CN107129431A - A kind of synthetic method of tribromoneoamyl alcohol - Google Patents
A kind of synthetic method of tribromoneoamyl alcohol Download PDFInfo
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- CN107129431A CN107129431A CN201710401445.4A CN201710401445A CN107129431A CN 107129431 A CN107129431 A CN 107129431A CN 201710401445 A CN201710401445 A CN 201710401445A CN 107129431 A CN107129431 A CN 107129431A
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- synthetic method
- pentaerythrite
- tribromoneoamyl
- tribromoneoamyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of tribromoneoamyl alcohol, belong to fire-retardant FRW technical field, this method is using pentaerythrite and reducing agent, bromine as initiation material, tribromoneoamyl alcohol is prepared through bromination, de- esterification two steps reaction, employ the operating procedure of brand-new production technology, reaction yield reaches as high as more than 95%, the inventive method is simple, reaction condition is gentle, it is easy to control, and energy consumption is low, respectively walk without harsh reaction condition, it is easy to industrialized production, high conversion rate, cost are low, product quality is high, environmentally friendly.
Description
Technical field
The present invention relates to a kind of synthetic method of tribromoneoamyl alcohol, belong to fire-retardant FRW technical field.
Background technology
Tribromoneoamyl alcohol is the brominated fire retardant of a class, and its bromine content is 73.79%, belongs to fatty bromine, contains with high bromine
Amount and special stability, hydrolytic resistance and photostability are especially prominent, because it contains reactable functional group hydroxyl, therefore can
Used using the reaction intermediate as HMW fire retardant or as reactive flame retardant.It is used as the one of HMW fire retardant
Individual response type intermediate, the highly dissoluble of tribromoneoamyl alcohol makes it very effective and combined with phosphorus, to be used as the anti-of polyurethane
Type fire retardant, the high bromine content of tribromoneoamyl alcohol and good intermiscibility are answered, applied in hard or flexibel polyurethane, Dou Nengti
The flame retardant rating of high polyurethane；Tribromoneoamyl alcohol can produce the resistance with carbamic acid ethyl group by its single hydroxyl functional response
Combustion type elastomer；In addition, tribromoneoamyl alcohol can be used in combination with dibromo neopentyl alcohol, to make full use of both hydroxyl functionals；Make
For a kind of reactive flame retardant, tribromoneoamyl alcohol is widely used in elastomer, coating and foams.
The method of traditional mode of production tribromoneoamyl alcohol typically uses sulfuric acid vapor phase method, i.e., sulfuric acid is added drop-wise to the hydrogen bromine of low concentration
In acid solution body, then reacted with pentaerythrite, the product colour that the method is obtained is deep, yield is low, and spent acid amount is big, right
Environment causes pollution, is unfavorable for industrialized production.
The content of the invention
The present invention provides a kind of synthetic method of tribromoneoamyl alcohol, and method is simple, and reaction condition is gentle, it is easy to control, easily
In industrialized production, product quality is high, environmentally friendly.
To achieve the above object, the present invention uses following technical scheme：
A kind of synthetic method of tribromoneoamyl alcohol, it is characterised in that comprise the following steps：
(1) pentaerythrite and reducing agent are added in organic solvent, are warming up to whole dissolvings；
(2) be added dropwise at reflux after bromine, completion of dropping continue flow back insulation 8-10h, in the process, bromine with
Reducing agent reaction obtains hydrogen bromide, and with hydrogen bromide substitution reaction occurs for pentaerythrite；
(3) distill after completion of the reaction to 140-150 DEG C, steam organic solvent, unreacted hydrogen bromide and reaction generation
Water；
(4) 80 DEG C are cooled to, into the Liquid Residue after above-mentioned distillation, catalyst is added, is passed through alcohol gas, react 4-6h；
(5) said mixture is cooled to 50 DEG C after the completion of reacting, dispersant is added, with 5%-10% sodium carbonate
Solution adjusts pH to neutrality；
(6) above-mentioned gained mixing organic matter is added to the water, crystallized, product is obtained through washing, dry, section.
It is preferred that, the mol ratio of the pentaerythrite and reducing agent is 1：2-4, the bromine rubs with the pentaerythrite
You are than being 2-4：1, the addition of the catalyst is the 2%-5% of the Liquid Residue quality, the alcohol gas and the season penta
The mol ratio of tetrol is 2-4：1, the addition of the dispersant is the 0.5%-1% of the mixture quality.
It is preferred that, the reducing agent is urea, ammoniacal liquor, the one or several kinds of hydrazine hydrate.
It is preferred that, the organic solvent is formic acid, acetic acid, propionic acid, benzoic acid, the one or more of boric acid.
It is preferred that, the mol ratio of the organic solvent and the pentaerythrite is 2-4:1.
It is preferred that, the catalyst be benzene sulfonic acid, butyl titanate, tetraisopropyl titanate, one kind of butter of tin or
It is several.
It is preferred that, the dispersant is OP-10, fatty alcohol ether phosphate, phenolic ether phosphate, hydroxyethyl cellulose, 12
The one or several kinds of sodium alkyl benzene sulfonate.
It is preferred that, the alcohol is the one or more in isopropanol, isooctanol.
It is preferred that, it is 100-180 DEG C that the temperature that alcohol gas reacted is passed through in the step (4).
It is preferred that, the crystallization temperature in the step (6) is 5-20 DEG C, and drying temperature is 85-105 DEG C.
The present invention advantageous effects be：Using pentaerythrite and reducing agent, bromine as initiation material, through bromination, de- ester
Change the reaction of two steps and prepare tribromoneoamyl alcohol, employ the operating procedure of brand-new production technology, reaction yield is reached as high as
More than 95%, cost is low, product quality is high, reaction condition is gentle, easily controllable, environmentally friendly.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of synthetic method of tribromoneoamyl alcohol, comprises the following steps：
(1) 136g pentaerythrites and 125g reducing agent urea are added in 220g organic solvent acetic acid, are warming up to 140 DEG C
All dissolvings；
(2) it is added dropwise at reflux after bromine 320g, completion of dropping and continues flow back insulation 10h, in the process, bromine
Hydrogen bromide is obtained with reducing agent urea reaction, with hydrogen bromide substitution reaction occurs for pentaerythrite；
(3) distill after completion of the reaction to 150 DEG C, steam the water of acetic acid, unreacted hydrogen bromide and reaction generation；
(4) 80 DEG C are cooled to, into the Liquid Residue after above-mentioned distillation, 8g catalyst butyl titanates is added, is passed through 180g
Isopropanol, reacts 5h, the temperature of reaction is 160 DEG C, isopropanol and the propyl acetate of generation is reclaimed in pilot process；
(5) 50 DEG C are cooled to after the completion of reacting, 2g dispersant fatty alcohol ether phosphates are added, stirring is to miscible, then
PH is adjusted to neutrality with 5% aqueous sodium carbonate；
(6) above-mentioned gained mixing organic matter is added in 2000g water and disperseed, crystallized, washing, dry, section
Product is obtained, crystallization temperature is 10 DEG C, and drying temperature is 95 DEG C.
Embodiment 2
A kind of synthetic method of tribromoneoamyl alcohol, comprises the following steps：
(1) 136g pentaerythrites and 140g reducing agent ammoniacal liquor are added in 240g organic solvent acetic acid, are warming up to 140 DEG C
All dissolvings；
(2) it is added dropwise at reflux after bromine 639g, completion of dropping and continues flow back insulation 9h, in the process, bromine
Hydrogen bromide is obtained with reducing agent urea reaction, with hydrogen bromide substitution reaction occurs for pentaerythrite；
(3) distill after completion of the reaction to 150 DEG C, steam the water of acetic acid, unreacted hydrogen bromide and reaction generation；
(4) 80 DEG C are cooled to, into the Liquid Residue after above-mentioned distillation, 16g catalyst butyl titanates is added, is passed through 240g
Isopropanol, reacts 6h, the temperature of reaction is 160 DEG C, isopropanol and the propyl acetate of generation is reclaimed in pilot process；
(5) 50 DEG C are cooled to after the completion of reacting, 6g dispersant fatty alcohol ether phosphates are added, stirring is to miscible, then
PH is adjusted to neutrality with 5% aqueous sodium carbonate；
(6) above-mentioned gained mixing organic matter is added in 4000g water and disperseed, crystallized, washing, dry, section
Product is obtained, crystallization temperature is 15 DEG C, and drying temperature is 100 DEG C.
Embodiment 3
A kind of synthetic method of tribromoneoamyl alcohol, comprises the following steps：
(1) 136g pentaerythrites and 135g reducing agent urea are added in 180g organic solvent acetic acid, are warming up to 140 DEG C
All dissolvings；
(2) it is added dropwise at reflux after bromine 480g, completion of dropping and continues flow back insulation 8h, in the process, bromine
Hydrogen bromide is obtained with reducing agent urea reaction, with hydrogen bromide substitution reaction occurs for pentaerythrite；
(3) distill after completion of the reaction to 150 DEG C, steam the water of acetic acid, unreacted hydrogen bromide and reaction generation；
(4) 80 DEG C are cooled to, into the Liquid Residue after above-mentioned distillation, 11g catalyst butyl titanates is added, is passed through 180g
Isopropanol, reacts 5h, the temperature of reaction is 160 DEG C, isopropanol and the propyl acetate of generation is reclaimed in pilot process；
(5) 50 DEG C are cooled to after the completion of reacting, 4g dispersant fatty alcohol ether phosphates are added, stirring is to miscible, then
PH is adjusted to neutrality with 5% aqueous sodium carbonate；
(6) above-mentioned gained mixing organic matter is added in 3000g water and disperseed, crystallized, washing, dry, section
Product is obtained, crystallization temperature is 20 DEG C, and drying temperature is 90 DEG C.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all skills in the present invention
On the basis of art scheme, those skilled in the art need not pay the various modifications that creative work can make or deformation still exists
In protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of tribromoneoamyl alcohol, it is characterised in that comprise the following steps：
(1) pentaerythrite and reducing agent are added in organic solvent, are warming up to whole dissolvings；
(2) it is added dropwise after bromine, completion of dropping and continues the insulation 8-10h that flows back, in the process, bromine and reduction at reflux
Agent reaction obtains hydrogen bromide, and with hydrogen bromide substitution reaction occurs for pentaerythrite；
(3) distill after completion of the reaction to 140-150 DEG C, steam the water of organic solvent, unreacted hydrogen bromide and reaction generation；
(4) 80 DEG C are cooled to, into the Liquid Residue after above-mentioned distillation, catalyst is added, is passed through alcohol gas, react 4-6h；
(5) said mixture is cooled to 50 DEG C after the completion of reacting, dispersant is added, with 5%-10% aqueous sodium carbonate
PH is adjusted to neutrality；
(6) above-mentioned gained mixing organic matter is added to the water, crystallized, product is obtained through washing, dry, section.
2. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the pentaerythrite and institute
The mol ratio for stating reducing agent is 1：The mol ratio of 2-4, the bromine and the pentaerythrite is 2-4：1, the catalyst plus
Enter the 2%-5% that amount is the Liquid Residue quality, the mol ratio of the alcohol gas and the pentaerythrite is 2-4：1, described point
The addition of powder is the 0.5%-1% of the mixture quality.
3. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the reducing agent is urine
Element, ammoniacal liquor, the one or several kinds of hydrazine hydrate.
4. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the organic solvent is first
Acid, acetic acid, propionic acid, benzoic acid, the one or more of boric acid.
5. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the organic solvent and institute
The mol ratio for stating pentaerythrite is 2-4:1.
6. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the catalyst is benzene sulphur
Acid, butyl titanate, tetraisopropyl titanate, the one or several kinds of butter of tin.
7. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that the dispersant is OP-
10th, fatty alcohol ether phosphate, phenolic ether phosphate, hydroxyethyl cellulose, the one or several kinds of neopelex.
8. a kind of synthetic method of tribromoneoamyl alcohol according to claim 1, it is characterised in that the alcohol be isopropanol,
One or more in isooctanol.
9. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that lead in the step (4)
It is 100-180 DEG C to enter the temperature that alcohol gas reacted.
10. the synthetic method of a kind of tribromoneoamyl alcohol according to claim 1, it is characterised in that in the step (6)
Crystallization temperature is 5-20 DEG C, and drying temperature is 85-105 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710401445.4A CN107129431B (en) | 2017-05-31 | 2017-05-31 | Synthetic method of tribromoneopentyl alcohol |
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| CN201710401445.4A CN107129431B (en) | 2017-05-31 | 2017-05-31 | Synthetic method of tribromoneopentyl alcohol |
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| CN107129431B CN107129431B (en) | 2020-07-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903163A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Preparation method of tribromoneopentyl alcohol |
| CN110903188A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Method for preparing tribromoneopentanol acetate |
| CN112778356A (en) * | 2020-12-26 | 2021-05-11 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
Citations (4)
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|---|---|---|---|---|
| US4929775A (en) * | 1989-05-30 | 1990-05-29 | Ethyl Corporation | Process for preparing brominated pentaerythritols |
| CN101016227A (en) * | 2007-02-08 | 2007-08-15 | 宜兴市中正化工有限公司 | Synthetic method and refining for tribromoneoamyl alcohol |
| CN101979390A (en) * | 2010-09-14 | 2011-02-23 | 华东理工大学 | Bithiazole derivates and use thereof |
| CN106589189A (en) * | 2016-11-18 | 2017-04-26 | 寿光市泰源化工有限公司 | Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production |
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2017
- 2017-05-31 CN CN201710401445.4A patent/CN107129431B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929775A (en) * | 1989-05-30 | 1990-05-29 | Ethyl Corporation | Process for preparing brominated pentaerythritols |
| CN101016227A (en) * | 2007-02-08 | 2007-08-15 | 宜兴市中正化工有限公司 | Synthetic method and refining for tribromoneoamyl alcohol |
| CN101979390A (en) * | 2010-09-14 | 2011-02-23 | 华东理工大学 | Bithiazole derivates and use thereof |
| CN106589189A (en) * | 2016-11-18 | 2017-04-26 | 寿光市泰源化工有限公司 | Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production |
Non-Patent Citations (2)
| Title |
|---|
| 化学工业部天津化工研究院等: "《化工产品手册 无机化工产品》", 31 October 1993 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903163A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Preparation method of tribromoneopentyl alcohol |
| CN110903188A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Method for preparing tribromoneopentanol acetate |
| CN110903163B (en) * | 2019-09-17 | 2023-01-03 | 丛强 | Preparation method of tribromoneopentyl alcohol |
| CN110903188B (en) * | 2019-09-17 | 2023-01-03 | 丛强 | Method for preparing tribromoneopentanol acetate |
| CN112778356A (en) * | 2020-12-26 | 2021-05-11 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
| CN112778356B (en) * | 2020-12-26 | 2022-07-01 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
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Denomination of invention: A synthetic method of tribromo neopentyl alcohol Effective date of registration: 20211022 Granted publication date: 20200724 Pledgee: Postal Savings Bank of China Limited Shouguang sub branch Pledgor: SHANDONG RIXING NEW MATERIAL CO.,LTD. Registration number: Y2021980011152 |
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