Nitrilkautschuke und deren Herstellung in organischen Lösungsmitteln

Nitrile rubbers and production of same in organic solvents

Caoutchouc nitrile et sa fabrication dans des solvants organiques

Abstract

Nitrile rubber comprises: (a) repeating units derived from at least one conjugated diene, at least one alpha , beta -unsaturated nitrile and optionally at least one further copolymerizable monomer; and (b) at least one structural element comprising substituted thiocarbonyl moiety (I), substituted hydrocarbon moiety (II) or (V), or substituted trithiocarbonate moiety (III) or (IV). Nitrile rubber comprises: (a) repeating units derived from at least one conjugated diene, at least one alpha , beta -unsaturated nitrile or optionally at least one further copolymerizable monomers; and (b) at least one structural element comprising substituted thiocarbonyl moiety of formula (Z-(M) n-(X) t-C(=S)-S-) (I), substituted hydrocarbon moiety of formula (-(M) m-R) (II) or (Z-(M) n-) (V), or substituted trithiocarbonate moiety of formula (-S-C(=S)-S-) (III) or (-S-C(=S)-S-(M) m-R) (IV). Z : H, optionally branched, saturated, mono- or polyunsaturated alkyl, saturated, mono- or polyunsaturated carbo- or heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, NH 2, amido, hydroxyimino, carbamoyl , alkoxycarbonyl, halo, OH, phosphonato, phosphinato, alkylthio, arylthio, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfonic acid, sulfamoyl, silyl, silyloxy, nitrile, carbonyl, carboxyl, oxycarbonyl, oxysulfonyl, oxo, thioxo, borate, selenate, epoxy, cyanate, thiocyanate, isocyanate, thioisocyanate or isocyanide; R : Z (when m is not equal to zero) or Z 1>(when m = 0), where Z and R are substituted with F, Cl, Br or I, alkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroaryl alkyl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, carbamoyl, carbonyl, carboxy, oxycarbonyl, oxysulfonyl or epoxy; M : thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfonic acid, sulfamoyl, carbonyl, carboxyl, oxycarbonyl, oxysulfonyl, oxo, thioxo, epoxy, cyanate, thiocyanate, isocyanate, isocyanide or thioisocyanate, or repeating units of at least one mono- or polyunsaturated monomers comprising optionally conjugated dienes, alkynes or vinyl compounds, or structural element, which is a derived polymer comprising polyether, preferably polyalkylene glycol ether or polyalkylene oxide, polysiloxane, polyol, polycarbonate, polyurethane, polyisocyanate, polysaccharide, polyester or polyamide; n, m : 0-10000; t : 0 or 1 (when n = 0) or 1 (when n is not equal to zero); X : C(Z 2), N(Z), P(Z), P(=O)(Z), O, S, S(=O) or S(=O) 2; and Z 1>H, optionally branched, saturated, mono- or polyunsaturated alkyl, saturated, mono- or polyunsaturated carbo- or heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, NH 2, amido, carbamoyl, alkoxy, aryloxy, alkylthio, arylthio or sulfanyl. Independent claims are also included for: (1) producing nitrile rubbers, comprising (i) carrying out radical polymerization of at least one conjugated diene, at least one alpha , beta -unsaturated nitrile and optionally at least one further copolymerizable monomer, in presence of at least one organic solvent and at least one regulator, and (ii) optionally subsequently hydrogenating, where the regulator comprises substituted thiocarbonyl moiety of formula (Z-(M) n-(X) t-C(=S)-S-(M) m-R) (XI); (2) vulcanizable mixture comprising the nitrile rubber, at least one crosslinking agent, optionally at least one filler and optionally at least one further rubber additive; (3) preparing vulcanisate comprising crosslinking the vulcanizable mixture, preferably by adding at least one crosslinking agent or by photochemical activation; and (4) vulcanisate, preferably molding, obtainable by the above method.
Bereitgestellt wird ein neues Verfahren zur Herstellung von Nitrilkautschuken durch radikalische Polymerisation in einem organischen Lösungsmittel und in Gegenwart spezieller Regler-Substanzen. An diese Polymerisation kann sich eine Hydrierung zu ebenfalls neuen hydrierten Nitrilkautschuken anschließen, vorteilhafterweise erfolgt die Hydrierung ebenfalls in organischen Lösungsmittel. Die erhaltenen optional hydrierten Nitrilkautschuke zeichnen sich dadurch aus, dass sie in der Polymerhauptkette bzw. als Endgruppen Fragmente der eingesetzten Regler-Substanzen aufweisen. Sie können mit einer breiten Vielfalt von Molekulargewichten und Polydispersitätsindices hergestellt werden, insbesondere mit sehr geringen Polydispersitätsindices.

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