NO173650B - PROCEDURE FOR THE PREPARATION OF HALOGENATED IMIDES - Google Patents
PROCEDURE FOR THE PREPARATION OF HALOGENATED IMIDES Download PDFInfo
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- NO173650B NO173650B NO88883003A NO883003A NO173650B NO 173650 B NO173650 B NO 173650B NO 88883003 A NO88883003 A NO 88883003A NO 883003 A NO883003 A NO 883003A NO 173650 B NO173650 B NO 173650B
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- anhydride
- hydrazine
- halogenated
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- acid
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- 150000003949 imides Chemical class 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 25
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 claims 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract 2
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- -1 hydrohalide Chemical compound 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000588145 Homo sapiens Microtubule-associated tumor suppressor 1 Proteins 0.000 description 1
- 102100031550 Microtubule-associated tumor suppressor 1 Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- 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
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- 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
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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)
- Indole Compounds (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en syntese av polyhalogenimider, mere spesielt amider avledet fra halogenert dikarbok-sylsyrer som tetrabromphalsyre. The present invention relates to a synthesis of polyhalogenimides, more particularly amides derived from halogenated dicarboxylic acids such as tetrabromophalic acid.
Polyhalogenimidene og spesielt tetrabromphalimidene og bis-tetrabromphalimidene er velkjente forbindelser som finner anvendelse som flammehemmere i tallrike brennbare materialer, spesielt i plastmaterialer (se for eksempel en artikkel av S.M. Spatz et al med tittelen "Some N-substituted tetrabrom-ophtalimide fire-retardant additives" i "Industrial and Engineering Chemistry Product Research and Development" vol. 8, n° 4 (1969) side 397-398, samt US-PS 3 873 567 og FR-PS 2 369 261 og Japansk søknad 74-045062 og 75-064337). The polyhalogenimides and especially the tetrabromophalimides and bis-tetrabromophalimides are well-known compounds that find use as flame retardants in numerous combustible materials, especially in plastic materials (see for example an article by S.M. Spatz et al entitled "Some N-substituted tetrabromo-ophthalmide fire-retardant additives" in "Industrial and Engineering Chemistry Product Research and Development" vol. 8, n° 4 (1969) pages 397-398, as well as US-PS 3,873,567 and FR-PS 2,369,261 and Japanese application 74-045062 and 75-064337 ).
Imidlertid gir de fremstillingsprosesser som beskrives i disse referanser dårlige utbytter og gir produkter som meget hyppig inneholder flyktige stoffer ved anvendelses-temperaturen i visse polymermaterialer og som kan medføre korrosjon av formen. Videre vil ved deres fremstilling anvendelsen av organiske oppløsningmidler (spesielt xylen, toluen, alkohol, edikksyre) hyppig valgt på grunn av deres tendens til sammen med vann og danne azeotropblandinger som tillater å føre ut kondensasjonsvannet dannet ved imiderings-reaksjonen eller ved oppløsning av det halogenerte dikarbok-sylsyreanhidrid, kostbare operasjoner for å separere og gjenvinne disse oppløsningsmidler samt tørkemidler tilpasset fjerning av organiske oppløsningsmiddeldamper. However, the production processes described in these references give poor yields and produce products that very often contain volatile substances at the application temperature in certain polymer materials and which can lead to corrosion of the mold. Furthermore, in their preparation, the use of organic solvents (especially xylene, toluene, alcohol, acetic acid) will frequently be chosen because of their tendency to combine with water and form azeotrope mixtures that allow the condensation water formed by the imidation reaction or by dissolving the halogenated dicarboxylic acid anhydride, expensive operations to separate and recover these solvents as well as drying agents adapted to the removal of organic solvent vapors.
De ovenfor nevnte mangler møter man spesielt når det gjelder polyhalogenimider avledet fra hydrazin og halogenerte dikarboksylsyreanhydrider. Det er imidlertid funnet at det ikke er uungåelig å benytte et organisk oppløsningsmiddel for å oppløse anhydride og/eller å fjerne kondensasjonsvann og at man ved å arbeide i vandig medium under visse betingelser kan oppnå relativt høye utbytter og dette uten forurensende avløp, produkter som uten forutgående rensing egner seg perfekt til flammehemmingsmaterialer for makromolkylære stoffer og deriblant de som benyttes ved høye temperaturer, spesielt over 250°C. The above-mentioned shortcomings are particularly encountered in the case of polyhalogenimides derived from hydrazine and halogenated dicarboxylic anhydrides. However, it has been found that it is not inevitable to use an organic solvent to dissolve anhydrides and/or to remove condensation water and that by working in an aqueous medium under certain conditions relatively high yields can be achieved and this without polluting effluents, products which without prior cleaning is perfectly suited to flame retardant materials for macromolecular substances and including those used at high temperatures, especially above 250°C.
I henhold til dette angår foreliggende oppfinnelse en fremgangsmåte for fremstilling av halogenerte imider ved kondensering av hydrazin og halogenert dikarboksylsyreanhydrid og denne fremgangsmåte karakteriseres ved at man går ut fra en vandig anhydridoppløsning eller -dispersjon med en pH-verdi under 7 under anvendelse av et anhydrid med formelen: According to this, the present invention relates to a method for the production of halogenated imides by condensation of hydrazine and halogenated dicarboxylic acid anhydride and this method is characterized by starting from an aqueous anhydride solution or dispersion with a pH value below 7 using an anhydride with the formula:
der there
X betyr et brom- eller kloratom, m er et helt tall fra 2 til 4, n og p er hele tall fra 0 til 2 eller en blanding av slike anhydrider, idet reaksjonen gjennomføres i vandig medium ved en temperatur fra 40 til 225°C, fortrinnsvis under trykk ved en temperatur på minst 140 °C, idet man arbeider med et molforhold anhydrid:hydrazin under 2. X means a bromine or chlorine atom, m is an integer from 2 to 4, n and p are integers from 0 to 2 or a mixture of such anhydrides, the reaction being carried out in an aqueous medium at a temperature from 40 to 225°C , preferably under pressure at a temperature of at least 140 °C, working with an anhydride:hydrazine molar ratio below 2.
I henhold til oppfinnelsen kan man benytte et enkelt anhydrid eller en blanding av to eller flere slike. De kommersielle anhydrider inneholder hyppig en liten mengde mineralsyrer med kan benyttes per se uten foregående rensing. According to the invention, a single anhydride or a mixture of two or more such anhydrides can be used. The commercial anhydrides often contain a small amount of mineral acids and can be used per se without previous purification.
Man har fastslått at man oppnår spesielt gunstige resultater når den vandige anhydrid-oppløsning eller -dispersjon som benyttes er sur eller sterkt sur (pH verdi under 7). It has been established that particularly favorable results are obtained when the aqueous anhydride solution or dispersion used is acidic or strongly acidic (pH value below 7).
Mengden vann som utgjør reaksjonsmediet ved prosessen ifølge oppfinnelsen kan variere innen vide grenser og den eneste betingelse er at den må være tilstrekkelig stor til å sikre dispersjon i tilstrekkelig grad for reaktantene og tillate en god omrøring. Denne betingelse blir generelt realisert ved å benytte en vannmengde slik at faststoffinnholdet i reaksjonsmediet ligger mellom 5 og 75 vekt-# og fortrinnsvis mellom 20 og 40 vekt-56. The amount of water that constitutes the reaction medium in the process according to the invention can vary within wide limits and the only condition is that it must be sufficiently large to ensure sufficient dispersion of the reactants and allow good stirring. This condition is generally realized by using an amount of water such that the solids content in the reaction medium is between 5 and 75 wt-# and preferably between 20 and 40 wt-56.
Reaksjonen kan gjennomføres under atmosfærisk trykk ved en temperatur fra 40 til 100°C eller under betingelser som medfører trykk ved en temperatur helt opp til 225°C. Fortrinnsvis arbeider man mellom 100 og 225°C, noe som tilsvarer ett trykk på mellom 1 og ca. 25 bar. The reaction can be carried out under atmospheric pressure at a temperature from 40 to 100°C or under conditions that involve pressure at a temperature up to 225°C. Preferably, you work between 100 and 225°C, which corresponds to a pressure of between 1 and approx. 25 bars.
Hydrazin i form av hydrat ved et hydraziniumsalt (for eksempel sulfat, hydrogenhalogenid, acetat) kan benyttes som sådan eller under form av en fortynnet vandig oppløsning. Fortrinnsvis benyttes hydrazinhydrat i form av en vandig oppløsning av kommersiell type. Fremgangsmåten ifølge oppfinnelsen blir fordelaktig gjennomført ved progressivt å innføre hydrazin i den halogenerte anhydridoppløsning eller -dispersjon som på forhånd er oppvarmet og holdt under omrøring. Hydrazine in the form of hydrate of a hydrazinium salt (for example sulfate, hydrogen halide, acetate) can be used as such or in the form of a dilute aqueous solution. Preferably, hydrazine hydrate is used in the form of an aqueous solution of commercial type. The method according to the invention is advantageously carried out by progressively introducing hydrazine into the halogenated anhydride solution or dispersion which has been previously heated and kept under stirring.
Reaksjonsvarigheten kan variere innen vide grenser, men ligger generelt mellom 1 og 20 timer. Efter avkjøling av reaksjonsmediet blir den faste oppnådde oppløsning filtrert og eventuelt vasket med vann til nøytral tilstand og derefter tørker man produktet ved vanlige tørkemetoder. The reaction duration can vary within wide limits, but is generally between 1 and 20 hours. After cooling the reaction medium, the solid solution obtained is filtered and optionally washed with water to a neutral state and then the product is dried using normal drying methods.
Molforholdet anhydridrhydrazin kan ha forskjellige verdier. Hvis man benytter en verdi nær 2 og en temperatur minst lik 140°C består det oppnådde produkt generelt av bisimid som tilsvarer den følgende generelle formel: The molar ratio of anhydride hydrazine can have different values. If one uses a value close to 2 and a temperature at least equal to 140°C, the product obtained generally consists of bisimide which corresponds to the following general formula:
der A betyr den benyttede halogenerte anhydridrest. where A means the halogenated anhydride residue used.
Ved lavere temperaturer inneholdt det oppnådde produkt i tillegg til bisimid med formel (III) en variabel andel som kan gå opp i 80 vekt-# av en i det vesentlige ekvimolar blanding av det halogenerte utgangsanhydrid og N-amino-imid tilsvarende den generelle formel: At lower temperatures, the product obtained contained, in addition to bisimide of formula (III), a variable proportion that can amount to 80 wt-# of an essentially equimolar mixture of the halogenated starting anhydride and N-amino-imide corresponding to the general formula:
der A har den samme betydning som ovenfor idet dette N-amino-imid kan foreligge i form av salt, (sulfat, hydrohalogenid, acetat). Mengden av produktet som oppnås av bis-imid (III) er generelt om så større jo nærmere reaksjonstemperaturen er 140°C eller derover. where A has the same meaning as above in that this N-amino-imide can exist in the form of a salt (sulphate, hydrohalide, acetate). The amount of product obtained from bis-imide (III) is generally greater the closer the reaction temperature is to 140°C or above.
Hvis man benytter et forhold under 1 eller nær 1 oppnår man i det vesentlige N-amino-imid med den generelle struktur (IV). Når det ønskede produkt er N-amino-imid benyttes en hydrazin-mengde som ligger mellom den støkiometriske og et 50$ molart overskudd og fortrinnsvis et forhold anhydrid:hydrazin i det vesentlige lik 1. If you use a ratio below 1 or close to 1, you essentially obtain N-amino-imide with the general structure (IV). When the desired product is N-amino-imide, an amount of hydrazine is used that lies between the stoichiometric and a 50% molar excess and preferably an anhydride:hydrazine ratio essentially equal to 1.
Hvis man benytter et molarforhold anhydrid:hydrazin mellom 1 og 2 oppnår man en blanding av forprodukter inneholdende om så mere bis-imid jo nærmere forholdet ligger 2 og tempera-turen er høy. If you use a molar ratio of anhydride:hydrazine between 1 and 2, you obtain a mixture of precursors containing about the more bis-imide the closer the ratio is to 2 and the higher the temperature.
Når det dreier seg om rene bis-imider, blandinger av bis-imid + N-amino-imid + anhydrid, eller N-amino-imid, egner produktene som oppnås ved oppfinnelsens fremgangsmåte seg spesielt godt som flammehemmere i plastmaterialer av enhver type. Deres innarbeiding i slike stoffer kan gjennomføres på en hvilken som helst kjent måte i doseringer som går fra 5 til 40$ i forhold til vekten av det brennbare materialet. When it comes to pure bis-imides, mixtures of bis-imide + N-amino-imide + anhydride, or N-amino-imide, the products obtained by the method of the invention are particularly suitable as flame retardants in plastic materials of any type. Their incorporation into such substances can be carried out in any known manner in dosages ranging from 5 to 40% in relation to the weight of the combustible material.
De følgende eksempler der alle vektdeler og prosentandeler er på vektbasls, illustrerer oppfinnelsen uten å begrense den. The following examples, in which all parts by weight and percentages are by weight, illustrate the invention without limiting it.
Produktende er identifisert ved CHN og IR. Product ends are identified by CHN and IR.
Utbyttene er uttrykt i forhold til anhydridet. The yields are expressed in relation to the anhydride.
Eksempel 1. Example 1.
I en glassreaktor med rørverk og tilbakeløpskjøler dispergeres i 2000 deler destillert vann 429 deler kommersielt tetraklorsthalsyreanhydrid. pH-verdien i suspensjonen er 1.5. In a glass reactor with piping and reflux cooler, 429 parts of commercial tetrachlorophthalic anhydride are dispersed in 2,000 parts of distilled water. The pH value in the suspension is 1.5.
Efter å ha bragt suspensjonen til 60°C tilsettes progressivt i løpet av 20 - 30 minutter 75 deler 100 #-ig hydrazinhydrat og reaksjonsblandingen bringes derefter til 100°C. Man tilsetter derefter 1000 deler destillert vann og holder det hele ved 100° C i ytterligere 10 timer. Man oppnår så en suspensjon som avkjøles og filtreres over en Btichner-trakt. Efter vasking med vann inntil en nøytral pH-verdi og tørking under trykk ved 110 - 120°C oppnår man med et utbytte på over 97$ et hvitt produkt hvis elementanalyse og IR-analyse bekrefter strukturen: After bringing the suspension to 60°C, 75 parts of 100 #-ig hydrazine hydrate are progressively added over 20 - 30 minutes and the reaction mixture is then brought to 100°C. 1000 parts of distilled water are then added and the whole is kept at 100° C for a further 10 hours. A suspension is then obtained which is cooled and filtered over a Btichner funnel. After washing with water until a neutral pH value and drying under pressure at 110 - 120°C, a white product is obtained with a yield of over 97$, whose elemental analysis and IR analysis confirm the structure:
Eksempel 2. Example 2.
Man arbeider som i eksempel 1 ved i 4000 deler vann og dispergerer 445 deler kommersielt klorendisyreanhydrid. One works as in example 1 with 4,000 parts of water and dispersing 445 parts of commercial chlorinated anhydride.
pH-verdien i suspensjonen er 2.5. The pH value in the suspension is 2.5.
Man setter progressivt 60 g 100 %- ig hydrazinhydrat til suspensjonen som er bragt til 98°C. Efter 10 timers til-bakeløp ved denne temperatur avkjøles det hele og man separer produktet ved filtrering. 60 g of 100% hydrazine hydrate is progressively added to the suspension which has been brought to 98°C. After 10 hours of reflux at this temperature, the whole is cooled and the product is separated by filtration.
Efter vasking inntil nøytral pH-verdi og tørking under undertrykk ved 110 - 120°C oppnås i et utbytte på over 90% et grått produkt hvis element- og IR-analyse bekrefter struk- After washing until a neutral pH value and drying under reduced pressure at 110 - 120°C, a yield of over 90% is obtained, a gray product whose elemental and IR analysis confirms struc-
turen : the trip:
Eksempel 3. Example 3.
Til en 6 liters autoklav utstyrt med rørverk settes 1392 deler tetrabromftalsyreanydrid i 4000 deler vann. pH-verdien i dispersjonen er 1.5. 1392 parts of tetrabromophthalic anhydride in 4000 parts of water are added to a 6 liter autoclave equipped with piping. The pH value in the dispersion is 1.5.
Man bringer det hele til 60°C og tilsetter derefter progressivt 225 deler 100 %- ig hydrazinhydrat. Man bringer suspensjonen til 125°C under trykk og holder denne temperatur i 10 timer. The whole is brought to 60°C and then 225 parts of 100% hydrazine hydrate are progressively added. The suspension is brought to 125°C under pressure and maintained at this temperature for 10 hours.
Efter dette reaksjonstidsrom avkjøles det hele og man separerer produktet ved filtrering. After this reaction time, the whole thing is cooled and the product is separated by filtration.
Efter vasking inntil nøytral pH-verdi og tørking under undertrykk ved 110 - 120°C oppnår man med et utbytte over 90% et gult produkt hvis element- og IR-analyse antyder struk- After washing to a neutral pH value and drying under reduced pressure at 110 - 120°C, a yellow product is obtained with a yield of over 90%, whose elemental and IR analysis suggests struc-
turen : the trip:
Eksempel 4. Example 4.
Man arbeider som i eksempel 3, men benytter et 100 %- ig molart overskudd av hydrazinhydrat. Man oppnår det samme produkt som i eksempel 3 i et utbytte på 97.4 %. One works as in example 3, but uses a 100% molar excess of hydrazine hydrate. The same product as in example 3 is obtained in a yield of 97.4%.
Eksempel 5. Example 5.
I en 4 liters autoklav utstyrt med rørverk dispergeres 883 deler kommersiell tetrabromftalsyreanhydrid i 2600 deler destilert vann, man bringer mediet under omrøring til en temperatur på 170°C, noe som tilsvarer et trykk på mellom 7.6 og 8 bar. In a 4 liter autoclave equipped with piping, 883 parts of commercial tetrabromophthalic anhydride are dispersed in 2600 parts of distilled water, the medium is brought to a temperature of 170°C while stirring, which corresponds to a pressure of between 7.6 and 8 bar.
Ved hjelp av en pumpe innføres progressivt i den omrørte suspensjon 53 deler hydrazinhydrat, 100 % fortynnet med 200 deler destilert vann (molforhold ATBP:HH =1.8). Using a pump, 53 parts of hydrazine hydrate, 100% diluted with 200 parts of distilled water (molar ratio ATBP:HH = 1.8) are progressively introduced into the stirred suspension.
Man holder reaksjonsmediet i 6 timer, hele tiden ved 170°C, avkjøler det derefter, filtrerer og vasker. Efter tørking ved 100 til 110°C under undertrykk oppnås med et utbytte på 95 % et hvit produkt som inneholder: The reaction medium is kept for 6 hours, the entire time at 170°C, then cooled, filtered and washed. After drying at 100 to 110°C under reduced pressure, a white product containing:
83 % N,N'-bis(tetrabromftalimid) 83% N,N'-bis(tetrabromophthalimide)
14 % N-aminotetrabromsthalimid 14% N-aminotetrabromothalimide
3 % tetrabromftalsyreanhydrid 3% tetrabromophthalic anhydride
Eksempel 6. Example 6.
Effektiviteten for produktene ifølge oppfinnelsen som brannhemmings- og flammehemmingsmidler for plastmaterialer er prøvet i henhold til en generell prøvemetode som følger: ved hjelp av en planet-blander blandes bestanddelene i de i den følgende tabell angitte mengder der harpiksen i form av pulver eller granulat med midler som skal prøves og even-tuelle additiver (antimontrioksid, parafin). Efter homo-genisering ekstruderer man blandingen ved hjelp av en vanlig e. struder (dobbeltskrue, monoskrue eller "Buss"), eventuelt utstyrt med avgassingsmidler idet man arbeider ved den antydede ekstruderingstemperatur ved å mate til harpiks og bindemiddel ved smeltetemperaturen for polymeren. Den oppnådde forbindelse, eventuelt granulert, omdannes derefter til prøverstykker ved hjelp av en injeksjonspresse som arbeider ved hensiktsmessige temperaturer. Disse prøve-stykker blir derefter underkastet normale flammemotstands-prøver UL94 ved 3.2 og 1.6 mm (Norm NF T51072 ) og 10 % oksygenindeks (Norm NF T51071). The effectiveness of the products according to the invention as fire retardants and flame retardants for plastic materials has been tested according to a general test method as follows: with the help of a planetary mixer, the components are mixed in the amounts indicated in the following table where the resin in the form of powder or granules with agents to be tested and any additives (antimony trioxide, paraffin). After homogenization, the mixture is extruded using a conventional e. extruder (twin screw, single screw or "Buss"), optionally equipped with degassing agents while working at the indicated extrusion temperature by feeding the resin and binder at the melting temperature of the polymer. The compound obtained, optionally granulated, is then converted into test pieces by means of an injection press operating at appropriate temperatures. These test pieces are then subjected to normal flame resistance tests UL94 at 3.2 and 1.6 mm (Norm NF T51072) and 10% oxygen index (Norm NF T51071).
Tabell A oppsummerer de oppnådde resultater når det gjelder polybutylentereftalat (kommersielt tilgjengelig TMN0-ORGATER). Table A summarizes the results obtained in the case of polybutylene terephthalate (commercially available TMN0-ORGATER).
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO931915A NO300644B1 (en) | 1987-07-24 | 1993-05-26 | Use of halogenated imides as flame retardants in plastic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8710586A FR2618430B1 (en) | 1987-07-24 | 1987-07-24 | PROCESS FOR THE PREPARATION OF HALOGENATED IMIDES AND THEIR APPLICATION AS FLAME RETARDANTS |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO883003D0 NO883003D0 (en) | 1988-07-05 |
| NO883003L NO883003L (en) | 1989-01-25 |
| NO173650B true NO173650B (en) | 1993-10-04 |
| NO173650C NO173650C (en) | 1994-01-12 |
Family
ID=9353574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO883003A NO173650C (en) | 1987-07-24 | 1988-07-05 | Procedure for the preparation of halogenated imides |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0300879B1 (en) |
| JP (2) | JPH0686426B2 (en) |
| KR (1) | KR0130475B1 (en) |
| CN (1) | CN1025611C (en) |
| AT (1) | ATE199713T1 (en) |
| AU (1) | AU617337B2 (en) |
| CA (1) | CA1338354C (en) |
| DE (1) | DE3856460D1 (en) |
| DK (2) | DK170772B1 (en) |
| FI (1) | FI92390C (en) |
| FR (1) | FR2618430B1 (en) |
| IL (1) | IL86673A (en) |
| NO (1) | NO173650C (en) |
| NZ (1) | NZ225530A (en) |
| PT (1) | PT88091B (en) |
| SG (1) | SG70567A1 (en) |
| ZA (1) | ZA884650B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2615510B1 (en) * | 1987-05-18 | 1991-09-06 | Atochem | PROCESS FOR THE PREPARATION OF HALOGENATED IMIDES |
| US4997953A (en) * | 1989-10-23 | 1991-03-05 | Ethyl Corporation | Process for preparing N,N'-bis(tetrabromophthalimide) |
| US5076970A (en) * | 1990-05-29 | 1991-12-31 | Ethyl Corporation | Flame retardant n,n'-bis(tetrabromophthalimide) composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3873567A (en) * | 1968-09-05 | 1975-03-25 | Universal Oil Prod Co | N-substituted polybromoaromatic ortho-dicarboximides |
| US3734925A (en) * | 1971-02-08 | 1973-05-22 | Tenneco Chem | N-amino-3,4-dimethyl-6-isobutyl-phthalimides |
| US4087441A (en) * | 1976-07-19 | 1978-05-02 | Cities Service Company | Process for preparing aromatic bisimides |
| DE2648970A1 (en) * | 1976-10-28 | 1978-05-11 | Dynamit Nobel Ag | AZOMETHINIMIDE |
| FR2369261A1 (en) * | 1976-10-28 | 1978-05-26 | Dynamit Nobel Ag | Flame-retardant tetra:bromo-phthalimide derivs. - with good temp. stability and used in plastics, esp. polyterephthalate |
| CA1192559A (en) * | 1982-04-09 | 1985-08-27 | Ralph H. Hansen | Polymer parts and compound useful therein |
| FR2594121B1 (en) * | 1986-02-12 | 1989-05-05 | Atochem | PROCESS FOR THE PREPARATION OF HALOGENATED IMIDES, COMPOSITIONS CONTAINING THEM AND THEIR APPLICATION AS FLAME RETARDANTS |
-
1987
- 1987-07-24 FR FR8710586A patent/FR2618430B1/en not_active Expired - Lifetime
-
1988
- 1988-06-09 IL IL86673A patent/IL86673A/en not_active IP Right Cessation
- 1988-06-29 ZA ZA884650A patent/ZA884650B/en unknown
- 1988-07-05 NO NO883003A patent/NO173650C/en not_active IP Right Cessation
- 1988-07-07 CA CA000571396A patent/CA1338354C/en not_active Expired - Fee Related
- 1988-07-12 AT AT88401815T patent/ATE199713T1/en not_active IP Right Cessation
- 1988-07-12 DE DE3856460T patent/DE3856460D1/en not_active Expired - Lifetime
- 1988-07-12 SG SG1996008587A patent/SG70567A1/en unknown
- 1988-07-12 EP EP88401815A patent/EP0300879B1/en not_active Expired - Lifetime
- 1988-07-21 JP JP63182770A patent/JPH0686426B2/en not_active Expired - Lifetime
- 1988-07-22 PT PT88091A patent/PT88091B/en not_active IP Right Cessation
- 1988-07-22 NZ NZ225530A patent/NZ225530A/en unknown
- 1988-07-22 DK DK412988A patent/DK170772B1/en not_active IP Right Cessation
- 1988-07-22 AU AU19731/88A patent/AU617337B2/en not_active Ceased
- 1988-07-22 FI FI883475A patent/FI92390C/en not_active IP Right Cessation
- 1988-07-23 KR KR1019880009272A patent/KR0130475B1/en not_active IP Right Cessation
- 1988-07-23 CN CN88104597A patent/CN1025611C/en not_active Expired - Fee Related
-
1993
- 1993-10-13 JP JP5280149A patent/JPH0768407B2/en not_active Expired - Lifetime
-
1995
- 1995-03-13 DK DK024795A patent/DK24795A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2618430A1 (en) | 1989-01-27 |
| ATE199713T1 (en) | 2001-03-15 |
| KR0130475B1 (en) | 1998-04-09 |
| DK24795A (en) | 1995-03-13 |
| FI92390B (en) | 1994-07-29 |
| FI92390C (en) | 1994-11-10 |
| AU617337B2 (en) | 1991-11-28 |
| NO883003L (en) | 1989-01-25 |
| IL86673A (en) | 1993-01-31 |
| ZA884650B (en) | 1989-09-27 |
| DK412988D0 (en) | 1988-07-22 |
| AU1973188A (en) | 1989-01-27 |
| NZ225530A (en) | 1989-08-29 |
| FI883475A0 (en) | 1988-07-22 |
| EP0300879B1 (en) | 2001-03-14 |
| NO883003D0 (en) | 1988-07-05 |
| FI883475A (en) | 1989-01-25 |
| DK412988A (en) | 1989-01-25 |
| SG70567A1 (en) | 2000-02-22 |
| CN1031372A (en) | 1989-03-01 |
| KR890002282A (en) | 1989-04-10 |
| NO173650C (en) | 1994-01-12 |
| FR2618430B1 (en) | 1991-02-15 |
| CN1025611C (en) | 1994-08-10 |
| JPS6447765A (en) | 1989-02-22 |
| DK170772B1 (en) | 1996-01-15 |
| JPH0686426B2 (en) | 1994-11-02 |
| JPH06228365A (en) | 1994-08-16 |
| CA1338354C (en) | 1996-05-28 |
| DE3856460D1 (en) | 2001-04-19 |
| IL86673A0 (en) | 1988-11-30 |
| EP0300879A1 (en) | 1989-01-25 |
| JPH0768407B2 (en) | 1995-07-26 |
| PT88091A (en) | 1989-06-30 |
| PT88091B (en) | 1995-03-31 |
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