WO2005016863A1 - Procede de production d'esters de tetrabromobenzoate - Google Patents

Procede de production d'esters de tetrabromobenzoate Download PDF

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WO2005016863A1
WO2005016863A1 PCT/US2003/023636 US0323636W WO2005016863A1 WO 2005016863 A1 WO2005016863 A1 WO 2005016863A1 US 0323636 W US0323636 W US 0323636W WO 2005016863 A1 WO2005016863 A1 WO 2005016863A1
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Prior art keywords
ester
reactor
tetrabromobenzoate
alcohol
mixture
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PCT/US2003/023636
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English (en)
Inventor
Stephen B. Falloon
David W. Bartley
James D. Siebecker
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Great Lakes Chemical Corporation
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Application filed by Great Lakes Chemical Corporation filed Critical Great Lakes Chemical Corporation
Priority to CN038268582A priority Critical patent/CN1819988B/zh
Priority to JP2005507850A priority patent/JP4464921B2/ja
Priority to EP03818188A priority patent/EP1658261A1/fr
Priority to PCT/US2003/023636 priority patent/WO2005016863A1/fr
Priority to KR1020067001932A priority patent/KR101000245B1/ko
Priority to AU2003304412A priority patent/AU2003304412A1/en
Publication of WO2005016863A1 publication Critical patent/WO2005016863A1/fr
Priority to IL173238A priority patent/IL173238A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/32—Decarboxylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to methods for synthesizing tetrabromobenzoate esters and, more particularly, to a method for synthesizing tetrabromobenzoate esters from tetrabromophthalic anhydride using a process that provides high yields.
  • Tetrabromobenzoate esters have been formed as minor by-products in the synthesis of tetrabromophthalate diesters from tetrabromophthalic anhydride. However, these by-products are considered undesirable in the synthesis of tetrabromophthalate diesters and, therefore, the process has been refined to avoid the production of tetrabromobenzoate esters. Tetrabromobenzoate esters have also been synthesized directly through the esterification of tetrabromobenzoic acid using a metal or organometallic esterification catalyst. Unfortunately, tetrabromobenzoic acid is not readily available and, therefore, must be synthesized prior to esterification.
  • tetrabromobenzoate ester compounds have been prepared from tetrabromophthalic anhydride using a one-pot batch synthesis in which tetrabromophthalic anhydride is reacted in a single reactor with an appropriate alcohol in the presence of a decarboxylation catalyst to form the tetrabromobenzoate ester. More specifically, the tetrabromophthalic anhydride is reacted with the alcohol at low reactor temperatures to form a half-ester intermediate.
  • the reactor is then heated to higher temperatures and the half-ester intermediate, in the presence of a decarboxylation catalyst, forms the tetrabromobenzoate ester.
  • this reaction scheme yields a product containing the target compound tetrabromobenzoate ester and a significant amount of tetrabromophthalate diester.
  • the reaction product often has an undesirable amber color. Therefore, a need remains for a more efficient process for producing tetrabromobenzoate esters.
  • the present provides a method for preparing tetrabromobenzoate ester from tetrabromophthalic anhydride comprising the steps of combining the tetrabromophthalic anhydride and an alcohol in at least one reaction vessel to form a first reaction mixture; heating the first reaction mixture to a temperature that favors partial esterification over complete esterification to form a tetrabromophthalate half- ester intermediate mixture; feeding the tetrabromophthalate half-ester intermediate mixture and a catalyst to at least one heated reactor having a temperature that favors decarboxylation over esterification; and maintaining the at least one reactor at the temperature that favors decarboxylation over esterification to produce a tetrabromobenzoate ester-containing product.
  • the temperature that favors partial esterification over complete esterification is between about 70°C and about 130°C, and the temperature that favors decarboxylation over esterification is between about 190°C and about 205°C.
  • the method of the present invention maybe conducted continuously, semi-continuously or in batch.
  • the alcohol has the general formula ROH, wherein R is an organic group having up to about 30 carbon atoms.
  • the catalyst may be any compound that promotes the decarboxylation reaction over the esterification reaction. Appropriate catalysts may include carbonates, alkali bicarbonates, alkalis, and mixtures thereof.
  • the present invention further provides a method for the preparation of tetrabromobenzoate esters comprising the steps of feeding either tetrabromophthalic anhydride, tetrabromophthalic diacid, or mixture thereof, and an alcohol to at least one reactor wherein the first of the at least one reactor contains a product mixture, the product mixture comprising tetrabromobenzoate ester, the at least one reactor having a temperature that favors decarboxylation over esterification; and maintaining the at least one reactor at the temperature that favors decarboxylation over esterification to produce a tetrabromobenzoate-containing product.
  • the present invention is directed to a method for converting tetrabromophthalic anhydride to a selected tetrabromobenzoate ester.
  • the conversion of tetrabromophthalic anhydride to tetrabromobenzoate ester includes two steps. The first step involves the partial esterification of tetrabromophthalic anhydride with an appropriate alcohol to produce the intermediate, tetrabromophthalate half-ester, which also bears a carboxylic acid group.
  • the half-ester intermediate proceeds, in the presence of a decarboxylation catalyst, by either a decarboxylation or esterification reaction to produce the selected tetrabromobenzoate ester or tetrabromophthalate diester, respectively.
  • a decarboxylation catalyst for either a decarboxylation or esterification reaction to produce the selected tetrabromobenzoate ester or tetrabromophthalate diester, respectively.
  • the process of the present invention favors the decarboxylation reaction and, therefore, produces a higher product ratio of tetrabromobenzoate to tetrabromophthalate diester.
  • the general synthetic process is shown in Scheme I below, wherein the group R generally represents an organic group having up to about 30 carbon atoms:
  • the first step of the process involves combining the tetrabromophthalic anhydride and an alcohol in a suitable reaction vessel to form a first reaction mixture, and subjecting the first reaction mixture to conditions that favor the formation of the tetrabromophthalate half-ester.
  • the tetrabromophthalic anhydride is reacted with an alcohol under conditions that favor the partial, rather than complete, esterification of the tetrabromophthalic anhydride.
  • Such conditions may include a reaction temperature below about 130°C. Particularly, it has been found that heating the first reaction mixture to a temperature between about 70°C and about 130°C favors partial esterification rather than complete esterification.
  • reaction mixture heating the reaction mixture to between about 90°C and about 130°C has produced particularly favorable results. Reaction temperatures between about 90°C and about 120°C may produce even more favorable results. Furthermore, factors such as the reactivity of the particular alcohol used and the amount of excess alcohol present in the reaction may influence the optimum temperature.
  • the reaction temperature may be maintained for about 1-4 hours or until formation of the half-ester is complete.
  • the resulting tetrabromophthalate half- ester intermediate mixture preferably comprises a conversion of at least about 50 mole % of the tetrabromophthalic anhydride to the half-ester, and more preferably about a 95 mole % conversion.
  • the half-ester may be useful to maintain the half- ester intermediate mixture at an elevated storage temperature to prevent the formation of solids.
  • the ideal storage temperature will depend upon factors such as the alcohol used in the reaction and the amount of excess alcohol present in the half-ester intermediate mixture. For instance, it has been found that when 2-ethylhexanol is used, maintaining the storage temperature above 90°C helps to prevent crystallization of the half-esters, while maintaining the storage temperature below 120°C helps to prevent or limit formation of the phthalate diester.
  • Suitable reaction vessels for the partial esterification step include stirred tank reactors and hot tube reactors. This partial esterification step may be conducted in batch, semi-continuous, or continuous fashion.
  • stirred tank reactors connected in series When run continuously, one or more stirred tank reactors connected in series may be employed, or alternatively, a series of tube reactors may be used.
  • no catalyst is needed to promote the formation of the half- ester.
  • current commercial tetrabromophthalic anhydride typically contains a small amount of residual mineral acid from the manufacturing process, it may be useful to add a small amount of weak base to neutralize the acid. If left unneutralized, the acid may promote formation of the corresponding ether from two molecules of the selected alcohol, the ether having the formula R-O-R, with the R group being described below.
  • the weak base used to neutralize the acid may also function as the catalyst for promoting decarboxylation over esterification in the second step.
  • alkali carbonates, alkali bicarbonates and caustic alkalis can serve as the neutralizing agent/decarboxylation catalyst.
  • Sodium and potassium carbonate and bicarbonate, lithium carbonate and sodium aluminate may be particularly useful.
  • the amount of weak base to be added depends upon the amount of residual mineral acid contained in the particular lot of tetrabromophthalic anhydride being used. The manufacturer of the tetrabromophthalic anhydride typically provides this information. Based on the acid content, the amount of weak base may then be calculated to provide from about 1.0 to about 1.5 equivalents of base per equivalent of acid. Larger amounts may be used, but may result in the need for additional purification of the reaction product.
  • the alcohol used in the partial esterification step has the general formula ROH, in which R is an organic group having up to about 30 carbon atoms in a linear or branched arrangement.
  • the organic group of the alcohol may also be substituted with one or more groups such as alkoxy, halo, amino, thio, and the like.
  • Alcohols particularly useful in the present invention include alcohols having a boiling point of above about 160°C. Of these alcohols, those having a boiling point below about 230°C are preferred. These alcohols allow the decarboxylation reaction to proceed at a reasonable rate, while still allowing for ease of stripping the excess alcohol from the product at the end of the reaction.
  • Particularly useful alcohols are non-halo genated, non-sulfur-containing, and non-nitrogen-containing alcohols. Branched chain alcohols are particularly useful. Mixtures of alcohols having less than perfect separation may also be used. Appropriate alcohols with boiling points between about 160°C and about 230°C include 2-(2-methoxy)ethoxyethanol, 2-butoxyethanol, 3,3-diethoxy-l- propanol, di(propylene glycol) methyl ether, 2-ethyl-l-hexanol, 3-ethyl-l-hexanol, 3,4-dimethyl-l-hexanol, 3,5-dimethyl-l-hexanol, 3 -methyl- 1-heptanol, 4-methyl-l- heptanol, 2-octanol, 5-methyl- 1-heptanol, 3-octanol, 2-propyl-l-pentanol, 2,6- dimethyl-4-heptanol
  • the first step of the process may be carried out in an inert solvent, such as a high boiling ether, in near stoichiometric amounts of the alcohol (e.g., 1.0 to 1.25 mole equivalents).
  • inert solvents particularly useful in the present invention have a boiling point of between about 160°C and about 230°C, such as, for example, 2-ethoxyethylether, also known as diethylene glycol diethyl ether.
  • ethers of diethylene glycol may also be suitable, such as the dimethyl, dipropyl, dibutyl and dihexyl ethers.
  • Mixed ethers such as the methylethyl ether of diethylene glycol are also suitable, as are aromatic ethers such as diphenyloxide.
  • Hydrocarbon solvents may be useful, including high boiling materials such as 1,2-diphenylethane.
  • the inert solvent should have solubility properties that allow the reaction to proceed at a reasonable rate, particularly by accommodating the solubility of the polar intermediate (or its salt complex).
  • alcohols with boiling points below 160°C may be used.
  • such alcohols with boiling points as low as about 100°C maybe used in conjunction with a high boiling solvent.
  • non-halogenated, non-sulfur-containing, non-nitrogen-containing alcohols with boiling points above about 130°C may be used.
  • Branched chain alcohols are particularly effective.
  • Examples of appropriate alcohols with boiling points lower than about 160°C include 2-ethoxyethanol, amyl alcohol, 2-methyl-l -butanol, 3-methyl-l- butanol, 3-ethoxy-l-propanol, 2-ethyl-l -butanol, 4-methyl-2-pentanol, 2,4-dimethyl- 3-pentanol, acetol, 2-butyne-l-ol, 3-butyn-l-ol, l-pentyn-3-ol, 2-pentyn-l-ol, 3- pentyn-1-ol, 4-pentyn-l-ol, 4-pentyn-2-ol, cyclobutanemethanol, 3-methyl-2-buten-l- ol, 3-methyl-3-buten-l-ol, 2-penten-l-ol, 4-penten-l-ol, 1-pentanol, cyclohexanol, 1- hexen-3-ol,
  • the second step of the process involves reacting the tetrabromophthalate half-ester intermediate mixture, either by a non-continuous process or in a continuous fashion, with a catalyst in one or more suitable reactors under conditions that favor decarboxylation over esterification to produce a benzoate- containing product mixture.
  • a stirred tank reactor has been found to be a suitable reactor. However, it is also contemplated that tube reactors may also be used. Furthermore, feeding the tetrabromophthalate half-ester to multiple reactors connected in series has demonstrated unpredictably favorable results.
  • the catalyst used in the second step should be a catalyst that favors decarboxylation over esterification.
  • catalysts examples include alkali carbonates, alkali bicarbonates and caustic alkalis. Sodium and potassium carbonate and bicarbonate, lithium carbonate and sodium aluminate may be particularly useful. As is noted above, these compounds may also be used as a neutralizing agent in the partial esterification step to neutralize any residual mineral acid.
  • the catalyst loading may affect the product ratio of tetrabromobenzoate ester to tetrabromophthalate ester. For instance, in the case of a lower catalyst loading, the decarboxylation step may be slower, which may allow greater formation of diester.
  • Aromatic Ether By-Product With a higher catalyst loading, lower amounts of diester are formed but increasing amounts of other by-products, such as the aromatic ether shown below, have been observed. In addition, the use of an excess of strong base as the catalyst/neutralization agent may also increase the formation of the aromatic either by-product shown below.
  • catalyst loading below 25 mole percent based upon the tetrabromophthalic anhydride charge has been particularly effective. More particularly, catalyst loading below 15 mole percent has demonstrated good results. Further favorable results have been achieved using catalyst loading between about 1 mole percent and 15 mole percent. It is believed that the selection of the proper catalyst, catalyst loading and reaction conditions, may result in a benzoate ester product having less than about 1% (GC area percent) of the aromatic ether by-product. It should also be understood that some catalysts yield a lighter colored product.
  • the conditions that favor decarboxylation may also include reaction vessel temperatures above about 160°C.
  • the esterification reaction may compete significantly with the decarboxylation reaction resulting in an end product containing a substantial amount of the tetrabromophthalic diester. More particularly, temperatures above about 180°C have been found to favor the decarboxylation reaction over the esterification reaction, and temperatures below about 215°C are particularly useful. Temperatures between about 190°C and about 215°C have been shown to favor considerably decarboxylation. Moreover, temperatures between about 190°C and about 210°C have produced favorable results. More particularly, temperatures between 200°C and 205°C have produced particularly favorable results.
  • the first step involves forming the half-ester intermediate mixture as described above.
  • the tetrabromophthalate half-ester intermediate mixture is fed, either by a batch process or in a continuous fashion, to one or more suitable reactors containing an amount of tetrabromobenzoate and having a temperature that favors decarboxylation over esterification.
  • the half- ester intermediate reacts with a catalyst favoring decarboxylation over esterification as described above.
  • the decarboxylation catalyst may be included in the half-ester feed stream or, alternatively, may be present in the reaction vessel with the tetrabromobenzoate ester. It may be useful to add the half-ester intermediate mixture to the reactor or reactors at a rate that prevents the reactor temperature from dropping below the favorable range.
  • the second step of the process may be performed in non-continuous or continuous fashion.
  • the temperature and agitation are maintained until the reaction is complete, generally about 2-8 hours, with the composition of the product determined by liquid chromatography if so desired.
  • the tank reactor may be partially drained, leaving in the reactor an amount of crude product (a "heel") sufficient to permit agitation.
  • the drained product washed and stripped of excess alcohol.
  • the heel in the reactor at the temperature favoring decarboxylation may then accept more half-ester intermediate mixture and aid in rapidly increasing the temperature of the half-ester intermediate mixture into the temperature range favoring decarboxylation.
  • the high temperature decarboxylation process may be thus repeated.
  • the resulting tetrabromobenzoate ester-containing product has a clear, light amber color and comprises at least about 75% tetrabromobenzoate ester, and more favorably at least about 85% tetrabromobenzoate ester.
  • the amount of the heel remaining in the reactor influences the temperature of the blended heel and half-ester intermediate.
  • the heat transfer characteristics of the tank reactor and the rate at which the half-ester intermediate mixture is added to the reactor also influences both the temperature of the blended heel and half-ester intermediate and the through put of the process. In the continuous procedure, as the half-ester intermediate mixture is added, the product of the reactor may be removed to maintain a constant fill level.
  • the product being removed during the continuous procedure may contain a quantity of half-ester. Therefore, it may be useful to feed the product continuously to one or more additional reactors connected in series and maintained at temperatures within the decarboxylation favorable range described above. It may also be advantageous to filter, wash, and/or vacuum strip the product to remove any excess unreacted alcohol. The unreacted alcohol may be recycled back into the process.
  • the resulting tetrabromobenzoate ester-containing product has a clear, light amber color and comprises at least about 75% tetrabromobenzoate ester, and more favorably at least about 85% tetrabromobenzoate ester.
  • the half-ester intermediate is formed in- situ by feeding the starting materials, tetrabromophthalic anhydride and alcohol, either separately or as a slurry, directly to a heated reactor containing an amount of tetrabromobenzoate ester and having a temperature that favors decarboxylation over esterification.
  • the acid neutralizing agent/decarboxylation catalyst may be included in the starting material feed stream or may be present in the reaction vessel with the tetrabromobenzoate ester.
  • the full esterification of tetrabromophthalic anhydride is a two step process, and also because the decarboxylation step will not occur until the half-ester is formed, the half-ester forms first followed by the competing diesterification and decarboxylation reactions.
  • the elevated temperature of the heated reactor and the presence of a decarboxylation catalyst promotes the formation of the tetrabromobenzoate ester over the diester.
  • the process of this embodiment may also be conducted in non- continuous form or continuous form.
  • a tetrabromobenzoate ester and decarboxylation catalyst may be added to a reactor, such as a stirred tank reactor, filling the reactor to between about 10% and about 50% full by volume, more preferably to between about 20% and about 50% full, and even more advantageously to between about 20% and about 30% full.
  • the reactor may then be heated to the previously described temperatures that favor decarboxylation over esterification.
  • the starting materials namely tetrabromophthalic anhydride and alcohol, may then be added to the hot tetrabromobenzoate ester mixture with agitation and at a rate that prevents the temperature from falling below the decarboxylation favorable range and until the reactor reaches a desired fill level.
  • the decarboxylation catalyst may either be charged to the reactor along with the tetrabromobenzoate ester, or may be added along with the starting materials. As described previously, the amount of decarboxylation catalyst will be between about 1 mole % and about 25 mole % based on the tetrabromophthalic anhydride.
  • reaction vessel may be filled to between about 60% and about 90%o by volume with tetrabromobenzoate ester and decarboxylation catalyst.
  • the mixture may be heated as previously described to temperatures that favor decarboxylation over esterification.
  • the starting materials may then be added at a rate that prevents the temperature from falling below the favorable range.
  • the product of the vessel may be removed to maintain a constant fill level of between about 60% and about 90%.
  • the product being removed may contain a quantity of half-ester. Therefore, the product may be fed continuously to one or more additional reactors, which are connected in series and are maintained at temperatures within the decarboxylation favorable range described above.
  • the final product may optionally undergo one or more work-up or finishing steps, such as filtration, aqueous washings, and a vacuum strip to remove excess unreacted alcohol.
  • the unreacted alcohol may be recycled back into the process.
  • the resulting tetrabromobenzoate ester-containing product has a clear, light amber color and comprises at least about 75% tetrabromobenzoate ester, and more favorably at least about 85% tetrabromobenzoate ester.
  • tetrabromophthalic anhydride as a starting material
  • the process of the present invention may alternatively use tetrabromophthalic diacid as a starting material.
  • the anhydride may be a more desirable starting material due to its commercial availability, its reactivity towards formation of the half-ester, and the minimal evolution of water during formation of the half-ester.
  • the ring-brominated benzoates produced in accordance with the invention are useful as flame retardants in a variety of polymer resin systems.
  • the bromobenzoate compound can be incorporated into thermoset polymers such as polyurethanes by including the bromobenzoate in the polyurethane mixture as the polymer is prepared. This process has been referred to as the "one-shot” technique, and is described with more particularity in common reference materials such as the Modern Plastics Encyclopedia, Vol. 71, No. 12 (1994).
  • bromobenzoates into polyvinyl chlorides maybe accomplished either by including the desired tetrabromobenzoate ester in the mixture as the polyvinyl chloride is being formed, or by incorporating the bromobenzoate into polymerized polyvinyl chloride.
  • Specific techniques for incorporating additives such as bromobenzoates into thermoplastics such as PVC are known to the art and may be used to accomplish that step. It should be understood that the level of bromobenzoate incorporated into the polymer resin to provide an effective flame retarding amount will vary widely in accordance with many factors such as the particular resin used, the application contemplated, other additives present, etc.
  • the bromobenzoate will be incorporated at levels above about 2% of the total system weight. Levels below about 50% are particularly effective, and levels between about 2% and 30% have demonstrated good results. Finally, levels between about 5% and 30% are exceptionally effective.
  • other conventional additives may also be incorporated into the polymer systems.
  • the bromobenzoate product can be incorporated along with other brominated flame retardant compounds. Flame retardant materials such as oxides of Group V elements, especially antimony oxides, and/or phosphorous-containing compounds, can also be included.
  • Additional conventional additives may include antioxidants, antistatic agents, colorants, fibrous reinforcements, fillers, foaming blowing agents, catalysts, heat stabilizers, impact modifiers, lubricants, plasticizers, processing aids, UV light stabilizers, and crosslinking/curing agents.
  • the reactants listed in Table 1 were charged into a glass lined reactor under agitation. The mixture was heated to 120°C over a 1 hour period and then held at 120°C for 2 hours. The resulting intermediate was essentially the 2-ethylhexyl half-ester of tetrabromophthalic anhydride dissolved in excess 2-ethylhexanol. Then, a portion of this mixture was then transferred to another glass lined reactor. The mixture was heated to 200°C over a 1 hour period and then held at 200°C for 8 hours. The water of the reaction (generated by the formation of the undesired tetrabromophthalate diester) was separated from the reaction product.
  • the reaction mixture was then continuously fed to the first of two glass lined reactors connected in series, both having a temperature of about 200°C. As the first reactor became full, the reaction mixture was drained to the second reactor. The reactors were maintained at 200°C. The residence time in each reactor was 3.4 hours. As the second reactor became full, the reaction material from the second reactor was drained to a glass-lined reaction vessel and washed with water. The reaction stream was then fed to a decanter to remove the water. The reaction stream was then fed to a wiped film evaporator (WFE) having an oil temperature of about 235°C and vacuum pressure of between about 3 mmHg and 7 mmHg to remove the excess 2-ethylhexanol. The resulting product was a clear amber liquid that tested using HPLC and the Gardner Color Test and the results are listed below in Table 2. TABLE 2
  • Example II The comparison of the results of both Example I and Example ⁇ , illustrated in Table 2, demonstrates that the process of the present invention, as compared to the prior art Batch Synthesis process, yields approximately 16.9% more of the targeted product, 2-ethylhexyltetrabromobenzoate ester.
  • the reaction product of the present invention process has a lighter amber color, which is typically more desirable than the darker amber color of the product produced by the prior art Batch Synthesis process.
  • the tetrabromophthalic anhydride and 2-ethylhexanol were combined and slurried to form a first reaction mixture.
  • This first reaction mixture was heated briefly to about 125°C to form a nearly clear solution.
  • the first reaction mixture was transferred to a heated, metered addition funnel, which was connected to a reactor.
  • the crude benzoate ester from a previous run along with the sodium bicarbonate were charged into the second reactor and heated to 205 °C. Over about a three hour period the first reaction mixture was metered into the second reactor, followed by a hold period of about six hours.
  • the crude product was water washed and excess alcohol was stripped on a wiped film evaporator at a temperature of about 175°C and a vacuum of between 3-5 mmHg.
  • the finished product contained about 77% 2-ethylhexyltetra-bromobenzoate and 21% bis(2-ethylhexyl)tetrabromophthalate, and had a Gardner Color result of 9- 10.

Abstract

L'invention concerne un procédé de préparation d'un ester de tétrabromobenzoate à partir d'un anhydride tétrabromophthalique, consistant à faire réagir l'anhydride tétrabromophthalique avec un catalyseur et un alcool à une température favorisant l'estérification partielle plutôt que l'estérification complète de l'anhydride tétrabromophthalique, afin de former un mélange de réaction d'un demi-ester de tétrabromophthalate, et à injecter ledit mélange de réaction dans au moins un réacteur ayant et maintenant une température favorisant la décarboxylation par rapport à la estérification, afin d'obtenir un produit contenant un ester de tétrabromobenzoate. La température favorisant l'estérification de l'anhydride tétrabromophthalique se situe entre environ 70°C et 130°C. La température favorisant la décarboxylation par rapport à l'estérification se situe entre environ 190°C et 205°C. Le produit contenant un ester de tétrabromobenzoate comprend au moins environ 85% d'un ester de tétrabromobenzoate. Ledit réacteur peut comprendre deux ou plusieurs réacteurs connectés les uns aux autres en série.
PCT/US2003/023636 2003-07-29 2003-07-29 Procede de production d'esters de tetrabromobenzoate WO2005016863A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN038268582A CN1819988B (zh) 2003-07-29 2003-07-29 生产四溴苯甲酸酯的方法
JP2005507850A JP4464921B2 (ja) 2003-07-29 2003-07-29 テトラブロモ安息香酸エステルの製造方法
EP03818188A EP1658261A1 (fr) 2003-07-29 2003-07-29 Procede de production d'esters de tetrabromobenzoate
PCT/US2003/023636 WO2005016863A1 (fr) 2003-07-29 2003-07-29 Procede de production d'esters de tetrabromobenzoate
KR1020067001932A KR101000245B1 (ko) 2003-07-29 2003-07-29 테트라브로모벤조에이트 에스테르의 제조방법
AU2003304412A AU2003304412A1 (en) 2003-07-29 2003-07-29 Process for producing tetrabromobenzoate esters
IL173238A IL173238A (en) 2003-07-29 2006-01-19 Methods for producing tetrabromobenzoate esters

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JP (1) JP4464921B2 (fr)
KR (1) KR101000245B1 (fr)
CN (1) CN1819988B (fr)
AU (1) AU2003304412A1 (fr)
IL (1) IL173238A (fr)
WO (1) WO2005016863A1 (fr)

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CN103467705A (zh) * 2013-09-26 2013-12-25 南京年吉冷冻食品有限公司 一种阻燃型聚氨酯硬质泡沫塑料的制备方法
WO2019164763A1 (fr) * 2018-02-22 2019-08-29 Exxonmobil Research And Engineering Company Huiles de base d'huile lubrifiante à base de monoester de benzoate à faible viscosité et faible volatilité et leurs procédés d'utilisation

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CN103232379B (zh) * 2013-04-09 2016-01-13 山东润科化工股份有限公司 一种四溴苯酐二醇的合成方法
CN106187758A (zh) * 2016-07-22 2016-12-07 潍坊玉成化工有限公司 一种四溴苯甲酸异辛酯的合成方法
CN111286083A (zh) * 2020-03-30 2020-06-16 广州埃登达化工有限公司 一种溴类阻燃剂及其制备方法
CN115124425B (zh) * 2022-06-27 2023-10-17 浙江海昇药业股份有限公司 一种3,5-二溴-4-羟基苯甲酸二聚物、合成方法及其应用

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US5049697A (en) * 1987-09-21 1991-09-17 Atochem North America, Inc. High yield method for preparation of dialkyl esters of polyhaloaromatic acids
WO1996032438A1 (fr) * 1995-04-11 1996-10-17 Great Lakes Chemical Corporation Benzoates utilises comme agents ignifugeant et/ou plastifiants
US5637757A (en) * 1995-04-11 1997-06-10 Great Lakes Chemical Corporation One-pot synthesis of ring-brominated benzoate compounds
WO1998057920A2 (fr) * 1997-06-18 1998-12-23 Great Lakes Chemical Corporation Nouveaux plastifiants ignifuges

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US5049697A (en) * 1987-09-21 1991-09-17 Atochem North America, Inc. High yield method for preparation of dialkyl esters of polyhaloaromatic acids
WO1996032438A1 (fr) * 1995-04-11 1996-10-17 Great Lakes Chemical Corporation Benzoates utilises comme agents ignifugeant et/ou plastifiants
US5637757A (en) * 1995-04-11 1997-06-10 Great Lakes Chemical Corporation One-pot synthesis of ring-brominated benzoate compounds
WO1998057920A2 (fr) * 1997-06-18 1998-12-23 Great Lakes Chemical Corporation Nouveaux plastifiants ignifuges

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467705A (zh) * 2013-09-26 2013-12-25 南京年吉冷冻食品有限公司 一种阻燃型聚氨酯硬质泡沫塑料的制备方法
WO2019164763A1 (fr) * 2018-02-22 2019-08-29 Exxonmobil Research And Engineering Company Huiles de base d'huile lubrifiante à base de monoester de benzoate à faible viscosité et faible volatilité et leurs procédés d'utilisation

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KR20060079185A (ko) 2006-07-05
IL173238A (en) 2012-06-28
AU2003304412A1 (en) 2005-03-07
JP4464921B2 (ja) 2010-05-19
CN1819988A (zh) 2006-08-16
JP2007521229A (ja) 2007-08-02
CN1819988B (zh) 2010-12-08
IL173238A0 (en) 2006-06-11
EP1658261A1 (fr) 2006-05-24
KR101000245B1 (ko) 2010-12-10

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