Arylene sulfide polymers
AssigneePhillips Petroleum Company
InventorsJon F. Geibel, Robert W. Campbell, Guy Senatore, Fernando C. Vidaurri, Mark A. Haney
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Abstract
A process for the production of arylene sulfide polymers is provided which comprises subjecting a mixture of at least one first sulfur source, at least one second sulfur source comprised of at least one organic monothiol compound, at least one polyhalo-substituted aromatic compound and at least one polar organic compound to polymerization conditions sufficient to produce the arylene sulfide polymer. The organic monothiol compound can be added at any time prior to substantial completion of polymerization to provide arylene sulfide polymers of increased extrusion rate.
Claims38
A process for preparing arylene sulfide polymer comprising
- 1) admixing at least one first sulfur source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at least one polyhalo-substituted aromatic compound, at least one polar organic compound and a second sulfur source comprised of at least one organic monothiol compound represented by the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen, and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino, and alkylsulfonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium, and y is the valence of M and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z, to form an admixture;
- and
- 2) subjecting said admixture to polymerization conditions sufficient to produce a polymerization reaction mixture comprising said arylene sulfide polymer.
A process for preparing arylene sulfide polymer comprising
- 1) admixing at least one first sulfur source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at least one polyhalo-substituted aromatic compound, and at least one polar organic compound to form an admixture;
- and
- 2) subjecting said admixture to polymerization conditions sufficient to produce a polymerization reaction mixture comprising said arylene sulfide polymer wherein there is added to said polymerization reaction mixture after polymerization commences but prior to substantial completion of polymerization a second sulfur source comprised of at least one organic monothiol compound having the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen, and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloaklyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino, an d alkylsuflonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium and y is the valence of M and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z.
A process for preparing arylene sulfide polymer comprising adding, prior to substantial completion of polymerization, a second sulfur source comprised of at least one organic monothiol compound to a polymerization reaction mixture comprised of at least one first sulfur source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at least one polyhalo-substituted aromatic compound, and at least one polar organic compound;
- wherein said organic monothiol compound is represented by the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen, and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino, and alkylsulfonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium, and y is the valence of M, and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z;
- and recovering said arylene sulfide polymer from said polymerization reaction mixture.
In a process for preparing arylene sulfide polymer comprising admixing components comprised of at least one first sulfur source source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at least one polyhalo-substituted aromatic compound, and at least one polar organic compound under polymerization conditions sufficient to produce said arylene sulfide polymer, the improvement comprising admixing as a further component a second sulfur source comprised of at least one organic monothiol compound represented by the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen, and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino, and alkylsulfonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium, and y is the valence of M and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z.
A method for increasing the extrusion rate of arylene sulfide polymer prepared by subjecting components comprised of at least one first sulfur source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at least one polyhalo-substituted aromatic compound, and at least one polar organic compound to polymerization conditions sufficients to produce said arylene sulfide polymer, said method comprising adding as a further component a second sulfur source comprised of at least one organic monothiol compound represented by the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen, and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino, and alkylsulfonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium, and y is the valence of M and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z.
A process for preparing arylene sulfide polymer comprising adding to a polymerization reaction mixture comprised of at least one polyhalo-substituted aromatic compound, at least one polar organic compound, and at least one first sulfur source selected from the group consisting of hydrogen sulfide, alkali metal sulfides and alkali metal hydrosulfides, at any time prior to substantial completion of polymerization, a second sulfur source, comprised of at least one organic monothiol compound represented by the formula Z-S-R' wherein Z is a halogen-free cyclic organic radical selected from the group consisting of carbocyclic and heterocyclic radicals having a 1 to 4 heteroatoms as cycle members and wherein each said heteroatom is selected from the group consisting of nitrogen, oxygen and sulfur and wherein Z has from 0 to about 4 substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkanoyl, alkanoyloxy, aroyl, alkoxycarbonyl, alkanamido, alkylamino and alkylsulfonyl radicals, R' is selected from the group consisting of H and M/y where M is a metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium, and y is the valence of M and wherein the -S-R' of said Z-S-R' is attached directly to a carbon atom which is a cycle member of said Z.
Dependencies are inferred from the claim text.