CN104892349A - Preparation method of hexabromocyclododecane - Google Patents
Preparation method of hexabromocyclododecane Download PDFInfo
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- CN104892349A CN104892349A CN201510288324.4A CN201510288324A CN104892349A CN 104892349 A CN104892349 A CN 104892349A CN 201510288324 A CN201510288324 A CN 201510288324A CN 104892349 A CN104892349 A CN 104892349A
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- hexabromocyclododecane
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- bromination
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- cyclododecatriene
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Abstract
The invention discloses a preparation method of hexabromocyclododecane. The preparation method comprises three steps of bromination, washing separation and drying, wherein the bromination step comprises the steps of respectively dropwise adding raw materials including cyclododecatriene and bromine into a mixed solvent of isobutanol and dichloroethane, and heating to 50+/-2 DEG C in three stages of the dropwise adding process, wherein the molar ratio of bromine to cyclododecatriene is (3.05-3.08) to 1, and the total reaction time is 3-4 hours; the washing separation step comprises the steps of adding a solid phase separated from a finished solution of the bromination reaction into the prepared mixed solvent of dichloroethane and isobutanol, after uniformly stirring and mixing, separating the solid phase out, adding ethanol, and washing twice, so as to obtain the filtered solid phase; the drying step comprises the step of drying the solid phase obtained in the washing separation step at 80+/-2 DEG C, so as to obtain a white solid powder product. According to the preparation method of hexabromocyclododecane, completely-bromized impurities which are entrained by the product and can influence the melting point are removed by virtue of a solvent washing method, so that the product impurity is improved, and the melting point of products is increased.
Description
Technical field
The invention belongs to organic bromide and prepare synthetic technology.
Technical background
Hexabromocyclododecane is the combustion inhibitor special of polystyrene foamed and extruded polystyrene.Commercially available hexabromocyclododecane product fusing point is on the low side, how at about 150 DEG C, easily decomposes in material processing, affects outward appearance and the performance of finished product.
Summary of the invention
For the problem that existing hexabromocyclododecane product fusing point is on the low side, the invention provides a kind of dystectic hexabromocyclododecane preparation method, adopt the method for solvent wash, product is carried secretly the complete impurity removing of the non-bromination that can affect fusing point, improve product purity, product fusing point is raised.
Hexabromocyclododecane preparation method involved in the present invention comprises bromination, washing is separated, dry three steps.
1. bromination
Bromine and cyclododecatriene are added dropwise in the mixed solvent of isopropylcarbinol and ethylene dichloride respectively and react, control reaction rate of addition, drip and terminate rear insulation slaking.
In mixed solvent, the mass ratio of isopropylcarbinol and ethylene dichloride is 0.4 ~ 0.45:1.
The participation bromine of total reaction and the mol ratio of cyclododecatriene are 3.05 ~ 3.08:1, and the mass ratio of cyclododecatriene and solvent is 1:3.
In the mixed solvent of isopropylcarbinol and ethylene dichloride, first add the bromine of total reaction 10% ~ 15%, then cyclododecatriene and remaining bromine are added dropwise in mixed solvent respectively simultaneously, control reaction rate of addition and temperature of reaction, dropwise at 1.5 ~ 2h.
Dropping process divides three sections to be warming up to 50 DEG C ± 2 DEG C, and total reaction time is 3 ~ 4 hours.Control to be warming up to 30 DEG C ± 2 DEG C in dropping process 0 ~ 1/3 period; Dripped for 1/3 ~ 2/3 period, be warming up to 40 DEG C ± 2 DEG C; Dripped for 2/3 ~ 3/3 period, be warming up to 50 DEG C ± 2 DEG C.
After dropping terminates, bromination reaction completes liquid and keeps temperature 50 C ± 2 DEG C slaking 2h.
2. washing is separated
Bromination reaction is completed isolated solid phase in liquid and add the mixed solvent that ethylene dichloride and isopropylcarbinol prepare, isolate solid phase again after being uniformly mixed, then add washing with alcohol 2 times, obtain filtering solid phase.The quality such as the cyclododecatriene added in the mixed solvent added and bromination " step ".
3. dry
Dry at the solid phase that washing separation obtains is placed in 80 DEG C, obtain hexabromocyclododecane product.
Embodiment
By embodiment, technical scheme of the present invention is further illustrated.Embodiment:
Take 63.6g ethylene dichloride and 26.6g isopropylcarbinol is mixed with mixed solvent, in mixed solvent, add 12.3g bromine again, and then utilize two constant pressure funnel adding 30.5g cyclododecatriene and residue 79.7g simple substance bromine respectively in mixed solvent, drip cyclododecatriene and bromine simple substance.Be warming up to 30 DEG C ± 2 DEG C, after dripping 40min; Temperature is increased to 40 DEG C ± 2 DEG C, drips 40min; Be warming up to 50 DEG C ± 2 DEG C, continue to drop to end, total time for adding is 115 minutes.Keep 50 DEG C ± 2 DEG C slaking 2h.After slaking, leave standstill and treat solid phase liquid phase separation, liquid phase is gone out just.In solid phase, add 30g mixed solvent, stir 1 ~ 2min, leave standstill and treat solid-liquid separation, just go out upper phase.Solid phase uses 30g washing with alcohol 2 times again, suction filtration.Solid phase after filtration is placed in baking oven 80 DEG C of oven dry are set, obtain white powder hexabromocyclododecane solid.Product fusing point is up to 195.3 DEG C.
Claims (6)
1. a hexabromocyclododecane preparation method, utilizes bromine and cyclododecatriene to carry out bromination reaction and prepares hexabromocyclododecane, it is characterized in that: comprise bromination, washing is separated, drying step;
Described bromination step, is added dropwise to bromine and cyclododecatriene respectively in the mixed solvent of isopropylcarbinol and ethylene dichloride and reacts, and controls reaction rate of addition, drips and terminate rear insulation slaking; In mixed solvent, the mass ratio of isopropylcarbinol and ethylene dichloride is 0.4 ~ 0.45:1; The participation bromine of total reaction and the mol ratio of cyclododecatriene are 3.05 ~ 3.08:1, and the mass ratio of cyclododecatriene and solvent is 1:3;
Described washing separating step, completes isolated solid phase in liquid and adds the mixed solvent that ethylene dichloride and isopropylcarbinol prepare, isolate solid phase again, then add washing with alcohol 2 times, obtain filtering solid phase after being uniformly mixed by bromination reaction;
Described drying step, is separated washing the solid phase drying obtained and obtains hexabromocyclododecane product.
2. hexabromocyclododecane preparation method according to claim 1, it is characterized in that, in described bromination step, in the mixed solvent of isopropylcarbinol and ethylene dichloride, first add the bromine of total reaction 10% ~ 15%, then cyclododecatriene and remaining bromine are added dropwise in mixed solvent respectively simultaneously, control reaction rate of addition and temperature of reaction, dropwise at 1.5 ~ 2h.
3. hexabromocyclododecane preparation method according to claim 2, is characterized in that, described dropping process divides three sections to be warming up to 50 DEG C ± 2 DEG C, and total reaction time is 3 ~ 4 hours; Control to be warming up to 30 DEG C ± 2 DEG C in dropping process 0 ~ 1/3 period; Dripped for 1/3 ~ 2/3 period, be warming up to 40 DEG C ± 2 DEG C; Dripped for 2/3 ~ 3/3 period, be warming up to 50 DEG C ± 2 DEG C.
4. hexabromocyclododecane preparation method according to claim 2, is characterized in that, after described dropping terminates, bromination reaction completes liquid and keeps temperature 50 C ± 2 DEG C slaking 2h.
5. hexabromocyclododecane preparation method according to claim 1, is characterized in that, in described washing separating step, and the quality such as cyclododecatriene added in the mixed solvent added and bromination step.
6. hexabromocyclododecane preparation method according to claim 1, is characterized in that, in described drying step, dry at the solid phase that washing separation obtains is placed in 80 DEG C, obtains hexabromocyclododecane product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510288324.4A CN104892349B (en) | 2015-05-29 | 2015-05-29 | A kind of HBCD preparation method |
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| CN201510288324.4A CN104892349B (en) | 2015-05-29 | 2015-05-29 | A kind of HBCD preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949031A (en) * | 2016-07-19 | 2016-09-21 | 山东东信化学工业有限公司 | Preparation process for hexabromocyclododecane |
| CN106146254A (en) * | 2016-06-04 | 2016-11-23 | 上海大学 | The synthetic method of hydroxyl HBCD |
-
2015
- 2015-05-29 CN CN201510288324.4A patent/CN104892349B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 蔡荣华等: "六溴环十二烷合成的溶剂－ 催化剂体系研究", 《盐业与化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146254A (en) * | 2016-06-04 | 2016-11-23 | 上海大学 | The synthetic method of hydroxyl HBCD |
| CN105949031A (en) * | 2016-07-19 | 2016-09-21 | 山东东信化学工业有限公司 | Preparation process for hexabromocyclododecane |
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