CN102617496B - Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate - Google Patents
Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate Download PDFInfo
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- CN102617496B CN102617496B CN201210038841.2A CN201210038841A CN102617496B CN 102617496 B CN102617496 B CN 102617496B CN 201210038841 A CN201210038841 A CN 201210038841A CN 102617496 B CN102617496 B CN 102617496B
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- dibromopropyl
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- isocyanurate
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Abstract
The invention discloses a synthetic method of tris (2, 3-dibromopropyl) sulfone isocyanurate, and belongs to the field of flame retardants. The synthetic method is characterized in that alcohols solvent is added in a three-mouth flask, then metered TAIC (triallyl isocyanurate) is added, the temperature rises to reach 0 to 40 DEG C, metered bromine is dripped when being stirred, heat-insulating reaction is performed for 0.5 to 5 hours after the dripping is finished, and temperature falls to reach 0 to 10 DEG C; suction filtration is carried out, and mother liquor is recycled; filter cakes are added water, bromine removing agent water solution is added, stirring and suction filtration are carried out, and the filter cakes are washed through water; and then drying is carried out so as to obtain the tris (2, 3- dibromopropyl) sulfone isocyanurate. The provided preparation method leads tris (2, 3-dibromopropyl) sulfone isocyanurate to be separated out at the same time when being generated so as to obtain crystalline products, solves the problem that tris (2, 3-dibromopropyl) sulfone isocyanurate is difficult to separate out, leads solvent to be recycled, reduces distillation, improves yield coefficient, achieves low equipment investment and low energy consumption, and accords with the requirements of green production.
Description
Technical field
The invention belongs to flame retardant area, relate to the method that one is prepared three (2,3-dibromopropyl) isocyanuric acid ester.
Background technology
Three (2,3-dibromopropyl) isocyanuric acid esters (TBC), are a kind of additive flame retardants, are widely used in polypropylene, ABS and polystyrene plastic.
German patent DE 2244543 has described three (2,3-dibromopropyl) production method of isocyanuric acid ester, the method is used methylene dichloride to make solvent, and cyanacrylate (TAIC) reacts with bromine and generates three (2,3-dibromopropyl) isocyanuric acid ester, then add sherwood oil to make product precipitation, filter, filter cake grinds in methyl alcohol, and water cleans, dry, obtain target product.
JP 56053668 A have disclosed and have used tetracol phenixin to make the production method of solvent, and in tetracol phenixin, bromine reacts with cyanacrylate and generates three (2,3-dibromopropyl) isocyanuric acid ester, then adds precipitation agent octane that it is separated out.
In JP2000053658, describe, in dichloromethane solvent, after cyanacrylate reacts with bromine, use methyl alcohol to make precipitation agent.JP2000053658 not only mentions methylene dichloride, has also mentioned chloroform, tetracol phenixin, ethylene dichloride, methylene bromide etc. and has done reaction solvent, has methyl alcohol, ethanol, Virahol, pentane, a hexane as precipitation agent.
Japanese Patent JP1999228549 uses heptane to do precipitation agent, and reaction solvent is still methylene dichloride.
Domestic Liu Han tiger is waited people (fire retardant material and technology, 1991 (2): 29-33) also to study use methylene dichloride and does reaction solvent, and hexanaphthene, No. 120 gasoline etc. does the production technology of precipitation agent.
The people (CN1733709A) such as Peter Wei Le use methylene dichloride to make solvent, allow bromine and cyanacrylate generation addition reaction produce three (2,3-dibromopropyl) isocyanuric acid ester, in the product obtaining and methylene dichloride mixed solution, add porous polypropylene, slight vacuum steams methylene dichloride, obtain including three (2,3-dibromopropyl) isocyanuric acid ester product of polypropylene 50%.
In prior art, use precipitation agent, the a large amount of energy consumptions of separation consumes of precipitation agent and reaction solvent, it is a large factor that causes production cost high, and some precipitation agent is difficult to separate with reaction solvent, for example, use methylene dichloride is made reaction solvent, methyl alcohol does precipitation agent system, due to methylene dichloride and the formation of methanol azeotropic liquid, use distillation way thoroughly they to be separated, in the methylene dichloride steaming, contain 10% methyl alcohol, must methyl alcohol be washed away by washing, waste resource, also causes very large pollution.
The people such as Peter Wei Le add porousness polypropylene, need to add 50% more than, efficiently solve this problem, but in product, contain up to 50% polypropylene.Flame retardant agent content in flame-retardant master batch, generally higher than 70%, is difficult to adopt this series products.
Summary of the invention
The deficiency existing for prior art, the present invention proposes a kind of new three (2,3-dibromopropyl) isocyanuric acid ester manufacture method, avoided separating of reaction solvent and precipitation agent, reduced energy consumption, improved production efficiency, reduced production cost.
Technical problem to be solved by this invention is to realize by following technical scheme, it is characterized in that:
100ml alcoholic solvent is added to there-necked flask, then add the cyanacrylate of metering, be warming up to 0-40 ℃, preferably 25-30 ℃, stirs the lower metering bromine that drips, after being added dropwise to complete, insulation reaction 0.5-5 hour, preferably 2-3 hour, is cooled to 0-10 ℃, suction filtration, mother liquor reuse, filter cake is added to the water, and adds except the bromide aqueous solution, stir, excessive bromine with remove bromide and react and enter the aqueous solution.Suction filtration, filter cake washes with water 2 times, then dries, and obtains product three (2,3-dibromopropyl) isocyanuric acid ester, and product fusing point is greater than 105 ℃.
In described method, the alcoholic solvent using is for the various alcohol of C2-C9, as ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, hexanol, 2-Ethylhexyl Alcohol etc.Can use their middle one, also can use their mixture.
In described method, the mass ratio of bromine used and cyanacrylate is 1.8: 1-2.2: 1, and the mass ratio of cyanacrylate and solvent is 5: 85-20: 40.
In described method, mother liquor can repeat to apply mechanically,, in mother liquor, add the cyanacrylate of metering, be warming up to and add bromine temperature, stir the lower metering bromine that drips, adopt the mode identical with neat solvent to produce three (2,3-dibromopropyl) isocyanuric acid ester.
In described method, due to the loss of mother liquor, in the time of actual production, the mother liquor lacking supplements with neat solvent.
In described method, used except bromide can be the reducing substanceses such as S-WAT, hydrazine hydrate, sodium formiate, can be also the alkaline matters such as sodium carbonate, sodium hydroxide and ammonia, can use separately, also can use their mixture.Except the consumption of bromide is according to solution acidity and fixed, add except bromide, after stirring reaction, the acidity of solution requires, for pH 4-10, to be preferably pH 6-8.
Beneficial effect of the present invention:
Due to three (2,3-dibromopropyl) the special molecular structure of isocyanuric acid ester, while using the chloroparaffins such as methylene dichloride to make reaction solvent, exist three (2,3-dibromopropyl) isocyanuric acid ester to be difficult to separate out problem, have to add precipitation agent or a large amount of sorbent material.
Using advantage of the present invention is significantly, and it adopts alcohol to make solvent, makes three (2,3-dibromopropyl) isocyanuric acid ester generate in separate out, obtain crystalline product, solved three (2,3-dibromopropyl) isocyanuric acid ester difficulty and separated out problem; Use the present invention, solvent is single solvent, need not build rectifying tower and separate chloroparaffin and precipitation agent, and facility investment is supported, and energy consumption is low; Solvent of the present invention can recycle, and has reduced distillation, has improved yield, has also reduced pollution, meets the requirement of green production.
Embodiment
The present invention is further elaborated by the following examples.
Example 1
Agitator is being housed, thermometer, in the 500ml four-hole bottle of prolong, add 200ml 2-Ethylhexyl Alcohol, 30g cyanacrylate, be cooled to 25 ℃ with frozen water, stir the lower 60g of dropping bromine, after being added dropwise to complete, insulation reaction 2h, then be cooled to 10 ℃ with frozen water, suction filtration, obtaining 180ml mother liquor is retained in reagent bottle, solid is put into beaker, add 100ml pure water, then adjusting the pH of solution with sodium sulfite solution is 6-8, stir, suction filtration, dry, obtain white three (2, 3-dibromopropyl) isocyanuric acid crystalline esters, 108 ℃ of fusing points, yield 95%.
Example 2
Agitator is being housed, thermometer, in the 500ml four-hole bottle of prolong, add mother liquor and the 20ml 2-Ethylhexyl Alcohol of 180ml example 1, 30g cyanacrylate, be cooled to 20-25 ℃ with frozen water, stir the lower 60g of dropping bromine, after being added dropwise to complete, insulation reaction 2h, then be cooled to 5-10 ℃ with frozen water, suction filtration, mother liquor retains, solid is put into beaker, add 100ml pure water, then adjusting the pH of solution with sodium sulfite solution is 6-8, stir, suction filtration, dry, obtain white three (2, 3-dibromopropyl) isocyanuric acid crystalline esters, 106 ℃ of fusing points, yield 99%.
Example 3
Agitator is being housed, thermometer, in the 500ml four-hole bottle of prolong and dropping funnel, add 200ml Virahol, 30g cyanacrylate, be cooled to 10 ℃ with frozen water, stir the lower 60g of dropping bromine, after being added dropwise to complete, be warming up to 25 ℃, insulation reaction 2h, then be cooled to 5 ℃ with frozen water, suction filtration, the 183ml mother liquor obtaining is retained, solid is put into beaker, add 100ml pure water, then adjusting the pH of solution with sodium sulfite solution is 6-8, stir, suction filtration, dry, obtain white three (2, 3-dibromopropyl) isocyanuric acid crystalline esters, 110 ℃ of fusing points, yield 96%.
Example 4
Agitator is being housed, thermometer, in the 500ml four-hole bottle of prolong and dropping funnel, add mother liquor and the 17ml Virahol of 183ml example 3, 30g cyanacrylate, be cooled to 10 ℃ with frozen water, stir the lower 60g of dropping bromine, after being added dropwise to complete, insulation reaction 2h, then be cooled to 5 ℃ with frozen water, suction filtration, mother liquor retains, solid is put into beaker, add 100ml pure water, then adjusting the pH of solution with sodium sulfite solution is 6-8, stir, suction filtration, dry, obtain white three (2, 3-dibromopropyl) isocyanuric acid crystalline esters, 107 ℃ of fusing points, yield 98%.
Claims (2)
1. one kind three (2,3-dibromopropyl) isocyanuric acid ester synthetic method, it is characterized in that: alcoholic solvent is added to there-necked flask, then add the cyanacrylate of metering, the mass ratio of cyanacrylate and solvent is 5: 85～20: 40, and described solvent is wherein a kind of or their mixture of ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, hexanol, 2-Ethylhexyl Alcohol; Then be warming up to 25-30 ℃, stir the lower bromine that drips metering, the mass ratio of bromine and cyanacrylate is 1.8: 1～2.2: 1, after being added dropwise to complete, insulation reaction 2-3 hour, is cooled to 0-10 ℃, suction filtration, mother liquor reuse, filter cake is added to the water, add sodium sulfite aqueous solution, stirring and making the pH of solution is 6-8, suction filtration, filter cake washes with water, then dry, obtain product three (2,3-dibromopropyl) isocyanuric acid ester.
2. according to claim 1 three (2,3-dibromopropyl) isocyanuric acid ester synthetic method, described mother liquor can repeat to apply mechanically the cyanacrylate that adds metering in mother liquor, be warming up to and add bromine temperature, stir the lower metering bromine that drips, adopt the method identical with neat solvent to produce three (2,3-dibromopropyl) isocyanuric acid ester, the mother liquor lacking supplements with neat solvent.
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| CN201210038841.2A CN102617496B (en) | 2012-02-15 | 2012-02-15 | Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate |
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| CN201210038841.2A CN102617496B (en) | 2012-02-15 | 2012-02-15 | Synthetic method of tris (2,3-dibromopropyl) sulfone isocyanurate |
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| CN102617496B true CN102617496B (en) | 2014-05-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694186B (en) * | 2014-01-06 | 2015-10-14 | 中国石油大学(华东) | A kind of three (2,3-dibromopropyl) isocyanuric acid ester production method |
| CN105061343A (en) * | 2015-08-07 | 2015-11-18 | 上海交通大学 | Tri(2,3-dibromopropyl)triallyisocyanurate hapten, and preparation and application |
| CN109776438A (en) * | 2019-03-27 | 2019-05-21 | 山东润科化工股份有限公司 | A kind of heat-staple TBC method for synthesizing flame retardant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2244543A1 (en) * | 1972-09-11 | 1974-04-11 | Interorgana Chemiehandel Gmbh | Tri-(2,3-dibromopropyl)-isocyanurate - prepd by brominating triallylisocya-nurate, useful as flame retardant for polyurethanes etc |
| JPS5653668A (en) * | 1979-10-08 | 1981-05-13 | Nippon Kasei Kk | Preparation of tris 2,3-dibromopropyl isocyanurate |
| SU1006433A1 (en) * | 1981-08-13 | 1983-03-23 | Предприятие П/Я Г-4302 | Process for preparing 1,3,5-tris-(2,3-dibromopropyl)-isocyanurate |
| JP2000053658A (en) * | 1998-08-06 | 2000-02-22 | Tosoh Corp | Production of tris(dibromopropyl) isocyanurate |
| CN1733709A (en) * | 2004-08-14 | 2006-02-15 | 德古萨股份公司 | Method for preparing solid(2,3- dibrompropyl) isocyanurate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173092A (en) * | 1993-12-20 | 1995-07-11 | Manac Inc | Method for producing high melting point crystal of 2,3-dibromopropyl compound |
| JP4288715B2 (en) * | 1998-02-18 | 2009-07-01 | 東ソー株式会社 | Method for producing tris (dibromopropyl) isocyanurate |
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- 2012-02-15 CN CN201210038841.2A patent/CN102617496B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2244543A1 (en) * | 1972-09-11 | 1974-04-11 | Interorgana Chemiehandel Gmbh | Tri-(2,3-dibromopropyl)-isocyanurate - prepd by brominating triallylisocya-nurate, useful as flame retardant for polyurethanes etc |
| JPS5653668A (en) * | 1979-10-08 | 1981-05-13 | Nippon Kasei Kk | Preparation of tris 2,3-dibromopropyl isocyanurate |
| SU1006433A1 (en) * | 1981-08-13 | 1983-03-23 | Предприятие П/Я Г-4302 | Process for preparing 1,3,5-tris-(2,3-dibromopropyl)-isocyanurate |
| JP2000053658A (en) * | 1998-08-06 | 2000-02-22 | Tosoh Corp | Production of tris(dibromopropyl) isocyanurate |
| CN1733709A (en) * | 2004-08-14 | 2006-02-15 | 德古萨股份公司 | Method for preparing solid(2,3- dibrompropyl) isocyanurate |
Non-Patent Citations (2)
| Title |
|---|
| 叶昌焰.氰尿酸系列精细化工产品.《川化》.2000,(第3期),1-7. |
| 氰尿酸系列精细化工产品;叶昌焰;《川化》;20000815(第3期);1-7 * |
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