GRAFT POLYARYLETHER COPOLYMERS

Abstract

The invention relates to a graft polyarylether (PAE) copolymer (P1), a process for preparing the graft PAE copolymer (P1) from a side-chain allyl/vinylene-functionalized PAE copolymer (P0) via free radical reaction with vinyl pyrrolidone, and the use of the graft PAE copolymer (P1) in the preparation of an article, such as a membrane or a part thereof. The graft PAE copolymer (P1) comprises at least two types of recurring units, one of which having side-chain grafted poly(vinylpyrrolidone). The invention also relates to an amorphous side-chain allyl/vinylene-functionalized polyaryletherketone copolymer (P0).

Claims

1. A graft polyarylether (PAE) copolymer (P1) comprising: collectively at least 50 mol. % of sulfone recurring units (R.sub.P1a) of formula (M1) and functionalized sulfone recurring units (R*.sub.P1a) of formula (N1), said mol. % being based on the total number of moles of recurring units in the graft PAE copolymer (P1): ##STR00029## or collectively at least 50 mol. % of ketone recurring units (R.sub.P1b) of formula (M2) and functionalized ketone recurring units (R*.sub.P1b) of formula (N2), said mol. % being based on the total number of moles of recurring units in the graft PAE copolymer (P1): ##STR00030## wherein the molar ratio of recurring units (R.sub.P1a)/recurring units (R*.sub.P1a) or recurring units (R.sub.P1b)/recurring units (R*.sub.P1b) is at least 1/5 and at most 100/1; and 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 0 or an integer from 1 to 4; T is selected from the group consisting of a bond; C(CH.sub.3).sub.2; SO.sub.2; O; S; C(O); C(CF.sub.3).sub.2; C(CCl.sub.2); C(CH.sub.3)(CH.sub.2CH.sub.2COOH); NN; and R.sub.aCCR.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 the following formulae (G.sub.N1) to (G.sub.N10) and any combinations thereof: ##STR00031## ##STR00032## in which W in the group G.sub.N is selected from the group consisting of a bond, SO.sub.2, C(CH.sub.3).sub.2 and any combination thereof, each k in the group G.sub.N is independently 0 or an integer from 1 to 4; the two grafted polymers P.sub.2 in the group G.sub.N, being the same or different from each other, are grafted poly(vinylpyrrolidone) polymers (PVP); and the two I in the group G.sub.N, being the same or different from each other, represent a fragment of a free radical initiator and/or a fragment of a PVP polymer.

2. The graft polyarylether copolymer (P1) of claim 1, wherein the sulfone recurring units (R.sub.P1a) is of formula (M1a), (M1b), or (M1c): ##STR00033## 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; and each i is independently 0 or an integer from 1 to 4.

3. The graft polyarylether copolymer (P1) of claim 1, wherein i is zero for each R.sub.1.

4. The graft polyarylether copolymer (P1) of claim 1, wherein the ketone recurring units (R.sub.P1b) is of formula (M2a): ##STR00034##

5. The graft polyarylether copolymer (P1) of claim 1, comprising collectively at least 80 mol. % of sulfone recurring units (R.sub.P1b) and (R*.sub.P1b) or ketone recurring units (R.sub.P1a) and (R*.sub.P1a), said mol. % being based on the total number of moles of recurring units in the graft PAE copolymer (P1).

6. The graft polyarylether copolymer (P1) of claim 1, wherein k is 0 in recurring units (R*.sub.P1a) or (R*.sub.P1b).

7. The graft polyarylether copolymer (P1) of claim 1, wherein the molar ratio of sulfone recurring units (R.sub.P1a)/recurring units (R*.sub.P1a) or ketone recurring units (R.sub.P1b)/recurring units (R*.sub.P1b) is from 1/4 to 50/1.

8. The graft polyarylether copolymer (P1) of claim 1, wherein each of the grafted polymer P.sub.2 in the group G.sub.N of any of the formulae (G.sub.N1) to (G.sub.N10) in recurring units (R*.sub.P1a) or (R*.sub.P1b) comprises at least 50 mol. % of recurring units Rp of formula (P): ##STR00035## said mol. % being based on the total number of recurring units of the grafted polymer P.sub.2, in which n in formula (P) is an integer of at least 3 and at most 200.

9. The graft polyarylether copolymer (P1) of claim 1, not being crosslinked.

10. The graft polyarylether copolymer (P1) of claim 1, containing less than 2 wt % of free vinyl pyrrolidone or free poly(vinyl pyrrolidone), based on the total weight of the graft PAE polymer (P1).

11. An amorphous side-chain olefin functionalized polyaryletherketone copolymer (P0) comprising: collectively at least 50 mol. % of ketone recurring units (R.sub.P0b) of formula (M2) and functionalized ketone recurring units (R*.sub.P0b) of formula (N0), said mol. % being based on the total number of moles of recurring units in the copolymer (P0): ##STR00036## 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 0 or an integer from 1 to 4; G.sub.P is selected from the group consisting of at least one of the following formulae (G.sub.P1), (G.sub.P2) and (G.sub.P3): ##STR00037## wherein W in the group G.sub.P is selected from C(CH.sub.3).sub.2 and/or a bond; each k in the group G.sub.P is independently 0 or an integer from 1 to 4; and wherein the molar ratio of ketone recurring units (R.sub.P0b)/recurring units (R*.sub.P0b) is at least 1/5 and at most 100/1.

12. (canceled)

13. A process for preparing the graft polyarylether copolymer (P1) of claim 1, comprising: reacting, in a solvent S.sub.1, a side-chain allyl/vinylidene-functionalized polyarylether copolymer (P0) with vinyl pyrrolidone monomer in the presence of at least one free radical initiator, to form the graft polyarylether copolymer (P1); and removing any free poly(vinyl pyrrolidone) and optionally any unreacted vinyl pyrrolidone monomer and/or unreacted free radical initiator from the formed graft PAE copolymer (P1) to generate a purified the graft PAE copolymer (P1), wherein the allyl/vinylidene-functionalized polyarylether copolymer (P0) comprises: collectively at least 50 mol. % of sulfone recurring units (R.sub.P0a) of formula (M1) and functionalized sulfone recurring units (R*.sub.P0a) of formula (N0), said mol. % being based on the total number of moles of recurring units in the copolymer (P0): ##STR00038## or collectively at least 50 mol. % of ketone recurring units (R.sub.P0b) of formula (M2) and functionalized ketone recurring units (R*.sub.P0b) of formula (N0), said mol. % being based on the total number of moles of recurring units in the copolymer (P0): ##STR00039## 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 0 or an integer from 1 to 4; T is selected from the group consisting of a bond; C(CH.sub.3).sub.2; SO.sub.2; O; S; C(O); C(CF.sub.3).sub.2; C(CCl.sub.2); C(CH.sub.3)(CH.sub.2CH.sub.2COOH); NN; and R.sub.aCCR.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 (G.sub.P1), (G.sub.P2) and (G.sub.P3): ##STR00040## wherein W in the group G.sub.P is selected from the group consisting of a bond, C(CH.sub.3).sub.2, SO.sub.2 and any combination thereof; each k in the group G.sub.P is independently 0 or an integer from 1 to 4; and wherein the molar ratio of sulfone recurring units (R.sub.Poa)/recurring units (R*.sub.POa) or ketone recurring units (R.sub.P0b)/recurring units (R*.sub.P0b) is at least 1/5 and at most 100/1; and wherein the number of moles of functionalized recurring units (R*.sub.POa) or (R*.sub.P0b) in the PAE copolymer (P0) used in the reaction mixture is n.sub.1; the number of moles of vinyl pyrrolidone monomer used in the reaction mixture is n.sub.2, and the molar ratio n.sub.2/n.sub.1 is at least 3 and at most 200.

14. The process of claim 13, wherein the reacting step is carried out with at least one of the following conditions: in the presence of 2,2-Azobis(2-methylpropionitrile) (AIBN) or 2,2-azobis(2,4-dimethylvaleronitrile (ADVN) as at least one free radical initiator; and/or the solvent S.sub.1 being a polar aprotic solvent selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMS02), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfone or sulfolane), 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 mixtures thereof; and/or at a reaction temperature from 10 C. to 200 C.; and/or in the absence of a crosslinking agent, in the absence of radiation and/or in the absence of radiation initiator.

15. A method for preparing an article, comprising forming the article from a solution comprising the graft polyarylether copolymer (P1) of claim 1.

16. An article comprising the graft polyarylether copolymer (P1) of claim 1.

17. The article according to claim 16, being selected from the group consisting of membranes; fibers; sheets; solution processed films; and solution processed monofilaments.

18. The article according to claim 16, being a membrane or a part of a membrane, said membrane being selected from the group consisting of proton exchange membranes, membranes for bioprocessing, hemodialysis membranes, membranes for food and beverage filtration, and membranes for water purification.

19. The graft polyarylether copolymer (P1) of claim 1, wherein T is selected from the group consisting of a bond, C(CH.sub.3).sub.2 and SO.sub.2.

20. The graft polyarylether copolymer (P1) of claim 1, wherein the molar ratio of sulfone recurring units (R.sub.P1a)/recurring units (R*.sub.P1a) or ketone recurring units (R.sub.P1b)/recurring units (R*.sub.P1b) is from 1/3 to 40/1.

Description

EXAMPLES

Raw Materials

[0287] K.sub.2CO.sub.3 (potassium carbonate), available from Armand products [0288] daBPA (2,2-diallyl Bisphenol A), available from Sigma-Aldrich, U.S.A. [0289] DCDPS (4,4-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers [0290] DHDPS (4,4-dihydroxydiphenyl sulfone or Bisphenol S), available from Konishi chemicals, Japan. [0291] DFBP (4,4-difluorobenzophenone), available from Sigma-Aldrich, U.S.A. [0292] Resorcinol, available from Sigma-Aldrich, U.S.A. [0293] DMAc (dimethylacetamine), available from Sigma-Aldrich, U.S.A. [0294] NMP (2-methyl pyrrolidone), available from Sigma-Aldrich, U.S.A. [0295] Sulfolane, available from Chevron Phillips [0296] AIBN (azobisisobutyronitrile), available from Sigma-Aldrich, U.S.A. [0297] Vinyl pyrrolidone (VP), available from Sigma-Aldrich, U.S.A. [0298] Methanol, available from Sigma-Aldrich, U.S.A. [0299] Ethyl acetate, available from Sigma-Aldrich, U.S.A.

Test Methods

GPC Method 1 for Measuring Molecular Weight (Mn, Mw)

[0300] Instrument: Waters 515 pump, Waters 717plus autosampler, Waters 2487 Absorbance Detector, Waters 2414 Refractive Index Detector [0301] Columns: Two Agilent PLgel MiniMix-D, 5 um, 2504 mm (Part #PL1510-5504)+Agilent Mix Guard, 5 um, 504.6 mm (Part #PL1510-1504) [0302] Column Temperature: 45 C [0303] Mobile Phase: N,N-Dimethylacetamide+0.1M LiBr [0304] Flow Rate: 0.3 ml/min [0305] Injection Volume: 20 ul [0306] UV Detection: 270 nm [0307] RI Detection: +polarity [0308] Calibration: Agilent EasiCal PS-2 GPC/SEC Standards (Part #PL2010-0601). Standards are dissolved in Mobile Phase.

[0309] Sample Preparation: Weigh 30 mg of sample into a 20 ml glass vial with PTFE lined cap. Add 5 mL of DMAC Mobile Phase. Heat to 105 C with stirring to complete dissolution. Filter through 0.2 um PTFE syringe filter into a 4 ml autosampler vial

GPC Method 2 for measuring Molecular weight (Mn, Mw)

[0310] 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 L 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.

Thermal Gravimetric Analysis (TGA)

[0311] 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.

.SUP.1.H NMR

[0312] .sup.1H NMR spectra were measured using a 400 MHz Bruker spectrometer with TCE as the deuterated solvent. All spectra are reference to residual proton in the solvent.

DSC

[0313] 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.

[0314] 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

[0315] 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.

FTIR

[0316] Because the vinyl pyrrolidone is a liquid and highly water soluble and because of the extensive washing, filtration and drying of the graft copolymer (P1) samples, there should be non-detectable free vinyl monomer in the dried sample of graft copolymer (P1). Nonetheless, free residual vinyl monomer can be detected by FTIR using a Bruker Optics Vertex 70 FTIR Bench with MIR source. The spectra were obtained in absorption mode across a diamond ATR crystal.

[0317] The procedure for FTIR analysis for the referenced samples was as follows: [0318] a background spectrum was established with fresh 18 megohm water; [0319] a drop of polymer sample was applied to the ATR crystal to ensured its complete coverage; [0320] 32 replicate scans of the spectrum were gathered to produce an average response; [0321] the following correction to each spectrum was applied: [0322] Extended ATR correction for Diamond [0323] Atmospheric correction for water and CO.sub.2 [0324] Baseline correctionNormalize all spectra together based on their Max-min peak values. [0325] the normalized spectra were overlaid; and [0326] the peak heights at 1641 cm.sup.1 were visually compared.

I. Preparation of Side Chain Allyl/Vinylene-Functionalized PAES Copolymer (P0-A)

[0327] The PAES copolymer (P0-A) was prepared according to Scheme 1.

[0328] To generate the recurring units (R.sub.P0a), 4,4-dichlorodiphenyl sulfone (DCDPS) and 4,4-dihydroxydiphenyl sulfone or Bisphenol S (DHDPS) were used while diallyl bisphenol A (daBPA) and DCDPS were used to generate the recurring units (R*.sub.P0a). The target mol. % for recurring units (R*.sub.P0a) in the side-chain allyl/vinylene-functionalized polymer (P0-A) was 9.1 mol. % to achieve a molar ratio of recurring units (R.sub.P0a)/recurring units (R*.sub.P0a) of 10:1. That is to say, the value n in Scheme 1 for the main recurring unit (R.sub.P0a) should be about 90.9 mol. %, and the combined values: m1+m2+m3 for the three illustrated functionalized recurring units (R*.sub.P0a) should be 9.1 mol. %, said mol. % being based on the total number of moles of recurring units in the PAES copolymer (P0-A).

[0329] The polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1594.2 g, 6.37 moles) and daBPA (197.25 g; 0.64 mole) were added to the vessel first, followed by the addition of potassium carbonate (977.14 g; 7.07 moles) and NMP (4018.9 g).

[0330] The reaction mixture was heated from room temperature to 190 C. using a 10 C./min heating ramp. The temperature of the reaction mixture was maintained for around six hours, depending upon the viscosity of the solution. The reaction was terminated by adding excess DCDPS (140.7 g) thereby allowing the DCDPS to end cap the polymer for another 30 minutes and then stopping the heat. The reaction mixture was filtered, coagulated into methanol. The polymer was then washed with methanol and water and again with methanol and dried at 110 C.

Characterization of the PAES Copolymer (P0-A)

GPC Method 2:

[00001]$\begin{array}{c}{M}_w=58566g/\mathrm{mol},M_n=21327g/\mathrm{mol},\mathrm{PDI}=2.75\\ \mathrm{TGA}:488C.\\ \mathrm{DSC}:\mathrm{Tg}=218C.\end{array}$

[0331] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2-diallyl bisphenol A monomer in the polymer (P0-A).

[0332] The estimated olefin content measured by .sup.1H NMR was 8.97 mol %. This value provided an actual molar ratio of recurring units (R.sub.P0a)/recurring units (R*.sub.P0a) of 10.15:1. The actual value n in Scheme 1 for the main recurring unit (R.sub.P0a) of PAES copolymer (P0-A) was 91.03 mol. %.

II. Preparation of Graft PAES Copolymer (P1-A) by Free Radical Reaction

[0333] The graft PAES copolymer (P1-A) was prepared according to Scheme 2. The actual value n in Scheme 2 for the main recurring unit (R.sub.P1a) in PAES copolymer (P1-A) was 91.03 mol. %, same as PAES copolymer (P0-A).

[0334] The reaction took place in a 2-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. A sample of the side chain allyl/vinylene-functionalized PAES copolymer (P0-A) (64 g containing 0.024 moles of olefinic double bonds) and vinyl pyrrolidone (184.32 g; 1.658 moles) were added to the reactor and this mixture was dissolved in anhydrous NMP (1727 g) and heated to 65 C. The molar ratio of number of moles of vinyl pyrrolidone monomer to the number of moles of the functionalized recurring units in the PAES copolymer (P0-A) was 69.1. The reaction was purged with nitrogen for 30 minutes and then AIBN (2.34 g) was added in a single portion. The reaction was allowed to continue for 12 hours at 65 C. After 12 hours, the reaction mixture was cooled and about 70-80% of the solvent distilled off under reduced pressure. The copolymer (P1-A) was isolated by coagulating in ethyl acetate and the copolymer (P1-A) was washed repeatedly with hot water until no free polyvinyl pyrrolidone was detected in the water washes via FTIR. The purified copolymer (P1-A) was dried at 100 C. under high vacuum.

Characterization of Graft Polyarylethersulfone Copolymer (P1-A)

GPC Method (RI Detector):

[00002]$\begin{array}{c}\mathrm{Mn}=80752g/\mathrm{mol},\mathrm{Mw}=672825g/\mathrm{mol}=8.3\\ \mathrm{DSC}:\mathrm{Tg}=209C.\\ \mathrm{TGA}:414C.\end{array}$

[0335] The estimation of mol % of PVP in the copolymer (P1-A) was analyzed by .sup.1H NMR in deuteriated TCE solvent by integrating the peaks attributed to polyvinylpyrrolidone attached to the polyarylethersulfone using the following equation:

[00003]$\mathrm{mol}\mathrm{PVP}=\frac{\frac{\left(\mathrm{PVP}-\mathrm{PSU}\right)}{\#H\mathrm{PVP}}}{\left(\frac{\left(\mathrm{PVP}-\mathrm{PSU}\right)}{\#H\mathrm{PVP}}+\frac{\mathrm{PSU}}{\#H\mathrm{PSU}}\right)}$

in which PVP and PSU would denote the sum of all the hydrogen protons of PVP and PSU signals respectively; and in which #H PVP and #H PSU denote the number of protons corresponding to the PVP and PSU molecules, respectively. Then, the PVP weight content (wt. %) in the graft polyarylethersulfone copolymer (P1-A) sample was calculated based on the following equation:

[00004]$\begin{array}{cc}\mathrm{wt}.\%\mathrm{PVP}=\left(\left(\mathrm{mol}\mathrm{PVP}\right)\left(\mathrm{molecular}\mathrm{weight}\mathrm{PVP}\right)\right)/\left(\left(g\mathrm{PVP}+g\mathrm{PSU}\right)\right),& \left(100\right)\end{array}$

in which the mol PVP was measured by .sup.1H NMR as described above; the molecular weight of PVP was 111.1 g/mol and the denominator term: (g PVP+g PSU) was the weight of the graft polyarylethersulfone copolymer (P1-A) sample used for .sup.1H NMR analysis.

[0336] .sup.1H NMR: 56.2 wt. % PVP

III. Preparation of Side Chain-Allyl/Vinylene-Functionalized PAEK Copolymer (P0-B)

[0337] The PAEK copolymer (P0-B) was prepared according to the Scheme 3.

[0338] To generate the recurring units (R.sub.P0b), 4,4-difluorobenzophenone (DFBP) and resorcinol were used, while to generate the recurring units (R*.sub.P0b), diallyl bisphenol A (daBPA) and DFBP were used. The target mol. % for recurring units (R*.sub.P0b) in the side-chain allyl/vinylene-functionalized polymer (P0-B) was 60 mol. % to achieve a molar ratio of recurring units (R.sub.P0b)/recurring units (R*.sub.P0b) of 2:3. That is to say, the value n in Scheme 3 for the main recurring unit (R.sub.P0b) should be about 40 mol. %, and the value 1-n for the functionalized recurring units (R*.sub.P0b) should be 60 mol. %, said mol. % being based on the total number of moles of recurring units in the PAEK copolymer (P0-B).

[0339] The polymerization took place in a 1-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers: DFBP (283.66 g; 1.3 moles), resorcinol (57.25 g; 0.52 mole) and daBPA (240.55 g; 0.78 mole) were added to the vessel first, followed by the addition of potassium carbonate (188.64 g; 1.365 moles) and sulfolane (1235 g). The reaction mixture was heated from room temperature to 210 C. using a 15 C./mi heating ramp. The temperature of the reaction mixture was maintained for around five hours, depending upon the viscosity of the solution. The reaction was terminated by stopping the heat to the reactor vessel and by diluting with cold sulfolane. The reaction mixture was filtered; the PAEK copolymer (P0-B) was coagulated into methanol and then dried at 110 C.

Characterization of PAEK Copolymer (P0-B)

GPC Method (RI Detector):

[00005]$\begin{array}{c}\mathrm{Mw}=54998g/\mathrm{mol},\mathrm{Mn}=17477g/\mathrm{mol},\mathrm{PDI}=3.14\\ \mathrm{TGA}:428C.\\ \mathrm{DSC}:\mathrm{Tg}=121C.\end{array}$

[0340] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2-diallyl bisphenol A monomer in the polymer (P0-B).

[0341] The estimated olefin content measured by .sup.1H NMR was 65.6 mol %. This value provided an actual molar ratio of recurring units (R.sub.P0b)/recurring units (R*.sub.P0b) of 0.52:1. The actual value n in Scheme 3 for the main recurring unit (R.sub.P0b) in PAEK copolymer (P0-B) was 34.6 mol. %.

[0342] The PAEK copolymer (P0-B) was amorphous, as there was no Tm observed via DSC.

IV. Preparation of Graft PAEK Copolymer (P1-B) by Free Radical Reaction

[0343] The graft PAEK copolymer (P1-B) was prepared according to Scheme 4. The actual value n in Scheme 4 for the main recurring unit (R.sub.P1b) in PAEK copolymer (P1-B) was 34.6 mol. %, same as PAEK copolymer (P0-B).

[0344] The reaction took place in a 2-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. A sample of the allyl/vinylene-functionalized PAEK copolymer (P0-B) (12.2 g containing 0.035 moles of unsaturated groups) and vinyl pyrrolidone (268 g; 2.41 moles) were added to the reactor vessel, and the mixture was dissolved in anhydrous NMP (1588 g) and heated to 65 C. The molar ratio of number of moles of vinyl pyrrolidone monomer to the number of moles of the functionalized recurring units in the amorphous PAEK copolymer (P0-B) was 69:1. The reaction vessel was purged with nitrogen for 30 minutes, and then AIBN (3.35 g) was added in a single portion. The reaction was allowed to continue for 12 hours at 65 C. After this period of 12 hours, the reaction mixture was cooled, and about 70-80% of the NMP solvent distilled off under reduced subatmospheric pressure. The PAEK copolymer (P1-B) was isolated by coagulating in ethyl acetate. The graft PAEK copolymer (P1-B) precipitate was washed repeatedly with hot water until no free polyvinyl pyrrolidone was detected in the water washes via FTIR. The purified graft PAEK copolymer (P1-B) was dried at 100 C. under high vacuum.

Characterization of Graft PAEK Copolymer (P1-B)

GPC Method (RI Detector):

[00006]$\begin{array}{c}\mathrm{Mw}=309148g/\mathrm{mol},\mathrm{Mn}=47468g/\mathrm{mol},\mathrm{PDI}=6.5\\ \mathrm{TGA}:411C\\ \mathrm{DSC}:\mathrm{Tg}=126C.\end{array}$

[0345] Nitrogen content: 9.89 wt. %

[0346] The nitrogen content came from the PVP attached to the parent polyarylether polymer (P0-B) and was measured by elemental analysis for which the method was described above.

[0347] The graft PAEK copolymer (P1-B) was amorphous, as there was no Tm observed via DSC.

[0348] 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.

##STR00025##

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##STR00028##