WO1991018041A1 - Functional polymers derived from arylene polysulphides, and production method therefor - Google Patents

Functional polymers derived from arylene polysulphides, and production method therefor Download PDF

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Publication number
WO1991018041A1
WO1991018041A1 PCT/BE1991/000029 BE9100029W WO9118041A1 WO 1991018041 A1 WO1991018041 A1 WO 1991018041A1 BE 9100029 W BE9100029 W BE 9100029W WO 9118041 A1 WO9118041 A1 WO 9118041A1
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WIPO (PCT)
Prior art keywords
arylene
groups
polysulphides
production method
polymers derived
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PCT/BE1991/000029
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French (fr)
Inventor
Daniel Daoust
Pierre Godard
Jacques Devaux
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Solvay & Cie
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Publication of WO1991018041A1 publication Critical patent/WO1991018041A1/en

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    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
    • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
    • C08G75/0222—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur containing nitrogen
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C08G75/0295—Modification with inorganic compounds
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/18—Polysulfoxides

Definitions

  • the invention relates to functional polymers derived from arylene polysulfides and a process for their production.
  • Arylene polysulfides particularly phenylene polysulfide, are well known in the art and used primarily to be made into injected parts resistant to high temperatures. These polymers, insoluble at room temperature in the usual solvents can be prepared for example by reaction of an optionally substituted dihalobenzene (or a mixture of these) with a source of sulfides such as sodium sulfide in a polar aprotic solvent as the
  • N-methylpyrrolidone This type of preparation is described in US Pat. No. 3,354,129 to Phillips Petroleum.
  • the present invention therefore relates to an arylene polysulfide containing both sulfoxide groups and nitro groups.
  • a process for obtaining these polymers derived from PPS consists in oxidizing the sulphide groups (-S-) of PPS into sulphoxide groups (-S0-) and optionally in sulphone groups (-S02-), on the one hand, and to introduce nitro groups (-N02) on the other hand.
  • This oxidation can be carried out by any reactive agent capable of oxidizing and nitrating the PPS, in solution or in suspension in the pure or diluted reactive agent. It can be a combination of separate oxidizing and nitrating agents or, preferably, a single agent combining the two functions. Mention may be made, as such agent, of nitric acid, by means of which the PPS is not only oxidized but also nitrated. The oxidation is furthermore mainly limited to obtaining sulfoxide groups, especially when the nitric acid is diluted in a solvent such as methanesulfonic acid.
  • the PPS thus obtained can be easily dissolved in most of the usual solvents, in particular in phenolic solvents such as meta-cresol or in organic acids such as methanesulfonic acid. Such solutions can then be used in all methods requiring the use of homogeneous solutions such as, for example, analytical methods.
  • the PPS thus functionalized can also be coupled with other polymers and / or mineral fillers.
  • Polymers which can be used for this coupling are, for example, elastomers carrying epoxy groups or silicone elastomers. Such coupling can be achieved for example in an extruder.
  • EXAMPLE 3 g of phenylene polysulphide (-li n 0.20 dl / g to 4 g / 1 in alpha-chloronaphthalene at 206 ° C) prepared from p-dichlorobenzene and sodium sulfide. The suspension is stirred at 0 ° C until complete dissolution. The resulting solution is poured into 200 ml of demineralized water and the precipitate is washed with water. The polymer obtained is then dried. The presence of sulfoxide and nitro groups is clearly visible by conventional IR spectroscopic examination (see attached figure).

Abstract

An arylene polysulphide containing both sulphoxide groupings and nitro groupings.

Description

Polymères fonctionnels dérivés de polysulfures d'arylène et procédé pour les fabriquer Functional polymers derived from arylene polysulfides and process for their manufacture
L'invention concerne des polymères fonctionnels dérivés de polysulfures d'arylène et un procédé pour les fabriquer.The invention relates to functional polymers derived from arylene polysulfides and a process for their production.
Les polysulfures d'arylène, en particulier le polysulfure de phénylène, sont bien connus dans la technique et utilisés princi- paiement pour être transformés en pièces injectées résistant aux hautes températures. Ces polymères, insolubles à température ambiante dans les solvants usuels peuvent être préparés par exemple par réaction d'un dihalobenzène éventuellement substitué (ou d'un mélange de ceux-ci) avec une source de sulfures comme le sulfure de sodium dans un solvant polaire aprotique comme laArylene polysulfides, particularly phenylene polysulfide, are well known in the art and used primarily to be made into injected parts resistant to high temperatures. These polymers, insoluble at room temperature in the usual solvents can be prepared for example by reaction of an optionally substituted dihalobenzene (or a mixture of these) with a source of sulfides such as sodium sulfide in a polar aprotic solvent as the
N-méthylpyrrolidone. Ce type de préparation est décrite dans le brevet US 3354129 de Phillips Petroleum.N-methylpyrrolidone. This type of preparation is described in US Pat. No. 3,354,129 to Phillips Petroleum.
La modification des polysulfures d'arylène par oxydation par l'eau oxygénée est décrite dans le brevet US 4563509 de Phillips Petroleum. Les polymères ainsi obtenus sont décrits comme étant des polymères thermodurcissables et ne sont pas réputés contenir des groupes fonctionnels qui peuvent être mis à profit, par la suite, par exemple pour être couplés avec d'autres polymères. Or, il peut être intéressant de disposer de polysulfures d'arylène présentant des groupes fonctionnels réactifs afin de pouvoir l'engager dans une réaction de couplage avec un autre partenaire pour fabriquer par exemple des copolymeres à blocs de propriétés modifiées.The modification of arylene polysulphides by oxidation with hydrogen peroxide is described in US Patent 4,563,509 to Phillips Petroleum. The polymers thus obtained are described as being thermosetting polymers and are not deemed to contain functional groups which can be used subsequently, for example to be coupled with other polymers. However, it may be advantageous to have arylene polysulphides having reactive functional groups in order to be able to engage it in a coupling reaction with another partner to manufacture, for example, block copolymers with modified properties.
On a, dès lors, cherché à dérivatiser les polysulfures d'arylène et plus particulièrement le polysulfure de phénylène, (dénommés PPS dans la suite de la description, par souci de simplification) par action d'autres réactifs.We have therefore sought to derivatize arylene polysulfides and more particularly phenylene polysulfide (called PPS in the following description, for the sake of simplification) by the action of other reagents.
Ces recherches ont conduit à la découverte d'un nouveau polymère dérivé du PPS. La présente invention concerne dès lors un polysulfure d'arylène contenant à la fois des groupements suifoxydes et des groupements nitro. Un procédé d'obtention de ces polymères dérivés du PPS consiste à oxyder les groupements sulfures (-S-) du PPS en groupements sulfoxydes (-S0-) et éventuellement en groupements sulfones (-S02-), d'une part, et à introduire des groupements nitro (-N02) d'autre part.This research led to the discovery of a new polymer derived from PPS. The present invention therefore relates to an arylene polysulfide containing both sulfoxide groups and nitro groups. A process for obtaining these polymers derived from PPS consists in oxidizing the sulphide groups (-S-) of PPS into sulphoxide groups (-S0-) and optionally in sulphone groups (-S02-), on the one hand, and to introduce nitro groups (-N02) on the other hand.
Cette oxydation peut être effectuée par n'importe quel agent réactif apte à oxyder et à nitrer le PPS, en solution ou en suspension dans l'agent réactif pur ou dilué. Il peut s'agir d'une combinaison d'agents oxydant et nitrant distincts ou, de préférence, d'un agent unique réunissant les deux fonctions. A titre de pareil agent, on peut citer l'acide nitrique, grâce auquel le PPS est non seulement oxydé mais également nitré. L'oxydation se limite en outre principalement à l'obtention de groupes sulfoxydes surtout lorsque l'acide nitrique est dilué dans un solvant comme l'acide methanesulfonique.This oxidation can be carried out by any reactive agent capable of oxidizing and nitrating the PPS, in solution or in suspension in the pure or diluted reactive agent. It can be a combination of separate oxidizing and nitrating agents or, preferably, a single agent combining the two functions. Mention may be made, as such agent, of nitric acid, by means of which the PPS is not only oxidized but also nitrated. The oxidation is furthermore mainly limited to obtaining sulfoxide groups, especially when the nitric acid is diluted in a solvent such as methanesulfonic acid.
Le PPS ainsi obtenu peut être aisément solubilisé dans la plupart des solvants usuels, en particulier dans les solvants phénoliques tels que le méta-crésol ou dans les acides organiques tels que l'acide methanesulfonique. De telles solutions peuvent ensuite être utilisées dans tous les procédés nécessitant l'utilisation de solutions homogènes tels que, par exemple, les procédés analytiques.The PPS thus obtained can be easily dissolved in most of the usual solvents, in particular in phenolic solvents such as meta-cresol or in organic acids such as methanesulfonic acid. Such solutions can then be used in all methods requiring the use of homogeneous solutions such as, for example, analytical methods.
Le PPS ainsi fonctionnalisé peut être également couplé avec d'autres polymères et/ou des charges minérales. Des polymères utilisables pour ce couplage sont par exemple des élastomères porteurs de groupements époxy ou des élastomères siliconés. Pareil couplage peut être réalisé par exemple en extrudeuse.The PPS thus functionalized can also be coupled with other polymers and / or mineral fillers. Polymers which can be used for this coupling are, for example, elastomers carrying epoxy groups or silicone elastomers. Such coupling can be achieved for example in an extruder.
L'exemple suivant est destiné à illustrer l'invention. Exemple On ajoute à 200 ml d'un mélange d'acide nitrique (65 % en poids) et d'acide methanesulfonique (1:5 vol:vol) refroidi à 0°C, 3 g de polysulfure de phénylène (-lin = 0.20 dl/g à 4 g/1 dans l'alpha-chloronaphtalène à 206°C) préparé au départ de p-dichlorobenzène et de sulfure de sodium. La suspension est agitée à 0°C jusqu'à dissolution complète. La solution résultante est versée dans 200 ml d'eau déminéralisée et le précipité est lavé par de l'eau. Le polymère obtenu est ensuite séché. La présence de groupements sulfoxydes et nitro est clairement visible par examen spectroscopique IR effectué de manière conventionnelle (voir figure annexée). The following example is intended to illustrate the invention. EXAMPLE 3 g of phenylene polysulphide (-li n = 0.20 dl / g to 4 g / 1 in alpha-chloronaphthalene at 206 ° C) prepared from p-dichlorobenzene and sodium sulfide. The suspension is stirred at 0 ° C until complete dissolution. The resulting solution is poured into 200 ml of demineralized water and the precipitate is washed with water. The polymer obtained is then dried. The presence of sulfoxide and nitro groups is clearly visible by conventional IR spectroscopic examination (see attached figure).

Claims

R E V E N D I C A T I O N SR E V E N D I C A T I O N S
1 - Polysulfure d'arylène contenant à la fois des groupements sulfoxydes et des groupements nitro.1 - Arylene polysulphide containing both sulphoxide groups and nitro groups.
2 - Polysulfure d'arylène selon la revendication 1, caractérisé en ce qu'il contient en outre des groupements sulfone.2 - Arylene polysulfide according to claim 1, characterized in that it also contains sulfone groups.
3 - Polysulfure d'arylène selon la revendication 2, caractérisé en ce que le rapport molaire entre les groupements sulfoxydes et les groupements sulfones est supérieur à 1.3 - Arylene polysulfide according to claim 2, characterized in that the molar ratio between the sulfoxide groups and the sulfone groups is greater than 1.
4 - Procédé pour la fabrication du polysulfures d'arylène selon les revendications 1 à 3, caractérisé en ce que le poly¬ sulfure d'arylène est mis en contact avec un agent d'oxydation et un agent de nitration.4 - Process for the manufacture of arylene polysulfides according to claims 1 to 3, characterized in that the polyarylene sulfide is brought into contact with an oxidizing agent and a nitrating agent.
5 - Procédé de fabrication selon la revendication 4, caractérisé en ce que l'agent d'oxydation et de nitration est l'acide nitrique.5 - The manufacturing method according to claim 4, characterized in that the oxidation and nitration agent is nitric acid.
6 - Procédé de fabrication selon la revendication 5, caractérisé en ce que l'acide nitrique est dilué dans de l'acide methanesulfonique. 6 - The manufacturing method according to claim 5, characterized in that the nitric acid is diluted in methanesulfonic acid.
PCT/BE1991/000029 1990-05-16 1991-05-15 Functional polymers derived from arylene polysulphides, and production method therefor WO1991018041A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623638A1 (en) * 1993-05-04 1994-11-09 Hoechst Aktiengesellschaft Oxidized poly(arylene sulfide)
WO1995005894A1 (en) * 1993-08-24 1995-03-02 Hoechst Aktiengesellschaft Filter material and a method of removing nitrogen oxides from gases and liquids
WO1996015178A1 (en) * 1994-11-09 1996-05-23 Hoechst Aktiengesellschaft Oxidation of sulphurous polymers with no2/n2o¿4?
EP0776348B1 (en) * 1994-08-15 1999-11-10 Ticona GmbH Mixtures of liquid crystal polymers and polyarylene sulphoxides, foams made of such mixtures, process for producing the same and their use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326865A (en) * 1963-03-27 1967-06-20 Dow Chemical Co Sulfoxide resins
US3948865A (en) * 1974-10-31 1976-04-06 Phillips Petroleum Company Chemical treatment of arylene sulfide polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326865A (en) * 1963-03-27 1967-06-20 Dow Chemical Co Sulfoxide resins
US3948865A (en) * 1974-10-31 1976-04-06 Phillips Petroleum Company Chemical treatment of arylene sulfide polymers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623638A1 (en) * 1993-05-04 1994-11-09 Hoechst Aktiengesellschaft Oxidized poly(arylene sulfide)
US6020442A (en) * 1993-05-04 2000-02-01 Ticona Gmbh Oxidized polyarylene sulfides
WO1995005894A1 (en) * 1993-08-24 1995-03-02 Hoechst Aktiengesellschaft Filter material and a method of removing nitrogen oxides from gases and liquids
TR28492A (en) * 1993-08-24 1996-08-12 Hoechst Ag Filter material and method for removing nitrogen oxides from gases and liquids.
US5792437A (en) * 1993-08-24 1998-08-11 Hoechst Aktiengesellschaft Filter material and method of removing oxides of nitrogen from gases and liquids
EP0776348B1 (en) * 1994-08-15 1999-11-10 Ticona GmbH Mixtures of liquid crystal polymers and polyarylene sulphoxides, foams made of such mixtures, process for producing the same and their use
WO1996015178A1 (en) * 1994-11-09 1996-05-23 Hoechst Aktiengesellschaft Oxidation of sulphurous polymers with no2/n2o¿4?

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