FUNCTIONALIZED POLY(ARYL ETHER SULFONES) COPOLYMERS

Abstract

The invention relates to a side-chain functionalized copolymer (P1) and to the process for preparing the side-chain functionalized copolymer (P1). The present invention also relates to the use of the copolymer (P1) in the preparation of a membrane, a composite material or a coating.

Claims

1. A copolymer (P1) comprising: recurring units (R.sub.P1) of formula (M): ##STR00022## recurring units (R*.sub.p1) of formula (N): ##STR00023## wherein each R.sub.1 is independently selected from the group consisting of a 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; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—;—C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.aC═CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m— and —(CF.sub.2).sub.m— with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof; G.sub.N is selected from the group consisting of at least one of the following formulas formulae: ##STR00024## each k is independently selected from 0 to 4; each j is independently selected from 3 to 7; each R.sub.2 is independently selected from the group consisting of: —(CH.sub.2)u—COOH, with u being selected from 1 to 5, —(CH.sub.2)k—OH, with k being selected from 1 to 5, —(CH.sub.2)p—NR.sub.aR.sub.b, with p being selected from 1 to 5, and a and b being independently a C1-C6 alkyl or H, with the provisio that R.sub.a and R.sub.b are not both CH.sub.3, —(CH.sub.2)q—SO.sub.3Na, with q being selected from 1 to 5, —(CH.sub.2)a—COCH.sub.3, with a being selected from 0 to 10 —(CH.sub.2)r—Si (OCH.sub.3).sub.3, with r being selected from 1 to 5, —(CH.sub.2)s—(CF.sub.2)t—CF.sub.3, with s being selected from 1 to 5 and t being selected from 1 to 10, —CO—R.sub.c, with R.sub.c being a C1-C6 alkyl or H, H, —(CH.sub.2)v—CH.sub.3, with v being selected from 5 to 30, and —(CH.sub.2)w—Ar, with w being selected from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings.

2. The copolymer (P1) of claim 1, wherein T in recurring units (R.sub.P1) is selected from the group consisting of a bond, —SO.sub.2— and —C(CH.sub.3).sub.2—.

3. The copolymer (P1) of claim 1, wherein i is zero for each R.sub.1 of recurring units (R.sub.P1) and recurring units (R*.sub.p1).

4. The copolymer (P1) of claim 1, wherein k is 0 and j is 3 in recurring units (R*.sub.P1).

5. The copolymer (P1) of claim 1, wherein the molar ratio of recurring units (R.sub.P1)/recurring units (R*.sub.p1) varies between 0.01/100 and 100/0.01.

6. The copolymer (P1) of claim 1, wherein recurring units (R.sub.P1) are according to formula (M1): ##STR00025##

7. The copolymer (P1) of claim 1, wherein R.sub.2 in formulae (G.sub.N1), (G.sub.N2), (G.sub.N3), (G.sub.N4), (G.sub.N5) or (G.sub.N6) is independently selected from the group consisting of: —CH.sub.2— COOH, —(CH.sub.2).sub.2—OH, —(CH.sub.2).sub.2—NH.sub.2, —(CH.sub.2).sub.3— SO.sub.3Na, —(CH.sub.2).sub.3—Si (OCH.sub.3).sub.3, —(CH.sub.2).sub.2—(CF.sub.2).sub.7—CF.sub.3, —C═O—H, —(CH.sub.2).sub.9—CH.sub.3, —CH.sub.2-Ph, with Ph being benzene.

8. The copolymer (P1) of claim 1, comprising collectively at least 50 mol. % of recurring units (R.sub.P1) and (R*.sub.P1), based on the total number of moles in the copolymer (P1).

9. A process for preparing copolymer (P1) comprising reacting in a solvent a copolymer (P0) comprising: recurring units (R.sub.P0) of formula (M): ##STR00026## recurring units (R*.sub.P0) of formula (P): ##STR00027## wherein each R.sub.1 is independently selected from the group consisting of a 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; each i is independently selected from 0 to 4; T is selected from the group consisting of a bond, —CH.sub.2—; —O—; —SO.sub.2—;-5-; —C(O)—; —C(CH.sub.3).sub.2—;—C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.aC═CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m— and —(CF.sub.2).sub.m— with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof, G.sub.P is selected from the group consisting of at least one of the following formulae: ##STR00028## each k is independently selected from 0 to 4, with a compound of formula (I): R.sub.2—SH wherein R.sub.2 is selected from the group consisting of: —(CH.sub.2)u—COOH, with u being selected from 1 to 5, —(CH.sub.2)k—OH, with k being selected from 1 to 5, —(CH.sub.2)p—NR.sub.aR.sub.b, with p being selected from 1 to 5, and a and b being independently a C1-C6 alkyl or H, with the provisio that R.sub.a and R.sub.b are not both CH.sub.3, —(CH.sub.2)q—SO.sub.3Na, with q being selected from 1 to 5, —(CH.sub.2)a—COCH.sub.3, with a being selected from 0 to 10 —(CH.sub.2)r—Si (OCH.sub.3).sub.3, with r being selected from 1 to 5, —(CH.sub.2)s—(CF.sub.2)t—CF.sub.3, with s being selected from 1 to 5 and t being selected from 1 to 10, —CO—R.sub.c, with R.sub.c being a C1-C6 alkyl or H, —(CH.sub.2)v—CH.sub.3, with v being selected from 5 to 30, and —(CH.sub.2)w—Ar, with w being selected from 1 to 10 and Ar comprising 1 to 10 one or two aromatic or heteroaromatic rings, wherein the molar ratio of compound (0/polymer (P0) varies between 0.01/100 and 100/0.01, at a temperature ranging from 10° C. and 300° C.

10. The process of claim 9, being carried out in a solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole, chloroform, dichloromethane (DCM) and sulfolane.

11. The process of claim 9, being carried out in the presence of: at least one free radical initiator, and/or at least one catalyst.

12. The process of claim 9, being carried out in the presence of a base.

13. The process of claim 9, being carried out by exposing the reaction mixture to UV light at a wavelength ranging from 300 nm to 600 nm.

14. The process of claim 9, wherein the functionalized PAES copolymer (P0) comprises collectively at least 50 mol. % of recurring units (R.sub.P0) and (R*.sub.P0), based on the total number of moles in the copolymer (P0).

15. The process of claim 9, wherein the functionalized PAES copolymer (P0) is prepared by condensation of at least one aromatic dihydroxy monomer (a1), with at least one aromatic sulfone monomer (a2) comprising at least two halogen substituents at at least one allyl-substituted aromatic dihydroxy monomer (a3).

16. A method for preparing a membrane, a composite material or a coating, comprising using the copolymer of claim 1.

17. The process of claim 11, being carried out in the presence of: 2,2′-Azobis(2-methylpropionitrile) (AIBN) as at least one free radical initiator, and/or at least one catalyst selected from peroxides and hydroperoxides.

18. The process of claim 12, wherein the base is selected from the group consisting of N-Ethyl-N—(propan-2-yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine.

Description

EXAMPLES

[0146] Raw Materials

[0147] DCDPS (4,4′-dichlorodiphenyl sulfone), available from Solvay Specialty Polymers

[0148] BPA (bisphenol A), available from Covestro, U.S.A.

[0149] BP (biphenol), polymer grade available from Honshu Chemicals, Japan

[0150] daBPA (2,2′-diallyl Bisphenol), available from Sigma-Aldrich, U.S.A.

[0151] K.sub.2CO.sub.3 (Potassium Carbonate), available from Armand products

[0152] NaHCO.sub.3(Sodium bicarbonate), available from Solvay S. A., France

[0153] NMP (2-methyl pyrrolidone), available from Sigma-Aldrich, U.S.A.

[0154] MCB (methylchlorobenzene), available from Sigma-Aldrich, U.S.A.

[0155] DMSO (dimethylsulfoxide), available from Sigma-Aldrich, U.S.A.

[0156] DCM (dichloromethane), available from Sigma-Aldrich, U.S.A.

[0157] AIBN (Azobisisobutyronitrile), available from Sigma-Aldrich, U.S.A.

[0158] Mercaptoethanol (HSCH.sub.2CH.sub.2OH), available from Sigma-Aldrich, U.S.A.

[0159] Thioglycolic acid (HS—CH.sub.2—COOH), available from Sigma-Aldrich, U.S.A.

[0160] Benzyl mercaptan, 1-decanethiol, 1H,1H,2H,2H-Perfluoro-1-decanethiol and Cysteamine hydrochloride available from Sigma-Aldrich, U.S.A. Jeffamine® M-2095, available from Hunstman

[0161] DPA, 2,2-dimethoxy-2-phenylacetophenone, available from Sigma-Aldrich, U.S.A.

[0162] Test Methods

[0163] GPC-Molecular Weight (Mn, Mw)

[0164] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5p mixed D columns with 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 μL of a 0.2 w/v % solution in mobile phase was selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn, weight average molecular weight Mw, higher average molecular weight Mz, were reported.

[0165] Thermal Gravimetric Analysis (TGA)

[0166] TGA experiments were carried out using a TA Instrument TGA Q500.

[0167] TGA measurements were obtained by heating the sample at a heating rate of 10° C./min from 20° C. to 800° C. under nitrogen.

[0168] .sup.11-/NMR

[0169] .sup.1H NMR spectra were measured using a 400 MHz Bruker spectrometer with TCE or DMSO as the deuterated solvent. All spectra are reference to residual proton in the solvent.

[0170] DSC

[0171] 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. 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 and Tm values were provided using the second heat curve unless otherwise noted.

[0172] Contact Angle

[0173] The contact angle of the films was measured using a KRUSS EASYDROP instrument according to ASTM D5946-09.

[0174] I. Preparation of Allyl/Vinylene-Modified PSU Copolymer (P0-A)

[0175] The functionalized PPSU polymer (P0-A) was prepared according to the Scheme 1.

[0176] The copolymerization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers 4,4′-dichlorodiphenyl sulfone (143.58 g), Bisphenol A (102.73 g) and 2,2′-diallyl Bisphenol (15.42 g) are added to the vessel first, followed by the addition of potassium carbonate (78.29 g), NMP (690 g) and MCB (170 g) as the azeotropic distillation solvent.

[0177] The reaction mixture is heated from room temperature to 190° C. using a 1° C./min heating ramp. The temperature of the reaction mixture is maintained for six to eight hours, depending upon the viscosity of the solution. The reaction is terminated by stopping the heating. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0178] The copolymer (P0-A) is in the form of a racemate product. Due to the presence of the base and high temperature during polymerization, the 2,2′-diallyl bisphenol monomer racemizes during polymerization in such a way that the position of the double bond changes along the side chains. This leads to the formation of molecules differing from each others by the fact that the double bond may be at the end of the side chain or one carbon before the end of the side chain, as shown above.

[0179] Characterization of the ally//Vinylene-Modified PSU Copolymer (POA)

[0180] GPC: Mn=10,948 g/mol, Mw=37,123 g/mol, PDI=3.39

[0181] TGA: 474° C.

[0182] DSC: 175° C.

[0183] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicates the incorporation of the 2,2′-diallyl BPA monomer in the polymer.

[0184] II. Preparation of Allyl/Vinylene-Modified PPSU Copolymer (P0-B)

[0185] The functionalized PPSU polymer (P0-B) was prepared according to the Scheme 2.

[0186] The copolymerization takes place in a kettle type reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet, a thermocouple and a dean stark trap. The monomers 4,4′-dichlorodiphenyl sulfone (143.58 g), biphenol (88.45 g) and 2,2′-diallyl Bisphenol (7.71 g) are added to the vessel first, and purged with nitrogen for 30 minutes. The sulfolane (470 g) is then added to the vessel, as well as the potassium carbonate (78 g).

[0187] The reaction mixture is then heated to 210° C. When the reaction mixture reaches this temperature, the reaction is maintained for 6 to 8 hours. After this time the heating is stopped and the reaction mixture is allowed to cool to room temperature and. The reaction mixture is filtered, coagulated into methanol and washed with hot deionized water.

[0188] The copolymer (P0-B) is in the form of a racemate product.

[0189] Characterization of the Allyl/Vinylene-Modified PPSU Copolymer (P0-B)

[0190] GPC: Mn=26430 g/mol, Mw=126547 g/mol, PDI=4.78

[0191] TGA: 493° C.

[0192] DSC: 199° C.

[0193] .sup.1H NMR:

[0194] The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.2-6.4 ppm which indicates the incorporation of the 2,2′-diallyl BPA monomer in the polymer.

[0195] III. Preparation of Allyl/Vinylene-Modified PES Copolymer (P0-C)

[0196] The functionalized PES polymer (P0-C) was prepared according to the Scheme 3.

[0197] The copolymerization takes place in a kettle type reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet, a thermocouple and a dean stark trap. The monomers 4,4′-dichlorodiphenyl sulfone (146.45 g), 4,4′-dihydroxydiphenyl sulfone (112.37 g) and 2,2′-diallyl Bisphenol (15.72 g) are added to the vessel first, and purged with nitrogen for 30 minutes. The NMP (283 g) is then added to the vessel, as well as the potassium carbonate (69.8 g).

[0198] The reaction mixture is then heated to 190° C. When the reaction mixture reaches this temperature, the reaction is maintained for 6 to 8 hours. After this time the heating is stopped and the reaction mixture is allowed to cool to room temperature and. The reaction mixture is filtered, coagulated into methanol and washed with hot deionized water.

[0199] The copolymer (P0-C) is in the form of a racemate product.

[0200] Characterization of the Allyl/Vinylene-Modified PES Copolymer (P0-C)

[0201] GPC: Mw=29,997 g/mol, Mn=12,042 g/mol, PDI=2.49

[0202] TGA: 415° C.

[0203] DSC: Tg=214° C.

[0204] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicates the incorporation of the 2,2′-diallyl BPA monomer in the polymer.

##STR00010##

##STR00011##

##STR00012##

[0205] IV. Preparation of Functionalized PSU Copolymer (P1) by Free Radical Reaction

[0206] General Procedure:

[0207] 50 g of allyl/vinylene-modified copolymer (P0-A) prepared according to I. above (Scheme 1) is dissolved in 200 g of NMP at a temperature between 60 and 70° C. The compound of formula (I) is then added to the reaction vessel and stirred. The free radical initiator is then added to the reaction vessel and stirred under N.sub.2 for 6 to 12 hours. The temperature is maintained at 70° C. for 6 to 12 hours. The reaction mixture is then coagulated in methanol and dried at 110° C.

Example 1. Preparation of OH-Functionalized PSU Copolymer (P1-A)

[0208] The functionalized PSU polymer (P1-A) was prepared according to the general procedure above with 35.34 g of mercaptoethanol (HSCH.sub.2CH.sub.2OH) and 2.45 g of AIBN, according to Scheme 4.

[0209] Characterization

[0210] GPC: Mw=121,318 g/mol, Mn=18,756 g/mol, PDI=6.47

[0211] DSC: Tg=160° C.

[0212] TGA: 376° C. (this single peak indicates the absence of free mercaptoethanol).

[0213] .sup.1H NMR: The hydroxyl functionalization was detected by the complete absence of the olefinic proton signals at 6.2 ppm and the appearance of two triplets at 3.5 ppm and 2.6 ppm indicating the presence of the —CH.sub.2CH.sub.2OH groups.

[0214] The quantitative estimation of the hydroxyl functionalization was analyzed by titrating the hydroxyl groups. Hydroxyl content: 750 ueq/g.

Example 2. Preparation of COOH-Functionalized PSU Copolymer (P1-B)

[0215] The functionalized PSU polymer (P1-B) was prepared according to the general procedure with 41.67 g of thioglycolic acid (HS—CH.sub.2—COOH) and 2.45 g of AIBN, according to Scheme 5.

[0216] Characterization

[0217] DSC: Tg=156° C.

[0218] TGA: 371° C.

[0219] .sup.1H NMR: The carboxyl functionalization was detected by the complete absence of the olefinic proton signals at 6.2 ppm and the appearance of a new singlet at ˜3 ppm.

[0220] The quantitative estimation of the carboxylic acid functionalization was analyzed by titrating the acid groups.

[0221] Carboxyl acid content: 971 ueq/g

[0222] The functionalized PSU copolymer (P1-B) was then coupled with Jeffamine® M-2095 using CU coupling agent, according to Scheme 6 copolymer (P1-13′).

[0223] More precisely, 4 g of copolymer (P1-B) was dissolved in 25 g of NMP at 70° C. and then 200 mg of carbodiimidazole were added to the solution with stirring under N.sub.2 for 30 minutes. 8.22 g of Jeffamine® M-2095 were then dissolved in another 25 g of NMP and then added in a single portion to the reaction mixture. The reaction was maintained at 70° C. for 12 hours. The solution was then precipitated in methanol and dried under vacuum.

[0224] .sup.1H NMR: The presence of the —CH.sub.2CH.sub.2—O— groups was identified by a large signal at 3.67 ppm.

[0225] Carboxyl acid content: 133 ueq/g

Example 3. Preparation of Amine-Functionalized PSU Copolymer (P1-C)

[0226] The functionalized PSU polymer (P1-C) was prepared according to the general procedure with 51.39 g of cysteamine hydrochloride (HSCH.sub.2CH.sub.2NH.sub.2.Math.HCl), 38 g of sodium bicarbonate in 100 g of DMSO and 2.45 g of AlBN, according to Scheme 7.

[0227] Characterization

[0228] GPC: Mw=49,116 g/mol, Mn=8506 g/mol, PDI=5.77DSC: 175° C. TGA: 427° C.

[0229] .sup.1H NMR: The amino functionalization was detected by the complete absence of the olefinic proton signals at 6.2 ppm and the appearance of triplet at 2.18 ppm which is not present in copolymer P0-A.

[0230] The quantitative estimation of the amine functionalization was analyzed by titrating the amine groups.

[0231] Amine content: 1180 ueq/g

[0232] The functionalized PSU copolymer (P1-C) was then further modified by bubbling methyl chloride throught the solution at 70° C. obtained in the former step, according to Scheme 8-copolymer (P1-C′).

[0233] The methyl chloride was bubbled in large excess through a methyl chloride lecture bottle.

[0234] Characterization

[0235] .sup.1H NMR: A large single peak at 2.85 ppm corresponding to the tetra-methyl ammonium groups was observed.

[0236] GPC:Mw:26474 g/mol, Mn:11367 g/mol, PDI:2.33.

[0237] FTIR: A strong signal around 1684 cm.sup.−1 is seen which is absent in the starting polymer and can be attributed to the quaternary ammonium side chains.

[0238] DSC: Tg=140° C.

Example 4. Preparation of Sulfonate-Functionalized PSU Copolymer (P1-D)

[0239] The functionalized PSU polymer (P1-D) was prepared according to the general procedure with 40.27 g of sodium thiopropane sulfonate, 80 g of DMSO and 1.5 g of AIBN according to Scheme 9.

[0240] Characterization

[0241] GPC: Mw=55,134 g/mol, Mn=27,484 g/mol, PDI=2.01 DSC: 161.95° C.

[0242] .sup.1H NMR: The functionalization was detected by the complete absence of the olefinic proton signals at 6.2 ppm and the appearance of distorted sextet at 1.6 ppm indicating the presence of the —CH.sub.2CH.sub.2CH.sub.2SO.sub.3Na groups.

[0243] The resulting copolymer was water-soluble, indicating the covalent attachment of the highly polar sodium sulfonate side-groups to the parent copolymer P0-A which is not water soluble.

Example 5. Preparation of Aliphatic-Functionalized PSU Copolymer (P1-E)

[0244] The functionalized PSU polymer (P1-E) was prepared according to the following procedure: 10 g of allyl/vinylene-modified copolymer (P0-A) prepared according to I. above is dissolved in 40 g of NMP at a temperature of 70° C. 13 g of decanethiol is then added to the reaction vessel and stirred. 100 mg of free radical initiator is then added to the reaction vessel and stirred under N.sub.2 for 6 to 12 hours. The temperature is maintained at 70° C. for 6 to 12 hours. The reaction mixture is then coagulated in methanol and dried at 110° C. Scheme 10.

[0245] Characterization

[0246] TGA: 373° C.

[0247] DSC: 106° C.

[0248] GPC:Mw:100,652 g/mol, Mn:1,8902 g/mol, PDI:5.3

[0249] .sup.1H NMR: Presence of a distorted triplet at 0.9 ppm and large alkyl signal at 1.3 ppm, and complete disappearance of the alkene signals present in the parent copolymer.

Example 6. Preparation of Fluoro-Functionalized PSU Copolymer (P1-F)

[0250] The functionalized PSU polymer (P1-F) was prepared according to the following procedure: 48 g of allyl/vinylene-modified copolymer (P0-A, unfiltered) prepared according to I. above is dissolved in 50 g of DMAcc at a temperature of 70° C. 25 g of 1H,1H,2H,2H-Perfluoro-1-decanethiol is then added to the reaction vessel and stirred. 1.64 g of free radical initiator (AIBN) is then added to the reaction vessel and stirred under N.sub.2 for 6 to 12 hours. The temperature is maintained at 70° C. for 6 to 12 hours. The reaction mixture is then coagulated in methanol and repeatedly washed with solvent to remove any excess thiol and dried at 110° C.

[0251] Characterization

[0252] DSC: The DSC of this copolymer was unique with two distinct thermal transitions—one at 77° C. perhaps could be attributed to the fluorinated side chains and the other at 140° C. attributed to the main chain polysulfone backbone.

[0253] FTIR: A strong band at 1204 cm.sup.−1 is evidence of a fluorocarbon which is absent in the parent polymer

[0254] The copolymer was then cast into a film and the surface contact angle was measured. The contact angle for the copolymer (P1-F) was equal to ⊖=125.5°, whereas the contact angle for the copolymer (P0-A) was equal to equals ⊖=81°, indicating the presence of the fluorinated side-chains affecting the surface characteristics of the polymer.

Example 7. Preparation of Aryl-Functionalized PSU Copolymer (P1-G)

[0255] The functionalized PSU polymer (P1-F) was prepared according to the following procedure: 8.3 g of allyl/vinylene-modified copolymer (P0-A, unfiltered) prepared according to I. above is dissolved in 41.7 g of NMP at a temperature of 70° C. 9 g of benzylmercaptan is then added to the reaction vessel and stirred. 0.4 g of free radical initiator is then added to the reaction vessel and stirred under N.sub.2 for 6 to 12 hours. The temperature is maintained at 70° C. for 6 to 12 hours. The reaction mixture is then coagulated in methanol and dried at 110° C.

[0256] Characterization

[0257] GPC: Mw=142,528 g/mol, Mn=20,868 g/mol, PDI: 6.83

[0258] DSC: 106.4° C.

[0259] H NMR: The NMR spectrum showed a large singlet —CH.sub.2—S of the benzyl mercaptan residue at 3.66 ppm and complete disappearance of the alkene proton signals present in the parent copolymer.

[0260] IV. Preparation of functionalized PSU copolymer (P1) by UV radiation

[0261] The functionalized PSU polymer (P1-A) was prepared in one step, according to Scheme 11.

[0262] 4 g of copolymer P0-A was dissolved in 6 g of NMP or DCM. 0.56 g of mercaptoethanol were then added, as well as 230 mg of 2,2-dimethoxy-2-phenylacetophenone. The reaction vessel was exposed to UV radiation 365 nm (100 watt, UVP Blak-Ray B-100AP) at room temperature for 10 hours. The reaction solution was then precipitated in methanol and the precipitate was washed several times with methanol and then dried. The resultant polymer was tested for the presence of hydroxyl groups by titration.

[0263] Characterization

[0264] In NMP

[0265] GPC:Mw:40247 g/mol, Mn:8,101 g/mol, PDI:4.97.

[0266] Hydroxyl endgroups: 291+-40 ueg/g

[0267] In DCM

[0268] GPC: Mw:8956 g/mol, Mn:5,261 g/mol, PDI:5.88.

[0269] Hydroxyl endgroups: 683 ueq/g

[0270] V. Preparation of Functionalized PSU Copolymer (P1) by Base-Catalyzed Reaction

Preparation of OH-Functionalized PSU Copolymer (P1-A)

[0271] The functionalized PSU polymer (P1-A) was prepared according to the general procedure with 35.34 g of mercaptoethanol (HSCH.sub.2CH.sub.2OH) and 2.45 g of diisopropylamine, according to Scheme 12.

[0272] 50 g of allyl/vinylene-modified copolymer (P0-A) prepared according to I. above is dissolved in 200 g of NMP at a temperature of 65° C. 35.34 g of mercaptoethanol were then added to the reaction vessel and stirred. 2.45 g of diisopropyl amine were then added and stirred under N.sub.2 for 72 hours. The reaction mixture was then coagulated in methanol and dried at 110° C. The resultant polymer was tested for the presence of hydroxyl groups by titration.

[0273] Characterization

[0274] GPC:Mw: 69,667 g/mol, Mn=14,774 g/mol, PDI=4.72.

[0275] Aliphatic Hydroxy: 108 ueq/g

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