CN102617496A - 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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- CN102617496A CN102617496A CN2012100388412A CN201210038841A CN102617496A CN 102617496 A CN102617496 A CN 102617496A CN 2012100388412 A CN2012100388412 A CN 2012100388412A CN 201210038841 A CN201210038841 A CN 201210038841A CN 102617496 A CN102617496 A CN 102617496A
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- dibromopropyl
- 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 for a kind of preparation three (2, the 3-dibromopropyl) isocyanuric acid ester.
Background technology
Three (2, the 3-dibromopropyl) isocyanuric acid ester (TBC) is a kind of additive flame retardant, is widely used in Vestolen PP 7052, ABS and the polystyrene plastic.
German patent DE 2244543 has been described the working method of three (2, the 3-dibromopropyl) isocyanuric acid ester, and this method uses methylene dichloride to make solvent; Cyanacrylate (TAIC) generates three (2, the 3-dibromopropyl) isocyanuric acid ester with the bromine reaction, adds sherwood oil then and makes the product deposition; Filter, filter cake grinds in methyl alcohol, and water cleans; Oven dry obtains target product.
JP 56053668 A have disclosed and have used tetracol phenixin to make the working method of solvent, and in tetracol phenixin, bromine and cyanacrylate reaction generate three (2, the 3-dibromopropyl) isocyanuric acid ester, add the precipitation agent octane then it is separated out.
What in JP2000053658, describe is in dichloromethane solvent, after cyanacrylate and the bromine reaction, to 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, as precipitation agent methyl alcohol, ethanol, Virahol, pentane, hexane is arranged.
Japanese Patent JP1999228549 then uses heptane to do precipitation agent, and reaction solvent is still methylene dichloride.
People such as domestic Liu Han tiger (fire retardant material and technology, 1991 (2): 29-33) also having studied the use methylene dichloride does reaction solvent, and hexanaphthene, No. 120 gasoline etc. is done the production technology of precipitation agent.
People (CN1733709A) such as Peter Wei Le use methylene dichloride to make solvent; Let bromine and cyanacrylate generation addition reaction produce three (2; The 3-dibromopropyl) isocyanuric acid ester adds porous polypropylene in product that obtains and methylene dichloride mixed solution, slight vacuum steams methylene dichloride; Obtain including three (2, the 3-dibromopropyl) isocyanuric acid ester product of Vestolen PP 7052 50%.
In the prior art, use precipitation agent, the separation consumes mass energy consumption of precipitation agent and reaction solvent; Be a big factor that causes production cost high, and some precipitation agent is difficult to separate with reaction solvent, for example; The use methylene dichloride is made reaction solvent, methyl alcohol is done the precipitation agent system, because methylene dichloride and methyl alcohol form azeotropic liquid, uses the distillation way thoroughly they to be separated; Contain 10% methyl alcohol in the methylene dichloride that steams; Must be through washing with the methyl alcohol flush away, the waste resource also causes very big pollution.
People such as Peter Wei Le add the porousness Vestolen PP 7052, need to add 50% more than, efficiently solve this problem, but contain in the product up to 50% Vestolen PP 7052.Flame retardant agent content in the flame-retardant master batch generally is higher than 70%, is difficult to adopt this series products.
Summary of the invention
To the deficiency that prior art exists, the present invention proposes a kind of new three (2, the 3-dibromopropyl) isocyanuric acid ester method of manufacture, has avoided separating of reaction solvent and precipitation agent, has reduced energy consumption, has improved production efficiency, has reduced production cost.
Technical problem to be solved by this invention is to realize through following technical scheme, it is characterized in that:
The 100ml alcoholic solvent is added there-necked flask, add the cyanacrylate of metering then, be warming up to 0-40 ℃, preferred 25-30 ℃; Stir and drip the metering bromine down, after being added dropwise to complete, insulation reaction 0.5-5 hour, preferred 2-3 hour; Be cooled to 0-10 ℃, suction filtration, the mother liquor reuse, filter cake adds in the entry; Add to remove the bromide aqueous solution, stir, excessive bromine with remove the bromide reaction and get into the aqueous solution.Suction filtration, filter cake are with water washing 2 times, and oven dry obtains product three (2, the 3-dibromopropyl) isocyanuric acid ester then, and the product fusing point is greater than 105 ℃.
In the said method, employed alcoholic solvent is the various alcohol of C2-C9, like ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, hexanol, 2-Ethylhexyl Alcohol etc.Can use their intermediary a kind of, also can use their mixture.
In the said method, the mass ratio of used bromine and cyanacrylate is 1.8: 1-2.2: 1, and the mass ratio of cyanacrylate and solvent is 5: 85-20: 40.
In the said method, mother liquor can repeat to apply mechanically, and, in mother liquor, adds the cyanacrylate of metering that is, is warming up to add the bromine temperature, stirs and drips the metering bromine down, adopts the mode identical with neat solvent to produce three (2, the 3-dibromopropyl) isocyanuric acid ester.
In the said method, because the loss of mother liquor, when actual production, the mother liquor that lacks replenishes with neat solvent.
In the said method, used to remove bromide can be reducing substanceses such as S-WAT, Hydrazine Hydrate 80, sodium formiate, can be alkaline matters such as yellow soda ash, sodium hydroxide and ammonia also, can use separately, also can use their mixture.The consumption that removes bromide adds and removes bromide according to solution acidity and fixed, and behind the stirring reaction, the acidity of solution requires to be to be preferably pH 6-8 by pH 4-10.
Beneficial effect of the present invention:
Because three (2, the 3-dibromopropyl) isocyanuric acid ester specific molecule structure, chloroparaffins such as use methylene dichloride exist three (2, the 3-dibromopropyl) isocyanuric acid ester to be difficult to separate out problem when making reaction solvent, 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, and three (2, the 3-dibromopropyl) isocyanuric acid ester is separated out when generating, and obtains the crystalline product, has solved three (2, the 3-dibromopropyl) isocyanuric acid ester difficulty and has separated out problem; Use the present invention, solvent is a 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
Below through embodiment the present invention is done further elaboration.
Instance 1
Whisking appliance is being housed, is adding the 200ml 2-Ethylhexyl Alcohol in the TM, the 500ml four-hole bottle of prolong, the 30g cyanacrylate is cooled to 25 ℃ with frozen water; Stir down and drip the 60g bromine, after being added dropwise to complete, insulation reaction 2h is cooled to 10 ℃ with frozen water then; Suction filtration obtains the 180ml mother liquor and is retained in the reagent bottle, and solid is put into beaker, adds the 100ml pure water; Use sodium sulfite solution to transfer the pH of solution to be 6-8 then, stir, suction filtration, oven dry; Obtain white three (2, the 3-dibromopropyl) isocyanuric acid crystalline esters, 108 ℃ of fusing points, yield 95%.
Instance 2
Whisking appliance is being housed, is adding the mother liquor and the 20ml 2-Ethylhexyl Alcohol of 180ml instance 1 in the TM, the 500ml four-hole bottle of prolong, the 30g cyanacrylate is cooled to 20-25 ℃ with frozen water; Stir down and drip the 60g bromine, after being added dropwise to complete, insulation reaction 2h is cooled to 5-10 ℃ with frozen water then; Suction filtration, mother liquor keeps, and solid is put into beaker, adds the 100ml pure water; Use sodium sulfite solution to transfer the pH of solution to be 6-8 then, stir, suction filtration, oven dry; Obtain white three (2, the 3-dibromopropyl) isocyanuric acid crystalline esters, 106 ℃ of fusing points, yield 99%.
Instance 3
Whisking appliance is being housed, is adding the 200ml Virahol in the TM, the 500ml four-hole bottle of prolong and tap funnel, the 30g cyanacrylate is cooled to 10 ℃ with frozen water; Stir down and drip the 60g bromine, after being added dropwise to complete, be warming up to 25 ℃, insulation reaction 2h is cooled to 5 ℃ with frozen water then; Suction filtration keeps the 183ml mother liquor that obtains, and solid is put into beaker, adds the 100ml pure water; Use sodium sulfite solution to transfer the pH of solution to be 6-8 then, stir, suction filtration, oven dry; Obtain white three (2, the 3-dibromopropyl) isocyanuric acid crystalline esters, 110 ℃ of fusing points, yield 96%.
Instance 4
Whisking appliance is being housed, is adding the mother liquor and the 17ml Virahol of 183ml instance 3 in the TM, the 500ml four-hole bottle of prolong and tap funnel, the 30g cyanacrylate is cooled to 10 ℃ with frozen water; Stir down and drip the 60g bromine, after being added dropwise to complete, insulation reaction 2h is cooled to 5 ℃ with frozen water then; Suction filtration, mother liquor keeps, and solid is put into beaker, adds the 100ml pure water; Use sodium sulfite solution to transfer the pH of solution to be 6-8 then, stir, suction filtration, oven dry; Obtain white three (2, the 3-dibromopropyl) isocyanuric acid crystalline esters, 107 ℃ of fusing points, yield 98%.
Claims (6)
1. one kind three (2, the 3-dibromopropyl) isocyanuric acid ester compound method is characterized in that: alcoholic solvent is added there-necked flask, add the cyanacrylate of metering then, be warming up to 0-40 ℃; Preferred 25-30 ℃, stir and drip the metering bromine down, after being added dropwise to complete, insulation reaction 0.5-5 hour; Preferred 2-3 hour, be cooled to 0-10 ℃, suction filtration, mother liquor reuse; Filter cake adds in the entry, adds to remove the bromide aqueous solution, stirs suction filtration; Filter cake is used water washing, and oven dry obtains product three (2, the 3-dibromopropyl) isocyanuric acid ester then.
2. according in the said method of claim 1; Employed alcoholic solvent is the various alcohol of C2-C9; Like ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, hexanol, 2-Ethylhexyl Alcohol etc., can use their intermediary a kind of, also can use their mixture.
3. according in the said method of claim 1, the mass ratio of cyanacrylate and solvent is 5: 85-20: 40.
4. according in the said method of claim 1, mother liquor can repeat to apply mechanically, promptly; The cyanacrylate that in mother liquor, adds metering is warming up to and adds the bromine temperature, stirs and drips the metering bromine down; Adopt the mode identical to produce three (2, the 3-dibromopropyl) isocyanuric acid ester with neat solvent.
5. according in the said method of claim 4, because the loss of mother liquor, when actual production, the mother liquor that lacks replenishes with neat solvent.
6. according in claim 1, the 4 said methods, used to remove bromide can be reducing substanceses such as S-WAT, Hydrazine Hydrate 80, sodium formiate, also can be alkaline matters such as yellow soda ash, sodium hydroxide and ammonia; Can use separately, also can use their mixture, the consumption that removes bromide is according to solution acidity and fixed; Add and remove bromide; Behind the stirring reaction, the acidity of solution requires to be preferably pH 6-8 for pH 4-10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN102617496A true CN102617496A (en) | 2012-08-01 |
| CN102617496B CN102617496B (en) | 2014-05-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694186A (en) * | 2014-01-06 | 2014-04-02 | 中国石油大学(华东) | Production method of tri (2,3-dibromo propyl) isocyanurate |
| 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 (7)
| 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 |
| JPH07173092A (en) * | 1993-12-20 | 1995-07-11 | Manac Inc | Method for producing high melting point crystal of 2,3-dibromopropyl compound |
| JPH11228549A (en) * | 1998-02-18 | 1999-08-24 | Tosoh Corp | Production of tris(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 |
-
2012
- 2012-02-15 CN CN201210038841.2A patent/CN102617496B/en not_active Expired - Fee Related
Patent Citations (7)
| 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 |
| JPH07173092A (en) * | 1993-12-20 | 1995-07-11 | Manac Inc | Method for producing high melting point crystal of 2,3-dibromopropyl compound |
| JPH11228549A (en) * | 1998-02-18 | 1999-08-24 | Tosoh Corp | Production of tris(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 (1)
| Title |
|---|
| 叶昌焰: "氰尿酸系列精细化工产品", 《川化》, no. 3, 15 August 2000 (2000-08-15), pages 1 - 7 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694186A (en) * | 2014-01-06 | 2014-04-02 | 中国石油大学(华东) | Production method of tri (2,3-dibromo propyl) isocyanurate |
| 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 |
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| CN102617496B (en) | 2014-05-21 |
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