POLYMER MANUFACTURING PROCESS USING A POLY(ARYLETHERSULFONE) AS A REACTANT

Abstract

A process for the manufacture of a polyarylethersulfone PAES (P2) using recycled polymeric material, comprising heating a reaction medium (RM) comprising a recycled polymeric material containing a polyarylethersulfone PAES (P1), at least one monomer (M), an alkali salt-forming agent (A) and a polar aprotic solvent (S) to reach a reaction temperature of at least 150 C. to form a PAES (P2); and separating the forned PAES (P2) from the reaction medium. The PAES (P1) recycle ratio may be from 100 wt. % to 1 wt. %. The recycled polymeric material added to the reaction medium may further include other polymer(s), solid fillers, and/or additives. The monomer (M) may be at least one aromatic diol monomer (AA) and/or at least one aromatic dihalo monomer (BB). The diol (AA) may comprise bisphenol A, bisphenol S, biphenol, a 1,4:3,6-dianhydrohexitol sugar diol and/or tetramethyl bisphenol F, and the dihalo (BB) may comprise non-sulfonated and/or disulfonated dihalodiphenylsulfone.

Claims

1. A process for producing a polyarylethersulfone (P2) using a recycled polymeric material comprising a polyarylethersulfone (P1) as a reactant, comprising adding a polar aprotic solvent (S) to a reactor vessel; adding a recycled polymeric material containing a polyarylethersulfone (P1) to the reactor vessel; adding an alkali salt-forming agent (A) to the reactor vessel; adding at least one monomer (M) selected from the group consisting of at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB) to the reactor vessel; whereby said adding steps form a reaction medium (RM) comprising the recycled polymeric material containing the polyarylethersulfone (P1), the at least one monomer (M), the alkali salt-forming agent (A), and the polar aprotic solvent (S), heating the reaction medium to reach a reaction temperature of at least 150 C. and at most 290 C. to form a polyarylethersulfone (P2); and separating the formed polyarylethersulfone (P2) from the reaction medium; wherein the alkali salt-forming agent (A) is an alkali metal carbonate and/or an alkali metal hydroxide; and wherein the polyarylethersulfone (P1) comprises at least 50 wt. %, based on the total weight of the PAES (P1), of a sulfone polymer selected from the group consisting of: PPSU, PSU, PES, sulfonated PSU (sPSU), sulfonated PES (sPES), sulfonated PPSU (sPPSU), any polymer derived from a diol monomer selected from isosorbide and/or tetramethyl bisphenol F and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and/or dihalodiphenylsulfone, any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, isosorbide, tetramethyl bisphenol F, and/or hydroquinone and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and/or dihalodiphenylsulfone, a block polymer in the form A-B or A-B-A, comprising at least one block having one recurring unit selected from those of formulae (L), (L), (N), (N), (O), (O), (Q), (Q), and at least one block having one recurring unit selected from those of formulae (T), (T), (U), (U), (V), (V), (W), (W), (U*), (V*), (W*); a block copolymer in the form A-B or A-B-A, comprising at least one block having one recurring unit selected from those of formulae (L), (L), (N), (N), (O), (O), (Q), (Q), and at least one polyalkylene oxide or polyvinylpyrrolidone (PVP) block, such as a PEG block, PPG block or a PVP block; and any combination of two or more thereof, wherein the formulae (L), (L), (N), (N), (O), (O), (Q), (Q), (T), (T), (U), (U), (V), (V), (W), (W), (U*), (V*), (W*) are as follows: ##STR00009## ##STR00010## ##STR00011## wherein: each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and each i is independently an integer of 1 to 4.

2. The process of claim 1, wherein: the aromatic diol monomers (AA) are selected from the group consisting of 4,4-biphenol, bisphenol A, bisphenol S, isosorbide, isomannide, isoidide, tetramethyl bisphenol F, hydroquinone, and any combination thereof, preferably selected from the group consisting of 4,4-biphenol, bisphenol A, bisphenol S, tetramethyl bisphenol F, hydroquinone, and any combination thereof, and/or the aromatic dihalo monomer (BB) is selected from the group consisting of 4,4-difluorodiphenylsulfone (DFDPS), 4,4-dichlorodiphenylsulphone (DCDPS), disulfonated DCDPS, disulfonated DFDPS, and any combination thereof, preferably selected from the group consisting of DCDPS, disulfonated DCDPS, and combination thereof; and/or the polar aprotic solvent (S) is selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfone or sulfolane), N-alkyl-2-pyrrolidone like N-Methyl-2-pyrrolidone (NMP), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-monoxide, and any combination thereof.

3. The process of claim 1, wherein said polyarylethersulfone (P1) is derived by condensation from at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB), and wherein: the added aromatic diol monomer (AA) is the same or different than the aromatic diol monomer (AA); and/or the added aromatic dihalo monomers (BB) are the same or different than the aromatic dihalo monomer (BB).

4. (canceled)

5. The process of claim 1, wherein the polyarylethersulfone (P1) is selected from the group consisting of PPSU, PSU, PES, sulfonated PSU sulfonated PES, sulfonated PPSU, any polymer derived from a diol monomer selected from isosorbide and/or tetramethyl bisphenol F and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and/or dihalodiphenylsulfone, any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, isosorbide, tetramethyl bisphenol F, and/or hydroquinone and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and/or dihalodiphenylsulfone, a block polymer in the form A-B or A-B-A, comprising at least one sulfone polymer block having one recurring unit selected from those of PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one block having one recurring unit made from tetramethyl bisphenol F and sulfonated or non-sulfonated dihalodiphenylsulfone or from a 1,4:3,6-dianhydrohexitol sugar diol and sulfonated or non-sulfonated dihalodiphenylsulfone; a block copolymer in the form A-B or A-B-A, comprising at least one block polymer having one recurring unit selected from those of PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one polyalkylene oxide or polyvinylpyrrolidone (PVP) block, such as a PEG block, PPG block or a PVP block; and any combination of two or more thereof.

6. The process of claim 1, wherein the recycled polymeric material further comprises another polymer (P3) which is different than the polyarylethersulfone (P1), and wherein the recycled polymeric material includes a blend of the polyarylethersulfone (P1) and the other polymer (P3) and/or a block copolymer comprising at least one block of the polyarylethersulfone (P1) and at least one block of the other polymer (P3).

7. The process of claim 1, wherein the recycled polymeric material further comprises a non-polymeric filler, such as particulate mineral fillers, carbon fibers, and/or glass fibers.

8. The process of claim 1, wherein the recycled polymeric material comprises at least one material selected from the group consisting of post-consumer polymeric articles, post-industrial polymeric articles including article scraps, off-specification polyarylethersulfone products; and any combination thereof.

9. The process of claim 1, wherein the added polyarylethersulfone (P1) is a PES, the formed polyarylethersulfone (P2) is a PES homopolymer or copolymer, and the at least one monomer (M) added to the reactor vessel is Bisphenol S; or the added polyarylethersulfones (P1) is a PSU, the formed polyarylethersulfone (P2) is a PSU homopolymer or copolymer, and the at least one monomer (M) added to the reactor vessel is Bisphenol A; or the added polyarylethersulfone (P1) is a PPSU, the formed polyarylethersulfone (P2) is a PPSU homopolymer or copolymer, and the at least one monomer (M) added to the reactor vessel is 4,4-biphenol.

10. The process of claim 1, wherein: the polyarylethersulfone (P2) has an Mw (P2) which is within +/35% of the Mw.sub.(P1) of the polyarylethersulfone (P1), wherein the Mw.sub.(P1) and Mw.sub.(P2) are measured via GPC method using methylene chloride as the mobile phase and calibrated with polystyrene standards; and/or the polyarylethersulfone (P2) has a PDI.sub.P2 value which is within +/35% of the PDI.sub.P1 value of the polyarylethersulfone (P1), wherein a PDI is the ratio of weight average molecular weight (Mw) over the number average molecular weight (Mn), each of Mw and Mn being measured via GPC method using methylene chloride as mobile phase and calibrated with polystyrene standards.

11. The process of claim 1, wherein the polyarylethersulfone (P2) has an Mw.sub.(P2) of at least 40 kDa, said Mw.sub.(P2) being measured via GPC method using methylene chloride as mobile phase and calibrated with polystyrene standards.

12. The process of claim 1, wherein the recycled polymeric material comprising the polyarylethersulfone (P1) is added to the reactor vessel in solid forms, or in form of a solution or slurry in which at least part of the polyarylethersulfone (P1) is dissolved before being added to the reactor vessel.

13. The process of claim 1, wherein the separating step includes coagulation of the polyarylethersulfone (P2), and/or the process further comprises at least one of the following steps, between the reaction step and the separation step: cooling the reaction medium; adding a solvent (S.sub.q), which is the same or different than the polar aprotic solvent (S), to quench the reaction medium; and/or adding an end-capping agent to convert hydroxyl end groups of the formed polyarylethersulfone (P2) to less reactive end groups.

14. The process of claim 1, being carried out with a recycle ratio of polyarylethersulfone (P1) in the reaction medium from 100 wt. % to 1 wt. %, said recycle ratio is calculated as the ratio of the weight of the added polyarylethersulfone (P1) based on the combined weight of the added polyarylethersulfone (P1) and the maximum weight of the PAES polymer which would be theoretically produced based on the equimolar stoichiometry of polycondensation of monomers (AA) and (BB) when both diol monomer (AA) and dihalo monomer (BB) are added to the reactor medium.

15. The process of claim 1, wherein the at least one monomer (M) comprises at least one aromatic diol monomer (AA), and wherein the condensation reaction is being carried out with a molar ratio of the alkali salt-forming salt to the diol monomer (AA) being at least 1 and at most 2, and/or the diol (AA) and the alkali salt-forming agent (A) are added to the reactor vessel in the form of an alkali salt (AAA) of the diol (AA).

16. The process of claim 1, wherein the reaction temperature is at least 160 C.; and/or at most 350 C.

17. A polyarylethersulfone (P2) obtained by the process of claim 1.

18. An article comprising the polyarylethersulfone (P2) of claim 17.

19. The article of claim 18, selected from the group consisting of membranes, fibers, sheets, solution-processed films, solution-processed monofilaments, and any combination thereof.

20. The process of claim 1, wherein the recycled polymeric material comprises at least an article selected from the group consisting of membranes, automotive components, electronic components, consumer product components such as baby bottles, composites, battery components, and any combinations thereof.

21. The process of claim 6, wherein the other polymer (P3) is a pore-forming polymer selected from the group consisting of polyvinylpyrrolidone (PVP), a polyalkylene oxide and combination thereof.

Description

EXAMPLES

[0270] The invention will be now described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention. As used in the Examples, E denotes an embodiment of the present invention and CE denotes a counter-example.

GPC Method for Measuring Mn, Mw (Sulfone GPC Method #1)

[0271] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5p mixed D columns with a guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 20 L of a 0.2 w/v % solution in the mobile phase was selected. Calibration was performed with 10 or 12 narrow molecular weight polystyrene standards. The number average molecular weight Mn and weight average molecular weight Mw were reported and the PDI=Mw/Mn was calculated.

Example 1: PES Recycle

Raw Materials for Samples EJ-E2, CE3, CE4, E5

[0272] Na.sub.2CO.sub.3 (sodium carbonate), available from Solvay France [0273] DCDPS (4,4-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers [0274] DHDPS (4,4-dihydroxydiphenyl sulfone or Bisphenol S), available from Sigma-Aldrich [0275] Sulfolane, available from ChevronPhillips Chemicals [0276] Methyl Chlorde available from Matheson Gas [0277] Methanol, available from Sigma-Aldrich [0278] PES.sub.1: Veradel 3000MP PES, manufactured by Solvay Specialty Polymers with Mw=64,145; Mn=19,145; PDI=3.35
Synthesis of PES Samples E1-E2: PES Polymerization Process with 20 wt. % Added PES Used as a Reactant

[0279] For preparing PES Samples E1 and E2, the monomers DHDPS and DCDPS with a 1 mol. % excess (relative to DHDPS amount), meaning that the molar ratio of DCDPS/DHDPS was 1.01, and the Veradel 3000MP (PES.sub.1) was first added to a 1.0-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. Then sodium carbonate was added to achieve an 18% molar excess of Na.sub.2CO.sub.3 (relative to DHDPS amount), meaning that the molar ratio of Na.sub.2CO.sub.3/DHDPS was 1.18. The reaction medium was heated from room temperature to 227+/2 C. over 90 mins. The polymerization temperature of the reaction medium was maintained for around 3.6 to 4.1 hours, depending upon the viscosity of the solution. The polymerization was carried out at a polymer concentration of 26.4 wt. % in the reaction medium. The reaction was terminated by adding methyl chloride (1 g/min) and end-capping the polymer at 2272 C. for another 30 minutes. The reaction medium was quenched by dilution with sulfolane to achieve a 15 wt. % polymer content. The termination was thus carried out at polymerization temperature (227 C.) before the quench with additional sulfolane. After quenching, the reaction medium was filtered through a 2.7-m glass fiber filter pad under nitrogen pressure and coagulated into the water with a volume ratio of polymer solution/water of 1:5 using a high-speed Waring blender. The coagulated polymer was then washed five times with hot water (70 C.) and dried at 110 C. in an oven under a vacuum overnight.

[0280] The difference between Samples E1 and E2 was that the polymerization for Sample E1 was terminated earlier (3.6 hrs) than for Sample E2 (4.1 hrs).

Synthesis for Sample CE3 (Counter-Example)PES Polymerization Process (without PES Used as a Reactant)

[0281] For Sample CE3, the polymerization took place in the same way as described above for Samples E1 and E2, except that no PES was added to the reaction medium and the reaction time was 4.6 hrs.

[0282] The Mw, Mn, and PDI (via sulfone GPC method) of the PES polymers resulting after coagulation and drying in Samples E1, E2, and CE3 are reported in Table 1.

[0283] It was observed that the resulting polymer with added 20 wt. % PES.sub.1 as a reactant in Sample E2 had similar Mw and Mn values to CE3 without PES.sub.1 reactant when the reaction times were similar.

[0284] For Sample E2, there was a small reduction in Mw (7%) relative to the control Sample CE3. This is in contrast with a loss of 35% in Mw for a shorter reaction time for sample E1 relative to the control CE3.

[0285] There was also a reduction in PDI value for Samples E1 (25%) and E2 (18%) relative to the control Sample CE3.

Synthesis for Sample E4: PES Polymerization Process Using 10 wt. % PES.SUB.1 .Recycle

[0286] The polymerization took place in the same way as described for Sample E2, except that the coagulated polymer for Sample E4 was further washed once with methanol after the five washes with hot water (70 C.). Additionally, only 10 wt. % of PES.sub.1 was used to form Sample E4 (compared to 20 wt. % PES.sub.1 in Samples E1 & E2).

Synthesis for Sample CE5 (Counter-Example)PES Polymerization Process (without PES Addition)

[0287] The polymerization to form Sample CE5 took place in the same way as described for Sample CE3, except that the coagulated polymer was further washed once with methanol after the five washes with hot water (70 C.) to yield PES Sample CE5.

[0288] The Mw, Mn, and PDI (via sulfone GPC method) of the PES polymers resulting after coagulation and drying in Samples CE4 and E5 are also reported in TAble 1.

TABLE-US-00001 TABLE 1 wt. %* Reaction % % PES PES.sub.1 time change change sample added (hrs) **Mw in Mw **Mn PDI in PDI E1 20 3.6 30,489 35% 12,707 2.40 25% E2 20 4.1 43,420 7% 16,554 2.62 18% CE3 4.6 46,832 14,691 3.19 E4 10 4.6 57,034 10% 18,477 3.09 8% CE5 4.1 63,306 18,800 3.37 PES.sub.1 n/a 64,145 19,145 3.35 **Sulfone GPC method #1 using methylene chloride as mobile phase

[0289] It was observed that the resulting PES in Sample E4 with 10 wt. % PES.sub.1 addition as reactant had similar Mw and Mn values to Sample CE5 without added PES.sub.1 when the reaction conditions (including reaction times) were similar.

[0290] For Sample E4, there was a small reduction in Mw (10%) relative to the control Sample CE5, and also a small reduction in PDI value (8%) relative to the control Sample CE5.

Example 2PES Recycle

GPC Method for Measuring Mn, Mw

[0291] The same sulfone GPC method #1 as described above was used.

Raw Materials for Samples E6-E12 & CE13

[0292] Na.sub.2CO.sub.3 (sodium carbonate) available from Solvay [0293] DCDPS (4,4-dichlorodiphenyl sulfone) available from Solvay Speciality Polymers [0294] DHDPS (4,4-dihydroxydiphenyl sulfone or Bisphenol S) available from Sigma-Aldrich [0295] Sulfolane available from ChevronPhillips Chemicals [0296] PES.sub.2: Veradel 3300 PES manufactured by Solvay Specialty Polymers with Mw=45249; Mn=15244; PDI=2.97; in powder form [0297] PES.sub.3: Veradel 3000MP PES manufactured by Solvay Specialty Polymers with Mw=67559; Mn=18013; PDI=3.75; in powder form [0298] PES.sub.4: Veradel 3300 PES manufactured by Solvay Specialty Polymers with Mw=45735; Mn=14785; PDI=3.09; in pellet form

Synthesis for PES Sample E6PES Manufacture Using 100 wt. % PES Powder Recycle

[0299] PES.sub.2 powder (Mw=45249) (232 g) was loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. This reaction medium was heated under stirring conditions at 50 RPM in a continuous flow of nitrogen. After the partial dissolution of the polymer around 100 C., 4,4-dihydroxydiphenyl sulfone (DHDPS) (2.5 g, 0.01 mol) and sodium carbonate (6.0 g, 0.0566 mol) was added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 227 C. for 3.5 to 4 hours. The molecular weight growth of the polymerization was monitored via GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Subsequently, methyl chloride was purged through the reaction medium to endcap the polymer chains for 30 minutes. The reaction medium was subjected to coagulation in 1.5-liter deionized water in a Waring blender to obtain a coagulated polymer. The coagulated polymer was washed with cold and hot water in Ace Glass Instatherm extraction kettle until the residual solvent amount decreased to about 0.3 wt. %. The resulting washed polymer powder was dried at 120 C. for 24 hours. A mass of 212 g dried PES polymer (Sample E6) was obtained with a yield of about 91%.

Synthesis for PES Sample E7PES Manufacture Using 30 wt. % PES Powder Recycling

[0300] DCDPS (102.459 g, 0.357 mol), DHDPS (87.5 g, 0.35 mol), and PES.sub.3 powder (Mw=67559) (69.6 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring conditions at 200 RPM in a continuous flow of nitrogen. After the dissolution of the monomers at around 70 C., sodium carbonate (47.908 g, 0.413 mol) was added to the reaction medium. The reaction medium was heated at 227 C. for 4 hours. The molecular weight growth of the polymerization was monitored via GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Subsequently, methyl chloride was purged through the reaction medium to endcap the polymer chains for 30 minutes. The reaction medium was then pressure filtered through a 2.7-micron glass fiber filter pad using an Advantec filtration system. The filtered reaction medium was subjected to coagulation in 1.5-liter deionized water in a Waring blender to obtain a coagulated polymer. The coagulated polymer was washed with cold and hot water in Ace Glass Instatherm extraction kettle until the residual solvent amount decreased to about 0.3 wt. %. The resulting washed polymer solid was dried at 120 C. for 24 hours. A mass of 189 g dried PES polymer powder (Sample E7) was obtained with a yield of about 81%.

Synthesis for PES Samples E8a & E8bPES Manufacture Using 50 wt. % PES Powder Chemical Recycling

[0301] DCDPS (73.185 g, 0.255 mol) and DHDPS (62.5 g, 0.25 mol), PES.sub.3 powder (Mw=67559) (116 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring at 200 RPM in a continuous flow of nitrogen. After the dissolution of the monomers at around 70 C., sodium carbonate (31.27 g, 0.295 mol) was added to the reaction medium. The remaining procedure was similar to Example 6 to obtain 196 g of dried PES polymer (Sample E8a) with a yield of about 84%.

[0302] The procedure was repeated under the same conditions as described above, except using a slightly different reaction time, to produce another dried PES Sample E8b.

Synthesis for PES Samples E9a & E9bPES Manufacture Using 70 wt. % PES Powder Chemical Recycling

[0303] DCDPS (43.911 g, 0.153 mol), DHDPS (37.5 g, 0.15 mol), and PES.sub.3 powder (Mw=67559) (162.4 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The remaining procedure was similar to Example 6 to yield 186 g of dried PES polymer (Sample E9a) with a yield of about 80%.

[0304] The procedure was repeated under the same conditions as described above for Sample E9a, except using a slightly different reaction time, to produce another dried PES Sample E9b.

Synthesis for PES Samples E10a & E10bPES Manufacture Using 90 wt. % PES Powder Chemical Recycling

[0305] DCDPS (14.637 g, 0.051 mol) and DHDPS (12.5 g, 0.05 mol), PES.sub.3 powder (Mw=67559) (208.8 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring conditions at 50 RPM in a continuous flow of nitrogen. After the dissolution of the monomers and PES.sub.3 powder at around 90 C., sodium carbonate (6.254 g, 0.059 mol) was added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 217 C. for 3 to 4 hours. The molecular weight growth of the polymerization was monitored via GPC. The remaining procedure was similar to Example 7 to yield 208 g of dried PES polymer Sample E10a with a yield of about 89%.

[0306] The procedure was repeated under the same conditions as described above, except using a slightly different reaction time, to produce another dried PES Sample E10b.

Synthesis for PES Sample E11PES Manufacture Using 95 wt. % PES Powder Chemical Recycling

[0307] DCDPS (7.318 g, 0.0255 mol), DHDPS (6.25 g, 0.025 mol), and PES.sub.3 powder (Mw=67559) (208.8 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring conditions at 50 RPM in a continuous flow of nitrogen. After the dissolution of the monomers and PES.sub.3 powder at around 90 C., sodium carbonate (6.254 g, 0.059 mol) was added to the reaction medium. The remaining procedure was similar to Example 7 to obtain 206 g of dried PES polymer (Sample E11) with a yield of about 88%.

Synthesis for PES Sample E12PES Manufacture Using 100 wt. % PES Pellets Chemical Recycling

[0308] PES.sub.4 pellets (Mw=45735) (232 g) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring conditions at 20 RPM in a continuous flow of nitrogen. After the partial dissolution of the PES.sub.4 pellets around 130 C., DHDPS (2.5 g, 0.01 mol) and sodium carbonate (6.0 g, 0.0566 mol) were added to the reaction medium. The stirring speed was slowly increased to 200 RPM. The reaction medium was heated at 227 C. for 3 to 4 hours. The molecular weight growth of the polymerization was monitored via GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Subsequently, methyl chloride was purged through the reaction medium to endcap the polymer chains for 30 minutes. The reaction medium was subjected to coagulation in 1.5 liters of deionized water in a Waring blender to obtain a coagulated polymer. The coagulated polymer was washed with cold (30 C.) and hot (80 C.) water in Ace Glass Instatherm extraction kettle until the residual solvent amount decreased to about 0.3 wt. %. The resulting washed polymer solid was dried at 120 C. for 24 hours. A mass of 208 g dried PES Sample E12 was obtained with a yield of about 89%.

Synthesis for PES Sample CEM (Counter-Example)PES Manufacture without PES Recycling

[0309] DCDPS (146.37 g, 0.51 mol) and DHDPS (125 g, 0.50 mol) were loaded in a 1.25-liter glass polymerization reactor along with 460 ml of sulfolane. The reaction medium was heated under stirring conditions at 50 RPM in a continuous flow of nitrogen. After the dissolution of the monomers at around 70 C., sodium carbonate (63 g, 0.59 mol) was added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 227 C. for 3 to 4 hours. The remaining procedure was similar to Example 7 to yield 197 g of dried PES Sample CE13 with a yield of about 84.9%.

[0310] The Mw, Mn, and PDI (via sulfone GPC method #1 as described above) of the PES Samples E6 to E12 and CE13 resulting after coagulation and drying are reported in Table 2.

TABLE-US-00002 TABLE 2 Type of recycle molar Sam- PES ratio DCDPS/ Time ple added wt. % DHDPS hr **Mw **Mn PDI E6 PES.sub.2 100 0 3.5 46177 15193 3.04 (powder) E7 PES.sub.3 30 1.02 4 48901 15237 3.21 E8a PES.sub.3 50 1.02 4 43774 14450 3.03 E8b PES.sub.3 50 1.02 3.75 44233 14436 3.06 E9a PES.sub.3 70 1.02 3.75 48022 15108 3.17 E9b PES.sub.3 70 1.02 3 44746 14614 3.06 E10a PES.sub.3 90 1.02 2.8 47635 15091 3.16 E10b PES.sub.3 90 1.02 4.5 43763 14587 3 E11 PES.sub.3 95 1.02 3 44039 14709 2.99 E12 PES.sub.4 100 0 4 44978 14825 3.03 (pellets) CE13 1.02 4 45676 15644 2.92 **sulfone GPC method #1 using methylene chloride as mobile phase

[0311] For PES Samples E7-E12, there was only a small change in Mw (from 4.2% to 7.1%) relative to the control Sample CE13. There was also a slight increase in PDI value by 2.4% to 9.9% relative to the control Sample CE13.

Example 3: PES Recycle

GPC Method for Measuring Mn, Mw

[0312] The same sulfone GPC method #1 as described above was used.

Raw Materials for Samples E14 & E15

[0313] Na.sub.2CO.sub.3 (sodium carbonate) available from Solvay [0314] DHDPS (4,4-dihydroxydiphenyl sulfone or Bisphenol S) available from Sigma-Aldrich [0315] Sulfolane, available from ChevronPhillips Chemicals [0316] PES.sub.5: Ultrason E020 PES manufactured by BASF with Mw=66842 g/mol; Mn=20205 g/mol; PDI=3.3 in form of flakes

Synthesis for Sample E14PES Manufacture Using 100 wt. % PES Pellet Recycle

[0317] PES.sub.5 powder (Mw=66842) 40 g was slowly added in a 250 ml-four neck round bottom flask containing 80 ml of sulfolane. The reaction medium was heated under stirring conditions at 50 RPM in a continuous flow of nitrogen. After the complete dissolution of the PES.sub.5 polymer, the stirring speed was increased to 200 RPM. Once the reaction temperature reached 220 C., 4,4-Dihydroxydiphenyl sulfone (DHDPS) (0.431 g, 1.7 mmol) and sodium carbonate (0.91 g, 8.5 mmol) were added to the reaction medium. The reaction medium was heated at 227 C. for 3.5 h. Molecular weight growth of the polymerization was monitored via GPC (with methylene chloride as the mobile phase). At first, the PES.sub.5 polymer was depolymerized from Mw-66842 Da to Mw-34490 Da, then re-polymerized into a molecular weight Mw of 44258 Da. The polymerization reaction was quenched by adding 45 ml of sulfolane. Subsequently, MeCl was purged through the reaction medium to endcap the polymer chains for 30 minutes. The reaction mass was coagulated in 1.2-liter deionized (MilliQ) water in a Waring blender. The resulting polyarylether polymer powder was extracted with cold and hot water in Ace Glass Instatherm extraction kettle until the residual solvent amount came down to below 0.3 wt. %. A polymer powder was dried at 120 C. for 24 hours.

[0318] The Mw, Mn, and PDI of the PES polymer Sample E14 resulting after coagulation and drying and compared to the starting PES material: PES.sub.5 which was added to the reaction medium to make Sample E14 are reported in Table 3.

TABLE-US-00003 TABLE 3 recycle molar PES PES ratio DCDPS/ Time sample added wt. % DHDPS hr **Mw **Mn PDI E14 PES.sub.5 95 0 3.5 44258 12985 3.4 PES.sub.5 66842 20205 3.3 **sulfone GPC method #1 using methylene chloride as mobile phase

[0319] For Sample E14 sample with close to 100% PES recycle, there was a reduction in Mw (34%) relative to the initial PES.sub.5 polymer. There was also a very small increase in PDI value by 3% relative to the PES.sub.5 polymer.

Example 4: PES-Based Membrane Fiber Recycle

GPC Method for Measuring Mn, Mw

[0320] Same sulfone GPC method #1 as described above was used.

Raw Materials for Sample E1S

[0321] Na.sub.2CO.sub.3 (sodium carbonate), available from Solvay [0322] DHDPS (4,4-dihydroxydiphenyl sulfone or Bisphenol S), available from Sigma-Aldrich [0323] Sulfolane, available from ChevronPhillips Chemicals [0324] PES.sub.6: Hollow fiber dialyzer DORA B-13PF from Bain medical equipment (GuangZhou) Co. LTD based on PES of Mw=66619, Mn=21277, PDI=3.13. Elemental analysis was made with an Elementar Vario MICRO cube CHNS analyzer. The PVP content in the PES-based membrane fibers was found to be 5 wt. %.

Synthesis for Sample E15PES Manufacture Using PES-Based Hemodialysis Membrane Filter (100 wt. % Recycle)

[0325] Hemodialysis PES.sub.6 membrane fibers (Mw=66619 Da) were used as a reactant for Sample E15. The fibers (42 g) were cut into small pieces and slowly added to a 250 mL-four neck round bottom flask containing 80 ml of sulfolane. To the reactor, 4,4-dichlorodiphenylsulphone (DCDPS) (1.25 g, 4.38 mmol), 4,4-Dihydroxydiphenyl sulfone (DHDPS) (1.075 g, 4.3 mmol) were then added. The reaction medium was heated at 180 C. under stirring conditions at 50 RPM in a continuous flow of nitrogen. After complete dissolution of the fibers and monomers, the stirring speed was increased to 200 RPM. Once the reaction temperature reached 220 C., sodium carbonate (2.32 g, 21.9 mmol) was added to the reaction medium. The reaction medium was heated at 227 C. for 4.5 h. The molecular weight growth of the polymerization was monitored via GPC. At first, the polymer was depolymerized from Mw-66619 Da to Mw-22865-Da and then re-polymerized into the desired molecular weight of 45500-Da.

[0326] The polymerization reaction was quenched by adding 45 mL of sulfolane. Subsequently, MeCl was purged through the reaction medium to end cap the polymer chains for 30 minutes. The reaction mass was coagulated in 1.2-liter deionized (Milli Q) water in a Waring blender. A polymer powder was extracted with cold and hot water in Ace Glass Instatherm extraction kettle until the residual solvent amount came down to below 0.3 wt. %. The polymer powder was dried at 120 C. for 24 hrs.

[0327] The Mw, Mn, and PDI of the PES polymer Sample E15 resulting after coagulation and drying are reported in Table 4 and compared to the starting PES material: PES.sub.6 material which was added to the reaction medium to make Sample E15.

TABLE-US-00004 TABLE 4 wt. % molar PES PES recycle DCDPS/ Time sample added ratio DHDPS hr **Mw **Mn PDI E15 PES.sub.6 100 0 4.5 46824 14715 3.18 PES.sub.6 66619 21277 3.13 **GPC (Sulfone) method using methylene chloride as mobile phase

[0328] For Sample E15 sample with 100 wt. % PES.sub.6 recycle, there was a reduction in Mw (30%) relative to the initial PES.sub.6 polymer. There was also a very small increase in PDI value by 1.6% relative to the recycled PES.sub.6 polymer.

Example 5: PSU Recycle and PSU/PVP Recycle

Test Methods

GPC Method for Measuring Mn, Mw

[0329] Same sulfone GPC method #1 as described above was used.

Thermal Gravimetric Analysis (TGA)

[0330] TGA experiments were carried out using a TA Instrument TGA Q500. TGA measurements were obtained by heating the sample at a heating rate of 10 C./min from 20 C. to 800 C. under nitrogen.

DSC

[0331] DSC was used to determine glass transition temperatures (Tg) and melting points (Tm)if present. DSC experiments were carried out using a TA Instrument Q100.

[0332] DSC curves were recorded by heating, cooling, re-heating, and then re-cooling the sample between 25 C. and 320 C. at a heating and cooling rate of 20 C./min. All DSC measurements were taken under a nitrogen purge. The reported Tg values (and if any, Tm values) were provided using the second heat curve unless otherwise noted.

Elemental Analysis

[0333] The elemental composition of some polymer samples was determined using a Perkin Elmer 2400 CHN Element Analyzer. The polymer samples were combusted based on the classical Pregl-Dumas method. The resultant combustion gases were completely reduced to CO.sub.2, H.sub.2O, N.sub.2, and SO.sub.2. Then the gases were separated via Frontal Chromatography. As the gases eluted they were measured by a thermal conductivity detector to determine quantitative amounts of Carbon, Hydrogen, Nitrogen, and Sulfur.

Quantification of PVP by .SUP.H.NMR Analysis

[0334] Samples are dissolved in deuterated 1,1,2,2-tetrachloroethane. All samples were run on a Bruker 400 MHz NMR, with a D1 set to 15 seconds and 64 scans. Data were processed using MestReNova software. Integrations of relevant peaks were performed and the following equations were used to determine the weight percent (wt. %) of PVP in the sample:

[00001]$\mathrm{mol}\mathrm{PVP}=\frac{\frac{\left(\mathrm{PVP}-\mathrm{PSU}\right)}{\#H\mathrm{PVP}}}{\left(\frac{\left(\mathrm{PVP}-\mathrm{PSU}\right)}{\#H\mathrm{PVP}}+\frac{\mathrm{PSU}}{\#H\mathrm{PSU}}\right)}$$\mathrm{wt}\%\mathrm{PVP}=\frac{\left(\mathrm{mol}\mathrm{PVP}\right)\left(\mathrm{molecular}\mathrm{weight}\mathrm{PVP}\right)}{\left(g\mathrm{PVP}+g\mathrm{PSU}\right)}\left(100\right)$ [0335] in which [0336] PVP and would denote the sum of all the hydrogen protons of PVP; [0337] PSU would denote the sum of all the hydrogen protons of PVP between 7 to 9 ppm; [0338] #H PVP and #H PSU denote the number of protons corresponding to the PVP and PSU molecules; [0339] molecular weight of PVP=111.1 g/mol; and [0340] g PVP+g PSU=weight of the sample;

Raw Materials for Samples CE16-E21

[0341] N-methylpyrrolidone (NMP) available from Sigma-Aldrich [0342] K.sub.2CO.sub.3 (Potassium Carbonate) available from Armand Products [0343] Bisphenol A BPA (4,4-dihydroxydiphenyl sulfone), available from Covestro [0344] DCDPS (4,4-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers [0345] Methyl chloride available from Matheson gas [0346] Methanol available from Sigma-Aldrich [0347] PSU.sub.1: Udel P-3500 pellets (Lot No. P060467C) manufactured by Solvay Specialty Polymers USA with Mw=78213 g/mol; Mn=21996 g/mol; PDI=3.55 measured via the sulfone GPC method #1 [0348] DSC=190.14 C. [0349] TGA=505.5 C.

[0350] PSU.sub.2: Udel P-3500 (Lot No. 1901009833) in pellet form, manufactured by Solvay Specialty Polymers USA with Mw=77267 g/mol; Mn=22542 g/mol; [0351] PDI=3.42 [0352] DSC=190.72 C. [0353] TGA=501.2 C.

[0354] PSU.sub.3: Fibers based on PSU-PVP based hemo-dialyzer from D. Braun [0355] Mw=82969 g/mol, Mn=22907 g/mol, PDI=3.6 [0356] DSC=186.7 C. [0357] TGA=516.1 C. [0358] PVP content: 3.89 wt. % by .sup.HNMR [0359] C: 71.97% [0360] H: 5.15% [0361] N: 0.45%

[0362] PVP (Polyvinyl Pyrrolidone) available from Alf Aesar with Mw=371165 g/mol, Mn=139881 g/mol, PDI=2.65 determined by the following GPC method #3:

[0363] Viscotek GPC Max (Autosampler, pump, and degasser) with a TDA302 triple detector array comprised of RALS (Right Angle Light Scattering), RI (Refractive Index), and Viscosity detectors were used. Samples were prepared as 2 mg/mL in DMAc/LiBr. Samples were run in NMP with 0.2 w/w % LiBr at 65 C. at 1.0 mL/min through a set of 3 columns: a guard column (CLM1019with a 20k Da exclusion limit), a high Mw column (CLM1013 exclusion of 10MM Daltons relative to Poly Styrene) and a low Mw column (CLM1011exclusion limit of 20k Daltons relative to PS). Calibration was done with a single, mono-disperse polystyrene standard of 100k Da. Light Scattering, RI, and Viscosity detectors were calibrated based on a set of input data supplied with the standards. Samples were prepared as about 2 mg/mL in NMP/LiBr. Viscotek's OMNISec v4.6.1 Software was used for data analysis.

[0364] The PVP had a DSC value of 174.48 C. (Tg) and an onset of degradation temperature (via TGA) of 401 C.

Synthesis of Sample CE16 (Counter-Example): Baseline PSU Producdon in NMP

[0365] Bisphenol A=BPA (182.63 g), DCDPS (229.72 g), K.sub.2CO.sub.3 (120.5 g), and NMP (532 g) were charged to a 1-L 4-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, thermocouple, and a dean-stark trap with a condenser. The respective weights of the ingredient used in the reaction medium are provided in TA. The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO.sub.3/BPA molar ratio was 1.09. The reactor was slowly heated with low agitator rpm was used to mix the material. The heating ramp rate was about 2.5-3 C./min till 190 C. When the temperature reached 190 C., the water of condensation was collected in the Deanstark trap. After the pre-determined torque or polymerization time had been reached, the reaction was stopped by terminating by passing excess methyl chloride. The cooled reaction medium was then filtered to remove the KCl salts and then coagulated into methanol and the coagulated polymer was washed with hot water (70 C.) and methanol and then dried in a vacuum oven at 110 C. for 12 hours.

[0366] This method yielded a baseline PSU Sample CE16, and its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (via DSC) are provided in Table 6.

Synthesis of Sample E17: PSU Production with 25 wt. % PSU Recycling in NMP

[0367] The synthesis was carried out using the same method as described for CE16, except that Udel PSU P-3500 pellets (PSU.sub.1) were additionally charged to the 1-L 4-necked resin kettle to achieve a PSU recycle ratio of 25 wt. %. The respective weights of the ingredients are provided in II The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO.sub.3/BPA molar ratio was 1.09. This yielded a PSU sample E17, and its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (via DSC) are provided in Table 6.

[0368] Elemental Analysis of sample E17: C=72.43%, H=4.88%, N<0.05%

Synthesis of Sample E18: PSU Production with 75% PSU Recycle Ratio in NMP

[0369] The synthesis was carried out using the same method as described for CE16, except that Udel PSU P-3500 pellets (PSU.sub.1) were additionally charged to the 1-L 4-necked resin kettle to achieve a PSU recycle ratio of 75 wt. %. The respective weights of the ingredients are provided in Table 5. The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO/BPA molar ratio was 1.09. This yielded a PSU sample E18, and its Mw, Mn, PDI (using the sulfone GPC method), TGA data, and Tg (via DSC) are provided in Table 6.

[0370] Elemental Analysis of sample E18: C=72.63%: H=5.09%; N<0.05%

Synthesis of Sample E19: PSU Production Containing 5 Wt. % PVP with 25 wt. % PSU Recycling in NMP

[0371] The synthesis was carried out using the same method as described for CE16, except that Udel PSU P-3500 pellets (PSU.sub.1) and PVP were additionally charged to the 1-L 4-necked resin kettle to achieve a PSU recycle ratio of 25 wt. %. The respective weights of the ingredients are provided in Table 5. The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO.sub.3/BPA molar ratio was 1.09. This yielded a PSU sample E19, and its Mw, Mn, PDI (using the sulfone GPC method), TGA data, and Tg (via DSC) are provided in Table 6.

[0372] The elemental analysis of sample E19 (C=72.4%, H=5.13%, N=0.09%) confirmed the presence of PVP in the resulting PSU sample E19. The PVP was present in the final PSU sample E19 as being physically and chemically bound PVP to the PSU polymer matrix.

Synthesis of Sample E20: Production of PSU/PVP Containing 5 Wt. % PVP with 75 wt. % PSU Recycling in NMP

[0373] The synthesis was carried out using the same method as described for CE16, except that Udel PSU P-3500 pellets (PSU.sub.2) and PVP were additionally charged to the 1-L 4-necked resin kettle to achieve a PSU recycle ratio of 75 wt. %. The respective weights of the ingredients are provided in Table 5. The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO.sub.3/BPA molar ratio was 1.09. This yielded a PSU sample E20, and its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (via DSC) are provided in Table 6.

[0374] Elemental Analysis for sample E20: C=72.2%, H=5.08%, N=0.28% confirmed the presence of PVP in the resulting PSU sample E20. The PVP was present in the final PSU sample E20 as being physically and chemically bound PVP to the PSU polymer matrix.

Synthesis of Sample E21: Production of PSU with 25% Braun Dialyzer Fibers in NMP

[0375] The synthesis was carried out using the same method as described for CE16, except that the fibers from Braun Dialyzer (PSU.sub.3) were additionally charged to the 1-L 4-necked resin kettle to achieve a PSU recycle ratio of 25 wt. %. The respective weights of the ingredients are provided in Table 5. The DCDPS/BPA molar ratio used in the reaction was 1.096 and the K.sub.2CO.sub.3/BPA molar ratio was 1.09. This yielded a PSU sample E21, and its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (via DSC) are provided in Table 6.

TABLE-US-00005 TABLE 5 Composition of reaction medium wt. % Type re- PSU cycle PSU DCDPS DHDPS K.sub.2CO.sub.3 PVP NMP added ratio (g) (g) (g) (g) (g) (g) CE16 229.72 182.63 120.5 532 E17 PSU.sub.1 25 88.50 172.28 136.96 90.4 532 E18 PSU.sub.1 75 265.5 57.43 45.65 30.13 532 E19 PSU.sub.1 25 88.50 172.31 137 90.4 4.4 532 E20 PSU.sub.2 75 265.52 57.45 45.69 30.32 13.29 531 E21 PSU.sub.3 25 88.5* 172.32 136.97 90.4 3.36 532 *this amount of PSU.sub.3 fibers includes about 3.89 wt. % of PVP

TABLE-US-00006 TABLE 6 PSU recycle type ratio wt. % DSC TGA added (wt. %) PVP **Mw **Mn PDI ( C.) ( C.) PSU.sub.1 78213 21996 3.55 190.1 505.5 PSU.sub.2 77267 22542 3.42 190.7 501.2 CE16 0 0 0 79370 25343 3.13 190.9 513.4 E17 PSU.sub.1 25 0 80856 22124 3.65 190.4 514.2 E18 PSU.sub.1 75 0 89810 22534 3.98 190.7 504.8 E19 PSU.sub.1 25 5 73489 20937 3.51 189.4 493.1 E20 PSU.sub.2 75 5 71295 21819 3.26 182.3 507.7 E21 PSU.sub.3 25 3.36 84737 24490 3.46 183.8 518.61 PSU.sub.3 3.89 82969 22907 3.6 186.7 516.1 **sulfone GPC method #1 using methylene chloride as mobile phase

[0376] Elemental Analysis for sample E21: C=72.53%, H=5.31%, N=0.11% confirmed the presence of PVP in the resulting PSU sample E21. The PVP was present in the final PSU sample E21 as being physically and chemically bound PVP to the PSU polymer matrix.

Example 6: PPSU Recycle

GPC Method for Measuring Mn. Mw (Sulfone GPC Method #2)

[0377] The following sulfone GPC method #2 was used for Samples E22-25._The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5 mixed D columns with a guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 15 L of a 0.2 w/v % solution in the mobile phase was selected. Calibration was performed with 10-point narrow molecular weight polystyrene standards. The injection volume for calibration standards was 75 L. The number average molecular weight Mn and weight average molecular weight Mw were reported, and the PDI=Mw/Mn was calculated.

Raw Materials for Samples E22-E25

[0378] Anhydrous Sulfolane available from Chevron Philiips Chemicals [0379] DMI (1,3-dimethyl-2-imidazolidinone) available from TCI Americas [0380] NMP (N-methylpyrrolidone) available from Sigma-Aldrich [0381] Anhydrous K.sub.2CO.sub.3 (potassium carbonate) of average particle size 30-40 m available from Armand Products [0382] biphenol (4,4-biphenol) available from Sigma-Aldrich [0383] DCDPS (4,4-dichlorodiphenyl sulfone) available from Solvay Speciality Polymers USA [0384] Methyl chloride available from Matheson Gas [0385] MCB (Monochlorobenzene) available from Sigma-Aldrich [0386] Methanol available from Sigma-Aldrich [0387] PPSU.sub.1: PPSU in coagulated form manufactured by Solvay Speciality Polymers USA of Mw=60,925 g/mol, Mn=28,501 g/mol, PDI=2.14 [0388] PPSU.sub.2: Radel R-5600 P NT PPSU in ground powder form available from Solvay Speciality Polymers USA of Mw=46,720 g/mol, Mn=20,104 g/mol, PDI=2.32. [0389] PPSU.sub.3: PPSU in coagulated form manufactured by Solvay Specialty Polymers USA of Mw=79,859 g/mol, Mn=34,451 g/mol, PDI=2.32 [0390] PPSU.sub.4: PPSU in coagulated form manufactured by Solvay Speciality Polymers USA of Mw=69,652 g/mol, Mn=31,259 g/mol, PDI=2.23 [0391] PPSU.sub.5: PPSU in coagulated form manufactured by Solvay Speciality Polymers USA of Mw=69,420 g/mol, Mn=31,334 g/mol, PDI=2.22

Synthesis Method for PPSU.SUB.1

[0392] To a 1-L 4-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, thermocouple, and a Dean-Stark trap with a condenser was charged biphenol, 130.34 g (0.70 mol), DCDPS, 203.02 g (0.707 mol), and anhydrous potassium carbonate, 101.58 g (0.735 mol). 420.48 g of DMI was added to the reactor. The reaction medium was stirred and heated via an external oil bath to an internal temperature of 200 C. over 90 minutes. The water of the reaction was collected in the dean-stark trap during the heat-up. After a pre-determined torque was reached the reaction medium was bubbled through gaseous methyl chloride for 30 min (1 g/min). 323 g of NMP was added to dilute the reaction medium. The reaction medium was pressured filtered through a 2.7 m glass fiber filter pad to remove the salts. The polymer solution was coagulated into methanol using a 1:5 polymer to methanol ratio using a Waring high-speed blender. The coagulated polymer was washed with methanol five times. The coagulated form was dried in a vacuum oven at 120 C. for 12-20 hours and analyzed for Mw, Mn, and PSI. The coagulated form was used in this example.

Synthesis method for PPSU.sub.4, PPSU.sub.5

[0393] To a 1-L 4-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, thermocouple, and a Dean-Stark trap with a condenser was charged biphenol, 83.80 g (0.45 mol), DCDPS, 131.17 g (0.4568 mol), and anhydrous potassium carbonate, 71.52 g (0.5175 mol). The contents were evacuated/purged three times using vacuum/nitrogen cycles. 420.48 g of sulfolane was added to the reactor. The reaction medium was stirred and heated via an external oil bath to an internal temperature of 210 C. over 90 minutes. The water of the reaction was collected in the dean-stark trap during the heat-up. After a pre-determined torque was reached the reaction medium was bubbled through gaseous methyl chloride for 30 min (1 g/min). 723.6 g of MCB and 61.92 g of sulfolane were added to dilute the reaction medium. The reaction medium was pressured filtered through a 2.7 m glass fiber filter pad to remove the salts. The polymer solution was coagulated into methanol using a 1:5 polymer to methanol ratio using a Waring high-speed blender. The coagulated polymer was washed with methanol five times and then dried in a vacuum oven at 120 C. for 12-20 hours.

Synthesis Method for PPSU.SUB.3

[0394] A 60-gallon Hasteloy reactor vessel was charged with sulfolane followed by the addition of biphenol, potassium carbonate, and DCDPS. DCDPS/biphenol molar ratio of 1.015 was used along with an 11 mol. % excess of potassium carbonate, relative to biphenol. Sulfolane was charged to achieve a 30 wt. % polymer concentration. The polymerization was carried out at 210 C. until the desired polymerization endpoint was achieved. MCB was added to quench the reaction followed by charging MeCl to terminate/endcap the polymerization. The reaction mixture was diluted with MCB and sulfolane to 10% polymer concentration. About 1-liter of the reaction mixture sample was pressure filtered to remove salts and coagulated/dried as described earlier.

General synthesis for PPSU Samples E22-E25:

[0395] Biphenol, DCDPS, a PPSU material (as reactant), K.sub.2CO.sub.3, and sulfolane were charged to a 1-L 4-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, thermocouple, and a Dean-Stark trap with a condenser to achieve a DCDPS/biphenol molar ratio of 1 or 1.015 (for E23) and a K.sub.2CO.sub.3/biphenol molar ratio of 1.15. The targeted polymer content in the reaction medium was 30 wt. %. Then the reactor was slowly heated (via an externally controlled oil bath) with stirring was used to mix the reaction medium. The reaction medium was heated to 210 C. over 90 minutes. After a pre-determined torque or polymerization time has been reached, gaseous MeCl was bubbled through the reaction medium for end-capping for 30 min at approximately 1 g/min. A mixture of 859 g of monochlorobenzene and 42 g of sulfolane was added to the polymerization mixture. The cooled reaction medium was then pressure-filtered to remove the formed KCl and unreacted K.sub.2CO.sub.3 salts and then coagulated into methanol using a 1:5 polymer to methanol ratio using a Waring high-speed blender. The coagulated polymer was washed with methanol five times and then dried in a vacuum oven at 120 and then d-20 hours.

[0396] The respective weights of the ingredients for PPSU Samples E22-E25 are provided in Table 7.

TABLE-US-00007 TABLE 7 Composition of reaction medium Type recycle PPSU ratio PPSU DCDPS Biphenol K.sub.2CO.sub.3 Sulfolane Sample added wt. % (g) (g) (g) (g) (g) E22 PPSU.sub.1 25 45.05 96.9 62.8 53.6 420.5 E23 PPSU.sub.2 50 90.1 65.6 41.9 35.8 420.5 E24 PPSU.sub.3 75 135.15 32.3 20.95 17.88 420.5 E25 PPSU.sub.4 90 81.1 12.92 8.38 7.15 420.5 PPSU.sub.5 81.1

[0397] The Mw, Mn, and PDI (using the GPC sulfone method #2) of the resulting PPSU Samples E22-E25 are reported in Table 8.

TABLE-US-00008 TABLE 8 PPSU recycle type ratio added (wt. %) **Mw **Mn PDI PPSU.sub.1 60925 28501 2.14 E22 PPSU.sub.1 25 58864 26543 2.14 PPSU.sub.2 48720 20104 1.64 E23 PPSU.sub.2 50 60545 28643 2.77 PPSU.sub.3 79859 34451 2.32 E24 PSSU.sub.3 75 75107 32482 2.31 PPSU.sub.4 69652 31259 2.23 PPSU.sub.5 69420 31334 2.22 E25 PSSU.sub.4 + 90 67588 28604 2.36 PSSU.sub.5 **sulfone GPC method #2 using methylene chloride as mobile phase

Example 7: PSU Manufacture Using 10 or 50 wt % PSU Recycle Radio

GPC Method for Measuring Mn, Mw

[0398] The GPC sulfone method #1 was used in this example.

Raw Materials for Samples CE27-CE29 & E30-E32

[0399] DMSO (dimethylsulfoxide) available from Fisher-Scientific [0400] NaOH (sodium hydroxide) available from Fisher-Scientific [0401] Bisphenol A BPA (4,4-dihydroxydiphenyl sulfone), available from Hexion [0402] DCDPS (4,4-dichlorodiphenyl sulfone) available from Solvay Speciality Polymers USA [0403] MeCl (methyl chloride) available from Matheson Gas [0404] PSU.sub.7: Udel P-3500 PSU in pellet form available from Solvay Speciality Polymers USA of Mw=78385 g/mol, Mn=22755 g/mol, PDI=3.44.

Strong Alkali Synthesis for Samples CE27-CE29 & E30-E32

[0405] PSU pellets (reactant) and a blend of DMSO+MCB (319 g) were charged to a 1-L 4-necked resin kettle (reactor) equipped with an overhead stirrer, a nitrogen inlet, thermocouple, Barrett trap, and reflux condenser. A pressure equalizing funnel containing the caustic solution was attached to the head of the kettle. The reactor was purged with nitrogen until the PSU pellets dissolved. For samples made with a 10 wt. % PSU recycle ratio, the PSU pellets were dissolved at ambient temperature, and for the samples made with a 50 wt. % PSU recycle ratio, the PSU pellets were dissolved at 40 C. Upon dissolution, Bisphenol A was added to the kettle, the reaction medium was purged for 15 minutes and then heated to reflux, during which time the caustic was added to the reaction medium. Upon reflux, the reaction medium was allowed to dehydrate through the removal of a water/MCB mixture. During dehydration, a solution of DCDPS in MCB (129 g) was prepared in a heated pressure-equalizing funnel. Upon removal of all water added and formed in the reaction, the DCDPS solution was added to the kettle.

[0406] After a pre-determined torque or polymerization time has been reached, the mixture is diluted with 400 g MCB, while gaseous MeCl was bubbled through the reaction medium at approximately 1 g/min for 30 min for end-capping. Upon cooling, the reaction medium was further diluted with 400 g MCB and pressure-filtered to remove the formed NaCl salt. The filtered polymer solution was then coagulated into methanol using a 1:5 polymer to methanol ratio using a Waring high-speed blender. The coagulated polymer was washed with methanol five times and then dried in a vacuum oven at 120 C. for 12-20 hours.

[0407] The respective weights of the ingredients for PSU Samples CE27-CE29 & E30-E32 are provided in Table 10.

TABLE-US-00009 TABLE 10 Composition of reaction medium recycle molar molar ratio PSU.sub.7 DCDPS BPA NaOH DCDPS/ NaOH/ DMSO wt. % (g) (g) (g) (g) BPA * BPA ** (g) CE27 143.6 114.1 39.9 1.0005 1.9959 247.7 CE28 143.6 114.1 39.9 1.0005 1.9959 247.7 CE29 143.6 114.1 39.9 1.0005 1.9959 247.7 E30 10 22.1 129.2 102.7 36.1 1.0001 2.0063 247.7 E31 10 22.1 129.2 102.7 36.1 1.0001 2.0063 247.7 E32 50 110.6 71.8 57.1 20.9 0.9997 2.0892 247.7 * DCDPS/BPA molar ratio using MW.sub.DCDPS = 287.16 g/mol; MW.sub.BPA = 228.29 g/mol ** NaOH/BPA molar ratio using MW.sub.BPA = 228.29 g/mol; MW.sub.NaOH = 39.997 g/mol

[0408] The Mw, Mn, and PDI for the resulting PSU Samples CE27-CE29 & E30-E32 are reported in Table 11.

TABLE-US-00010 TABLE 11 PSU type PSU recycle added ratio (wt. %) **Mw **Mn PDI PSU.sub.7 78385 22755 3.44 CE27 76310 20593 3.71 CE28 73610 22237 3.31 CE29 77918 22711 3.43 E30 PSU.sub.7 10 78543 22979 3.42 E31 PSU.sub.7 10 77182 22979 3.42 E32 PSU.sub.7 50 59231 18863 3.14 **sulfone GPC method #1 using methylene chloride as mobile phase

[0409] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention.