WO1993025526A1 - N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et production de celui-ci dans l'acide acetique - Google Patents

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

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Publication number
WO1993025526A1
WO1993025526A1 PCT/EP1993/001403 EP9301403W WO9325526A1 WO 1993025526 A1 WO1993025526 A1 WO 1993025526A1 EP 9301403 W EP9301403 W EP 9301403W WO 9325526 A1 WO9325526 A1 WO 9325526A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
product
bis
tetrabromophthalimide
temperature
Prior art date
Application number
PCT/EP1993/001403
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 GB9212243A external-priority patent/GB2267706A/en
Application filed by Great Lakes Chemical (Europe) Ltd. filed Critical Great Lakes Chemical (Europe) Ltd.
Priority to AU43223/93A priority Critical patent/AU4322393A/en
Priority to EP93912875A priority patent/EP0644876A1/fr
Publication of WO1993025526A1 publication Critical patent/WO1993025526A1/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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

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 ultra-white N,N'-ethylene-bis-(tetrabromophthalimide) 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.
  • color is of particular importance.
  • 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 th-e color of the flame retardant.
  • flame retardant materials that have significant impurities which decompose, volatilize or sublime at polymer processing temperatures can cause undesired color, blowing and other problems in batches into which they are incorporated. Therefore, improved flame retardant materials will also demonstrate stability to higher temperatures in thermogravimetric analysis.
  • EBT N,N'-ethylene-bis-(tetrabromophthalimide)
  • 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.
  • Still another object of the invention is to provide a white EBT composition of high purity as can be demonstrated for example by thermogravimetric analysis.
  • N,N'-ethylene-bis(tetrabromophthalimide) product having a yellowness index of about 5 or less.
  • the product also has less than 1% weight loss in thermogravimetric analysis to 400°C.
  • this process is achieved by the steps of slurrying tetrabromophthalic anhydride into aqueous 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(tetrabromophthalimide) , 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 5 or less.
  • the product also has less than 1% weight loss in thermogravimetric analysis to ⁇ _00°C.
  • EBT compositions of this embodiment also preferably have a whiteness index of about 65 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 aqueous acetic acid medium. It has been discovered that by conducting this reaction in an aqueous acetic acid medium, EBT products of unprecedented whiteness and high purity can be obtained.
  • the acetic acid used as the reaction medium is preferably of high purity.
  • the use of acetic acid of 99%+ purity is preferred, and such grades are commercially available from many sources.
  • the aqueous acetic acid medium may be a 1% to 99% aqueous solution of acetic acid, although the medium will usually be at least 3% acetic acid.
  • the high quality white product of the invention can be produced in this wide range of aqueous acetic acid reaction mediums, also having the desirable high purity as exhibited by TGA.
  • advantages attach to processes conducted in dilute acetic acid and to those conducted in more concentrated acetic acid. For example, processes conducted in dilute acetic acid, say about 3% to about 10% acetic acid solutions, minimize reaction medium and reaction medium disposal costs.
  • processes conducted in more concentrated aqueous acetic acid say at least about 80% aqueous acetic acid, generate lower reaction pressures and offer other advantages such as those related to recovery of acetic acid in the medium.
  • the aqueous acetic acid mother liquors from a previous reaction medium can be reused in subsequent processes to generate the high quality white EBT product.
  • the mother liquors can optionally be treated by distillation or the like prior to reuse.
  • 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. As known and as used herein, ethylene diamine (“EDA”) 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.
  • EDA ethylene diamine
  • a slurry of tetrabromophthalic anhydride in the aqueous 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. Thereafter, 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.
  • EDA which may be in neat form or in a suitable solvent (in small amounts to maintain the essentially aqueous 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 stoichiometric 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 stoichiometric 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° to about 180°C, with those temperatures above about 150 C C being most preferred.
  • the water of reaction can remain in the reaction mixture, which can be agitated using conventional and commercially available agitation systems.
  • 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").
  • 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 more preferably about 5% to about 30% of the reacted medium) can -be isolated, e.g. by conventional centri ugation.
  • 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 and to complete 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 5 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 0 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%. Additionally, the resultant white EBT product o will typically have superior purity as has been demonstrated by TGA. For example, typical products have 1% weight loss at a temperature above about 400°C in TGA. Typical products also have melting point onsets above about 445°C, for instance usually in the range of about 460°C and above. 5
  • the EBT product can be milled during and/or after the drying operations, for example as occurs in a Winkworth 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 0 or less.
  • Another embodiment of the invention provides a flame retardant composition predominantly (i.e. about 95% or more) comprised of N,N'-ethylene-bis-(tetrabromophthalimide) and having a yellowness index of 5 or less.
  • the 5 product also has less than 1% weight loss in thermogravimetric analysis to 400°C.
  • This composition may be produced for example by the process described above and more particularly detailed in the Examples below.
  • the "yellowness index” is determined in accordance with ⁇ STM 1313 as can be measured by colorometer.
  • EBT compositions of this embodiment also preferably have a "whiteness index" (ASTM 1313) of about 65 or greater, more preferably about 70 or greater, and are advantageously at least 98% comprised of the EBT product.
  • ASTM 1313 whiteness index
  • Other preferred aspects of compositions of this embodiment are as set forth in the discussion of the first embodiment above and in the Examples which follow.
  • the EBT compositions of the invention are of unprecedented color and TGA 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. high-impact polystyrene and styrene copolymers; polyurethanes; polya ides; polyimides; polycarbonates; polyethers; acrylic resins; polyesters, e.g.
  • 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. Typically, 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 antioxidants, 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 2 To a 10 1. stainless steel autoclave fitted with overhead stirrer, vent, pressure gauge, temperature probe, pressurized addition funnel and with a heated oil jacket was added TBPA (1500 g., 3.23 mole, 2 micron) water (6000 mis) and acetic acid (200 mis) . The resulting slurry was heated to 96°C and ethylene diamine (97 g., 1.62 mole) added using nitrogen pressure over 10 seconds. The reaction was then heated to 170°C. These conditions where held for 16 hours. The reaction was then cooled to 50°C and filtered. The product was then dried at 200°C on a fluid bed drier. A white product was obtained showing the following characteristics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (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 aqueux afin de 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 obtenir le produit à base de N,N'-éthylène-bis(tétrabromophtalimide). L'invention se rapporte également à une composition ignifuge composée principalement de N,N'-éthylène-bis(tétrabromophtalimide) et présentant une couleur exceptionnelle et un niveau de pureté élevé.
PCT/EP1993/001403 1992-06-08 1993-06-01 N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et production de celui-ci dans l'acide acetique WO1993025526A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU43223/93A AU4322393A (en) 1992-06-08 1993-06-01 Ultra white n,n'-ethylene-bis(tetrabromophthalimide) and its production in aqueous acetic acid
EP93912875A EP0644876A1 (fr) 1992-06-08 1993-06-01 N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et production de celui-ci dans l'acide acetique

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9212243A GB2267706A (en) 1992-06-08 1992-06-08 Production of ultra-white N,N'-ethylene-bis (tetrabromophalmide)
GB9212243.1 1992-06-08
US95428092A 1992-09-30 1992-09-30
US07/954,280 1992-09-30
US08/588,624 US5744615A (en) 1992-06-08 1996-01-19 Ultra white N,N'-ethylene-bis(tetrabromophthalimide) and its production in aqueous acetic acid

Publications (1)

Publication Number Publication Date
WO1993025526A1 true WO1993025526A1 (fr) 1993-12-23

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PCT/EP1993/001403 WO1993025526A1 (fr) 1992-06-08 1993-06-01 N,n'-ethylene-bis(tetrabromophtalimide) ultra blanc et production de celui-ci dans l'acide acetique

Country Status (3)

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EP (1) EP0644876A1 (fr)
AU (1) AU4322393A (fr)
WO (1) WO1993025526A1 (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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092345A (en) * 1976-07-30 1978-05-30 Cities Service Company (Cyclo)alkylenediammonium-bis-tetrahalophthalates
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092345A (en) * 1976-07-30 1978-05-30 Cities Service Company (Cyclo)alkylenediammonium-bis-tetrahalophthalates
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
AU4322393A (en) 1994-01-04
EP0644876A1 (fr) 1995-03-29

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