WO1993025525A1 - N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et preparation de celui-ci dans l'acide acetique - Google Patents

N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et preparation de celui-ci dans l'acide acetique Download PDF

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Publication number
WO1993025525A1
WO1993025525A1 PCT/EP1993/001402 EP9301402W WO9325525A1 WO 1993025525 A1 WO1993025525 A1 WO 1993025525A1 EP 9301402 W EP9301402 W EP 9301402W WO 9325525 A1 WO9325525 A1 WO 9325525A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
product
bis
temperature
tetrabromophthalimide
Prior art date
Application number
PCT/EP1993/001402
Other languages
English (en)
Inventor
Brian Tarbit
Brian Adger
Paul Willett
Original Assignee
Great Lakes Chemical (Europe) Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9212090A external-priority patent/GB2267704A/en
Priority claimed from US07/954,281 external-priority patent/US5317048A/en
Application filed by Great Lakes Chemical (Europe) Ltd. filed Critical Great Lakes Chemical (Europe) Ltd.
Priority to AU43222/93A priority Critical patent/AU4322293A/en
Priority to EP93912874A priority patent/EP0644875A1/fr
Publication of WO1993025525A1 publication Critical patent/WO1993025525A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide

Definitions

  • the present invention relates generally to fire retardants for use in polymer compositions and the like. More particularly, the present invention relates to an ul ra-white N, '-ethylene-bis-( etrabromophthalimide) composition and to a method for its production.
  • Fire retardant compositions are performance chemicals that must meet exacting standards to gain acceptance and widespread use in industry. Among requirements for flarne retardants, color is of particular importance. For a majority of applications, it is desired that the flame retardant be as white as possible. This enables production of high quality white plastics, but is also important because polymer processors require that colors of end products result from the particular pigment utilized rather than its combination with the color of the flame retardant.
  • EBT EBT
  • Another object of this invention is to provide a uniquely white EBT composition for use as a flame retardant. Another object of the invention is to provide a method for producing a uniquely white EBT composition.
  • Another object of the invention is to provide a polymer composition and articles produced therefrom comprising the uniquely white EBT composition.
  • N,N'-ethylene-bis(tetrabromophthalimide) is then recovered in a white precipitate, which is dried, so as to form a N,N'-ethylene-bis(tetrabromophthalimide) product with a yellowness index of about 4 or less.
  • this process is achieved by the steps of slurrying tetrabromophthalic anhydride into acetic acid, adding ethylene diamine to the slurry at a temperature of at least about 80°C to form a reaction mixture, reacting the reaction mixture at a temperature of at least about 120°C to achieve at least 70% conversion to
  • N,N'-ethylene-bis(tetrabromophthalimide) recovering a precipitate from the reaction mixture including the N,N'-ethylene-bis(tetrabromophthalirnide) , and drying the precipitate to obtain a white particulate product predominantly comprised of
  • Another preferred embodiment of the invention relates to a flame retardant composition predominantly comprised of N,N'-ethylene-bis-(tetrabromophthalimide) and having a yellowness index of about 4 or less.
  • EBT compositions of this embodiment also preferably have a whiteness index of about 70 or greater.
  • Such EBT compositions have unprecedented color quality in combination with other advantageous features further described below.
  • a feature of this invention is the production of a highly white
  • N,N'-ethylene-bis(tetrabromophthalimide) product by reacting ethylene diamine and tetrabromophthalic anhydride in an acetic acid medium. It has been discovered that by conducting this reaction in an acetic acid medium, EBT products of unprecedented whiteness can be obtained.
  • the acetic acid used as the reaction medium starting material is preferably of high purity.
  • the use of acetic acid of 99%+ purity is preferred, and such grades are commercially available from many sources. It is most preferred that the initial water content of the acetic acid be less than about 0.1% although this has not been found to be critical to obtain desirable processes and products of the present invention.
  • the applicants have discovered that the presence of acetic anhydride in the acetic acid can lead to the formation of an impurity which adversely affects TGA's of the final product.
  • this impurity is diacylated amidic acid, that is, amidic acid that has been acylated at each nitrogen. Based on this discovery it is highly advantageous to employ acetic acid having low acetic anhydride content, such as less than about 0.1%.
  • the acetic acid used for the reaction medium may be regenerated from the mother liquors of a previous synthesis, while still obtaining the uniquely white product. This can be accomplished by treating the mother liquors from a previous reaction with sufficient acetic anhydride to remove the water present. This acetic anhydride treatment is desirably conducted at a temperature of about 0-150°C. Further, after this treatment, the liquors can be distilled before use in the subsequent reaction, although this has not proven to be necessary.
  • Tetrabromophthalic anhydride suitable for use in the process of the invention is commercially available. Particle sizes ranging up to 1000 microns or more are suitable for use in the invention, although it is preferable to use micronized material with an average particle diameter of less than about 50 microns. Additionally, the acid number of the TBPA is desirably less that about 0.2 mg/g to prevent formation of impurities, for example those which may be related to salts of the ethylene diamine.
  • ethylene diamine refers to 1,2-diaminoethane. This material is also available from commercial sources, and for use in the present invention preferably assays at 99%+ purity. In particular, it is highly desirable that the ethylene diamine be free from water and carbonate.
  • a slurry of tetrabromophthalic anhydride in the acetic acid medium may be formed in the reaction vessel, or may be formed and then provided to the reaction vessel.
  • the reaction vessel utilized will be able to withstand the pressure generated by the use of the acetic acid medium at the specified reaction temperatures.
  • the slurry is preheated to a temperature between about 80° and about 160°C, preferably about 90° to about 120°C, with agitation. This preheating can be for several hours or more but is preferably for a period up to about 1 hour.
  • the EDA is added while the slurry remains at a temperature of about 80° to about 160°C, more preferably about 90° to about 120°C.
  • the addition of EDA can be carried out over 1-2 hours or more, but is preferably carried out in less than about 10 minutes and more preferably less than about 5 minutes, for instance about 2 minutes or less.
  • the addition of EDA which is preferably in neat form but may also be in a suitable solvent (in small amounts to maintain the essentially acetic acid reaction medium sufficient to achieve the superior product color), is desirably achieved by blowing the EDA into the reaction vessel under pressure of an inert gas such as nitrogen to ensure a rapid addition and to ensure against hang-up in the lines.
  • an inert gas such as nitrogen
  • the EDA will be added in essentially stoichiornetric amount (i.e. essentially a 1:2 molar ratio) with respect to the TBPA. That is, about 1 mole of EDA will be added for every 2 moles of TBPA in the slurry. It is important that this stoichiornetric ratio be maintained since variations from it can lead to discolored product. For this reason, it is most preferable that the molar ratio of EDA to TBPA be kept in the range of 1:1.9 to 1:2.1. In highly advantageous reactions thus far, EDA to TBPA molar ratios of 1.01 to 2.00 have been employed while still acheiving 100% conversion of the TBPA to the amidic acid intermediate.
  • the reaction is conducted at a temperature of about 110° to about 250°C, more preferably about 120° Lo about 180°C, with those temperatures above about 150°C being most preferred.
  • the water of reaction can but does not necessarily remain in the reaction mixture, which can be agitated using conventional and commercially available agitation systems.
  • the reaction is continued at the reaction temperature preferably until at least about 70% conversion to the cyclized EBT product is obtained.
  • the termination of the reaction prior to achieving this 70% conversion results in substantial yellowing upon drying the precipitated material to achieve further cyclization and obtain the final dried product. For this reason it is even more preferred that the reaction be continued until conversion to the EBT product is essentially complete, e.g.
  • Conversion to the cyclized EBT product can be determined, for instance, by observing the water event (which occurs upon cyclization of the amidic acid intermediate to form the EBT final product) by thermogravimetric analysis ("TGA").
  • TGA thermogravimetric analysis
  • desirable reactions conducted at temperatures of about 160° to about 170°C have been continued for periods in the range of 10 hours or more to essentially complete conversion to the cyclized EBT product, although this duration will of course vary in accordance with factors such as the temperature of reacting.
  • the pressure of reacting has thus far been the autogenous pressure of the reaction mixture at the reaction temperature used, or slightly higher due to the pressurized nitrogen gas used during addition of the EDA.
  • reaction pressures of about 30 psi have been observed, although the pressure can be higher or lower and will of course vary with other reaction parameters.
  • the reaction mixture can be cooled to about 20° to about 100°C, more typically 80° to about 100°C, and the solids (typically up to about 40 weight% of the reacted medium and moie preferably about 5% to about 30% of the reacted medium) can be isolated, e.g. by conventional centrifugation.
  • the isolated product may then be washed, but it has advantageously been discovered that such washing is unnecessary to produce the high quality white products herein described.
  • the isolated solid EBT composition is dried, preferably at elevated temperature, to remove acetic acid a d to complete any residual cyclization to the EBT product.
  • the drying and residual cyclization can be conducted at any temperature, but this step is preferably conducted at a temperature of at least about 175°C and more typically at least about 200°C.
  • the duration of the drying will vary in accordance with many factors such as the particular drying temperature used and the qualities of the EBT material being dried.
  • the drying will in any event be of sufficient temperature and duration to essentially complete the residual cyclization to form a predominantly EBT product, which can be monitored by TGA.
  • TGA TGA
  • the EBT products typically have acid numbers of about 1 mg/g or less and more typically 0.5 mg/g or less. Bromine contents of the EBT products are usually at least about 65% and more usually about 65% to about 69%. Typical products also have melting point onsets above about 445°C, for instance usually in the range of about 460°C and above.
  • the EBT product can be milled during and/or after the drying operations, for example as occurs in a inkworth plough share type mixer. The dried product is then preferably micronized to provide an average particle diameter of about 5 microns or less, more preferably about 2 microns or less.
  • Another embodiment of the invention provides a flame retardant composition predominantly (i.e.
  • the EBT compositions of the invention are of unprecedented color quality and represent a highly significant improvement over materials previously reported in the literature or commercially available.
  • the EBT product of the invention can be incorporated as a flame retardant in virtually any flammable material, natural or man-made, but will usually be incorporated in flammable synthetic polymers using conventional compounding techniques.
  • the EBT product may be incorporated into crosslinked or non-crosslinked polymers of olefinic monomers, for example ethylene, propylene and butylene homopolymers or their copolymers with other polymerizable monomers; polymers of styrenic monomers, e.g.
  • polystyrene and styrene copolymers poly ⁇ rethanes; polyamides; polyimides; polycarbonates; polyethers: acrylic resins; polyesters, e.g. poly(ethyleneterephthalate) and poly(butyleneterephthalate; epoxy resins; alkyd resins; phenolics; elastomers, for example butadiene/styrene copolymers and butadiene/acrylonitrile copolymers; terpolymers of acrylonitrile, butadiene and styrene; natural rubber; butyl rubber; polysiloxanes; wool; cellulose; polyvinylchlorides , etc.
  • the level of EBT product incorporated into the flammable material will vary widely in accordance with many factors such as the particular flammable material used, the application contemplated, other additives present, etc.
  • the EBT will be incorporated at levels between about 1% and 50% of the total system weight, and more commonly between about 5% and 30% of the total system weight .
  • the EBT product can be incorporated along with other flame retardant materials such as oxides of Group V elements, especially antimony oxides.
  • Additional conventional additives may include aritioxidants, antistatic agents, colorants, fibrous reinforcements, fillers, foaming/blowing agents, catalysts, heat stabilizers, impact modifiers, lubricants, plasticizers, processing aids, UV light stabilizers, crosslinking/curing agents, etc.
  • EXAMPLE 4 To a 1 1. glass autoclave fitted with overhead stirrer, vent, pressure gauge, temperature probe, pressurized addition funnel and with a heated oil jacket was added TBPA (150 g., 0.323 mole, 2 micron) and acetic acid (600 mis). The resulting slurry was heated to 102°C and ethylene diamine (9.74 g., 0.1623 mole) adde'd using nitrogen pressure over 5 seconds. The reaction was then heated to 160°C. These conditions were held for 12 hours. The reaction was then cooled to 80°C and filtered. The product was then oven dried at 200°C. A white product was obtained showing the following
  • a process was performed using propionic acid instead of the acetic acid. As is shown, the process and its product are substantially inferior as compared to those of the invention. Accordingly, to a 1 1. glass autoclave fitted with overhead stirrer, vent, pressure gauge, temperature probe, pressurized addition funnel and with a heated oil jacket was added TBPA (150 g., 0.323 mole, 2 micron) and propionic acid (600 mis). The resulting slurry was heated to 105°C and ethylene diamine (9.7 g., 0.161 mole) added using nitrogen pressure over 5 seconds. The reaction was then heated to 160°C. These conditions were held for 12 hours. The reaction was then cooled to 80°C and filtered. The product was then dried on a fluid bed drier at 200°C. A white product was obtained showing the following characteristics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Processus de préparation d'un produit très blanc à base de N,N'-éthylène-bis(tétrabromophtalimide), consistant à faire réagir de l'éthylènediamine et de l'anhydride tétrabromophtalique dans l'acide acétique pour produire du N,N'-éthylène-bis(tétrabromophtalimide); récupérer le N,N'-éthylène-bis(tétrabromophtalimide) dans un précipité blanc; et faire sécher le précipité de façon à former un produit à base de N,N'-éthylène-bis(tétrabromophtalimide). L'invention se rapporte également à une composition ignifuge principalement composée de N,N'-éthylène-bis(tétrabromophtalimide), et présentant un indice de jaune inférieur ou égal à 4 environ.
PCT/EP1993/001402 1992-06-08 1993-06-01 N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et preparation de celui-ci dans l'acide acetique WO1993025525A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU43222/93A AU4322293A (en) 1992-06-08 1993-06-01 Ultra white n,n'-ethylene-bis(tetrabromophthalimide) and its production in acetic acid
EP93912874A EP0644875A1 (fr) 1992-06-08 1993-06-01 N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et preparation de celui-ci dans l'acide acetique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9212090A GB2267704A (en) 1992-06-08 1992-06-08 Preparation of ultra-white N,N-ethylene-bis (tetrabromophthalimide)
GB9212090.6 1992-06-08
US07/954,281 US5317048A (en) 1992-09-30 1992-09-30 Ultra white N,N'-ethylene-bis(tetrabromophthalimide) and its production in acetic acid
US07/954,281 1992-09-30

Publications (1)

Publication Number Publication Date
WO1993025525A1 true WO1993025525A1 (fr) 1993-12-23

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EP (1) EP0644875A1 (fr)
AU (1) AU4322293A (fr)
WO (1) WO1993025525A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0698021A4 (fr) * 1993-05-04 1995-12-20 Great Lakes Chemical Corp Procedes a haute teneur en matieres solides destines a preparer des bisimides bromes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0348222A1 (fr) * 1988-06-23 1989-12-27 Albemarle Corporation Procédé de préparation d'un produit ignifugeant du type bisimide
EP0391666A1 (fr) * 1989-04-04 1990-10-10 Albemarle Corporation Procédé pour la préparation de produits bisimide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0348222A1 (fr) * 1988-06-23 1989-12-27 Albemarle Corporation Procédé de préparation d'un produit ignifugeant du type bisimide
EP0391666A1 (fr) * 1989-04-04 1990-10-10 Albemarle Corporation Procédé pour la préparation de produits bisimide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0698021A4 (fr) * 1993-05-04 1995-12-20 Great Lakes Chemical Corp Procedes a haute teneur en matieres solides destines a preparer des bisimides bromes
EP0698021A1 (fr) * 1993-05-04 1996-02-28 Great Lakes Chemical Corporation Procedes a haute teneur en matieres solides destines a preparer des bisimides bromes

Also Published As

Publication number Publication date
AU4322293A (en) 1994-01-04
EP0644875A1 (fr) 1995-03-29

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