CN114149376B - Preparation method of tris (2-hydroxyethyl) isocyanurate - Google Patents
Preparation method of tris (2-hydroxyethyl) isocyanurate Download PDFInfo
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- CN114149376B CN114149376B CN202111265169.6A CN202111265169A CN114149376B CN 114149376 B CN114149376 B CN 114149376B CN 202111265169 A CN202111265169 A CN 202111265169A CN 114149376 B CN114149376 B CN 114149376B
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- hydroxyethyl
- isocyanurate
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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 35
- 238000002360 preparation method Methods 0.000 title abstract description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 24
- 239000012043 crude product Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KCOPAESEGCGTKM-UHFFFAOYSA-N 1,3-oxazol-4-one Chemical compound O=C1COC=N1 KCOPAESEGCGTKM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OKBVVJOGVLARMR-QSWIMTSFSA-N cefixime Chemical compound S1C(N)=NC(C(=N\OCC(O)=O)\C(=O)N[C@@H]2C(N3C(=C(C=C)CS[C@@H]32)C(O)=O)=O)=C1 OKBVVJOGVLARMR-QSWIMTSFSA-N 0.000 description 1
- 229960002129 cefixime Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- B01J35/19—
Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps: reacting cyanuric acid with ethylene oxide in the presence of a catalyst I, a catalyst II and a solvent to obtain the tri (2-hydroxyethyl) isocyanurate; one of the key catalysts is a kind of "hard acid" (soft and hard acid base theory), and the addition amount is 0-3% of the mass of cyanuric acid. The preparation method provided by the invention can greatly weaken the polymerization side reaction participated by EO, and greatly improve the product yield and purity.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of tris (2-hydroxyethyl) isocyanurate.
Background
Tris (2-hydroxyethyl) isocyanurate (trade name: siek) is a trifunctional reactive small organic molecule which is useful as an intermediate in the synthesis of coatings, plasticizers, flame retardants, curing agents, pharmaceutical and agrochemical intermediates.
The early synthesis of Siek from cyanuric acid and Ethylene Oxide (EO) was reported by Allid, america, and the reaction equation is shown below, cyanuric acid loses proton under the action of alkaline catalyst to form N anion, and the product is obtained by attacking ethylene oxide. The side reaction is the decomposition product of the cefixime in an alkaline high-temperature system, namely 2-oxazolinone, EO self-polymerization, the oligomer formed by further polymerizing the product and EO, and the oligomer of the solvent and EO (when alcohol ether solvent is used as a reaction solvent). Therefore, the choice of the reaction solvent type and catalyst has a great influence on the product yield and purity.
In the existing Saike synthesis process, N-Dimethylformamide (DMF) is mostly adopted as a reaction solvent, no catalyst or inorganic strong base such as NaOH is additionally added as a catalyst, and the yield of the pure product (the quantitative analysis yield of high performance liquid chromatography) is about 70-80%. The EO self-polymerization can be initiated by alkaline substances generated by DMF self-decomposition, so that the yield is unstable, the process batch stability is poor, and the operation window is narrow. Researchers also adopt alcohol ether solvents such as ethylene glycol monomethyl ether and the like, the pure product yield is 70-85%, the yield is 82% in an acetone-water solvent system, when the alcohol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol, methanol, ethanol and the like are adopted as reaction solvents through detection analysis, oligomers formed by ring opening of alcohol ether and EO are detected in the system, so that the yield of the system is generally lower than that of a DMF system, and a large amount of polyether byproducts in the system influence the purity of the product, so that a fine purification process is needed to obtain high-purity Saik.
Therefore, how to control the side reaction, especially the polymerization process involving EO, and to improve the yield and purity of the product becomes a great difficulty.
Disclosure of Invention
The invention aims to provide a method for synthesizing tris (2-hydroxyethyl) isocyanurate, which can greatly weaken the polymerization side reaction participated by EO, so that the reaction yield is increased to be more than 90%, and the purity of a crude product is more than 90% (high performance liquid HPLC purity). The high crude product yield and purity greatly simplify the subsequent purification process and reduce the production cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
and (3) reacting cyanuric acid with ethylene oxide in the presence of a catalyst I, a catalyst II and a solvent to obtain the tri (2-hydroxyethyl) isocyanurate.
Preferably, the preparation method of the tri (2-hydroxyethyl) isocyanurate comprises the following steps:
mixing cyanuric acid, a catalyst I, a catalyst II and a solvent, heating, and then introducing ethylene oxide into the mixed solution for reaction to obtain the tri (2-hydroxyethyl) isocyanurate.
The catalyst I is selected from pyridine, triethylamine, dimethylamine, 1, 8-diazabicyclo [5.4.0 ]]Undec-7-ene (abbreviated DBU), na 2 CO 3 、NaHCO 3 、Li 2 CO 3 、LiCl、Cs 2 CO 3 One or more of CsF, naF, KF;
the catalyst II is a kind of hard acid (DOI: 10.1021/ja00905a 001) and is selected from one or more of boron trifluoride, trimethylchlorosilane and titanium tetrachloride;
the solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, methanol, ethanol, ethylene glycol monomethyl ether and water.
The addition amount of the catalyst I is 0.5-3% of the mass of cyanuric acid, preferably 0.5-1.5%; the addition amount of the catalyst II is 0-3% of the mass of cyanuric acid, preferably 0.1-1.5%; the addition amount of the solvent is 2-8 times, preferably 3-5 times, the mass of cyanuric acid; the usage amount of the ethylene oxide is 1.05-5 times of the mass of the cyanuric acid.
The reaction temperature is 64-140 ℃, preferably 100-120 ℃, the reaction time is not particularly limited, the specific reaction time can be determined according to monitoring, and the reaction time is optionally 0.5-3h.
The invention has the beneficial effects that:
according to the preparation method of the tri (2-hydroxyethyl) isocyanurate, provided by the invention, through the combination selection of the solvent and the two different types of catalysts added into a reaction system, particularly the addition of the catalyst II, the polymerization side reaction participated by EO can be greatly weakened, the product yield and purity can be greatly improved, the crude product yield can be improved to more than 90%, the purity of the purified product can be up to more than 90% (high performance liquid HPLC purity) without recrystallization, if the total yield of the further purified refined product of the product can still be up to more than 80%, the subsequent purification process is greatly simplified by the high reaction yield and the crude product purity, the production cost is reduced, and the specific requirements in the downstream high-end application scene are met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a liquid chromatogram of the wet crude product of example 1;
FIG. 2 is a liquid chromatogram of the product obtained after filtration and drying in example 1.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or instruments used are conventional chemical products which are commercially available without identifying manufacturers.
Example 1
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
412g of N, N-dimethylacetamide, 100g of cyanuric acid (purity 98%), 0.5g of dimethylamine and 1.2g of BF 3 ·Et 2 O(BF 3 46.5wt percent of the total weight of the catalyst is added into a 3L reaction kettle, the temperature is raised to 110 ℃, then 108g of ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to be 110 ℃, the reaction time is 2 hours, the reaction liquid is cooled to 30 ℃ after the reaction is finished, and N, N-dimethylacetamide is removed by reduced pressure distillation, so as to obtain 257g of wet crude tri (2-hydroxyethyl) isocyanurate; then 500mL of acetone was added to the wet crude, stirred at room temperature for 0.5 hours, and then filtered and dried186g of tris (2-hydroxyethyl) isocyanurate was obtained in 92% yield, and the tris (2-hydroxyethyl) isocyanurate product was analyzed by high performance liquid chromatography to have a purity of 94%.
Example 2
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
380g pyridine and 100g cyanuric acid (purity 98%) are added into a 3L reaction kettle, the temperature is raised to 110 ℃, 115g ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to be 110 ℃, the reaction time is 2.5h, the reaction liquid is cooled to 35 ℃ after the reaction is finished, pyridine is removed by reduced pressure distillation, 264g of a wet crude product of tri (2-hydroxyethyl) isocyanurate is obtained, 500mL of acetone is added into the wet crude product, the mixture is stirred for 0.5h at room temperature, 192g of tri (2-hydroxyethyl) isocyanurate is obtained by filtration and drying, the yield is 95%, and the purity of the tri (2-hydroxyethyl) isocyanurate product is 90% by high performance liquid chromatography analysis.
Example 3
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
2027g N-methylpyrrolidone, 1006g cyanuric acid (98% purity), 5g Cs 2 CO 3 And 6g BF 3 ·Et 2 O(BF 3 46.5wt percent of the total content of the three-in-one catalyst is added into a 20L reaction kettle, the temperature is raised to 110 ℃, 1091g of ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to be 110 ℃, the reaction time is 1.5h, the reaction liquid is cooled to 40 ℃ after the reaction is finished, the reaction liquid is discharged into 50L three-in-one equipment, 8580g of acetonitrile is added, the reaction liquid is stirred at 60 ℃ for 0.5h and then cooled to 10 ℃, 1927g of tris (2-hydroxyethyl) isocyanurate is obtained by filtering and drying in the three-in-one equipment, the yield is 95%, and the purity of the tris (2-hydroxyethyl) isocyanurate product is 93 percent by high performance liquid chromatography analysis.
Example 4
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
adding 412g of N, N-dimethylacetamide, 100g of cyanuric acid (purity is 98%), and 0.5g of dimethylamine into a 3L reaction kettle, heating to 110 ℃, pumping 108g of ethylene oxide by a feed pump for reaction, controlling the reaction temperature to 110 ℃, controlling the reaction time to 2 hours, cooling the reaction solution to 30 ℃ after the reaction is finished, and distilling under reduced pressure to remove the N, N-dimethylacetamide to obtain a wet crude product of the tri (2-hydroxyethyl) isocyanurate; then, 500mL of acetone was added to the wet crude product, stirred at room temperature for 0.5 hour, and then filtered and dried to obtain 155g of tris (2-hydroxyethyl) isocyanurate, the yield was 77%, and the tris (2-hydroxyethyl) isocyanurate product was analyzed to have a purity of 84% by high performance liquid chromatography.
Example 5
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
charging 412g of N, N-dimethylacetamide, 100g of cyanuric acid (purity is 98%), 0.5g of dimethylamine and 0.89g of trimethylchlorosilane into a 3L reaction kettle, heating to 110 ℃, pumping 108g of ethylene oxide by a charging pump for reaction, controlling the reaction temperature to 110 ℃ and the reaction time to 3h, cooling the reaction solution to 30 ℃ after the reaction is finished, and distilling under reduced pressure to remove the N, N-dimethylacetamide to obtain a wet crude product of tris (2-hydroxyethyl) isocyanurate; then, 500mL of acetone was added to the wet crude product, stirred at room temperature for 0.5 hour, and then filtered and dried to obtain 190g of tris (2-hydroxyethyl) isocyanurate, the yield was 94%, and the tris (2-hydroxyethyl) isocyanurate product was analyzed by high performance liquid chromatography to have a purity of 91%.
Example 6
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
200g of N, N-dimethylformamide, 104g of cyanuric acid (purity 98%), 2.9g of triethylamine and 0.21g of BF 3 ·Et 2 O(BF 3 46.5wt percent of the total weight of the catalyst is added into a 3L reaction kettle, the temperature is raised to 95 ℃, then 110g of ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to 95 ℃, the reaction time is 1h, after the reaction is finished, the reaction liquid is cooled to 30 ℃, and N, N-dimethylformamide is removed by reduced pressure distillation, so that a wet crude product of tris (2-hydroxyethyl) isocyanurate is obtained; then 300mL of acetone was added to the wet crude, stirred at room temperature for 0.5 hours, and filteredDrying to obtain 183g of tri (2-hydroxyethyl) isocyanurate with the yield of 90%, and analyzing the tri (2-hydroxyethyl) isocyanurate product by high performance liquid chromatography to obtain the product with the purity of 91%.
Example 7
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
394g of water, 100g of cyanuric acid (purity 98%), 1.45g of sodium carbonate and 3.16g of BF 3 ·Et 2 O(BF 3 46.5wt percent of the total weight of the three-2-hydroxyethyl isocyanurate is added into a 3L reaction kettle, the temperature is raised to 100 ℃, then 110g of ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to be 100 ℃, the reaction time is 1h, the reaction liquid is cooled to 40 ℃ after the reaction is finished, and water is removed by reduced pressure distillation, so that a wet crude product of the three-2-hydroxyethyl isocyanurate is obtained; then 500mL of acetone was added to the wet crude product, stirred at room temperature for 0.5 hour, and then the mixture was filtered and dried to obtain 198g of tris (2-hydroxyethyl) isocyanurate, the yield was 98%, and the tris (2-hydroxyethyl) isocyanurate product was analyzed by high performance liquid chromatography to have a purity of 91%.
Example 8
The embodiment provides a preparation method of tris (2-hydroxyethyl) isocyanurate, which comprises the following steps:
432g of methanol, 101g of cyanuric acid (purity 98%), 0.7g of KF and 1.2g of BF were reacted 3 ·Et 2 O(BF 3 46.5wt percent of the content is added into a 10L reaction kettle, the temperature is raised to 64 ℃, 112g of ethylene oxide is pumped into the reaction kettle by a feed pump for reaction, the reaction temperature is controlled to be 64 ℃, the reaction time is 0.5h, the reaction liquid is cooled to 10 ℃ after the reaction is finished, 187g of wet crude tri (2-hydroxyethyl) isocyanurate product is obtained through filtration and drying, the yield is 93%, and the purity of the tri (2-hydroxyethyl) isocyanurate product is 97 percent through high performance liquid chromatography analysis.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. A method for preparing tris (2-hydroxyethyl) isocyanurate, which is characterized by comprising the following steps:
reacting cyanuric acid with ethylene oxide in the presence of a catalyst I, a catalyst II and a solvent to obtain the tri (2-hydroxyethyl) isocyanurate;
the catalyst I is selected from dimethylamine, na 2 CO 3 、Li 2 CO 3 、Cs 2 CO 3 One or more of CsF, naF, KF;
the catalyst II is selected from one or more of boron trifluoride and trimethylchlorosilane.
2. The method for preparing tris (2-hydroxyethyl) isocyanurate according to claim 1, wherein the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, methanol, ethanol, ethylene glycol monomethyl ether, and water.
3. The method for preparing tris (2-hydroxyethyl) isocyanurate according to claim 1, wherein the addition amount of the catalyst I is 0.5-3% of the mass of cyanuric acid; the addition amount of the catalyst II is 0.1-1.5% of the mass of cyanuric acid; the addition amount of the solvent is 2-8 times of the mass of cyanuric acid.
4. The method for preparing tris (2-hydroxyethyl) isocyanurate according to claim 3, wherein the catalyst I is added in an amount of 0.5 to 1.5% by mass of cyanuric acid.
5. A method for preparing tris (2-hydroxyethyl) isocyanurate according to claim 3, wherein the solvent is added in an amount 3 to 5 times the mass of cyanuric acid.
6. The method for producing tris (2-hydroxyethyl) isocyanurate according to claim 1, wherein the reaction temperature is 64 to 140 ℃.
7. The method for producing tris (2-hydroxyethyl) isocyanurate according to claim 6, wherein the reaction temperature is 100 to 120 ℃.
8. The method for producing tris (2-hydroxyethyl) isocyanurate according to claim 1, wherein the amount of ethylene oxide is 1.05 to 5 times by mass as much as cyanuric acid.
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