In one embodiment, the inventive process comprises: (a) preparing a first slurry comprising a first particulate PAS resin and a polar organic compound, (b) heating the first slurry to a temperature in the range of about 20.degree. C. (68.degree. F.) to about 40.degree. C. (104.degree. F.) below the liquid-to-solid phase transitional temperature of the first particulate resin, and (c) rapidly cooling the first slurry to below about 50.degree. C. (122.degree. F.) below the liquid-to-solid phase transitional temperature of the first particulate resin in the polar organic compound to form a second slurry, comprising the polar organic compound and a polymeric mixture comprising a novel particulate high molecular weight PAS resin and a minor amount of a particulate low molecular weight PAS resin.In another embodiment, the inventive process comprises: (a) preparing a liquid mixture comprising a first particulate PAS resin and a polar organic compound, at a temperature above the solid-to-liquid phase transitional temperature of the first particulate resin, (b) slowly cooling the liquid mixture to between about 20.degree. C. (68.degree. F.) to about 40.degree. C. (104.degree. F.) below the liquid-to-solid phase transitional temperature of the first particulate PAS in the polar organic compound resin to form a first slurry comprising the polar organic compound and a second particulate PAS resin, and (c) rapidly cooling the first slurry to about 50.degree. C. (122.degree. F.) below the liquid-to-solid phase transitional temperature of the first particulate resin in the polar organic compound, thus forming a second slurry comprising the polar organic compound and a polymeric mixture comprising a third particulate high molecular weight resin, wherein third particulate resin, when recovered has a higher molecular weight than its respective first and second particulate resins, if recovered by conventional means.