CN115785011A - Bromo-triazine and preparation method thereof - Google Patents
Bromo-triazine and preparation method thereof Download PDFInfo
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- CN115785011A CN115785011A CN202310070014.XA CN202310070014A CN115785011A CN 115785011 A CN115785011 A CN 115785011A CN 202310070014 A CN202310070014 A CN 202310070014A CN 115785011 A CN115785011 A CN 115785011A
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- CTMFECUQKLSOGJ-UHFFFAOYSA-N 4-bromotriazine Chemical compound BrC1=CC=NN=N1 CTMFECUQKLSOGJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 91
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 69
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 35
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims abstract description 21
- 239000002585 base Substances 0.000 claims abstract description 15
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 99
- 239000000243 solution Substances 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000003918 triazines Chemical class 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VPGDQIZKDYWQPS-UHFFFAOYSA-N sodium;2,3,4-tribromophenol Chemical compound [Na].OC1=CC=C(Br)C(Br)=C1Br VPGDQIZKDYWQPS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 description 1
- ZITDOJMAOFWSQI-UHFFFAOYSA-N 4-(2,3,4-tribromophenoxy)triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=CC=NN=N1 ZITDOJMAOFWSQI-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides bromotriazine and a preparation method thereof, and relates to the technical field of chemical synthesis. The preparation method comprises the following steps: step one, adding tribromophenol into an organic solvent for dissolving, then adding strong base, controlling the pH value before adding cyanuric chloride to obtain a first mixed solution, cooling to 5-15 ℃, and then adding triethylamine, DMAP composite catalyst and cyanuric chloride into the first mixed solution to obtain a second mixed solution; and (3) heating the second mixed solution to over 38 ℃ for reaction, controlling the pH after the cyanuric chloride is added in the reaction process, adjusting the pH to over 12 after the reaction is finished, and separating out an organic phase. And step two, sequentially carrying out alkali washing, acid washing, crystallization and drying on the organic phase to obtain the bromotriazine solid. The invention further improves the purity and yield of the product by controlling the pH value. The purity of the bromotriazine prepared by the invention is not lower than 99 percent, and the yield is not lower than 97.5 percent.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to bromotriazine and a preparation method of the bromotriazine.
Background
The brominated triazine is also called tris (tribromophenoxy) triazine, is a novel flame retardant with bromine/nitrogen synergy, overcomes the defects of poor light resistance, easy color change and the like of tetrabromo and decabromo, is an upgraded substitute product of tetrabromo and decabromo, is a novel product specially developed for flame-retardant ABS, PBT, PC/ABS, HIPS and the like, and has good thermal stability, light resistance and electrical properties. The engineering plastic containing the product can be used for various injection molding and extrusion occasions and can meet various processing requirements.
The existing preparation method of the bromotriazine comprises the steps of adjusting the pH value of a tribromophenol solution to 11-13 by using a sodium hydroxide solution, adding a catalyst, adding cyanuric chloride at one time, and reacting for a period of time to generate a bromotriazine solution. The initial pH of the process is higher, cyanuric chloride is easy to hydrolyze under alkaline conditions, and the higher the pH is, the faster the cyanuric chloride is decomposed, so that the generated bromotriazine product has more impurities, the product yield is reduced, the tribromophenol conversion rate is low, and the raw material waste is caused.
The relevant reaction principle is as follows:
the patent with the publication number of CN113214175A and the publication number of 2021.05.10 takes 2,4,6-tribromophenol as a raw material and triethylamine as a catalyst for use, 2,4,6-tribromophenol and triethylamine are added into chlorobenzene at a constant speed for a dissolution reaction, cyanuric chloride and liquid alkali are uniformly added into a mixed solution and stirred for a condensation reaction, the mixed solution after the reaction is completed is added into a crystallization kettle, an entrainer is added for an azeotropic crystallization reaction, and then alkali washing, water washing and drying are carried out to obtain tribromophenoxytriazine.
The publication No. CN114349716A discloses a patent of 2022.04.15, phenol and an organic solvent are added into a reaction kettle, and then bromine and hydrogen peroxide are added to prepare an intermediate tribromophenol; the bromotriazine is prepared by catalyzing tribromophenol to react with cyanuric chloride under alkaline conditions by using a compound catalyst. And the pH is not detected in real time, and strong base is continuously used for adjusting the pH according to the change of the pH in the reaction process, so that the hydrolysis of cyanuric chloride is reduced, and the reaction efficiency is improved.
Disclosure of Invention
The inventor researches and discovers that: by analyzing the characteristic of easy decomposition of cyanuric chloride under alkaline conditions, the overall pH value of the reaction process is controlled to be 8.5-10, and meanwhile, by using a pH online detection technology, the pH value of the reaction stage is controlled in real time, and by controlling the pH value, the hydrolysis of cyanuric chloride is reduced, the reaction process is not influenced, and the purity and yield of the final product are improved. Meanwhile, the utilization rate of tribromophenol is improved, and the waste of raw materials is reduced.
The invention provides a preparation method of brominated triazine, which comprises the following steps:
step one, adding tribromophenol into an organic solvent for dissolving, then adding strong base, controlling the pH value before adding cyanuric chloride to obtain a first mixed solution, cooling to 5-15 ℃, and then adding triethylamine, DMAP composite catalyst and cyanuric chloride into the first mixed solution to obtain a second mixed solution; and (3) heating the second mixed solution added with the cyanuric chloride to over 38 ℃ for reaction, controlling the pH value after the cyanuric chloride is added in the reaction process, adjusting the pH value to over 12 after the reaction is finished, and separating out an organic phase.
And step two, sequentially carrying out alkali washing, acid washing, crystallization and drying on the organic phase to obtain the bromotriazine solid.
Wherein the pH value before cyanuric chloride is controlled to be less than or equal to 10 and more than 8 after cyanuric chloride is added, and the molar ratio of tribromophenol to strong base is 1:0.9 to 1.1, wherein the addition amount of the catalyst is 0.5 to 1 percent of the addition mass of tribromophenol, and the mass ratio of triethylamine to DMAP is 1:0.5 to 2, wherein the molar ratio of the cyanuric chloride to the tribromophenol is 1:2.8 to 3.2.
On the other hand, the invention provides the brominated triazine, which is prepared by the method, wherein the purity of the brominated triazine is not lower than 99%, and the yield is not lower than 95%.
Due to the adoption of the technical scheme, the invention at least obtains one of the following beneficial effects:
(1) Compared with the prior art, the invention uniformly controls the pH of the whole reaction to be 8.5 to 10. Because cyanuric chloride hydrolyzes under alkaline conditions, the more alkaline the hydrolysis is greater. The pH value of the solution is controlled to be 8.5 to 10 before cyanuric chloride is added in real time, and the pH value of the solution is controlled to be 9 to 10 after cyanuric chloride is added, so that the hydrolysis of cyanuric chloride is reduced, and the reaction process is not influenced.
(2) The invention further improves the purity and yield of the product by controlling the pH value. The purity of the bromotriazine prepared by the invention is not lower than 99 percent, and the yield is not lower than 97.5 percent.
(3) The method reduces cyanuric chloride hydrolysis, improves the utilization rate of tribromophenol, reduces raw material waste and saves cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a liquid chromatogram of the bromotriazine product of example 1;
FIG. 2 shows a liquid chromatogram of the brominated triazine product of comparative example 1;
figure 3 shows a liquid chromatogram of the brominated triazine product of comparative example 3.
Detailed Description
In order to more clearly explain the overall concept of the invention, the following detailed description is given by way of example in conjunction with the accompanying drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
In addition, in the description of the present invention, it is to be understood that the terms "top," "bottom," "inner," "outer," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present invention and simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated, and thus are not to be construed as limiting the present invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; the connection can be mechanical connection, electrical connection or communication; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In one exemplary embodiment of the present invention, the method of preparing bromotriazine comprises the steps of:
step one, adding tribromophenol into an organic solvent for dissolving at the temperature of 25-35 ℃, then adding strong base, and controlling the pH value before adding cyanuric chloride to be 8.5-10 to obtain a first mixed solution. The strong base can be sodium hydroxide solution with solute mass fraction of 10% or sodium hydroxide solid powder; the organic solvent may be dichloromethane. However, the present invention is not limited thereto. The solubility of tribromophenol in the solvent is greatly influenced by temperature, and the lower the temperature, the lower the solubility, so the temperature is controlled to be above 25 ℃, meanwhile, if dichloromethane is used as the organic solvent, the boiling point is 40 ℃, and when strong base is added, the reaction of the strong base and tribromophenol can release heat, so the temperature is controlled to be below 35 ℃. In addition, before adding cyanuric chloride, the pH is controlled to be 8.5 to 10, preferably 8.7 to 9.2, and the purpose of controlling the pH before adding the cyanuric chloride is to provide a proper alkaline condition for adding the cyanuric chloride later, if the pH is higher, the decomposition of the cyanuric chloride is faster, so that the product impurities are increased, the product yield is reduced, and the conversion rate of tribromophenol is low.
And then cooling to 5 to 15 ℃, and adding triethylamine, DMAP composite catalyst and cyanuric chloride into the first mixed solution to obtain a second mixed solution. For example, an ice water bath may be used for cooling. However, the present invention is not limited thereto. Because cyanuric chloride is easy to hydrolyze, the hydrolysis speed of cyanuric chloride can be reduced by reducing the temperature, the temperature range comprehensively considers the energy consumption and the indexes of the bromotriazine product, and the beneficial effect brought by continuously reducing the temperature in the temperature range is not obvious.
And (3) heating the second mixed solution to over 38 ℃, preferably 38 to 42 ℃, reacting for 1 to 3 hours, and controlling the pH value after cyanuric chloride is added to be 9 to 10 by dropwise adding strong base in the reaction process. Preferably, the pH after the cyanuric chloride is added is controlled to be 9.2 to 9.6. According to reaction research, the inventor finds that the first chlorine of cyanuric chloride reacts with tribromophenol faster, and the temperature rise process stage is basically completed, but the 2 nd and 3 rd chlorine in cyanuric chloride react relatively slower, and the temperature rise can improve the reaction rate, and then the highest temperature of the temperature rise is properly controlled according to the boiling point temperature of a solvent. For example, when methylene chloride, a solvent, is used for the reaction, the boiling point is about 40 ℃ and the temperature exceeds the boiling point of the solvent, so that the solvent loss increases. After the reaction, the pH was adjusted to 12 or more, and the organic phase was separated. The purpose of the pH adjustment to above 12 is to convert unreacted tribromophenol to tribromophenate, which is dissolved in the aqueous phase, to facilitate separation of the desired organic phase and ensure product purity.
Wherein, the pH can be controlled by adopting an online pH monitor, for example, in the reaction process, 0.2 to 1g of 10 percent sodium hydroxide solution is added every 5 to 12 minutes, and the pH is detected at any time. The hydrolysis speed of the cyanuric chloride is gradually increased along with the increase of the pH value in the system, and the cyanuric chloride is hydrolyzed more quickly when the pH value is larger. When the pH is lower, the ratio of tribromophenol to tribromophenate is insufficient, cyanuric chloride hydrolysis is relatively less, but the purity of the product is lower due to the insufficiency of tribromophenate, which is mainly characterized in that the impurity before the main peak of liquid chromatography is larger; when the pH value is higher, tribromophenol is completely converted into tribromophenate, cyanuric chloride is hydrolyzed relatively more, and cyanuric chloride is hydrolyzed more, so that the product purity is lower, and the impurities are larger after the main peak of liquid chromatography. In order to ensure that the prepared bromotriazine has higher purity and yield. In the application, the pH value before adding the cyanuric chloride is controlled to be less than or equal to the pH value after adding the cyanuric chloride is controlled to be less than or equal to 10 and more than 8. For example, in the present application, the pH before adding cyanuric chloride may be controlled to be from 8.3 to 10, and the pH after adding cyanuric chloride may be controlled to be from 9 to 10.
Wherein the molar ratio of tribromophenol to strong base is 1:0.7 to 1.3, wherein the adding amount of the catalyst is 0.5 to 1 percent of the adding mass of tribromophenol, and the mass ratio of triethylamine to DMAP is 1:0.5 to 2. Compared with a single catalyst, the triethylamine and DMAP composite catalyst is adopted in the catalyst, and the reaction time can be shortened by 35-50% by the composite catalyst. The molar ratio of the cyanuric chloride to the tribromophenol is 1:2.8 to 3.4. Preferably, the molar ratio of tribromophenol to strong base is 1: 0.9-1.1, wherein the addition amount of the catalyst is 0.6-0.9% of the addition mass of tribromophenol, and the mass ratio of triethylamine to DMAP is 1:0.8 to 1.5, wherein the molar ratio of the cyanuric chloride to the tribromophenol is 1:3 to 3.2.
And step two, sequentially carrying out alkali washing, acid washing, crystallization and drying on the organic phase to obtain the bromotriazine. The purpose of the alkaline washing is to further remove tribromophenol from the feed solution. The purpose of the acid washing is to convert the remaining catalyst triethylamine into water-soluble triethylamine hydrochloride for removal.
The specific preparation method of the brominated triazine can refer to the following steps:
step one, a reaction stage.
Adding tribromophenol into an organic solvent for dissolution reaction, heating and stirring while adding raw materials, wherein the heating temperature is 25-35 ℃, stirring at the speed of 200-300r/min for 10-15min to fully dissolve the raw materials, and adding deionized water and strong base into a synthesis kettle. The molar ratio of tribromophenol to strong base is 1:0.9 to 1.1, controlling the pH value of the solution to be 8.5 to 10 before adding cyanuric chloride, and stirring for 10 minutes to obtain a first mixed solution. Cooling to 5-15 ℃, adding a triethylamine and DMAP composite catalyst into the first mixed solution, wherein the adding amount of the catalyst is 0.5-1% of tribromophenol, and the mass ratio of triethylamine to 4-dimethylaminopyridine (DMAP for short) in the catalyst is 1: and (3) continuing stirring for 0.5 to 2, and adding cyanuric chloride to obtain a second mixed solution. The molar ratio of cyanuric chloride to tribromophenol is 1:2.8 to 3.2, heating the second mixed solution to 38 to 42 ℃, reacting 1~3 hours, adjusting the pH of a reaction system by using alkali liquor in the reaction process, controlling the pH after cyanuric chloride is added to be 9 to 10, adjusting the pH of feed liquid to be more than 12 after the reaction is finished, converting unreacted tribromophenol into tribromophenol sodium, dissolving the tribromophenol sodium in a water phase, and stirring for 10 minutes. Transferring the feed liquid into a separating funnel, standing and layering.
And step two, washing and purifying.
Transferring the lower-layer feed liquid after standing and layering into a flask, simultaneously adding a 1-5% sodium hydroxide solution, carrying out alkali washing on the feed liquid, further removing tribromophenol in the feed liquid, separating out the lower-layer feed liquid after washing is finished, and continuously carrying out acid washing, wherein the concentration of the used hydrochloric acid is 5-15%, and converting a catalyst triethylamine in the feed liquid into water-soluble triethylamine hydrochloride.
Step three, crystallization and separation.
The method comprises the following steps: and (3) adding the washed bromotriazine solution in the step two into a flask, adding deionized water into the flask, heating by using an electric heating sleeve, and heating to 70-90 ℃. The method firstly requires that the water temperature is higher than the boiling point of the solvent, the separation rate of the solvent is higher as the temperature difference higher than the boiling point of the solvent is larger, according to experimental experience, the solvent can be quickly evaporated when the water temperature is higher than or equal to 70 ℃, meanwhile, the temperature of evaporated solvent steam is higher as the water temperature is higher, the cold quantity required for condensing and recycling the solvent is increased, the water temperature is controlled to be 70-90 ℃ through the comprehensive consideration of distillation efficiency and energy consumption, the solvent is completely evaporated, then, the feed liquid is subjected to suction filtration, and the brominated triazine wet material obtained by suction filtration is put into an oven at the temperature of 105-125 ℃. The temperature of the oven is higher than the boiling point of water, the melting point of the bromotriazine is 227 ℃, and the temperature of the oven is comprehensively considered to be 105-125 ℃. Drying to obtain the brominated triazine product.
The second method comprises the following steps: and (2) adding deionized water into the flask, heating to 70-90 ℃, adding the washed bromotriazine solution obtained in the step two into the flask in a dropwise adding manner, keeping the temperature in the flask at 70-90 ℃ in the dropwise adding process, carrying out suction filtration on the feed liquid after the dropwise adding is finished, and drying the wet bromotriazine material in an oven to obtain a bromotriazine product.
Example 1
The pH =9 before cyanuric chloride addition and =9 after cyanuric chloride addition were controlled.
At 28 ℃, 135g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring for dissolution, 170g of 10% sodium hydroxide solution is added, then 10% sodium hydroxide solution is used for adjusting the pH value, the pH value is adjusted to 9, the solution is cooled to 10 ℃ by using an ice water bath, 0.5g of triethylamine and 0.5g of DMAP0.5g are added, the water bath is removed, and 25g of cyanuric chloride is added into the solution. After the cyanuric chloride is added, the temperature is raised to 40 ℃ for reaction for 1 hour, the pH of the feed liquid is monitored by using a pH meter in the reaction process, the pH =9 of the feed liquid is always kept, more than 10g of 10% sodium hydroxide solution is added into the feed liquid after the reaction is finished, and the pH of the feed liquid is more than or equal to 12; then, the organic phase is separated into four flasks by a separating funnel, then sodium hydroxide solution with the solute mass fraction of 3% is subjected to alkali washing, hydrochloric acid with the solute mass fraction of 8% is subjected to acid washing in sequence, and after washing is finished, the solvent in the organic phase is evaporated at 75 ℃ and dried to obtain the solid bromotriazine product.
The bromotriazine prepared in example 1 is white powder, and as shown in a liquid chromatogram in reference to fig. 1, the purity is 99%, and the yield is 97.5%.
Example 2
Based on example 1, with the difference that the mass ratio of triethylamine to DMAP is 1:1.6, controlling the pH =9 before adding cyanuric chloride and the pH =10 after adding cyanuric chloride.
135g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring at 28 ℃ to be dissolved, 170g of 10% sodium hydroxide solution is added, then 10% sodium hydroxide solution is used for adjusting the pH value to 9, the solution is cooled to 10 ℃ by using an ice water bath, 0.5g of triethylamine and 0.8g of DMAP0.8g are added, the water bath is removed, and 25g of cyanuric chloride is added into the solution. After the cyanuric chloride is added, adjusting the pH value of the feed liquid to 10, then heating to 40 ℃ for reaction for 1 hour, monitoring the pH value of the feed liquid by using a pH meter in the reaction process, supplementing 10% sodium hydroxide solution, always keeping the pH value of the feed liquid =10, and after the reaction is finished, dropwise adding more than 10g of 10% sodium hydroxide solution into the feed liquid, wherein the pH value of the feed liquid is more than or equal to 12; then, the organic phase is separated into a four-neck flask by using a separating funnel, then alkaline washing is carried out on a sodium hydroxide solution with the solute mass fraction of 3% and hydrochloric acid washing is carried out on the solute mass fraction of 8% in sequence, and after the washing is finished, the solvent in the organic phase is evaporated out at 75 ℃ and dried to obtain the solid bromotriazine product.
The bromotriazine prepared in example 2 was a white powder with a purity of 99.3% and a yield of 97.8%.
Example 3
Based on example 1, the difference is that the molar ratio of cyanuric chloride to tribromophenol is 1:2.9, pH =9 before cyanuric chloride addition and pH =9.5 after cyanuric chloride addition were controlled.
At 28 ℃, 130g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring for dissolution, 170g of 10% sodium hydroxide solution is added, then the pH value is adjusted by 10% sodium hydroxide solution, the pH value is adjusted to 9, the solution is cooled to 10 ℃ by using an ice water bath, 0.5g of triethylamine and 0.5g of DMAP0.5g are added, the water bath is removed, and 25g of cyanuric chloride is added into the solution. After the cyanuric chloride is added, adjusting the pH value of the feed liquid to 9.5, then heating to 40 ℃ for reaction for 1 hour, monitoring the pH value of the feed liquid by using a pH meter in the reaction process, supplementing 10% sodium hydroxide solution, and keeping the pH value of the feed liquid to be =9.5 all the time, after the reaction is finished, adding more than 10g of 10% sodium hydroxide solution into the feed liquid, wherein the pH value of the feed liquid is more than or equal to 12; then, the organic phase is separated into a four-neck flask by using a separating funnel, then alkaline washing is carried out on a sodium hydroxide solution with the solute mass fraction of 3% and hydrochloric acid washing is carried out on the solute mass fraction of 8% in sequence, and after the washing is finished, the solvent in the organic phase is evaporated out at 75 ℃ and dried to obtain the solid bromotriazine product.
The bromotriazine prepared in example 3 was a white powder with a purity of 99.1% and a yield of 97.6%.
Comparative example 1
On the basis of example 1, the difference is that the pH =12 before cyanuric chloride addition and the pH =12 after cyanuric chloride addition is controlled.
135g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring for dissolution, 170g of 10% sodium hydroxide solution is added, then 10% alkali liquor is used for regulating the pH value, the pH value is controlled to be 12, the solution is cooled to 15 ℃ by using ice water bath, 0.5g of triethylamine and 0.5g of DMAP0.5g are added, the water bath is removed, and 25g of cyanuric chloride is added into the solution at one time. After the cyanuric chloride is added, the temperature is raised to 40 ℃ for reaction for 1 hour, the pH value is controlled to be 12, after the reaction is finished, more than 10g of 10 percent sodium hydroxide solution is added into the feed liquid, and the pH value of the feed liquid is more than or equal to 12; and (2) dividing the organic phase into four-neck flasks by using a separating funnel, sequentially carrying out alkaline washing on a sodium hydroxide solution with the solute mass fraction of 3% and hydrochloric acid washing on the solute mass fraction of 8%, and evaporating and drying the solvent in the organic phase at 75 ℃ after washing to obtain a solid bromotriazine product.
The brominated triazine prepared in comparative example 1 was a white powder, as shown in FIG. 2, having a purity of 97.4% and a yield of 90.5%.
Comparative example 2
The difference is that 160g of 10% sodium hydroxide solution is added after the tribromophenol is dissolved, the pH =8 before cyanuric chloride is added and the pH =12 after cyanuric chloride is added, based on example 1.
135g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring for dissolution, 160g of 10% sodium hydroxide solution is added, then 10% alkali liquor is used for regulating the pH value, the pH value is controlled to be 8, the solution is cooled to 15 ℃ by using ice water bath, 0.5g of triethylamine and 0.5g of DMAP0.5g are added, the water bath is removed, and cyanuric chloride is added into the solution once. After the cyanuric chloride is added, adjusting the pH value of the feed liquid to 12, then heating to 40 to react for 1 hour, supplementing 10% sodium hydroxide solution in the reaction process to control the pH value to be 11, and after the reaction is finished, adding more than 10g of 10% sodium hydroxide solution into the feed liquid, wherein the pH value of the feed liquid is more than or equal to 12; and (2) dividing the organic phase into four-neck flasks by using a separating funnel, sequentially carrying out alkaline washing on a sodium hydroxide solution with the solute mass fraction of 3% and hydrochloric acid washing on the solute mass fraction of 8%, and evaporating and drying the solvent in the organic phase at 75 ℃ after washing to obtain a solid bromotriazine product.
The brominated triazine prepared in comparative example 2 is a white powder with a purity of 97.8% and a yield of 92.3%.
Comparative example 3
On the basis of example 1, with the difference that after the tribromophenol has dissolved, 160g of 10% sodium hydroxide solution is added, pH =8 before cyanuric chloride is added and pH =8 after cyanuric chloride is added.
135g of tribromophenol and 380g of dichloromethane are added into a four-neck flask with stirring for dissolution, 160g of 10% sodium hydroxide solution is added, then 10% alkali liquor is used for regulating the pH value, the pH value is controlled to be 8, the solution is cooled to 15 ℃ by using ice water bath, 0.5g of triethylamine and 0.5g of DMAP0.5g are added, the water bath is removed, and cyanuric chloride is added into the solution once. After the cyanuric chloride is added, the temperature is raised to 40 ℃ for reaction for 1 hour, 0.5g of 10% sodium hydroxide solution is added every 10 minutes in the reaction process, the pH is controlled to be 8, more than 20g of 10% sodium hydroxide solution is added into the feed liquid after the reaction is finished, and the pH of the feed liquid is more than or equal to 12; and (2) dividing the organic phase into four-neck flasks by using a separating funnel, sequentially carrying out alkaline washing on a sodium hydroxide solution with the solute mass fraction of 3% and hydrochloric acid washing on the solute mass fraction of 8%, and evaporating and drying the solvent in the organic phase at 75 ℃ after washing to obtain a solid bromotriazine product.
Comparative example 3 produced bromotriazine as a white powder, with a purity of 91.8% and a yield of 85.4%, as shown in fig. 3.
The test tables of the brominated triazine products prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
Fig. 1-3 are liquid chromatogram charts of brominated triazine products, and the detection conditions of liquid chromatogram are as follows:
firstly, a mobile phase: 100 percent of pure methanol, suction filtration and degassing.
The wavelength is detected: 254nm.
Flow rate: 1ml/min.
TABLE 1 test Table for bromotriazines
Referring to table 1, it can be seen from examples 1-3 that the bromotriazine prepared by the present application has a purity of not less than 99% and a yield of not less than 95%. Example 2 compared to example 1, except that the pH before addition of cyanuric chloride was controlled to be lower than the pH after addition of cyanuric chloride, the purity was somewhat higher. Comparative example 1 is compared to example 1 with the difference that the purity and yield are reduced when the pH is too high both before and after addition of cyanuric chloride. Comparative example 2 is different from example 1 in that, when the pH is too high after adding cyanuric chloride, the cyanuric chloride is hydrolyzed relatively much due to the conversion of tribromophenol to tribromophenate, resulting in a lower product purity. Comparative example 3 compared to example 1, at a lower pH, insufficient conversion of tribromophenol to tribromophenate and relatively less hydrolysis of cyanuric chloride occurred, but the product purity was lower due to insufficient tribromophenate.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A preparation method of brominated triazine is characterized by comprising the following steps:
step one, adding tribromophenol into an organic solvent for dissolving, then adding strong base, controlling the pH value before adding cyanuric chloride to obtain a first mixed solution, cooling to 5-15 ℃, and then adding triethylamine, DMAP composite catalyst and cyanuric chloride into the first mixed solution to obtain a second mixed solution; heating the second mixed solution added with the cyanuric chloride to over 38 ℃ for reaction, controlling the pH value after the cyanuric chloride is added in the reaction process, adjusting the pH value to over 12 after the reaction is finished, and separating out an organic phase;
secondly, sequentially carrying out alkali washing, acid washing, crystallization and drying on the organic phase to obtain a bromotriazine solid;
wherein the pH value before cyanuric chloride is controlled to be less than or equal to the pH value after cyanuric chloride is added is controlled to be less than or equal to 10 and more than 8, and the molar ratio of tribromophenol to strong base is 1:0.9 to 1.1, wherein the adding amount of the catalyst is 0.5 to 1 percent of the adding mass of tribromophenol, and the mass ratio of triethylamine to DMAP is 1:0.5 to 2, wherein the molar ratio of the cyanuric chloride to the tribromophenol is 1:2.8 to 3.2.
2. The preparation method according to claim 1, wherein the addition amount of the catalyst is 0.6-0.8% of the addition mass of tribromophenol.
3. The method according to claim 1, wherein the mass ratio of triethylamine to DMAP is 1:0.8 to 1.5.
4. The process according to claim 1, wherein the molar ratio of cyanuric chloride to tribromophenol is 1:3 to 3.1.
5. The method of claim 1, wherein the pH before adding cyanuric chloride is 9 and the pH after adding cyanuric chloride is 10.
6. The preparation method of the alkaline cleaning agent according to claim 1, wherein the alkaline cleaning agent adopts 1-5% sodium hydroxide solution by mass of solute.
7. The preparation method according to claim 1, wherein the acid washing is performed by using a hydrochloric acid solution with a solute mass fraction of 5% to 15%.
8. The method of claim 1, wherein the temperature of the crystallization process is 70 ℃ to 90 ℃.
9. The method according to claim 1, wherein the organic solvent is dichloromethane.
10. Brominated triazine, which is obtained by the production method according to any one of claims 1 to 9, and which has a purity of not less than 99% and a yield of not less than 95%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008071214A1 (en) * | 2006-12-14 | 2008-06-19 | Albemarle Corporation | Production of tris (2,4,6-tribromophenoxy-1,3,5-triazine) |
| CN102838554A (en) * | 2012-10-10 | 2012-12-26 | 孔庆池 | Novel method for synthesizing bromo-triazine |
| CN108640882A (en) * | 2018-06-07 | 2018-10-12 | 山东旭锐新材有限公司 | A kind of continuous production three（Tribromophenoxy）The method and its production equipment of triazine |
| CN114349716A (en) * | 2022-03-21 | 2022-04-15 | 山东海王化工股份有限公司 | Production process of high-whiteness high-thermal-stability bromotriazine |
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| WO2008071214A1 (en) * | 2006-12-14 | 2008-06-19 | Albemarle Corporation | Production of tris (2,4,6-tribromophenoxy-1,3,5-triazine) |
| CN102838554A (en) * | 2012-10-10 | 2012-12-26 | 孔庆池 | Novel method for synthesizing bromo-triazine |
| CN108640882A (en) * | 2018-06-07 | 2018-10-12 | 山东旭锐新材有限公司 | A kind of continuous production three（Tribromophenoxy）The method and its production equipment of triazine |
| CN114349716A (en) * | 2022-03-21 | 2022-04-15 | 山东海王化工股份有限公司 | Production process of high-whiteness high-thermal-stability bromotriazine |
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