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000007872 degassing Methods 0.000 claims description 28
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000009965 odorless effect Effects 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VAAUVRVFOQPIGI-SPQHTLEESA-N ceftriaxone Chemical compound S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C(=O)NN1C VAAUVRVFOQPIGI-SPQHTLEESA-N 0.000 description 1
- 229960004755 ceftriaxone Drugs 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of tris (hydroxyethyl) isocyanurate, belonging to the technical field of organic compound synthesis. The preparation method comprises the following steps: s1, adding cyanuric acid, a catalyst and ethylene carbonate into a reaction kettle, placing nitrogen, vacuumizing, heating and starting stirring; s2, after the temperature of the reaction kettle is increased to 80-100 ℃, introducing ethylene oxide for ring-opening etherification reaction; s3, after the ring-opening etherification reaction is finished, continuously heating to enable the unreacted phenolic hydroxyl in the cyanuric acid to react with the ethylene carbonate, and discharging carbon dioxide; and S4, after the reaction is finished, removing a small amount of unreacted complete ethylene carbonate and catalyst to obtain the tri-hydroxyethyl isocyanurate product. The preparation method disclosed by the invention is simple in procedure, does not need to recover solvents and crystallization processes, can obtain a odorless and high-purity tris (hydroxyethyl) isocyanurate product, and greatly widens the application range of the product.
Description
Technical Field
The invention relates to the technical field of synthesis of organic compounds, in particular to a preparation method of tris (hydroxyethyl) isocyanurate.
Background
Trihydroxyethyl isocyanurate (Siec) is used as an important trifunctional triazine monomer and fine organic chemical intermediate, and is widely used in the industries of producing heat-resistant and solvent-resistant paint, molding compound, reinforced plastic, adhesive, flame retardant and the like.
The current industrial preparation method of the tri-hydroxyethyl isocyanurate mainly comprises the following steps: dispersing cyanuric acid and an alkaline catalyst triethylamine in an organic solvent ethylene glycol monomethyl ether or methanol, introducing ethylene oxide for addition reaction, removing part of the organic solvent after the reaction is finished, decolorizing with activated carbon, cooling, crystallizing, centrifuging and drying to obtain a tri-hydroxyethyl isocyanurate product; distilling the crystallization mother liquor, recycling the solvent, and obtaining a liquid crude product of the Siek at the bottom of the kettle. Due to the high melting point (360 ℃) and high polarity of cyanuric acid, the dosage of the organic solvent in the process is more than twice that of the cyanuric acid serving as a raw material, so that the process flow is long and the energy consumption is high; meanwhile, the byproduct liquid ceftriaxone crude product in the process is cheap in price, and the yield is about 10-15% of the product of the tri-hydroxyethyl isocyanurate.
Aiming at the problems, chinese patent CN 113234033A discloses a method for preparing the tri-hydroxyethyl isocyanurate by catalyzing cyanuric acid ring-opening ethylene oxide by taking a mixture of an organic solvent DMF as a reaction solvent and tetramethyl ammonium chloride and triethylamine as a catalyst, so that the comprehensive yield of the product can be improved from the existing 88% to 95%; however, the organic solvent DMF has a high boiling point, which results in a certain amount of DMF remaining in the product, thereby affecting the odor of the product. US patent 3313812 discloses a method of preparing a product of tri-hydroxyethyl isocyanurate by dissolving cyanuric acid in tri-hydroxyethyl isocyanurate of not less than 50% by weight of cyanuric acid at 120-250 ℃ without adding solvent or catalyst during the reaction, and introducing ethylene oxide of not less than 3 times by mole of cyanuric acid; however, the purity of the product prepared by the process is low, and the product with high purity is also required to be obtained by a dissolution and recrystallization process. U.S. patent No. 6046326 discloses a polyol solution of tris (hydroxyethyl) isocyanurate obtained by reacting cyanuric acid with at least 3 times the molar amount of cyanuric acid of ethylene carbonate at 160-170 ℃ under open conditions with a small amount of polyol as solvent and a specific heterocyclic amine as catalyst, which can be directly used as a crosslinking agent for polyester. However, this process does not purify the product from the polyol, thereby limiting the range of applications for the product.
Therefore, there is a need to develop a process for preparing triethyleneisocyanurates having a high purity and no odor without recovering solvents and crystallization processes.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the tri-hydroxyethyl isocyanurate, which has simple procedures, does not need to recover solvents and crystallization processes, can obtain the tri-hydroxyethyl isocyanurate product with no smell and high purity, and greatly widens the application range of the product.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, adding cyanuric acid, a catalyst and ethylene carbonate into a reaction kettle, placing nitrogen, vacuumizing, heating and starting stirring;
s2, after the temperature of the reaction kettle is increased to 80-100 ℃, introducing ethylene oxide for ring-opening etherification reaction;
s3, after the ring-opening etherification reaction is finished, continuously heating to enable the unreacted phenolic hydroxyl in the cyanuric acid to react with the ethylene carbonate, and discharging carbon dioxide;
and S4, after the reaction is finished, removing a small amount of unreacted complete ethylene carbonate and catalyst to obtain the tri-hydroxyethyl isocyanurate product.
As a preferred embodiment of the present invention, the catalyst in step S1 is dimethylacetamide. The purity of the dimethylacetamide is more than or equal to 99.9 percent.
It is further preferred that the catalyst in step S1 is used in an amount of 1 to 5% by mass based on the sum of the masses of cyanuric acid, ethylene carbonate and ethylene oxide.
As a preferred embodiment of the present invention, the molar ratio of cyanuric acid to ethylene carbonate in the step S1 is 1:0.5-1.0.
In a preferred embodiment of the present invention, the temperature is raised to 60 to 80℃before stirring is started in step S1.
As a preferred embodiment of the invention, the reaction pressure of the ring-opening etherification reaction in the step S2 is less than or equal to 0.4Mpa, and the reaction time is 4-16 h.
As a preferred embodiment of the present invention, the molar ratio of cyanuric acid to ethylene oxide in step S2 is 1:2.05-2.55.
As a preferred embodiment of the present invention, the reaction temperature in step S3 is 140 to 170℃and the reaction time is 2 to 10 hours.
As a preferred embodiment of the present invention, the conditions for removing a small amount of unreacted complete ethylene carbonate and catalyst in step S4 are: the degassing pressure is less than or equal to 100pa, the degassing temperature is 170 ℃, and the degassing time is 2 hours.
As a preferred embodiment of the present invention, the purity of the tris (hydroxyethyl) isocyanurate obtained in step S4 is not less than 98.5%.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, ethylene carbonate is adopted to react with cyanuric acid, and is not only the solvent in the step S1, but also the raw material in the step S2 ring-opening etherification reaction, compared with the process for preparing the tri-hydroxyethyl isocyanurate by using the traditional solvent method, the method saves the step of recovering and applying the solvent;
2. in the invention, dimethylacetamide is used as a catalyst, and compared with the traditional process which uses fatty amine, aromatic amine and salt thereof as the catalyst, the catalyst has weak smell; combining the high vacuum and high temperature degassing technology to make the finally prepared tri-hydroxyethyl isocyanurate product basically odorless;
3. compared with the traditional preparation process, the preparation method can prepare the tri-hydroxyethyl isocyanurate product with high purity (more than or equal to 98.5 percent and LC) without a crystallization process, and the process is simpler.
4. Compared with the process which only uses ethylene carbonate and cyanuric acid as reaction raw materials, the method has the advantages of higher yield (more than or equal to 80 percent) and lower cost, and is suitable for industrialized mass production.
Drawings
FIG. 1 is a liquid chromatogram of a tris-hydroxyethyl isocyanurate product prepared in example 4 of the present invention.
Detailed Description
The preparation method of the tri-hydroxyethyl isocyanurate provided by the invention specifically comprises the following steps:
s1, adding cyanuric acid, a catalyst and ethylene carbonate into a pressure-resistant reaction kettle, replacing air with nitrogen for three times, vacuumizing, heating the pressure-resistant reaction kettle to 60-80 ℃, and starting stirring;
s2, after the temperature of the pressure-resistant reaction kettle is increased to 80-100 ℃, introducing ethylene oxide to carry out ring-opening etherification reaction under the reaction pressure of less than or equal to 0.4Mpa, wherein the reaction time is 4-16 h;
s3, after the ring-opening etherification reaction is finished, continuously heating to 140-170 ℃, reacting unreacted phenolic hydroxyl groups in cyanuric acid with ethylene carbonate for 2-10 hours under normal pressure, and discharging carbon dioxide generated by the reaction into the atmosphere through a pressure regulating valve;
s4, after the reaction is finished, removing a small amount of unreacted complete ethylene carbonate and catalyst under the conditions that the degassing pressure is less than or equal to 100pa and the degassing temperature is 170 ℃, and obtaining a tri-hydroxyethyl isocyanurate product with the purity of more than or equal to 98.5% (LC) after the degassing time is 2h.
In the preparation method, the molar ratio of the cyanuric acid to the ethylene carbonate in the step S1 is 1:0.5-1.0; the catalyst is dimethylacetamide, the purity of the dimethylacetamide is more than or equal to 99.9 percent, and the dosage of the catalyst is 1 to 5 per mill of the sum of the masses of cyanuric acid, ethylene carbonate and ethylene oxide; in the step S2, the molar ratio of cyanuric acid to ethylene oxide is 1:2.05-2.55.
In the preparation method, the reaction temperature of the step S2 is controlled to be 80-100 ℃, so that the catalyst dimethylacetamide can only catalyze cyanuric acid to open loop ethylene oxide at the temperature, and cyanuric acid and ethylene carbonate basically do not react. This is mainly due to: the ethylene carbonate is of a five-membered ring structure, the ring tension energy is small, and the ring is not basically opened in the temperature range; the ethylene oxide is of a three-membered ring structure, the ring tension can be far higher than that of ethylene carbonate of a five-membered ring structure, and the catalyst dimethylacetamide can well catalyze cyanuric acid to open the ring of the ethylene oxide in the temperature range. That is, the reaction rate constant of dimethylacetamide for catalyzing cyanuric acid to open ring ethylene oxide is far greater than the reaction rate constant (k) for catalyzing cyanuric acid to open ring ethylene carbonate in the temperature range 1 >>k 2 )。
In the above, k 1 Represents the reaction rate constant of catalyzing cyanuric acid to open ring ethylene oxide with catalyst dimethylacetamide; k (k) 2 The reaction rate constant of the catalyst dimethylacetamide for catalyzing the ring-opening of vinyl carbonate cyanuric acid is shown.
The product prepared by the method has high purity and does not need crystallization. This is mainly due to: the ethylene carbonate is of a five-membered ring structure, the structure is stable, the dihydroxyethyl isocyanurate also contains an active hydrogen structure (R-N-H), and the dimethylacetamide can better catalyze the ring-opened ethylene carbonate; while tris (hydroxyethyl) isocyanurate contains only relatively inert alcoholic hydroxyl structures, dimethylacetamide is not able to catalyze its ring-opened ethylene carbonate effectively. That is, in the reaction stage of the step S2, the reaction rate constant of the dimethylacetamide catalyzed dihydroxyethyl isocyanurate ring-opening ethylene carbonate is far greaterReaction rate constant (k) of vinyl carbonate ring-opened with triethylol isocyanurate 3 >>k 3' )。
In the above, k 3 Represents the reaction rate constant of the catalyst dimethylacetamide for catalyzing the dihydroxyethyl isocyanurate to open the ring of ethylene carbonate; k (k) 3' The reaction rate constant of the catalyst dimethylacetamide for catalyzing the ring-opening ethylene carbonate of the tri-hydroxyethyl isocyanurate is shown.
The invention will be described in further detail with reference to the drawings and the specific examples.
Example 1
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 220g of ethylene carbonate and 2.84g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced with nitrogen 3 times, vacuum was applied, and after the autoclave was warmed to 70 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the pressure-resistant reaction kettle is increased to 95 ℃, 555g of ethylene oxide is introduced, the reaction is continued for about 2 hours after about 4 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the ring-opening etherification reaction is finished, continuously heating the reaction kettle to 160 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 4 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing is finished, the reaction kettle is cooled to 140 ℃ and discharged to obtain about 1303g of a tris (hydroxyethyl) isocyanurate product.
Example 2
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 264g of ethylene carbonate and 4.33g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced 3 times with nitrogen, vacuum was applied, and after the autoclave was warmed to 80 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 85 ℃, 535g of ethylene oxide is introduced, about 10 hours is completed, the reaction is continued for about 2 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the ring-opening etherification reaction is finished, continuously heating the reaction kettle to 150 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 7 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1305g of a tris (hydroxyethyl) isocyanurate product.
Example 3
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 308g of ethylene carbonate and 1.47g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced 3 times with nitrogen, vacuum was applied, and after the autoclave was warmed to 75 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 100 ℃, 515g of ethylene oxide is introduced, the reaction is continued for about 2 hours after about 2 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 170 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 2 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S4, after the reaction is finished, keeping the temperature of the reaction kettle at 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1302g of a tris (hydroxyethyl) isocyanurate product.
Example 4
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 352g of ethylene carbonate and 5.95g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced with nitrogen 3 times, vacuum was applied, and after the autoclave was warmed to 70 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 85 ℃, 489g of ethylene oxide is introduced, the reaction is continued for about 2 hours after about 10 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 145 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 5 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1302g of a tris (hydroxyethyl) isocyanurate product.
Example 5
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 396g of ethylene carbonate and 4.53g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced 3 times with nitrogen, vacuum was applied, and after the autoclave was warmed to 65 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 90 ℃, 469g of ethylene oxide is introduced, the reaction kettle is continuously reacted for about 2 hours after about 6 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 150 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 1 hour, the gas in the reaction kettle is not discharged any more, and the reaction is continued for one hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1305g of a tris (hydroxyethyl) isocyanurate product.
Example 6
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 440g of ethylene carbonate and 7.69g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced with nitrogen 3 times, vacuum was applied, and after the autoclave was warmed to 60 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 80 ℃, 451g of ethylene oxide is introduced, about 13 hours is completed, the reaction is continued for about 3 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 140 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 5 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1302g of a tris (hydroxyethyl) isocyanurate product.
Comparative example 1
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 264g of ethylene carbonate and 4.33g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced 3 times with nitrogen, vacuum was applied, and after the autoclave was warmed to 80 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 85 ℃, 535g of ethylene oxide is introduced, about 10 hours is completed, the reaction is continued for about 2 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 120 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system.
And S4, after the reaction is carried out for 8 hours, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 150℃and discharged to obtain about 1233g of a tris (hydroxyethyl) isocyanurate product.
Comparative example 2
A method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 352g of ethylene carbonate and 5.95g of catalyst triethylamine are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced with nitrogen 3 times, vacuum was applied, and after the autoclave was warmed to 70 ℃, stirring was started.
S2, after stirring for 30min, the temperature of the reaction kettle is increased to 85 ℃, 489g of ethylene oxide is introduced, the reaction is continued for about 2 hours after about 10 hours, and the pressure of the reaction kettle is unchanged.
And S3, after the reaction is finished, continuously heating the reaction kettle to 145 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 5 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for one hour.
And S4, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing. After the degassing is finished, the reaction kettle is cooled to 140 ℃ and discharged to obtain about 1304g of the tris (hydroxyethyl) isocyanurate product.
Comparative example 3:
a method for preparing tris (hydroxyethyl) isocyanurate, which comprises the following steps:
s1, 645g of cyanuric acid, 1338g of ethylene carbonate and 2.84g of catalyst dimethylacetamide are added into a 2.5L pressure-resistant reaction kettle, and an ethylene oxide metering tank is connected with the pressure kettle. Air was replaced with nitrogen 3 times, vacuum was applied, and after the autoclave was warmed to 70 ℃, stirring was started.
S2, stirring for 30min, and then raising the temperature of the pressure-resistant reaction kettle to 160 ℃. As the reaction proceeds, the autoclave pressure increases gradually. When the pressure of the pressure-resistant reaction kettle is slightly higher than 1 atmosphere, the gas outlet at the top of the reaction kettle is connected with the oil seal, and then the valve of the gas outlet at the top of the reaction kettle is slowly opened, so that the generated carbon dioxide is discharged from the reaction system. The reaction is carried out for 9 hours, the gas in the reaction kettle is not discharged any more, and the reaction is continued for 1 hour.
And S3, after the reaction is finished, continuously heating the reaction kettle to 170 ℃ and degassing for 2 hours. After the degassing was completed, the reaction vessel was cooled to 140℃and discharged to obtain about 1305g of a tris (hydroxyethyl) isocyanurate product.
The purity and acid value of the tris (hydroxyethyl) isocyanurate products prepared in examples 1 to 6 and comparative examples 1 to 2 were measured using Liquid Chromatography (LC), and the measurement results are shown in table 1 and fig. 1.
TABLE 1 detection data for the Trihydroxyethyl isocyanurate products prepared in examples 1 to 6 and comparative examples 1 to 2
| Project | Purity/% | Yield/% | Smell of |
| Example 1 | 99.2 | 91.7 | Substantially odorless |
| Example 2 | 99.3 | 90.3 | Substantially odorless |
| Example 3 | 99.0 | 88.6 | Substantially odorless |
| Example 4 | 98.7 | 87.6 | Substantially odorless |
| Example 5 | 98.9 | 86.4 | Substantially odorless |
| Example 6 | 99.1 | 84.7 | Substantially odorless |
| Comparative example 1 | 78.6 | 85.4 | Substantially odorless |
| Comparative example 2 | 99.1 | 87.8 | Obvious fishy smell |
| Comparative example 3 | 98.8 | 65.8 | Substantially odorless |
As can be seen from Table 1 and FIG. 1, the tris (hydroxyethyl) isocyanurate product prepared by the preparation method of the present invention has higher purity and weaker odor. Comparative example 1 has a lower reaction temperature (120 ℃) in step S3 than in example 2, at which the ring-opening speed of ethylene carbonate is slow and the reaction is incomplete, resulting in lower yield and product purity of comparative example 1. Comparative example 2 compared with example 4, the catalyst was replaced with triethylamine, the triethylamine was heavy in smell, and the very little residue left the material with fishy smell. Comparative example 3 uses cyanuric acid and ethylene carbonate alone as raw materials, as opposed to ethylene oxide. In the scheme of taking cyanuric acid and ethylene carbonate as raw materials, a large amount of carbon dioxide is generated, so the reaction yield is lower.
In summary, the preparation method of the invention adopts the reaction of ethylene carbonate and cyanuric acid under the catalysis of the catalyst dimethylacetamide, does not need to recover solvents and have simple crystallization process and simple working procedures, and can obtain the product of the triethylenetetracyanurate with no smell and high purity, thereby greatly widening the application range of the product.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. A preparation method of tris (hydroxyethyl) isocyanurate is characterized by comprising the following steps: the method comprises the following steps:
s1, adding cyanuric acid, a catalyst and ethylene carbonate into a reaction kettle, placing nitrogen, vacuumizing, heating and starting stirring;
s2, after the temperature of the reaction kettle is increased to 80-100 ℃, introducing ethylene oxide for ring-opening etherification reaction;
s3, after the ring-opening etherification reaction is finished, continuously heating to enable the unreacted phenolic hydroxyl in the cyanuric acid to react with the ethylene carbonate, and discharging carbon dioxide;
and S4, after the reaction is finished, removing a small amount of unreacted complete ethylene carbonate and catalyst to obtain the tri-hydroxyethyl isocyanurate product.
2. The method for preparing the tri-hydroxyethyl isocyanurate according to claim 1, wherein: the catalyst in the step S1 is dimethylacetamide.
3. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the dosage of the catalyst in the step S1 is 1 to 5 per mill of the sum of the masses of cyanuric acid, ethylene carbonate and ethylene oxide.
4. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the molar ratio of cyanuric acid to ethylene carbonate in the step S1 is 1:0.5-1.0.
5. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: in the step S1, the temperature is raised to 60-80 ℃ before stirring is started.
6. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the reaction pressure of the ring-opening etherification reaction in the step S2 is less than or equal to 0.4Mpa, and the reaction time is 4-16 h.
7. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the molar ratio of cyanuric acid to ethylene oxide in the step S2 is 1:2.05-2.55.
8. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the reaction temperature in the step S3 is 140-170 ℃ and the reaction time is 2-10 h.
9. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the conditions for removing a small amount of unreacted complete ethylene carbonate and catalyst in step S4 are: the degassing pressure is less than or equal to 100pa, the degassing temperature is 170 ℃, and the degassing time is 2 hours.
10. The method for producing a tris (hydroxyethyl) isocyanurate according to claim 1 or 2, characterized in that: the purity of the tri-hydroxyethyl isocyanurate prepared in the step S4 is more than or equal to 98.5 percent.
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