DE1795204A1 - Process for the production of cyanamides from cyanazide and organic compounds - Google Patents

Process for the production of cyanamides from cyanazide and organic compounds

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Publication number
DE1795204A1
DE1795204A1 DE19651795204 DE1795204A DE1795204A1 DE 1795204 A1 DE1795204 A1 DE 1795204A1 DE 19651795204 DE19651795204 DE 19651795204 DE 1795204 A DE1795204 A DE 1795204A DE 1795204 A1 DE1795204 A1 DE 1795204A1
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Prior art keywords
cyanazide
cyanamides
organic compounds
hours
bath
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DE19651795204
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German (de)
Inventor
Marsh Frank Dennis
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C261/00—Derivatives of cyanic acid
    • C07C261/02—Cyanates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
    • C07D203/20—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carbonic acid, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/26—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/22—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification

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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)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Detergent Compositions (AREA)

Description

DR.-I NG. WALTER ABITZ 8 München 27, PienzenauerstraßeDR.-I NG. WALTER ABITZ 8 Munich 27, Pienzenauerstraße

DR DIETER MORF Telefon 483225 und 486415DR DIETER MORF Telephone 483225 and 486415

Telegramme: Chemindus München PatentanwälteTelegrams: Chemindus Munich patent attorneys

179520A179520A

22. August 1968 CR-62l6-I-Div./£ 36 434 Tr.A,August 22, 1968 CR-62l6-I-Div./£ 36 434 Tr.A,

P 14 68 799. 1 Tr.A.P 14 68 799. 1 Tr.A.

E. I. DU PONT DE NEMOURS AND COMPANY 10th and Market Streets, Wilmington, Del. 29898, V. St. A.E. I. DU PONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Del. 29898, V. St. A.

Verfahren zur Herstellung von Cyanamiden aus Cyan- μζίά und organischen VerbindungenProcess for the production of cyanamides from cyano and organic compounds

Gegenstand der Erfindung 1st ein Verfahren zur Herstellung von Cyanamiden aus Cyanazld und organischen Verbindungen* das dadurch gekennzeichnet ist« das« nan ein· aliphatisch ge· sättigte polyiiere Verbindung Mit Cyanasid bei einer Temperatur zwischen 23 und I50 0C, vorzugsweise zwischen 40 und 100 0C, gegebenenfalls in Gegenwart eines Inerten Reaktionsmittels« umsetzt. The invention 1st method for the preparation of cyanamides from Cyanazld and organic compounds * which is characterized in "that" nan a · aliphatic ge · saturated polyiiere connection with Cyanasid at a temperature between 23 and I50 0 C, preferably between 40 and 100 0 C, if appropriate in the presence of an inert reactant.

109886/1808109886/1808

BAD ORIGINALBATH ORIGINAL

CR-6216-I i CR-6216-I i

Der angewendete Druck ist nicht kritisch lind liegt in Abhängigkeit von der PALicht.tgke>t der Reaktionsfcellnehmer ijr, allgemeinen bei atmosphärischen oder leicht erhöhten Drücken.The pressure applied is not critical and is dependent from the light at atmospheric or slightly elevated pressures.

Die zur Ausführung der Reaktion notwendige Zeit variiert ν >η wenigen Minuten bei sehr reaktionsfähigen Verbindungen bis zu mehreren Stunden oder länger bei weniger reaktionsfähigen Verbindungen. Falls gewünscht, kann der Reaktionsvez'lau" durch Messen der entwickelten Sticketoffraenge verfolgt werden; für jedes reagierende Cyanazidmolekül wird ein Molekül Stickstoff in Freiheit gesetzt.The time required to carry out the reaction varies ν> η a few minutes for very reactive compounds up to several hours or longer for less reactive compounds. If desired, the reaction process " be followed by measuring the developed ticket quantity; for each reacting cyanazide molecule becomes one molecule Nitrogen released.

Das bei dem erJtindungsgeinässen Verfahren verwendete Cyanazid, M-.CN, iat explosiv, wenn es frei oder nahezu frei von Lösungsmittel ist und soll mit erosser Vorsicht gehandhabt werden. Με.η kann es jedoch mit verhältnlsmässiger Sicherheit in verdünnter oder massig konzentrierter Lösung verwenden.The cyanazide used in the process of the invention, M-.CN, iat explosive when free or nearly free of solvent is and should be handled with extreme caution. However, Με.η can be diluted with relative certainty or use a moderately concentrated solution.

Μεα kann das bei der Umsetzung zu verwendende Cyanazid vorher oder in situ herstellen. Ins eretereji Falle kann man ea wie folgt herstellen.Μεα can be the cyanazide to be used in the implementation beforehand or manufacture in situ. In the eretereji case one can ea as follows produce.

2 -2 -

109886/1508109886/1508

BADBATH

■τι/-. !·-3.fi■ τι / -. ! · -3.fi

Sin 125-π?!-Kolben, der wit einem Kühler, Thermometer, Magne ;-rührer, Gaseinlaitungsrchr und Stickstoffblaaenzklhler ausge · rüstet ist, wird in der Flamme getrocknet und un;er Stickstoff auf Raumtemperatur abgekühlt. Man gibt 16,25 g (0,25 Mol) Natriumazld und 48,5 ß (62,5 ml) trockenes Acetonitril hinzu und kühlt den Kolben in einem Eis-Salz-Bad auf -10 bis 0 0C. Durch den Kühler leitet man Eiswasser oder ein Kühlmittel von -5 bis 0 0C und destilliert unter guter Eewegung 20 ml (24,0 g, 0,39 Mol) Cyanchlorid mit solcher Geschwindigkeit in den Kolben, dass eine Temperatur unterhalb 12 0C aufrechterhalten bleibt. Nach Beendigung der Zugabe rührt man die Mischung eine halbe Stunde bei 0 bis 10 0C und lässt sie sich dann langsam innerhalb einer Stunde auf Raumtemperatur erwärmen. Obwohl an diesem Punkt die Umsetzung im wesentlichen beendet ist, kann man das Gemisch Über Nacht bei Rauntemperatur rühren. Überschüssiges CyanohloridSin 125 π - flask wit a condenser, thermometer, Magne;! Stirrers, Gaseinlaitungsrchr and Stickstoffblaaenzklhler out · is upgraded, dried and un in the flame; he cooled nitrogen to room temperature. 16.25 g (0.25 mol) of sodium azld and 48.5 μ (62.5 ml) of dry acetonitrile are added and the flask is cooled to -10 to 0 ° C. in an ice-salt bath to ice water or a coolant -5 to 0 0 C and distilled under good Eewegung 20 ml (24.0 g, 0.39 mol) of cyanogen chloride at such a speed in the piston, that a temperature is maintained below 12 0 C. After the addition is complete, the mixture is stirred for half an hour at 0 to 10 ° C. and then slowly warmed to room temperature over the course of an hour. Although the reaction is essentially complete at this point, the mixture can be stirred overnight at room temperature. Excess cyanogen chloride

entfernt nan durch etwa einstUndigee Evakuieren durch den gekühlten Kühler (0 0C) bei einen Druck«» 95 bis 120 mn, wobei gerührt wird. Di« in de« Kolben zurückbleibende Lösung filtriert man unter Stickstoff und wäscht den Fllter- removed by evacuating for about one hour through the cooled condenser (0 0 C) at a pressure of 95 to 120 mn, with stirring. The solution remaining in the flask is filtered under nitrogen and the filter

109886/1508109886/1508

BADBATH

CR-6216 -ICR-6216 -I

kuchen zweimal mit insgeeant 10 ml trockenem Acetonitril. Dae vereinigte Filtrat (67-72 nl), daß aus einer Lösung von Cyanazid in Acetonitril besteht, kann man sofort verwenden oder unter Stickstoff bei -20 0C aum späteren Gebrauch aufbewahren. cake twice with total 10 ml of dry acetonitrile. Dae combined filtrate (67-72 nl) that consists of a solution of acetonitrile in Cyanazid, one can use immediately or store under nitrogen at -20 0 C aum later use.

Cyanazid ist οtossempfindlich und bia zu einem gewissen Grad thermisch nicht bes^indig. Seine Lösungen in organischen Lösungsmitteln, z. B. Acetonitril, Ä'tkylacetat cde.r Toluol, sind jedoch bei Raumtemperatur mehrere Tage lang beat ändig und können 'bei Temperaturen unter 0 0C unbegrenzt gelagert werden. Die Lagerung a temp era tür soll nicht so niedrig sein, daso das Lösungsmittel fest oder die Löslichkeit deo Cyanaaidfi so weit vemindert wird, dass es sich als eine im T/eoentlichen lösungsmittelfreie, stoBBeapfindlieho, zweite Phase abtrennt· Bevorzugte Lagerungstenperaturen liegen bei -30 bis 0 0C*.Cyanazide is sensitive to bumps and bia to a certain extent not thermally sensitive. Its solutions in organic solvents, e.g. B. acetonitrile, Ä'tkylacetat cde.r toluene, but are beat änd several days at room temperature and can be stored indefinitely at temperatures below 0 0 C. Storage at temperature should not be so low that the solvent is solid or the solubility of the cyanaaidfi is reduced to such an extent that it separates as a generally solvent-free, shock-sensitive, second phase.Preferred storage temperatures are -30 to 0 0 C *.

Lösungen, die bis zu 90 # oder noch grüssere tiongen an Cyanazid in organischen Lösungsmitteln enthalten, kann man durch Urneetsung von Cyanchlorid mit entweder einem Alkali- oder Ammoniumazidj wie oben beschrieben, herstellen. Lösungen, die ungefähr 20 bis 40 Gew.# Cyanazid enthalten, werdeo jode oh wegen dqr Sicherheit und bequemen Handhabung bevorzugt.Solutions that contain up to 90% or even greater amounts of cyanazide in organic solvents can be prepared by dissolving cyanochloride with either an alkali or ammonium azide as described above. Solutions containing about 20 to 40% by weight of cyanazide are preferred for safety and convenience.

1 09i"8t/"1 50 81 09i "8t /" 1 50 8

BADBATH

CR-6216-I 5CR-6216-I 5

Wegen der relativen Unbeständigkeit des Cyanazids erzeugt man es am betten entweder in Gegenwart der aliphatisch gesättigten organischen Verbindung oder in Gegenwart eines Reaktion*« mediums» Bei dem letzteran Verfahren gibt man den aliphatisch gesättigten, organischen Reaktionsteilnehmer zum Medium, we\° ches das vorher hergestellte Cyanazid enthält. Alternativ kann man die Cyanazidlösung auch zum Reaktionsteilnehiner geben.Because of the relative instability of cyanazide, it is produced in bed either in the presence of the aliphatically saturated organic compound or in the presence of a reaction * « mediums »In the latter process, you give the aliphatic saturated, organic reactants to the medium, we \ ° ches contains the previously prepared cyanazide. Alternatively, the cyanazide solution can also be added to the reactant.

Im allgemeinen setzt man die organische Verbindung mit Cyanazid in im wesentlichen äquimolaren Anteilen um, doch kann autfh der eine oder der andere Reaktionsteilnehmer im Überschuss vorliegen.In general, the organic compound is reacted with cyanazide in essentially equimolar proportions, but it is possible autfh one or the other reactant is present in excess.

Verwendet man ein Reaktionsmedium, so soll es normalerweise flüssig sein und bei-der angewendeten Reaktionstemperatur gegenüber den Reaktionsteilnehowrn und Reaktionsprodukten In wesentlichen inert sein. Be versteht sich daher, dass nan in jede« einzelnen Fall das Medium In Anbetracht dtr angewendeten Reaktlon*bedingungen auswählen muss. Geeignete Re.aktionsmedien sind Propionitril, Acetonitril, Äthylacetat, /Vinylacetat, Dimethylformamid, 1,1,2,2-Tetrachloräthan, Isoootan, Jfethylenchlorid, Tetrachlorkohlenstoff und 1,2-Dibrommethan«If a reaction medium is used, it should normally be liquid and at the reaction temperature used towards the reaction participants and reaction products Be essentially inert. Be therefore understood that In every single case the medium In considering dtr must select the reaction conditions applied. Suitable Reaction media are propionitrile, acetonitrile, ethyl acetate, / Vinyl acetate, dimethylformamide, 1,1,2,2-tetrachloroethane, isootane, ethylene chloride, carbon tetrachloride and 1,2-dibromomethane «

109886/1508109886/1508

Beispiele von Polymerisat «ns welche Kohlenstoff-Wa'jcei stof t·- Binäun^en besritzen und dip im wesentlichen frei von uiii-recätt aliphatischen Kohlenstoff"Kohlenstoff-Bindungen süid, sind Polyethylen, Polyvinylfluorid, Polyvinylidenchlorid, Polyvinylacetat, Polystyrol, Poly-(methylvinylketon), Poly-(methylacrylat), Poly-(methylmethacrylat), Polyacrylnitril, Polypropylen, Polyisobutylen, hydrierter Naturkautschuk, Polypivalolacton, polyraerisierte Milch- und Glykclsäuren, Polyoxymethylene,· Copolymerisate von Formaldehyd mit Epoxyder4, z. Q. Äthylenoxyd, Copolymerisate von Formaldehyd mit Äthylen, Propylen usw., Copolymerisate von Trifluoracetaldehyd mit Formaldehyd unvt. Examples of polymer "n s which carbon Wa'jcei stof t * - ^ s Binäun besritzen and dip essentially free of aliphatic carbon uiii-recätt" carbon bonds süid are polyethylene, polyvinyl fluoride, polyvinylidene chloride, polyvinyl acetate, polystyrene, poly (methyl vinyl ketone), poly (methyl acrylate), poly (methyl methacrylate), polyacrylonitrile, polypropylene, polyisobutylene, hydrogenated natural rubber, polypivalolactone, polymerized lactic and glycolic acids, polyoxymethylene, copolymers of formaldehyde with epoxy 4 , e.g. of formaldehyde with ethylene, propylene, etc., copolymers of trifluoroacetaldehyde with formaldehyde unvt.

erfinduassgemäss erhHXtliohet! Cyanastide variisrer. in Abhängigkeit von der Anzahl der -CH-Stellen, die an der Umsetsimg raii Cyanazid teilnehmen. UnabhSneig von der Natur des Vorläufers, 1st die Orundumsetzung die gleiche und ergib' Produkte, die eine oder mehrere Cyanamidgruppen, d.-h. -NKCK-Gruppen«, enthalten., in welchen die freie Bindung direkt an das Kohlenstoffatom gebunden ist, an des das Wasserstoff« atom, welches zur Bildung der Cyanäruid-Gruppe abwanderte.» ui ■■jpi'Urtglich gebunden vmr.according to the invention Cyanastide variisrer. depending on the number of -CH sites that participate in the conversion of cyanazide. Regardless of the nature of the precursor, the orund conversion is the same and gives products containing one or more cyanamide groups, i.e. -NKCK groups ", in which the free bond is bonded directly to the carbon atom , to the hydrogen" atom that migrated to form the cyanoauride group. " ui ■■ jpi'Urtlich bound vmr.

109886/1508109886/1508

BAD ORIONS?BAD ORIONS?

CR-6216-ICR-6216-I

Die Produkte, die man erfindungsgemäsa aus gesättigten Polymerisaten erhält, stellen eine neue Klasse dar und bilden einen Tei? der Erfindung. Sie enthalten im allgemeinen Cyanamidgruppen, -HHCN, die am aliphtfcischen Kohlenstoff der Hauptkohlenstoff-Kette hängen, doch können sis auch einige -NHCN-Qruppon enthalten, die an Seitenkette*! im Polymerisat gebunden sind. Es iot nicht möglich, eine genaue Strukturformel dieser Produkte anzugeben, aber ip allgemeinen kann man sie ungefähr wie folgt darstellen:The products obtained according to the invention from saturated polymers receive, represent a new class and form a part? the invention. They generally contain cyanamide groups, - HHCN, which is the aliphatic carbon of the The main carbon chain is hanging, but some of them can too -NHCN-Qruppon contain the side chain *! in the polymer are bound. It iot not possible to give an exact structural formula these products indicate, but ip general one can represent them roughly as follows:

Q-C - CQ-C - C

R1 NHR 1 NH

CNCN

R2 R 2

titi

· ι· Ι

R1 R 1

- C-Q- C-Q

tu—^m (T n «ι ι tu— ^ m (T n «ι ι

R2 I? R 2 I?

C - C-Q ti βC - C-Q ti β

R NH CHR NH CH

worin die R->Reste die üben angegebene Bedeutung besitzen, Q ein Segment des Polymeri3atmo1ek.ü'ls darstellt und xt y in which the R-> radicals have the meaning given above, Q represents a segment of the polymer atom and x t y

508508

BAD ORIGINALBATH ORIGINAL

CR-6216-I g CR-6216-I g

und ζ Grundzahlen sind, die in der Grosso in Abhängigkeit von dem Molekulargewicht des Polymerisats schwanken. Im allgemeinen 1st die Summe von x, y und ζ gröseex· als 10·and ζ are basic numbers that vary in gross depending on the molecular weight of the polymer. In general, the sum of x, y and ζ is greater than 10

Das Vorliegen der Cyanaraid-Gruppe ergibt eine verbesserte Färbst off auf nähme., wie in den Beispielen 2, 4 und β gezeigt T/urde» Durch Hydrolyse öer Cyanamid-Gruppen enthaltenden Produkte gernä3S der Erfindung werden sie in Harnstoff ura gewendalt, wie in Beispiel 7 gezeigt ist. Dieäe Harnstoffe sind brauchbare Zwischenprodukte zur weiteren Modifizieruns, zum Beispiel durch Behandlung mit Aldehyd.The presence of the cyanamide group results in improved dye absorption, as shown in Examples 2, 4 and β. By hydrolysis of products containing cyanamide groups according to the invention, they are converted into urea, as in Example 7 is shown. The ureas are useful intermediates for further modification, for example by treatment with aldehyde.

B >? i β P i « 1 ."I ί B>? i β P i «1. " I ί

ilaü suspendiert 11,5 g (0,125 UoI) Potyrijaylfluorid in ' 250 al Äthylsoetät unä gil)t 10 ml (0,013 Mol) Cyaiiazid» H^OV, in AcefeoßitriZ hinzu. Das Gemisch erhitzt man ? Stunden unter Rücicflaee, trennt den Peststoff durch Filtration ab und fcroeknat ihn jxa Vakuurc» Die Sticksto^f-Elementarana^'se zeigi; die Anweaenheit von 2,26 $ Stickstoff; dies entopricht 7 Molji -ÄHON-Gruppeiu. Das fen te Produkt erhitzt man 4 Stunden unter Rückfluss in einer 10bigen wässrigen Salzsäui-elcsuns, entfernt dß3 gebildete feste Produkt durch Filtration, wäsoht.es eut nit Wasser und trocknet es .Ui .V^ui'5· Vjie Analyse aelgt, dass da3 Produkt 1-13 j6 Stickt'tcff enthält, was 4,2 Moi# »HHCIvilly-uruppen entspricht.11.5 g (0.125 UoI) of Potyrijaylfluorid in 250 ml of ethyl acetate inaccessible to 10 ml (0.013 mol) of cyaiiazide H ^ OV, in acefeosite, added. The mixture is heated? Hours under Rücicflaee, separates the pesticide by filtration and fcroeknat it jxa Vakuurc »Die Nitrogen Elementarana ^ 'se zeigi; the presence of $ 2.26 nitrogen; this includes 7 Molji-ÄHON-Gruppeiu. The fen te product is heated for 4 hours under reflux in an aqueous 10bigen Salzsäui-elcsuns removed DSS3 formed solid product by filtration, wäsoht.es eut nit water and dried .ui .V ^ u · i'5 Vjie analysis aelgt that da3 product contains 1-13 j6 Stickt'tcff, which corresponds to 4.2 Moi # »HHCIvilly-uruppen.

BADBATH

CK-3216 -I Q CK-3216-I Q

Beispiel 2 Example 2

Man gibt in einen KoIban, der ait' einem Thermomet92'; Magnetrüiirer und Kühler (welcher mit einem Feuchtigkeitsmesser verbunden ist) ausgerüstet ist, eine Äthylacetat-Löaung von CJyanazid (12,90 g, 0,195 Mol N5CN mit Äthylacetat auf 75 al verdünnt), und mehrere Streifen einer Polyäthylenfolie ("Alathoo-10f! DuPont-Hand elenaine für PolyäthylenharzeJ 0,0254 rrvu x.12,7 mn κ 50,3 cam). Dieses Geaiaoh rührt und erhitzt man 23 Stunden bei 47 bis 68 0C; während dieser Zeit werden ungefähr 0,2 MoL Stiokotoff in Freiheit gesetzLt. Bier.Folien trennt man von der lösung ab, wäepht fjie ait Aceton uttÄ trocknet nie. Das Ultrarotspektrurnr di*ßer Folien zeigt.Absorption bei 3f0 μ (NII), 4452 P (CH)-BUSSOr der normalen Ab8<>rpti<Jn für Polyäthylen.One puts in a KoIban, which is ait 'a Thermomet92'; A magnetic stirrer and cooler (which is connected to a moisture meter), an ethyl acetate solution of cyanoazide (12.90 g, 0.195 mol N 5 CN diluted to 75 al with ethyl acetate), and several strips of polyethylene film ("Alathoo-10 f ! DuPont-hand elenaine for PolyäthylenharzeJ 0.0254 rrvu x.12,7 mn κ cam 50.3) this mixture is stirred and heated Geaiaoh to 23 hours at 47-68 0 C;. during this time, approximately 0.2 mol in Stiokotoff Freedom according to beer. Foils are separated from the solution, washed with acetone uttÄ never dries. The infrared spectrum of these foils shows. Absorption at 3 f 0 μ (NII), 4 4 52 P (CH) -BUSSOr the normal Ab8 <> rpti <Jn for polyethylene.

Analyoe: Analyoe :

Gefunden; N 5,69-,
5,27Found; N 5,69-,
5.27

Venn man eine Probe dieser Folie in einer 1/iigen "Sevron!l-Oran5e (DuPont-IIandelonaae für Farbstoffe) sn.open-dlert und auf einem Dampfbad 1 Stunde erhitzt, nXumt sie le den FarbaJ.,off an, während die nichtraoaifiijiert.e Polyäthylen UBverändort bleibt»If a sample of this film is sn.opened in a 1 / iigen "Sevron ! L- Oran5e (DuPont-IIandelonaae for dyes) and heated on a steam bath for 1 hour, it turns on the Farba J. , Off while the nichtraoaifiijiert.e Polyethylene UBverändort remains »

103^8^/1508103 ^ 8 ^ / 1508

BAD ORIGINALBATH ORIGINAL

CR-6216 -I " 40 CR-6216 -I " 40

Einen Teil der in Polymerisat enthaltenen -WECIT-Gruppen hydrolisiert man sun entsprechenden Harnntoif, indem rna;i das Polymerisat nit uberschiiDFiger 15ΆβθΓ., wünori^er Salzsäure bei Raumtemperatur 48 Stunden rührt.. Das Ultrarot ·- spektrum dieser Polio aei^t keine Abaorptioneim 4»5 μ-Berelch (CN), doch eine starke Absorption la 3,1 bio 3,2 U-(K;) und 5,9 bis 7,0 u-Bereich. Eine Probe dioaer Folie wird leicht mit "Sevron"-Blue (DuPont-Handeflaname für Parbstoffö) gefärbt, wenn man ßio wie oben beschrieben behandelt,Some of the -WECIT groups contained in the polymer one hydrolyses sun corresponding urine by adding rna; i the polymer with excess 15ΆβθΓ., aqueous hydrochloric acid stirs at room temperature for 48 hours .. The ultrared · - spectrum of this polio aei ^ t no absorption in the 4 »5 μ range (CN), but a strong absorption la 3.1 bio 3.2 U- (K;) and 5.9 to 7.0 µ range. A sample of the foil becomes easy with "Sevron" blue (DuPont hand flaname for paraffin) colored if you treat ßio as described above,

B σ i s ρ i e 1 H B σ is ρ i e 1 H

Mehrere orientierte Polypropylen-Polienatreii'nn (0,0254 m..i v. 12-7 im χ 114,5 o^) cuspcnaiert man in einer Äthy3ac<5"fcat·· Lü3iinü von Cyauazid (12,9-ß» O,i95 Hol NrCN mit Äthylacetat au:? 75 nl vevdün.it) und erhitzt unter Rühren 24 Stunden- bei. 43 bis 52 0C; während dieser Zeit werden ungefähr 0,2 Hol Stickstoff In Freiheit o-e30tzt. Die Pellen tiennt nan von der; Genicch, wascht eic nit Aceton und trocknet ι ic.Several oriented polypropylene polynes (0.0254 m..i v. 12-7 in χ 114.5 o ^) are cusped in an ethy3ac <5 "fcat ·· Lü3iinü of cyauazid (12.9-ß» O , i95 Hol N r CN with ethyl acetate au :? 75 nl vevdün.it) and heated with stirring for 24 hour at 43 to 52 0 C;. during this time about 0.2 Get nitrogen In freedom -e30tzt o Pellen. tiennt nan von der; genicch, washes with acetone and dries ι ic.

l Gefunden: IJ 15,10, 15,63 l Found: IJ 15.10, 15.63

Die Ultrnrotanalysc κοί^ΐ eine starke Abcorption bei 3,0 bis 3,'-' μ XlU-') und 4,45, 4,6 μ (CH) auocer der woi-raalen Absorption für Polypropylen.The Ultrnrotanalysc κοί ^ ΐ a strong absorption at 3.0 to 3, '-' μ XlU- ') and 4.45, 4.6 μ (CH) auocer the woi-raalen absorption for polypropylene.

109886/1508
- 10 - 109886/1508
- 10 -

BADBATH

CR-6216-ICR-6216-I

Die Hydrolyse eines Teils dieser Folie wit 1 Salzsäure wie oben beschrieben, wandelt die Cyananiid-*?ruppen in Harnst off-Gr upi>en um; die«? zeigt sich im Ultrarctspcktrum durch das Yereehwinden der Absorptions-Peaks bei 4,45 und 4,6 μ und durch die Bildung neuer Peaks bei 5,9 bis 7,0 u,The hydrolysis of part of this film wit 1 Hydrochloric acid, as described above, converts the cyananiid groups in urine-off groups; the"? shows up in the ultra-dark spectrum by winding the absorption peaks at 4.45 and 4.6 μ and by the formation of new peaks at 5.9 to 7.0 u,

Beispiel 4Example 4

Ein Honv/oven-Polypropylen-iej-.tilgut behandelt man wie obenA Honv / oven polypropylene iej .tilgut is treated as above

• *-—-beschrieben mit Cyanasid -in Acetonitril. Kinen Teil des Ftodukts Iiydrolysiert man mit wässriger Salzsäure zum entsprechenden Harnetofi" vle bereits beschrieben. Jedee dieser Produkte erhitzt man eine Stunde auf ei*eD Danpfbau nit einer leisen Lösung vor "Sevron-Blue 2-G" (DuPont-IIandc^-Gnaise für Farbstoffe) und säuert o'it Essigsäure an· Die Produkte gind nach den V/aschien und Iroclcnen hollblau. Bas nicht modIaI-aierte Textilgut aus Polypropylen nimmt keinen Farbstoff an.• * -—- described with Cyanasid -in acetonitrile. No part of the product is hydrolysed with aqueous hydrochloric acid to give the corresponding uretofi " vle already described. Each of these products is heated for one hour on an oven with a quiet solution in front of" Sevron-Blue 2-G "(DuPont-IIandc ^ -Gnaise for Dyestuffs) and acidified with acetic acid · The products turn pale blue according to the colors and irokines. The unmodified textile material made of polypropylene does not accept any dyes.

Bei Verwendung von "Anthraquinbn-Blue SVP" (DuPont-IIanaelo-When using "Anthraquinbn-Blue SVP" (DuPont-IIanaelo-

r naiae für Farbstoffe) anstelle von "Sevron-Bli-e 2~G'! (BuPont-Hanäelaname für Farbstoffe) und gleicher Behänd l-ußg erg oben oich leuchtend blau gefärbte Produkte. Andere Farbstoff«, beispielsweise "Carainc 2-G", "Caprao^l-Ked-E" -and "Sevron-r naiae for dyes) instead of "Sevron-Bli-e 2 ~ G ' ! (BuPont-Hanäelaname for dyes) and the same handling above oich bright blue colored products. Other dyes", for example "Carainc 2-G" , "Caprao ^ l-Ked-E" -and "Sevron-

11 »11 »

109886/1508109886/1508

BAD ORIGINAL r BATH ORIGINAL r

179520A179520A

CR-6216-ICR-6216-I

Brilliant-Red' (DuPont-Kandelsnamen für Farbstoffe) ereob on Gloicherraaasen cine cute Farbstoff-Absorption.Brilliant-Red '(DuPont candelabra for dyes) ereob on Gloicherraaasen cine cute dye absorption.

Beispiel 5^ For example 5 ^

Mehrere· Streifen von Polyvinylfluorid-Folien (12,7 rua χ 101,6 πη χ 0,0254 mn) behandelt man 26 Stunden boi 46 bie 57 0C Liit Cyanasid in Äthylaoetat (N^CN, 17 g, 0,25 IJoI, mit Äthylacetat auf 50 mi verdünnt); während dieser Zeit wird Stiokotoff in Freiheit gesetzt. Die erhaltenen Folier. enthalten nach den Waschen nit Aceton und Trocknen 0,29 f* Stickstoff und zeilen im Ultrarotapektrum eine Absorption bei 3,0 u (KH) und 4,5, 4,6 u (CIT),Several strips of polyvinyl fluoride foils (12.7 rua χ 101.6 πη χ 0.0254 mn) are treated for 26 hours at 46 to 57 0 C with cyanaside in ethyl acetate (N ^ CN, 17 g, 0.25 IJoI, diluted to 50 ml with ethyl acetate); during this time Stiokotoff is set free. The obtained foils. After washing with acetone and drying, contain 0.29 f * nitrogen and lines in the ultra-red spectrum have an absorption of 3.0 u (KH) and 4.5, 4.6 u (CIT),

B e 1 β ρ i e 16B e 1 β ρ i e 16

Mehrere kleine Stückchen eines Gewobeo aus Polyplvalolacton-Fasera behandelt man mit einer Methylenchlorid-Lösung von Cyanazid (0,088 Hol, 5,9 g, nit Ch2Cl2 auf 75 ml verdünnt) 20 Stunden bei 39 bia 42 0C wie oben beschrieben« Das Gewebe trennt aan von der Lösung ab, wäscht eo hintereinander nit Aceton, Seifenwasser und echlieoslich ait destilliertem Waeser. Einezi Teil diesen Gewebes behandelt man 20 Stunden bei Eauntenperatur nit überechüsaiger, !Obiger Salzaäurc·.Several small pieces of a Gewobeo from Polyplvalolacton-Fasera is treated with a methylene chloride solution of Cyanazid (0.088 Hol, 5.9 g, Ch nit 2 Cl 2 to 75 ml,) for 20 hours at 39 bia 42 0 C as described above, "The Tissue is separated from the solution, washed one after the other with acetone, soapy water, and finally with distilled water. Part of this tissue is treated for 20 hours at low temperature with the above-mentioned hydrochloric acid.

109886/1508109886/1508

• 12 *■• 12 * ■

BAD ORIGINALBATH ORIGINAL

CR-6216-ICR-6216-I

D*as hydrolysiert Produkt färbt mar: erfolgreich mit "Anthraquinon-Blue" und "Gevron-Brilliaiit-Rod" (DuPont-Handolsnamen für Farbstoffe) an. Ein nicht modifiziertes Gewebe nimmt keinen Farbstoff an*The hydrolyzed product stains mar: successful with "Anthraquinone-Blue" and "Gevron-Brilliaiit-Rod" (DuPont handol name for dyes). An unmodified fabric will not accept dye *

ι
Beiepiol .7 ι
Beiepiol .7

15 g Polypivalolacton (bulk polypivalolocton·), in Form einea feinen Pulvere, ouopendiert man in einer Methylenchlorid-Lo-•uns von Cyanazid (If3CIi, 12,9 g, 0,19 'J.ol, mit GII2CIp auf 124 al verdünnt) und erhitzt unter Eühren etv.a 50 Stunden bei 42 0C. Durch Filtration dieses Gemisches trennt man ein gelbbraunes Pulver ab, dae 10,41 $ Stickstoff enthält. Einen Teil diesea Produktes riihrt Dan mit uberGchüssiger, 10biger Salzeäure 24 Stunden bei ^Raumtemperatur, filtriert, v/äscht mit Waaoer und trocknet eis.. Dieses hydrolyslerte Produkt enthält 7,8, 8,12 # Stickstoff.15 g of polypivalolactone (bulk polypivalolactone), in the form of a fine powder, is poured into a methylene chloride solution of cyanazide (If 3 CIi, 12.9 g, 0.19 % oil, with GII 2 CIp 124 diluted al) and heated under Eühren etv.a for 50 hours at 42 0 C. filtration of this mixture is separated to a tan powder from, dae 10.41 $ nitrogen. A part of this product is then stirred with excess hydrochloric acid for 24 hours at room temperature, filtered, washed with water and dried in ice. This hydrolysed product contains 7.8, 8.12% nitrogen.

Beispiel 8Example 8

Ein Alkyl-gekappteq Forraaldehyd-Po^mcrisat (15 ß, 0,5 Llol) suspendiert man in 300 ml Äthylacetat und gibt 20 ml (0,025 Mol) Cyanazid in Acetonitril hinzu. Man erhitzt daa GemischAn alkyl-capped forraaldehyde polymer (15 ß, 0.5 Llol) it is suspended in 300 ml of ethyl acetate and 20 ml (0.025 Mol) cyanazide in acetonitrile was added. The mixture is heated

- 13 -- 13 -

109886/1508109886/1508

BAD ORIGINALBATH ORIGINAL

0R-6216~I0R-6216 ~ I

3 Stunden am Rückfluss, kühlt ea ab und entfernt den Feotetoff mittels Filtration. Daa erhaltene, feste Produkt wäscht man 3 Stunden mit unter Rückfluss kochendem \7asoer und trocknet es. Eine Stickstoff-Elementarenalyse zeigt das Vorliegen von 3 Mo Iij an -EHCil&j-Gruppen.3 hours at reflux, ea cools and removes the Feotetoff by means of filtration. The solid product obtained is washed for 3 hours with refluxing water and it dries. A nitrogen elemental analysis shows the presence from 3 Mo Iij an -EHCil & j groups.

Beispiel 9Example 9

ν
Bin Copolymerisate das etwa 40 Gew.# Hexafluorpropylen und 60 Gew.# Vinylidenfluorid^ (36 g, 0,175 ilol) enthält, löst man in 300 ml an liüdkflusö. siedendem Acetonitril und f:igt 20 ml (0,024 "öl) Cyanazid !acetonitril hinzu· Die Lösung erhitzt man 2 Stunden unter Rückfluss, kühlt eio at, läset das Lösungsmittel abdampfen und behandalt den Rückstand 18 -Stunden mit heieoer, tÖliger, «rüeeriger Saleeäure. Bas err· -haltene, kautechukavti^e Produkt trocknet man und«führt eine Stickstoff-Elementaranaljree durch, die zeigt, dass 13 U an -BH-CNHo-Gruppen vorliegen.ν
A copolymer containing about 40% by weight of hexafluoropropylene and 60% by weight of vinylidene fluoride (36 g, 0.175 ilol) is dissolved in 300 ml of liüdkflusö. boiling acetonitrile and add 20 ml (0.024 "oil) of cyanazide / acetonitrile. The solution is heated under reflux for 2 hours, cooled, the solvent is allowed to evaporate and the residue is treated for 18 hours with hot, oily, oily meal acid The chewable product obtained is dried and a nitrogen elemental analysis is carried out, which shows that 13 U of -BH-CNHo groups are present.

If ~If ~

1Q9886/U081Q9886 / U08

BADBATH

Claims (3)

CR 6216-K>iv. ^* 22. August 5,9^^8CR 6216-K> iv. ^ * 22 August 5.9 ^^ 8 P1 a i e η t a η s ρ r Ü c h eP 1 a i e η ta η s ρ r Ü che ι. Verfahren zur Herstellung vor. Cyanamiden aus Cy&n&zid und organischem Verbindungen, dadurch gekennze:>.ohn3t, dass man ein?; aliphatisch gesättigte polymere Verbind'in£,· / mit 3yanaaJd bei einer Temperatur ssiiechen 2p und I50 °'·, vorzu£TSv:ei3e zwischen 4o und 100 0C, gegebenenfalls in Gegemvart einss inerten ReaktionsmitteXs umsetzt.ι. Method of manufacture before. Cyanamides from cy & n & zid and organic compounds, characterized by:>. Without knowing that one ?; aliphatic saturated polymeric Verbind'in £ · / with 3yanaaJd at a temperature ssiiechen 2p and I50 ° '·, vorzu £ TSV: ei3e between 4o and 100 0 C, optionally einss inert ReaktionsmitteXs reacted in Gegemvart. 2. Verfahren nach Anspruch 1, daduruh gekennzeichnet, daws ι ίιι die Ums3t::i.ing mit in situ gebildetem Cyanaxid curciifüart..2. The method according to claim 1, characterized daduruh, daws ι ίιι the Ums3t :: i.ing with in situ formed cyanaxide curciifüart .. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die aliphatisch gesättigte polymere Verbindung Polyäthylen, Polypropylen, Polyvinylfluorid oder Polypivaiolacton iet.3. The method according to claim 1 or 2, characterized in that that the aliphatically saturated polymeric compound is polyethylene, polypropylene, polyvinyl fluoride or polypivaiolactone iet. - 15 -109886/1508- 15 -109886/1508 BAD ORtGfNALBAD ORtGfNAL
DE19651795204 1964-07-16 1965-03-31 Process for the production of cyanamides from cyanazide and organic compounds Pending DE1795204A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307710A (en) * 2021-06-02 2021-08-27 南京理工大学 Porous azide/high-energy explosive micro-explosion sequence film and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5637651A (en) * 1994-09-08 1997-06-10 Bp Chemicals Limited Process for modifying a polyolefin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113307710A (en) * 2021-06-02 2021-08-27 南京理工大学 Porous azide/high-energy explosive micro-explosion sequence film and preparation method thereof

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