A process, and product produced therefrom, for preparing a high molecular weight poly(arylene sulfide ketone) from the reaction product of an alkali metal bisulfide with an alkali metal hydroxide, employing molar excess of alkali metal bisulfide with respect to the alkali metal hydroxide. A process, and product produced therefrom, for preparing a high molecular weight poly(arylene sulfide ketone) employing an alkali metal sulfide and an alkali metal hydrosulfide, wherein the alkali metal sulfide hydrosulfide is added in a molar excess with respect to the alkali metal hydrosulfide sulfide.
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1. A method for preparing a poly(arylene sulfide ketone) comprising:
contacting in a reaction mixture (a) at least one polyhalobenzophenone, employing about 1.004:1 to about 1.038:1 molar ratios #x2205;004 to about 0.038 molar excess of alkali metal hydrosulfide relative to said polyhalobenzophenone, and at least one of (b) or (c), wherein (b) is at least one alkali metal sulfide and at least one alkali metal hydrosulfide, and (c) is at least one alkali metal hydroxide and at least one alkali metal hydrosulfide, under polymerization conditions effective for producing the poly(arylene sulfide ketone);
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about 3.8 mole percent, preferably within the range of about 1 to about 3.5 mole percent, relative to the alkali metal sulfide amount as 100, again to assure a slight but essential excess of alkali metal hydrosulfide. The corresponding molar ratio of alkali metal hydrosulfide to alkali metal sulfide is in the range of about 1.004:1 #x2205;004:1 to about 1.038:1 #x2205;038:1, preferably int he in the range of about 1.01:1 #x2205;01:1 to about 1.035:1 #x2205;035:1.
The poly(arylene sulfide ketone)s prepared according to my processes will have an inherent viscosity of at least about 0.48, preferably from about 0.55 to about 0.77. The polymers have wide utility for film, fiber, moldings, and composite applications because of this high melting point and high molecular weight.
FIG. 1 is a graphical representation of the inherent viscosity of poly(phenylene sulfide ketone)s as representative of poly(arylene sulfide ketone)s prepared from the condensation reaction of a molar excess of NaSH with respect to NaOH of about 0 to about 5 moles percent in a polymerization mixture containing 4,4'dichlorobenzophenone and NMP. The graph indicates by the portion between the longer dashed line that poly(phenylene sulfide ketone)s having an inherent viscosity of at least about 0.55 are obtained when a molar excess of NaSH fo about 1 to about 3.5 mole percent was employed. The shorter dashed lines indicate that poly(phenylene sulfide ketone)s having an inherent viscosity of at least about 0.65 are obtained when a molar excess of NaSH versus NaOH of about 1.1 to 3.3 mole percent was employed. This is in sharp contrast to the poly(arylene sulfide ketone)s having an inherent viscosity of less than about 0.45 obtained by bringing together a dihalobenzophenone, an alkali metal bisulfide, and an alkali metal hydroxide at a stoichiometric molar ratio of about 1:1:1 and at a higher ratio of about 1:1.05:1.
My process employs a polyhalobenzophenone, preferably a dihalobenzophenone. The dihalobenzophenones can be represented by the formula: ##STR3## wherein each X is selected from the group consisting of chlorine, bromine, fluorine, and iodine. Among the polyhalobenzophenones which can be employed are 4,4'dichlorobenzophenone, 4,4'difluorobenzophenone, 4,4'dibromobenzophenone, 4,4'diiodobenzophenone, 2,4'dichlorobenzophenone, 2,4,4'trichlorobenzophenone, 2,4,4'triiodobenzophenone, 2,4,4'trifluorobenzophenone, 2,4,4'tribromobenzophenone, and the like, and mixtures thereof. The presently preferred dihalobenzophenone, due to its effectiveness and commercial availability, is 4,4'dichlorobenzophenone.
The alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. The alkali metal hydrosulfides (sometimes called bisulfides) include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures thereof. The alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof.
The preferred alkali metal sulfide, due to its effectiveness, is sodium sulfide (Na2 S). The preferred alkali metal hydrosulfide, due to its effectiveness, is sodium hydrogen sulfide (NaSH). The preferred alkali metal hydroxide, due to its effectiveness, is sodium hydroxide (NaOH).
The molar ratio of dihalobenzophenone: alkali metal sulfide should be held as close to stoichiometric ratio of 1:1 as possible in the condensation polymerization.
The solvents useful in the process of my invention are polar organic solvents which can be used with a dihalobenzophenone and an alkali metal sulfide in the production of poly(arylene sulfide ketone)s. These polar organic solvents include such as the amides and sulfones. Specific examples of such polar organic solvents include hexamethyl phosphoramide, tetramethylurea, N,N'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone (NMP), pyrrolidone, caprolactam, N-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, diphenyl sulfone, and the like, and mixtures thereof. The preferred polar organic solvent, due to its effectiveness and commercial availability, is NMP. The amount of solvent can vary, as is known in the art.
The order of addition of the ingredients used to prepare the poly(arylene sulfide ketone)s can be varied as desired. Generally, the alkali metal sulfide (such as Na2 S), and the alkali metal hydrosulfide (such as NaSH), or the alkali metal hydroxide (such as NaOH) and the alkali metal hydrosulfide (such as NaSH), and the dihalobenzophenone, (such as 4,4' dichlorobenzophenone), can be added to a reactor vessel in any order. The polar organic solvent, (such as NMP), will generally be added to the reaction mixture following the addition of the aforementioned ingredients.
Although the reaction temperature at which the polymerization sis conducted can vary over a wide range, generally it will be within the range of about 125°C to about 450°C, preferably about 175°C to about 350°C, most preferably about 225°C to about 275°C The reaction time can vary widely, depending in part on the reaction temperature, but generally will be within the range of about 10 minutes to about 72 hours, preferably about 1 hour to about 20 hours. The pressure should be sufficient to maintain the the reaction mixture substantially in the liquid phase. The pressure will generally be within the range of about 0 psig to about 300 psig, preferably 150 to about 250 psig.
The polymer can be recovered as desired, preferably by removing the polymer and solvent from a cooled reactor and recovering the polymer by filtration. The polymer can be subsequently washed with water and dried in a vacuum oven.
Examples provided are intended to assist in a further understanding of my invention. Particular materials employed, species, conditions, are intended to be further illustrative of my invention and not limitative of the reasonable scope thereof.
In this example the preparation of a poly(phenylene sulfide ketone) (PPSK) resin with equimolar amounts of NaSH and NaOH is described. To a 1-liter stainless steel reactor fitted with a double helical stirrer, nitrogen inlet tube, and rupture disc were charged: 41.63 grams of sodium hydrogen sulfide flakes (containing 58.17 weight-% NaSH, 0.35 weight-% Na2 S, and about 41.4 weight-% H2 O), 17.58 grams of sodium hydroxide pellets (98.2 weight-% NaOH, provided by Mallinckrodt, Inc., St. Louis, Mo.), 108.48 grams of 4,4'-dichlorobenzophenone (DCBP, provided by Aldrich Chemical Company, Milwaukee, Wisc.), and 343 grams (3.46 moles) of N-methyl-2-pyrrolidione (NMP). Thus an equal number of moles (0.432) of each of NaSH, NaOH, and DCBP were charged, and the molar H2 O: NaSH ratio was about 2.2:1.
The reactor was sealed, alternately pressured with 100 psig N2 and then vented so as to remove air. The reactor mixture was then stirred and heated to about 250°C (during a one hour period). This temperature was maintained for about 3 hours, while a pressure of about 180 psig was established. The reactor was then cooled to about 200° C., and 3 grams of DCBP plus 100 grams of NMP were charged for end-capping the formed PPSK polymer with DCBP. The reactor contents were again heated to about 250°C and kept at that temperature for about 1 hour.
The polymer of thi run (Run 1) was removed from the cooled reactor, recovered by filtration through a Buchner funnel, washed seven times with 2.5 liter aliquots of hot deionized water (about 70°C), and dried in a vacuum oven at about 80°C The inherent viscosity (IV) of the PPSK polymer measured at 30°C in a #200 viscometer using a 0.5 weight-% solution in concentrated H2 SO4 as solvent, was 0.45. Polymer yield was 73.6 grams.
In a second run (Run 2), an equimolar mixture of NaSH, NaOH, and DCBP in NMP was polymerized at essentially the same process conditions as described above, except that the mixture of NaSH, NaOH, H2 O, and NMP was first allowed to dehydrate at 0 psig and 160°-250°C before all DCBP was added to the cooled reactor (about 105°), and no end-capping with DCBP was carried out. Then the reactor was sealed and heated at 250°C/130 psig for 3 hours. The inherent viscosity of the washed and dried PPSK polymer was 0.28.
Runs 3-8 reflect the preparation of PPSK employing increased molar ratios of NaSH relative to NaOH, otherwise essentially in accordance with the procedure of Run 1 (no dehydration; polymerization of 250°C for 3 hours; end-capping with DCBP at 250°C for 1 hour; molar H2 O: NaSH ratio of about 2.2:1).
Results are summarized in Table I:
| TABLE I |
| ______________________________________ |
| Molar Molar Ratio |
| (IV) |
| Moles Moles Excess of Inherent |
| Run NaSH NaOH of NaSH NaSH to NaOH |
| Viscosity |
| ______________________________________ |
| 1 0.432 0.432 0 1:1 0.45 |
| 2 0.500 0.500 0 1:1 0.28 |
| 3 0.434 0.432 0.5% 1.005:1 0.49 |
| 4 0.432 0.426 1.4% 1.014:1 0.64 |
| 5 0.441 0.432 2.0% 1.020:1 0.73 |
| 6 0.443 0.432 2.5% 1.025:1 0.68 |
| 7 0.445 0.432 3.0% 1.030:1 0.77 |
| 8 0.449 0.432 4.0% 1.039:1 0.45 |
| 9 0.454 0.432 5.1% 1.051:1 0.33 |
| ______________________________________ |
Runs 3-8 demonstrate that when a small defined molar excess of alkali metal hydrosulfide is used, the IV of the resultant polymer product will be equal to or greater than the IV of polymer products resulting from the use of a stoichiometric amount of alkali metal hydrosulfide NaSH (Runs 1 or 2) or the use of a larger excess (Run 9) of alkali metal hydrosulfide. The data, plotted in FIG. 1, show that PPSK polymers having an inherent viscosity of at least about 0.45 were obtained when a molar excess of NaSH (versus NaOH) of about 0.4% to about 3.8% was employed in the reaction mixture.
Thermal transitions were measured for the PPSK resin produced in Run 5 employing a Perkin-Elmer DAC-2C differential scanning calorimeter equipped with a computerized data system and a Perkin-Elmer TADS-1 plotter. The polymer sample was heated at a rate of 20°C/minute.
Results obtained were: glass transition temperature Tg=144°C; crystallization temperature Tc=191°C; melting temperature Tm=340°C; melt crystallization temperature (upon cooling of the melt) Tmc=291°C
In this example, the preparation of PPSK, essentially in accordance with the procedure of Run 1 (Example I), employing Na2 S flakes (rather than NaSH and NaOH) is described. 56.88 grams of sodium sulfide flakes (containing about 59.3 weight-% Na2 S, about 1.3 weight-% NaSH, and about 39.4 weight-% H2 O, equal to 0.432 moles of Na2 S), plus, nd∅013 moles of NaSH and 1.25 moles of water), were reacted with 0.432 moles of DCBP in the presence of 3.46 moles of NMP.
The presence of NaSH was equivalent to a molar NaSH excess of about 3%. The IV of the formed PPSK resin (about 89 grams yield) was 0.58. Therefore, the use of an alkai metal sulfide such as Na2 S, plus a defined slight excess of alkali metal hydrosulfide, such as NaSH, clearly is effective and within the scope of this invention.
This example illustrates the curing of PPSK so as to further increase its molecular weight. The dark-colored resin prepared in Run 6 was placed in an air oven heated to 316°C The inherent viscosity of the polymer increased from an initial value of 0.68 to 0.84 after 30 minutes, and to 0.97 after 60 minutes. After heating for about 120 minutes, the polymer was no longer soluble in H2 SO4. Degassing of the polymer during curing, especially during the first hour, was observed.
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