SIDE-CHAIN FUNCTIONALIZED POLY (ARYL ETHER SULFONES) COPOLYMER COMPRISING REACTIVE END-GROUPS

Abstract

The invention pertains to a side-chain functionalized copolymer (P1) comprising reactive end-groups. The present invention also pertains to the preparation process of copolymer (P1) starting from copolymer (P0), as well as to the use of the copolymer (P1) in the preparation of a membrane, a composite material or a coating. The present invention also relates to a resin composition comprising at least the copolymer (P1) according to the present invention.

Claims

1. A copolymer (P1) comprising: recurring units (R.sub.P1) of formula (M): ##STR00019## recurring units (R*.sub.P1) of formula (N): ##STR00020## at least 50 μeq of hydroxyl end groups, amine end groups or acid end groups, 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; G.sub.N is selected from the group consisting of at least one of the following formulas: ##STR00021## each k is independently selected from 1 to 4; each j is independently selected from 3 to 7; T and Q are independently 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, 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 R.sub.a and R.sub.b being independently a C1-C6 alkyl or H, with the proviso that R.sub.a and R.sub.b cannot be 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 0 to 10 and Ar comprising 1 to 10 aromatic or heteroaromatic rings, wherein Ar is optionally substituted with NR.sub.aR.sub.b, each R.sub.3 is independently an alkyl group, an aryl group or an halogen group.

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 Q in formulas (G.sub.N1), (G.sub.N2) and/or (G.sub.N3) of recurring units (R*.sub.P1) is selected from the group consisting of a bond, —SO.sub.2— and —C(CH.sub.3).sub.2—.

4. 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).

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): ##STR00022##

7. The copolymer (P1) of claim 1, wherein R.sub.2 in formulas (G.sub.N1), (G.sub.N2) or (G.sub.N3) 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.7CF.sub.3, —C═O—H, —(CH.sub.2).sub.9—CH.sub.3, —CH.sub.2-Ph, with Ph being benzene, and -Ph-NH.sub.2, with Ph being benzene.

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

9. The copolymer (P1) of claim 1, having a number average molecular weight (Mn) of less than 20,000 g/mol, as determined by GPC.

10. A process for preparing a copolymer (P1), comprising reacting in a solvent a copolymer (P0) comprising: recurring units (R.sub.P0) of formula (M): ##STR00023## recurring units (R*.sub.P0) of formula (P): ##STR00024## at least 50 μeq of hydroxyl end groups, amine end groups or acid end groups, 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; G.sub.P is selected from the group consisting of at least one of the following formulas: ##STR00025## each k is independently selected from 0 to 4, T and Q are independently 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, 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 R.sub.a and R.sub.b being independently a C1-C6 alkyl or H, with the proviso that R.sub.a and R.sub.b cannot be 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-r, with w being selected from 0 to 10 and Ar comprising 1 to 10 aromatic or heteroaromatic rings, wherein Ar is optionally substituted with NR.sub.aR.sub.b, 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.

11. The process of claim 10, being carried out: in a solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (DMI), 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, in the presence of at least one free radical initiator, in the presence of at least one catalyst, and/or in the presence of a base.

12. A copolymer (P0) comprising: recurring units (R.sub.P0) of formula (M): ##STR00026## recurring units (R*.sub.P0) of formula (P): ##STR00027## at least 50 μeq of hydroxyl end groups, amine end groups or acid end groups, 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; G.sub.P is selected from the group consisting of at least one of the following formulas: ##STR00028## each k is independently selected from 0 to 4, T and Q are independently 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.

13. A method for the preparation of a membrane, a composite material or a coating, comprising using the copolymer (P1) of claim 1.

14. An epoxy resin composition comprising at least one epoxy compound and at least one copolymer (P1) according to claim 1.

15. The copolymer (P1) of claim 1, being used as a toughening agent in an epoxy, polyurethane or unsaturated polyester resin composition.

16. A method for the preparation of a membrane, a composite material or a coating, comprising using the copolymer (P0) of claim 12.

17. An epoxy resin composition comprising at least one epoxy compound and at least one copolymer (P0) according to claim 12.

18. The copolymer (P0) of claim 12, being used as a toughening agent in an epoxy, polyurethane or unsaturated polyester resin composition.

Description

EXAMPLES

[0168] Raw Materials

[0169] DCDPS (4,4′-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers

[0170] BPA (bisphenol A), available from Covestro, U.S.A.

[0171] BP (4,4′-biphenol), polymer grade available from Honshu Chemicals, Japan

[0172] daBPA (2,2′-diallyl Bisphenol), available from Sigma-Aldrich, U.S.A.

[0173] K.sub.2CO.sub.3 (Potassium Carbonate), available from Armand products

[0174] NaHCO.sub.3(Sodium bicarbonate), available from Solvay S.A., France

[0175] NMP (2-methyl pyrrolidone), available from Sigma-Aldrich, U.S.A.

[0176] AIBN (Azobisisobutyronitrile), available from Sigma-Aldrich, U.S.A.

[0177] Cysteamine hydrochloride, 3-Aminophenol available from Sigma-Aldrich, U.S.A.

[0178] ADVN (2,2′-Azobis (2,4 dimethylvaleronitrile)), available from Miller-Stephenson Chemical Co., Inc.

[0179] Test Methods

[0180] GPC—Molecular weight (Mn, Mw)

[0181] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5μ 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.

[0182] Thermal Gravimetric Analysis (TGA)

[0183] 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. The TGA values report the temperature of the onset of thermal decomposition.

[0184] .sup.1H NMR

[0185] .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.

[0186] DSC

[0187] 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.

[0188] Hydroxyl Titration

[0189] Hydroxyl groups were analyzed by dissolving a sample of the polymer in 5 ml of sulfolane:monochlorobenzene (50:50). 55 ml of methylene chloride was added to the solution and the sample was titrated with tetrabutyl ammonium hydroxide in toluene potentiometrically using Metrohm Solvotrode electrode & Metrohm 686 Titroprocessor with Metrohm 665 Dosimat. There were three possible equivalence points. The first equivalence point was indicative of strong acid. The second equivalence point was indicative of sulfonic hydroxyls. The third equivalence point was indicative of phenolic hydroxyls. Total hydroxyl numbers were calculated as a sum of phenolic and sulfonic hydroxyls.

[0190] Amine Titration

[0191] A sample of 0.2 to 0.3 g of polymer was dissolved in 55 mL of methylene chloride with stirring. 15 mL of glacial acetic acid was added. The sample was then titrated potentionmetrically with 0.1N perchloric acid in acetic acid using a Metrohm Titrando 809 Titrator with a Metrohm Solvotrode electrode. Perchloric acid titrant reacts with basic groups in the sample and produces an endpoint in the potential curve when all base has been neutralized. Two blanks and one control sample were tested prior to testing samples. Two replicates were run for each sample. The results were reported only after duplicate analyses agree within 5% for base concentration values above 100 μeq/g or were within 10 μeq/g for values below 100 μeq/g.

[0192] Calculation of Base Concentration:

[00001]$\left[\mathrm{Sample}\mathrm{base},\mu \mathrm{eq}/g\right]=\frac{\left(N\mathrm{perchloric}\mathrm{acid}\right)\times \left(V\mathrm{percloric}\mathrm{acid}-V\mathrm{blank}\right)\times 1000}{W\mathrm{sample}}$ [0193] N perchloric acid=number of moles of perchloric acid (N) [0194] V perchloric acid=volume of perchloric acid (mL) [0195] V blank=volume of blank (mL) [0196] W sample=weight of the sample (g)

[0197] The blank value is determined from the volume of titrant needed to achieve the same mV electrode potential as the sample titration endpoint potential.

[0198] Chlorine Analysis

[0199] Chlorine end groups were analysed using a ThermoGLAS 1200 TOX halogen analyzer. Samples between 1 mg and 10 mg were weighted into a quartz boat and inserted into a heated combustion tube where the sample was burned at 1,000° C. in an oxygen stream. The combustion products were passed through concentrated sulfuric acid scrubbers into a titration cell where hydrogen chloride from the combustion process was absorbed in 75% v/v acetic acid. Chloride entering the cell was then titrated with silver ions generated coulometrically. Percent chlorine in the sample was calculated from the integrated current and the sample weight. The resulting percent chlorine value was converted to chlorine end group concentration in micro equivalents per gram (μeq/g).

[0200] I. Preparation of Amine-Terminated, Allyl/Vinylene-Modified PSU Copolymer (P0-A)

[0201] The functionalized PSU polymer (P0-A) was prepared according to the Scheme 1.

[0202] The copolymerization takes place in a glass reactor vessel (2 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (430.47 g), BPA (257.51 g) and daBPA (86.97 g) are added to the vessel first, followed by the addition of K.sub.2CO.sub.3 (212.41 g), NMP (900 g).

[0203] 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 4 hours. K.sub.2CO.sub.3 (36 g) and 3-aminophenol (18.33 g) are then added and the reaction is continued for 4 hours. The reaction is terminated by stopping the heating. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0204] The copolymer is in the form of a racemate product. Due to the presence of the base and high temperature during polymerization, the daBPA 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 other 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 in Scheme 1.

[0205] Characterization

[0206] GPC: Mn=9,458 g/mol, Mw=24,952 g/mol, PDI=2.64

[0207] TGA: 397° C.

[0208] DSC: 160.5° C.

[0209] Amine groups: 212 μeq/g

[0210] .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 daBPA monomer in the polymer.

[0211] II. Preparation of Phenolic-Hydroxyl-Terminated, Allyl/Vinylene-Modified PSU Copolymer (P0-B)

[0212] The functionalized PSU polymer (P0-B) was prepared according to the Scheme 2.

[0213] The copolymerization takes place in a glass reactor vessel (2 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (430.47 g), BPA (257.51 g) and daBPA (86.97 g) are added to the vessel first, followed by the addition of K.sub.2CO.sub.3 (212.41 g), and NMP (900 g).

[0214] 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 4 hours. K.sub.2CO.sub.3 (24.87 g) and BPA (41 g) are added and then reaction is continued for 4 hours. The reaction is terminated by stopping the heating and oxalic acid (50 g) is added and stirred. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0215] Similarly to copolymer (P0-A), this copolymer (P0-B) is in the form of a racemate product.

[0216] Characterization

[0217] GPC: Mn=9,536 g/mol, Mw=24,327 g/mol, PDI=2.55

[0218] TGA: 411° C.

[0219] DSC: 154° C.

[0220] Hydroxyl: 210.7 μeq/g

[0221] Chlorine: 3.2 μeq/g

[0222] III. Preparation of Amine-Terminated, Allyl/Vinylene-Modified PPSU Copolymer (P0-A)

[0223] The functionalized PPSU polymer (P0-C) was prepared according to the Scheme 3.

[0224] The copolymerization takes place in a glass reactor vessel (2 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (430.74 g), BPA (210.04 g) and daBPA (86.97 g) are added to the vessel first, followed by the addition of K.sub.2CO.sub.3 (204.61 g), and NMP (900 g).

[0225] 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 4 hours. K.sub.2CO.sub.3 (36 g) and 3-aminophenol (18.33 g) are then added and the reaction is continued for 4 hours. The reaction is terminated by stopping the heating. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0226] Similarly to copolymer (P0-A), this copolymer (P0-C) is in the form of a racemate product.

[0227] Characterization

[0228] GPC: Mn=11,425 g/mol, Mw=39,759 g/mol, PDI=3.48

[0229] TGA: 422° C.

[0230] DSC: 179.21° C.

[0231] Amine groups: 212 μeq/g

[0232] .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 daBPA monomer in the polymer.

[0233] IV. Preparation of Amine-Terminated, Allyl/Vinylene-Modified PES Copolymer (P0-D) The functionalized PES polymer (P0-D) was prepared according to the Scheme 4.

[0234] 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 DCDPS (215.37 g), DHDPS (175.88 g) and daBPA (24.02 g) are added to the vessel first, followed by the addition of K.sub.2CO.sub.3 (101.72 g), NMP (340 g).

[0235] 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 4 hours. 3-aminophenol (18.33 g) is then added and the reaction is continued for 3 hours. The reaction is terminated by stopping the heating. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0236] Similarly to copolymer (P0-A), this copolymer (P0-D) is in the form of a racemate product.

[0237] Characterization

[0238] GPC: Mn=5,128 g/mol, Mw=9,550 g/mol, PDI=1.86

[0239] TGA: 426° C.

[0240] DSC: 187° C.

[0241] Amine groups: 227 μeq/g

[0242] .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 daBPA monomer in the polymer.

[0243] V. Preparation of Functionalized PSU Copolymer (P1-A)

[0244] The functionalized PSU polymer (P1-A) was prepared according to the following procedure according to Scheme 5.

[0245] The amine functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-A (100 g) and cysteamine hydrochloride (62.5 g) are dissolved at room temperature in NMP (900 g). The reaction mixture is purged with N.sub.2 for at least 45 minutes, then the reaction is heated to 50° C. and ADVN (4 g) is added. The reaction is allowed to proceed for 12 hours, after which the heating is stopped. The reaction mixture is then coagulated in 3,000 mL in which 50 g of K.sub.2CO.sub.3 is added. The coagulated polymer is then washed with water (3,000 mL) and then washed twice with methanol (3,000 mL) and then dried at 110° C.

[0246] Characterization

[0247] GPC: Mn=4,060 g/mol, Mw=8,258 g/mol, PDI=2.03

[0248] TGA: 302° C.

[0249] DSC: 150° C.

[0250] Amine groups: 944 μeq/g

[0251] VI. Preparation of Functionalized PSU Copolymer (P1-B)

[0252] The functionalized PSU polymer (P1-B) was prepared according to the following procedure according to Scheme 6.

[0253] The amine functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-B (50 g), cysteamine hydrochloride (48.1 g) are dissolved at room temperature in NMP (450 g). The reaction mixture is purged with N.sub.2 for at least 45 minutes, then the reaction is heated to 50° C. and ADVN (2.9 g) is added. The reaction is allowed to proceed for 12 hours, after which the heating is stopped. The reaction mixture is then coagulated in 3,000 mL in which 50 g of K.sub.2CO.sub.3 is added. The coagulated polymer is then washed with water (3,000 mL) and then washed twice with methanol (3,000 mL) and then dried at 110° C.

[0254] Characterization

[0255] GPC: Mn=2,878 g/mol, Mw=6,253 g/mol, PDI=2.17

[0256] TGA: 386° C.

[0257] DSC: 143.16° C.

[0258] Amine groups: 699 μeq/g

[0259] VII. Preparation of Functionalized PPSU Copolymer (P1-C)

[0260] The functionalized PPSU polymer (P1-0) was prepared according to the following procedure according to Scheme 7.

[0261] The amine functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-C (100 g), and cysteamine hydrochloride (62.5 g) are dissolved at room temperature in NMP (900 g). The reaction mixture is purged with N.sub.2 for at least 45 minutes, then the reaction is heated to 50° C. and ADVN (4 g) is added. The reaction is allowed to proceed for 12 hours, after which the heating is stopped. The reaction mixture is then coagulated in 3000 mL in which 50 g of K.sub.2CO.sub.3 is added. The coagulated polymer is then washed with water (3,000 mL) and then washed twice with methanol (3,000 mL) and then dried at 110° C.

[0262] Characterization

[0263] GPC: Mn=3,321 g/mol, Mw=6,130 g/mol, PDI=1.85

[0264] TGA: 302° C.

[0265] DSC: 170.3° C.

[0266] Amine groups: 900 μeq/g

[0267] VIII. Preparation of Functionalized PES Copolymer (P1-D)

[0268] The functionalized PES polymer (P1-D) was prepared according to the following procedure according to Scheme 8.

[0269] The amine functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-D (130 g), and cysteamine hydrochloride (63.6 g) are dissolved at room temperature in DMSO (640 g). The reaction mixture is purged with N.sub.2 for at least 45 minutes, then the reaction is heated to 70° C. and AIBN (8 g) is added. The reaction is allowed to proceed for 12 hours, after which the heating is stopped. The reaction mixture is then coagulated in 3000 mL in which 50 g of K.sub.2CO.sub.3 is added. The coagulated polymer is then washed with water (3,000 mL) and then washed twice with methanol (3,000 mL) and then dried at 110° C.

[0270] Characterization

[0271] GPC: Mn=4,603 g/mol, Mw=8,038 g/mol, PDI=1.75

[0272] TGA: 190° C.

[0273] DSC: 470° C.

[0274] Amine groups: 369 μeq/g

[0275] IX. Preparation of Functionalized PSU Copolymer (P1-E)

[0276] The functionalized PSU polymer (P1-E) was prepared according to the following procedure according to Scheme 9.

[0277] The carboxylic acid functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-A (120 g), and thioglycolic acid (13.81 g) are dissolved at room temperature in NMP (285 g). The reaction mixture is purged with N.sub.2 for at least 45 minutes, then the reaction is heated to 70° C. and AIBN (8.2 g) is added. The reaction is allowed to proceed for 12 hours, after which the heating is stopped. The reaction mixture is then coagulated in 3,000 mL of methanol. The coagulated polymer is then washed twice with methanol (3,000 mL) and then dried at 110° C.

[0278] Characterization

[0279] GPC: Mn=8,065 g/mol, Mw=18,380 g/mol, PDI=2.28

[0280] TGA: 390° C.

[0281] DSC: 162° C.

[0282] Carboxylic acid groups: 315 μeq/g

[0283] X. Preparation of Crosslinked Materials

[0284] The copolymer of Example 13 of U.S. Pat. No. 5,212,264 (Ciba) has been reproduced and crosslinked with different amounts of epoxy compounds.

[0285] 1. Synthesis of the Base Polymer

[0286] First the base polymer G was synthesized using the polymerization procedure explained in the patent.

[0287] Characterisation of the Polymer

[0288] Mw=78284 g/mol, Mn=28497 g/mol, PDI=2.75,

[0289] Chlorine end groups=45.6 ueq/g,

[0290] Phenolic end groups=6 ueq/g,

[0291] Relative viscosity=0.686375

[0292] Tg (DSC)=232.6° C.

[0293] 2. Chain Extension Using Bisphenol a Diglycidyl Ether (BGEBPA)

[0294] Procedure: Take 160.71 g of the reaction mixture of the DPS polymerization reaction (which contains 75 g of polymer), in a 500 mL round bottom flask with an overhead stirrer and strong N.sub.2 inflow. Heat the reaction mixture to 150° C. and then dropwise add 1.65 g of BGEBPA. Keep stirring this at 150° C. for 2 hours and then pour it on to a metal tray and crush it once it is cool. Dissolve the residue in the beaker with say 50 mL of NMP. Combine the residue and washings and then wash it three times with (acetone/water=80/20; 1 wash with water). Concentrated acetic acid is added during the aqueous extraction to liberate the OH end groups.

[0295] Characterisation of the Polymer

[0296] Mw=79,511 g/mol, Mn=32,458 g/mol, PDI=2.45,

[0297] Chlorine end groups=92.6 μeq/g,

[0298] Phenolic end groups=12.4 μeq/g,

[0299] Aliphatic side-chain hydroxyl groups (theoretical): 100.89 μeq/g

[0300] Tg (DSC)=226.73° C.

[0301] Relative viscosity=0.68481

[0302] 3. Crosslinking of the Above Polymer with Araldite® MY 0510

[0303] Procedure: Dissolve 46 mg of Araldite® MY 0510 in 2 g of methylene chloride and then add it to 5 g of the chain extended PPSU. Shake this mixture so that the polymer is uniformly coated with the epoxy solution. Leave it to dry over 48 h in the hood at RT. Crosslink at 150° C. for 12 hours.

[0304] Results: When the above polymer is crosslinked with equimolar N,N-Diglycidyl-4-glycidyloxyaniline the Tg of the resultant crosslinked material was 229.16° C. This was an increase of 2.39° C. as compared to the uncrosslinked base polymer.

[0305] 4. Crosslinking of the Copolymer P1-C of the Present Invention

[0306] Characterization of the Copolymer P1-C:

[0307] GPC: Mn=3,321 g/mol, Mw=6,130 g/mol, PDI=1.85

[0308] TGA: 302° C.

[0309] DSC: 170.3° C.

[0310] Amine groups (aliphatic amine side chain+aromatic amine end groups): 900 μeq/g

[0311] When the above polymer is crosslinked with equimolar amounts N,N-Diglycidyl-4-glycidyloxyaniline, the Tg of the resultant crosslinked material was 176.91° C. This was an increase of 6.61° C. as compared to the uncrosslinked base polymer.

[0312] The crosslinking experiment shows that the copolymer of the present invention has a denser network structure upon crosslinking as compared to the copolymer structure described in the prior art. This is attributed to the high concentrations of side-chain functional groups in the copolymer of the present invention, as compared to the copolymer described in U.S. Pat. No. 5,212,264 (Ciba). These copolymers depend upon an end-group chemistry which lead to copolymers having a reactivity which cannot be compared to the side-chain functionalization strategy of the present invention.

##STR00010##

##STR00011##

##STR00012##

##STR00013##

##STR00014##

##STR00015##

##STR00016##

##STR00017##

##STR00018##