DK170772B1 - Process for the preparation of halogen-containing imides - Google Patents
Process for the preparation of halogen-containing imides Download PDFInfo
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- DK170772B1 DK170772B1 DK412988A DK412988A DK170772B1 DK 170772 B1 DK170772 B1 DK 170772B1 DK 412988 A DK412988 A DK 412988A DK 412988 A DK412988 A DK 412988A DK 170772 B1 DK170772 B1 DK 170772B1
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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
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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
- C07D209/56—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
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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
- C08K5/16—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
Abstract
Description
i DK 170772 B1in DK 170772 B1
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af halogenerede imider ved kondensation af hydrazin og et anhydrid af halogenerede dicarboxylsyrer med en af formlerne som defineret i indledningen til krav 5 1.The present invention relates to a process for preparing halogenated imides by condensation of hydrazine and an anhydride of halogenated dicarboxylic acids with one of the formulas as defined in the preamble of claim 5 1.
Polyhalogenimiderne, især tetrabromphthalimiderne og bis-(tetrabromphthalimiderne), er velkendte forbindelser, der finder anvendelse som flammeforsinkelsesmiddel i talrige 10 brandbare materialer, især af plastmaterialer (se f.eks.The polyhaloimides, especially the tetrabromphthalimides and the bis (tetrabromphthalimides), are well known compounds which are used as flame retardants in numerous 10 combustible materials, especially of plastics materials (see e.g.
artiklen af S.M. Spatz et al med titlen "Some N-substituted tetrabromophtalimide fire-retardant additives" i Industrial and Engineering Chemistry Product Research and Development, bind 8, nr. 4 (1969) siderne 15 397-398, samt US patentskrift nr. 3 873 567 og i FR pa tentskrift nr. 2 369 261 og de japanske patentansøgninger nr. JP 74-045062 og 75-064337).the article by S.M. Spatz et al, entitled "Some N-Substituted Tetrabromophthalimide Four-Retardant Additives" in Industrial and Engineering Chemistry Product Research and Development, Vol. 8, No. 4 (1969) pages 15,397-398, and U.S. Patent No. 3,873,567 and in FR Patent Publication No. 2 369 261 and Japanese Patent Applications JP 74-045062 and 75-064337).
Fremstillingsmetoderne, der er beskrevet i de ovennævnte 20 publikationer, giver imidlertid middelmådige udbytter, og de fører til produkter, der meget hyppigt indeholder materialer, som er flygtige ved anvendelsestemperaturerne for visse polymere materialer, og som medfører korrosion af formene. Det er desuden en ulempe, at man ved de kend-25 te fremstillingsmetoder anvender organiske opløsningsmidler (især xylen, toluen, alkohol og eddikesyre), der hyp pigst er udvalgt p.g.a. deres evne til at danne azeotro-piske blandinger sammen med vand under medrivning af det kondensationsvand, som dannes ved imiddannelsesreaktion-30 en, eller som opløser det halogenerede anhydrid af di-carboxylsyre. Ved disse processer skal derfor udføres behandlinger til separation og genindvinding af disse opløsningsmidler, og der skal anvendes tørringsmidler, der er egnede til at fjerne dampe af de organiske opløsnings- 35 midler.However, the preparation methods described in the above-mentioned publications yield mediocre yields and lead to products that very frequently contain materials that are volatile at the application temperatures of certain polymeric materials and cause corrosion of the molds. In addition, it is a disadvantage that organic solvents (especially xylene, toluene, alcohol and acetic acid) are used in the known preparation methods, which are most often selected for the purpose. their ability to form azeotropic mixtures with water while entrapping the condensation water formed by the formation reaction or dissolving the halogenated anhydride of dicarboxylic acid. Therefore, in these processes, treatments must be performed for the separation and recovery of these solvents and drying agents suitable for removing vapors of the organic solvents must be used.
De ovennævnte ulemper optræder især i forbindelse med DK 170772 B1 2 polyhalogenimider, der er afledt af hydrazin og anhydri-der af halogenerede dlcarboxylsyrer. Det har nu vist sig, at det Ikke er absolut nødvendigt at anvende et organisk opløsningsmiddel til at opløse anhydridet og/eller fjerne 5 kondensationsvandet, og ved at arbejde i et vandigt medium kan man under visse betingelser endvidere opnå relativt høje udbytter og - uden at der opstår problemer mht. spildstrømme og miljøet - produkter, der uden forudgående oprensning egner sig perfekt til brandhæmning af 10 makromolekylære materialer, herunder sådanne hvis anvendelse finder sted ved høj temperatur, især højere end 250 °C.The above-mentioned drawbacks are particularly encountered in connection with DK 170772 B1 2 polyhalogenimides derived from hydrazine and anhydrides of halogenated dicarboxylic acids. It has now been found that it is not absolutely necessary to use an organic solvent to dissolve the anhydride and / or remove the condensation water, and by working in an aqueous medium it is also possible, under certain conditions, to obtain relatively high yields and - without problems with waste streams and the environment - products which, without prior purification, are perfectly suitable for fire retardation of 10 macromolecular materials, including those whose use occurs at high temperature, especially higher than 250 ° C.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at 15 reaktionen gennemføres i vandigt medium uden indhold af organiske opløsningsmidler ved en temperatur fra 40 til 225 °C og en pH-værdi lavere end 7 og med et molært forhold anhydrid/hydrazin mindre end 2.The process according to the invention is characterized in that the reaction is carried out in aqueous medium without containing organic solvents at a temperature of 40 to 225 ° C and a pH value lower than 7 and having a molar ratio of anhydride / hydrazine less than 2.
20 De anvendelige halogenerede anhydrider, som benyttes ved fremgangsmåden ifølge opfindelsen, er - anhydriderne af aromatiske dlcarboxylsyrer med den almene formel: 25 x c 9 n 30 hvori X betegner et bromatom eller et chloratom, m er et helt tal fra 2 til 4, n og p er hele tal fra 0 til 2; og - anhydrider af cycloaliphatiske dlcarboxylsyrer svarende 35 til formlen: DK 170772 B1 3 χΛ x^m. /° ao 5 hvor X betegner et bromatom eller et chloratom. Man anvender fortrinsvis anhydrider af 3,4- (eller 3,6- eller 4,5-) dibrom-phthalsyre, 3,4,6-tribrom-phthalsyre og te-trabromphthalsyre.The useful halogenated anhydrides used in the process of the invention are - the anhydrides of aromatic dicarboxylic acids of the general formula: 25 x c 9 n 30 wherein X represents a bromine atom or a chlorine atom, m is an integer from 2 to 4, n and p is integers from 0 to 2; and - anhydrides of cycloaliphatic dicarboxylic acids corresponding to the formula: DK 170772 B1 3 χΛ x ^ m. Where X represents a bromine atom or a chlorine atom. Anhydrides of 3,4- (or 3,6- or 4,5-) dibromo-phthalic acid, 3,4,6-tribromo-phthalic acid and tetra-bromophthalic acid are preferably used.
1010
Ifølge den foreliggende opfindelse kan man anvende et enkelt anhydrid eller en blanding af to eller flere anhydrider. De kommercielt tilgængelige anhydrider, der ofte indeholder en lille mængde af uorganiske syrer, kan an- 15 vendes, som de foreligger, uden forudgående oprensning.According to the present invention, a single anhydride or mixture of two or more anhydrides may be used. The commercially available anhydrides, which often contain a small amount of inorganic acids, can be used as they are without prior purification.
Man har således konstateret, at man opnår meget rene produkter i højt udbytte, når den vandige opløsning eller dispersion af anhydridet, der anvendes, er stærkt sur.Thus, it has been found that very pure products are obtained in high yield when the aqueous solution or dispersion of the anhydride used is highly acidic.
20 Den mængde vand, som udgør reaktionsmediet ved fremgangsmåden ifølge opfindelsen, kan variere inden for brede rammer, idet den eneste betingelse er, at den skal være tilstrækkelig stor til at sikre den ønskede dispersion af reaktionskomponenterne og at muliggøre en effektiv om- 25 røring. Denne betingelse kan i almindelighed realiseres ved anvendelsen af en sådan mængde vand, at indholdet af faste materialer i reaktionsblandingen ligger mellem ca.The amount of water constituting the reaction medium of the process according to the invention may vary within wide limits, the only condition being that it must be sufficiently large to ensure the desired dispersion of the reaction components and to allow an effective stirring. This condition can generally be realized by the use of such an amount of water that the content of solids in the reaction mixture is between about 10%.
5 og 75 vægt-%, fortrinsvis mellem 20 og 40 vægt-%.5 to 75% by weight, preferably between 20 and 40% by weight.
30 Reaktionen kan gennemføres ved atmosfæretrykket og en temperatur fra 40 °C til 100 °C, eller under tryk ved en højere temperatur, der kan gå helt op til 225 °C. Man arbejder fortrinsvis ved en temperatur mellem 100 °C og 225 "C, hvilket svarer til tryk mellem 1 og ca. 25 bar.The reaction can be carried out at atmospheric pressure and a temperature from 40 ° C to 100 ° C, or under pressure at a higher temperature which can go up to 225 ° C. It is preferred to operate at a temperature between 100 ° C and 225 ° C, which corresponds to pressures between 1 and about 25 bar.
Hydrazinet kan anvendes i form af hydratet eller et hy-draziniumsalt (f.eks. sulfat, hydrohalogenid eller ace- 35 DK 170772 B1 4 tat), som det foreligger, eller i form af en fortyndet vandig opløsning. Fortrinsvis anvendes hydrazinhydrat i form af en kommercielt tilgængelig vandig opløsning. Fremgangsmåden ifølge opfindelsen anvendes med fordel 5 ved, at hydrazinet indføres progressivt i den halogenerede anhydridopløsning eller dispersion, der forinden er opvarmet og holdt under omrøring.The hydrazine may be used in the form of the hydrate or a hydrazine salt (e.g., sulfate, hydrohalide or acetate) as it is present, or in the form of a dilute aqueous solution. Preferably, hydrazine hydrate is used in the form of a commercially available aqueous solution. Advantageously, the process of the invention is used by introducing the hydrazine progressively into the halogenated anhydride solution or dispersion previously heated and kept under stirring.
Reaktionens varighed kan variere inden for vide grænser; 10 men den ligger i almindelighed mellem 1 og 20 timer. Efter afkøling af reaktionsmediet frafiltreres den dannede suspension af fast materiale, hvorefter den eventuelt vaskes med vand indtil neutral reaktion, hvorpå reaktionsproduktet tørres ved hjælp af i og for sig kendte 15 midler til tørring.The duration of the reaction may vary within wide limits; 10, but it is generally between 1 and 20 hours. After cooling the reaction medium, the solid suspension formed is filtered off and then optionally washed with water until neutral reaction, whereupon the reaction product is dried by means known per se for drying.
Det molære forhold anhydrid/hydrazin kan antage forskellige værdier. Dersom man anvender et forhold tæt ved 2 og en temperatur, der mindst er lig med 140 °C, er det opnå-20 ede reaktionsprodukt i almindelighed sammensat af bis-imidet svarende til den i det følgende viste almene strukturformel; 9 9 25 /CV\ avX9/n—\jy o <5 30 hvori A betegner gruppen stammende fra det anvendte halogenerede anhydrid.The anhydride / hydrazine molar ratio can assume different values. If a ratio close to 2 and a temperature at least 140 ° C is used, the reaction product obtained is generally composed of the bis-imide corresponding to the general structural formula shown below; 9 9 25 / CV \ avX9 / n— \ jy o <5 30 wherein A represents the group derived from the halogenated anhydride used.
Ved lavere temperaturer omfatter det opnåede reaktionsprodukt udover bis-imidet med formlen (111) en variabel 35 mængdeandel, der kan nå op på 80 vægt-%, af en stort set ækvimolær blanding af det som udgangsmateriale anvendte halogenerede anhydrid og af N-amino-imid svarende til den DK 170772 B1 5 almene strukturformel: 0At lower temperatures, the reaction product obtained, in addition to the bis-imide of formula (111), comprises a variable 35 percent by weight, which can reach 80% by weight, of a substantially equimolar mixture of the halogenated anhydride used as a starting material and of N-amino acid. however, corresponding to the general structural formula: 0
MM
\ (IV)\ (IV)
c A N — NHc A N - NH
Vi / «We / «
OISLAND
hvori A har den ovenfor anførte betydning, Idet dette N-10 amino-imid kan foreligge i form af et salt (sulfat, hy-drohalogenld eller acetat). Indholdet af bls-lmld med formlen (III) 1 det opnåede reaktionsprodukt er 1 almindelighed desto større, jo nærmere reaktionstemperaturen er ved en temperatur på 140 °C eller endnu højere.wherein A is as defined above, since this N-10 amino-imide may be in the form of a salt (sulfate, hydrohalogen or acetate). The content of the flash reaction of formula (III) in the reaction product obtained is, in general, the greater the closer the reaction temperature is at a temperature of 140 ° C or even higher.
1515
Dersom man anvender et molforhold mindre end 1 eller i nærheden af 1, opnår man i hovedsagen N-amino-imidet med den almene strukturformel (IV). Når det tilstræbte reaktionsprodukt er N-amino-imidet, anvendes en mængde af hy-20 drazin mellem den støkiometriske mængde og 50% molært overskud, samt fortrinsvis et forhold anhydrid/hydrazin, der stort set er lig med 1.If a molar ratio of less than 1 or in the vicinity of 1 is used, the N-amino imide of the general structural formula (IV) is generally obtained. When the desired reaction product is the N-aminoimide, an amount of hydrazine is used between the stoichiometric amount and 50% molar excess, and preferably an anhydride / hydrazine ratio substantially equal to 1.
Dersom man anvender et molært forhold anhydrid/hydrazin 25 mellem 1 og 2, fås en blanding af de ovennævnte produkter indeholdende desto mere bis-imid, jo nærmere forholdet er ved værdien 2, og jo højere temperaturen er.If a molar ratio of anhydride / hydrazine 25 is used between 1 and 2, a mixture of the above products containing the more bis-imide is obtained, the closer the ratio is to the value 2 and the higher the temperature.
Hvad enten det drejer sig om rene bis-imider, om blan-30 dinger af bis-imid + N-amino-imid + anhydrid eller om N-amino-imid, egner de ved fremgangsmåden ifølge opfindelsen opnåede reaktionsprodukter sig særlig godt som flammeretarderende midler 1 plastmaterialer af vilkårlig art. Inkorporering af disse i sådanne plastmaterialer kan gen-35 nemføres ved enhver i sig selv kendt metode i doseringer fra 5 til 40% i forhold til vægten af det brandbare materiale.Whether pure bis-imides, mixtures of bis-imide + N-amino-imide + anhydride or N-amino-imide, the reaction products obtained by the process according to the invention are particularly suitable as flame retardants. 1 plastic materials of any kind. Incorporation of these into such plastic materials can be accomplished by any method known per se in dosages of from 5 to 40% by weight of the combustible material.
DK 170772 B1 6DK 170772 B1 6
De efterfølgende eksempler belyser opfindelsen nærmere. Procentandelene er udtrykt som vægt-%.The following examples further illustrate the invention. The percentages are expressed as% by weight.
Produkterne er identificeret ved elementæranalyse for CH 5 og N samt ved IR spektrograf!.The products are identified by elemental analysis for CH 5 and N as well as by IR spectrograph.
Udbyttet er udtrykt i forhold til anhydridet.The yield is expressed relative to the anhydride.
Eksempel 1 10 I en reaktor af glas, der er forsynet med en omrører og med en tilbagesvalingsanordning og indeholder 2000 dele destilleret vand, dispergeres 429 dele kommercielt tilgængeligt tetrachlorphthalsyreanhydrid. Suspensionens pH-15 værdi er 1,5.Example 11 In a glass reactor equipped with a stirrer and with a reflux device containing 2000 parts of distilled water, 429 parts of commercially available tetrachlorophthalic anhydride are dispersed. The pH value of the suspension is 1.5.
Efter at have opvarmet denne suspension til 60 °C i løbet af 20-30 minutter tilsættes progressivt 75 dele 100% hydrazinhydrat, hvorpå reaktionsblandingen opvarmes til 100 20 °C. Man tilsætter derpå 1000 dele destilleret vand og holder blandingen ved 100 °C i yderligere 10 timer. Derved fås en suspension, som køles og filtreres på en BUchner-tragt. Efter vask med vand til neutral pH-værdi og tørring under vacuum ved 110-120 °C opnås med et ud-25 bytte større end 97% et hvidt reaktionsprodukt, hvis elementæranalyse og IR spektrum bekræfter strukturformlen: 30 ^N-NH2 ί 35 DK 170772 B1 7After heating this suspension to 60 ° C over 20-30 minutes, 75 parts of 100% hydrazine hydrate is progressively added and the reaction mixture is heated to 100 20 ° C. 1000 parts of distilled water are then added and the mixture is maintained at 100 ° C for a further 10 hours. Thereby a suspension is obtained which is cooled and filtered on a BUchner funnel. After washing with water to neutral pH and drying under vacuum at 110-120 ° C, a yield greater than 97% yields a white reaction product whose elemental analysis and IR spectrum confirm the structural formula: 30 N-NH 2 170772 B1 7
Elementæranalyse for C, H og NElemental analysis for C, H and N
fundet teoretisk C% 32,3 32,5 5 H% 0,7 0,7 N% 9,0 9,5found theoretical C% 32.3 32.5 5 H% 0.7 0.7 N% 9.0 9.5
Eksempel 2 10 Man går frem analogt med eksempel 1, Idet man dlspergerer 1 4000 dele vand 445 dele kommerciel tilgængelig chloren-disyreanhydrid. Suspensionens pH-værdi er 2,5.Example 2 10 Analogous to Example 1, where 1 4000 parts of water are dispersed 445 parts of commercially available chlorene-diacid anhydride. The pH of the suspension is 2.5.
Til den til 98 °C opvarmede suspension sættes progressivt 15 60 g 100% hydrazinhydrat. Efter 10 timers reaktion ved denne temperatur afkøles blandingen, og reaktionsproduktet frasepareres ved filtrering.To the suspension heated to 98 ° C is added progressively 15 g of 100% hydrazine hydrate. After 10 hours of reaction at this temperature, the mixture is cooled and the reaction product separated by filtration.
Efter vask til neutral pH-værdi og tørring under vacuum 20 ved 110 °C-120 °C opnås et udbytte over 90% af et gråt produkt, hvis elementæranalyse og IR spektrum bekræfter strukturformlen:After washing to neutral pH and drying under vacuum 20 at 110 ° C-120 ° C, a yield of over 90% of a gray product is obtained, whose elemental analysis and IR spectrum confirm the structural formula:
a Sand S
25 01 - NH, aJ4A/ 2 ci o01 - NH, aJ4A / 2 ci o
Elementæranalyse for C, H og N 30 Målt Teoretisk C% 27,9 28,1 H% 1,7 1,1 N% 7,3 7,3 35 DK 170772 B1 8Elemental analysis for C, H and N 30 Measured Theoretical C% 27.9 28.1 H% 1.7 1.1 N% 7.3 7.3 35 DK 170772 B1 8
Eksempel 3 1 en autoklav på seks liter, der er forsynet med en omrører, Indføres 1392 dele tetrabromphthalsyreanhydrid 1 5 4000 dele vand. Dispersionens pH-værdi er 1,5.Example 3 In a six-liter autoclave equipped with a stirrer, 1392 parts of tetrabromphthalic anhydride are introduced into 5,000 parts of water. The pH of the dispersion is 1.5.
Blandingen opvarmes til 60 °C, hvorpå man progressivt tilsætter 225 dele 100% hydrazinhydrat. Suspensionen opvarmes til 125 °C under tryk, og man holder denne tempe-10 ratur i 10 timer. Efter denne reaktionstid afkøles blandingen og produktet frasepareres ved filtrering.The mixture is heated to 60 ° C, whereupon 225 parts of 100% hydrazine hydrate are progressively added. The suspension is heated to 125 ° C under pressure and this temperature is maintained for 10 hours. After this reaction time, the mixture is cooled and the product is separated by filtration.
Efter vask til neutral pH-værdi og tørring under vacuum ved 110 °C-120 °C, opnår man med et udbytte større end 15 90% et gult reaktionsprodukt, hvis elementæranalyse og IRAfter washing to neutral pH and drying under vacuum at 110 ° C-120 ° C, a yellow reaction product whose yield is greater than 15% is obtained, whose elemental analysis and IR
spektrum indikerer strukturformlen: 9spectrum indicates the structural formula: 9
Br,—ΙΟΙ ^ N - NH 20 ^ 6Br, —ΙΟΙ ^ N - NH 20 ^ 6
Elementæranalyse for C, H og NElemental analysis for C, H and N
25 fundet teoretisk C% 19,58 20,1 H% 0,32 0,4 N% 5,68 5,9 30 Eksempel 4Found theoretical C% 19.58 20.1 H% 0.32 0.4 N% 5.68 5.9 Example 4
Man går frem analogt med eksempel 3, idet man dog anvender et 100% molært overskud af hydrazinhydrat. Man opnår det samme reaktionsprodukt som i eksempel 3 med et udbyt-35 te på 97,4%.You proceed analogously to Example 3, however, using a 100% molar excess of hydrazine hydrate. The same reaction product is obtained as in Example 3 with a yield of 97.4%.
DK 170772 B1 9DK 170772 B1 9
Eksempel 5 1 en autoklave på 4 liter, som er forsynet med en omrører, dispergeres 883 dele kommercielt tilgængelig te-5 trabromphthalsyreanhydrid i 2600 dele destilleret vand. Dette medium opvarmes under omrøring til en temperatur på 170 °C, hvilket svarer til et tryk mellem 7,6 og 8 bar.Example 5 In a 4 liter autoclave equipped with a stirrer, 883 parts of commercially available tetrabromophthalic anhydride are dispersed in 2600 parts of distilled water. This medium is heated with stirring to a temperature of 170 ° C, which corresponds to a pressure between 7.6 and 8 bar.
Ved hjælp af en pumpe indføres progressivt i den under 10 omrøring værende suspension 53 dele 100% hydrazinhydrat, som er fortyndet med 200 dele destilleret vand (molært forhold ATBP/HH - 1,8).By means of a pump, 53 parts of 100% hydrazine hydrate, which is diluted with 200 parts of distilled water (molar ratio ATBP / HH - 1.8), is progressively introduced into the suspension under stirring.
Reaktionsmediet opretholdes i 6 timer ved 170 °C, hvorpå 15 blandingen afkøles, filtreres og vaskes. Efter tørring ved 100-110 °C under vacuum fås i et udbytte på 95% et hvidt produkt indeholdende: 83% N,N’-bis-(tetrabromphthalimid) 20 14% N-aminotetrabromphthalimid 3% tetrabromphthalsyreanhydridThe reaction medium is maintained for 6 hours at 170 ° C, after which the mixture is cooled, filtered and washed. After drying at 100-110 ° C under vacuum, in a yield of 95%, a white product is obtained containing: 83% N, N'-bis (tetrabromophthalimide) 14% N-aminotetrabromphthalimide 3% tetrabromophthalic anhydride
Eksempel 6 25 Effektiviteten af de ved fremgangsmåden ifølge opfindel sen fremstillede produkter som brandhæmmende midler for plastmaterialer afprøves ved den følgende almene fremgangsmåde : 30 Ved hjælp af et blandeapparat af planet-typen eller af "tromle"-typen blandes plastmaterialet i form af et pulver eller et granulat med det brandhæmmende middel, der skal afprøves, i de i efterfølgende tabel angivne indbyrdes mængdeforhold og med eventuelle additiver (antimon-35 trioxyd, paraffin). Efter homogenisering ekstruderes blandingen ved hjælp af en egnet ekstruder (af dobbelt-skruetype, enkeltskruetype eller af typen "Buss"), der DK 170772 B1 10 eventuelt er udstyret med midler til afgasning, idet man arbejder ved den ekstruderingstemperatur, der er befalet af leverandøren af kunstharpiksen, og som er afhængig af plastmaterialets smeltetemperatur. Det således opnåede 5 færdige plastmateriale, der eventuelt kan være i granuleret form, forarbejdes derpå til prøvestykker efter mål ved hjælp af en sprøjtestøbemasklne, som er indstillet på en passende temperatur. De dannede prøvestykker underkastes derpå de normaliserede afprøvninger for brandmod-10 standsdygtighed UL94 i tykkelsen 3,2 mm og 1,6 mm (den franske norm NF T51072) samt for oxygenindeks 0% (den franske norm NF T51071).Example 6 The effectiveness of the products produced by the process of the invention as flame retardants for plastics materials is tested by the following general procedure: a granulate having the fire-retardant to be tested in the proportional proportions given in the following table and with any additives (antimony trioxide, paraffin). After homogenization, the mixture is extruded using a suitable extruder (double-screw type, single-screw type or "Buss" type) which is optionally equipped with degassing means, operating at the extrusion temperature recommended by the supplier. of the resin and which is dependent on the melting temperature of the plastic material. The 5 finished plastic material thus obtained, which may optionally be in granulated form, is then processed into test pieces according to dimensions by means of an injection molding machine which is set at an appropriate temperature. The resulting specimens are then subjected to the normalized tests for fire resistance UL94 of thickness 3.2 mm and 1.6 mm (French standard NF T51072) and for oxygen index 0% (French standard NF T51071).
I efterfølgende tabel A er samlet de resultater, der er 15 opnået, når det drejer sig om polybutylen terephthalat (TMNO-ORGATER, der er granuleret og som markedsføres af ansøgeren).The following table A summarizes the results obtained for polybutylene terephthalate (granulated TMNO ORGATES marketed by the applicant).
TABEL ATABLE A
2020
Forsøg nr. I kon- II III IVExperiment No. I con- II III IV
trolcontrol
Brandhæmmende middel fra eksempel nr. Intet 13 5 25-----Fire retardant from Example No. None 13 5 25 -----
Sammensætning (vægtdele): - TMNO-ORGATER harpiks 1000 1000 1000 1000 - Brandhæmmende middel 0 142 160 186 - Antimontrioxid 0 74 76 78 - Paraffin 0 18 18 18Composition (parts by weight): - TMNO ORGATES resin 1000 1000 1000 1000 - Fire retardant 0 142 160 186 - Antimony trioxide 0 74 76 78 - Paraffin 0 18 18 18
Resultater af prøverne: 1Results of the tests: 1
30 - UL94 NC V0 VO VO30 - UL94 NC V0 VO VO
- 10% 22 27,6 32,2 31,3- 10% 22 27.6 32.2 31.3
Prøvestykkets farve hvidt elfen- gult elfenbens- benshvidt hvidt 35 ikke klassificeretColor of test piece white ivory yellow ivory white white 35 not classified
Claims (6)
Applications Claiming Priority (2)
| 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 |
| FR8710586 | 1987-07-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK412988D0 DK412988D0 (en) | 1988-07-22 |
| DK412988A DK412988A (en) | 1989-01-25 |
| DK170772B1 true DK170772B1 (en) | 1996-01-15 |
Family
ID=9353574
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK412988A DK170772B1 (en) | 1987-07-24 | 1988-07-22 | Process for the preparation of halogen-containing imides |
| DK024795A DK24795A (en) | 1987-07-24 | 1995-03-13 | Use of a fire retardant comprising halogenated imides |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK024795A DK24795A (en) | 1987-07-24 | 1995-03-13 | Use of a fire retardant comprising 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 |
| 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 |
| DE2648970A1 (en) * | 1976-10-28 | 1978-05-11 | Dynamit Nobel Ag | AZOMETHINIMIDE |
| 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 DE DE3856460T patent/DE3856460D1/en not_active Expired - Lifetime
- 1988-07-12 AT AT88401815T patent/ATE199713T1/en not_active IP Right Cessation
- 1988-07-12 EP EP88401815A patent/EP0300879B1/en not_active Expired - Lifetime
- 1988-07-12 SG SG1996008587A patent/SG70567A1/en unknown
- 1988-07-21 JP JP63182770A patent/JPH0686426B2/en not_active Expired - Lifetime
- 1988-07-22 AU AU19731/88A patent/AU617337B2/en not_active Ceased
- 1988-07-22 PT PT88091A patent/PT88091B/en not_active IP Right Cessation
- 1988-07-22 FI FI883475A patent/FI92390C/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
- 1988-07-23 CN CN88104597A patent/CN1025611C/en not_active Expired - Fee Related
- 1988-07-23 KR KR1019880009272A patent/KR0130475B1/en not_active IP Right Cessation
-
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 |
|---|---|
| DE3856460D1 (en) | 2001-04-19 |
| JPH0768407B2 (en) | 1995-07-26 |
| FI92390B (en) | 1994-07-29 |
| PT88091B (en) | 1995-03-31 |
| NO173650C (en) | 1994-01-12 |
| ZA884650B (en) | 1989-09-27 |
| CA1338354C (en) | 1996-05-28 |
| CN1025611C (en) | 1994-08-10 |
| FR2618430B1 (en) | 1991-02-15 |
| FI883475A (en) | 1989-01-25 |
| KR0130475B1 (en) | 1998-04-09 |
| IL86673A (en) | 1993-01-31 |
| NO883003L (en) | 1989-01-25 |
| NO173650B (en) | 1993-10-04 |
| CN1031372A (en) | 1989-03-01 |
| EP0300879A1 (en) | 1989-01-25 |
| IL86673A0 (en) | 1988-11-30 |
| FI883475A0 (en) | 1988-07-22 |
| NO883003D0 (en) | 1988-07-05 |
| SG70567A1 (en) | 2000-02-22 |
| NZ225530A (en) | 1989-08-29 |
| PT88091A (en) | 1989-06-30 |
| AU617337B2 (en) | 1991-11-28 |
| AU1973188A (en) | 1989-01-27 |
| KR890002282A (en) | 1989-04-10 |
| JPS6447765A (en) | 1989-02-22 |
| ATE199713T1 (en) | 2001-03-15 |
| FR2618430A1 (en) | 1989-01-27 |
| EP0300879B1 (en) | 2001-03-14 |
| DK412988D0 (en) | 1988-07-22 |
| JPH0686426B2 (en) | 1994-11-02 |
| DK412988A (en) | 1989-01-25 |
| FI92390C (en) | 1994-11-10 |
| JPH06228365A (en) | 1994-08-16 |
| DK24795A (en) | 1995-03-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PBP | Patent lapsed |