PROCESS FOR MODIFYING AN AROMATIC POLYETHER BACKBONE AND A MODIFIED POLYETHER OBTAINED BY THIS PROCESS

Abstract

It is provided a process for modifying an aromatic polyether backbone for obtaining a modified polyether comprising the steps of: a) providing the at least one aromatic polyether to be modified in dissolved state in an inert organic solvent, b) adding at least one modification reagent, c) adding at least one catalyst, d) carrying out the process until a desired degree of functionalization of said aromatic polyether backbone is reached, e) recovery of the modified aromatic polyether.

Claims

1. A process for modifying an aromatic polyether backbone, in particular for modifying an aromatic moiety of the aromatic polyether backbone, for obtaining a modified polyether comprising the steps of: a) providing at least one aromatic polyether to be modified in dissolved state in an inert organic solvent, b) adding at least one modification reagent, c) adding at least one catalyst, wherein the at least one catalyst is a boron trifluoride complex; d) carrying out the process until a desired degree of functionalization of said aromatic polyether backbone is reached, e) recovery of the modified aromatic polyether.

2. The process according to claim 1, wherein after step b) at least one second modification reagent is added.

3. The process according to claim 1, wherein prior to step e) at least one catalyst quencher is added.

4. The process according to claim 1, wherein at least one catalyst scavenger is added prior to step e).

5. The process according to claim 1, wherein prior to step e) both catalyst quencher and catalyst scavenger are added.

6. The process according to claim 1, wherein prior to step e) the reaction solvent replaced by workup solvent.

7. The process according to claim 1, wherein said aromatic polyether comprises at least one of the following repeating units: ##STR00061## wherein R.sup.a and R.sup.b represent substituents on the benzene ring and each independently comprises alkyl, -aryl, or -arylene-alkyl.

8. The process according to claim 1, wherein the inert organic solvent is selected from the group consisting of halogenated hydrocarbons, halogenated aromatics, nitroalkanes, nitroaromatics or mixture thereof.

9. The process according to claim 1, wherein the catalyst is selected from the group consisting of complexes of boron trifluoride with: ethers (dimethyl ether, diethyl ether, di-n-butyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, isopropyl acetate, methyl benzoate, ethyl benzoate, dimethyl succinate, methyl p-toluate, etc.), alcohols (methanol, ethanol, n-butanol, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, etc.), chloroalkanes (dichloromethane, 1,2-dichloroethane, etc.), nitroalkanes (nitromethane, nitroethane, 1-nitropropane, etc.), haloaromatics (chlorobenzene, chlorotoluene, bromobenzene, fluorobenzene, 1,2-difluorbenzene, hexafluorobenzene, alpha,alpha,alpha-trifluorotoluene, etc.), nitroaromatics (nitrobenzene, nitrotoluene, etc.), nitriles (acetonitrile, propionitrile, isobutyronitrile, benzonitrile, etc.), carboxylic acids (acetic acid, propionic acid, pivalic acid, benzoic acid, malonic acid, succinic acid, etc.), sulfonic acids (methanesulfonic acid, benzenesufonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.), water (monohydrate, dihydrate), sulfones (tetramethylene sulfone, dimethyl sulfone, diethyl sulfone, etc.), sulfoxides (dimethyl sulfoxide, diethyl sulfoxide, etc.), thioethers (methyl sulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, tetrahydrothiophene), mineral acids (phosphoric acid, sulfuric acid, etc.) any derivative thereof, and any combination thereof.

10. The process according to claim 1, wherein the catalyst quencher is selected from the group consisting of alkyl phosphates (trimethyl phosphate, triethyl phosphate, tributyl phosphate, etc.), carboxylic acid amides, (dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, N-butyl pyrrolidone, etc.), ureas (dimethylethylene urea, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, etc.), any derivative thereof, and any combination thereof.

11. The process according to claim 1, wherein the scavenger is selected from the group consisting of hydrofluoric acid salts (ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, rubidium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, etc.), sulfuric acid salts (sodium sulfate, potassium sulfate, etc.), phosphoric acid salts (trisodium phosphate, tripotassium phosphate, etc.), pyrophosphoric acid salts (sodium pyrophosphate, potassium pyrophosphate, etc.), any derivative thereof, and any combination thereof.

12. The process according to claim 1, wherein the at least one modifying reagent is selected from a group of compounds of the general structure 1 (GS1)
Fn-Sp-Lg(GS1) wherein Fn is functional moiety selected from structures of General formula 1 (GF1), or General formula 2 (GF2), or General formula 3 (GF3), or General formula 4 (GF4), or General formula 5 (GF5): ##STR00062## wherein Sp is spacing moiety selected from structure of General formula 6 (GF6): ##STR00063## wherein Lg is a leaving group moiety selected from structures of General formula 7 (GF7), or General formula 8 (GF8), or General formula 9 (GF9), or General formula 10 (GF10), or General formula 5 (GF5): ##STR00064## in which: W comprises CO (carbonyl) or SO.sub.2 (sulfonyl) group; X comprises NR.sup.111 (R.sup.111 selected from hydrogen or the group consisting of lower alkyl (C.sub.1-C.sub.10), O (oxygen), or direct bond; R.sup.11comprises (selected from) alkyl, heteroalkyl, -aryl, -arylene-alkyl, -alkylene-aryl, or -alkylene-arylene-alkyl (optionally substituted); R.sup.12comprises hydrogen or the group consisting of lower alkyl (C.sub.1-C.sub.10); Y comprises NR.sup.111, O (oxygen), or methylene group (optionally substituted); n represents an integer of 1 to 4; R.sup.13 and R.sup.14 independently each other comprises hydrogen, COOH, COOR.sup.111, CON(R.sup.111).sub.2, or the group consisting of lower alkyl (C.sub.1-C.sub.10); R.sup.21represents a substituent on the benzene ring and each independently comprises halo group, cyano group, trifluoromethylsulfonyl group, nitro group, trihalomethyl group, keto group, formyl group, carboxyl group, alkoxycarbonyl group, aminocarbonyl group, sulfonyl group, sulfonamide group; and m represents an integer of 0 to 4; Z comprises NH or O (oxygen).

13. A modified polyether obtainable in a process according to claim 1, wherein the at least one of the aromatic moieties in the polyether backbone is modified with at least one of the following groups having one of the general structure 2 (GS2):
Fn-Sp-Polyether(GS2) wherein Fn and Sp have the following meanings: Fn is functional moiety selected from structures of General formula 1 (GF1), or General formula 2 (GF2), or General formula 3 (GF3), or General formula 4 (GF4), or General formula 5 (GF5): ##STR00065## Sp is spacing moiety selected from structure of General formula 6 (GF6): ##STR00066##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0195] The solution is explained in more detail by means of the following Examples with reference to the Figures.

[0196] FIG. 1 shows a first embodiment of the process according to the solution.

[0197] FIG. 2 shows a second embodiment of the process according to the solution.

[0198] FIG. 3 shows a third embodiment of the process according to the solution.

[0199] FIG. 4 shows a fourth embodiment of the process according to the solution.

[0200] FIG. 5 shows a fifth embodiment of the process according to the solution.

DETAILED DESCRIPTION

[0201] The schemes of FIGS. 1-5 illustrate different alternatives of the present process.

[0202] FIG. 1 illustrates a first variant of the process of the solution with the steps of: [0203] (1) providing a polymer in a solvent system adapted to maintain the polymer in a dissolved state; [0204] (2) adding of a modification reagent; [0205] (3) adding of an appropriate catalyst to the solution of the step (2); [0206] (4) reacting of said modification reagent with the polymer until the reaction is completed; [0207] (5) adding of an appropriate catalyst scavenging reagent to the solution of the step (4); [0208] (6) recovery of the solid scavenged catalyst from the solution of the step (5); [0209] (7) recovery of the modified polymer from the solution of the step (6).

[0210] FIG. 2 illustrates a second variant of the process of the solution with the steps of: [0211] (1) providing a polymer in a solvent system adapted to maintain the polymer in a dissolved state; [0212] (2) adding of a modification reagent; [0213] (3) adding of an appropriate catalyst to the solution of the step (2); [0214] (4) reacting of said modification reagent with polymer until the reaction is completed; [0215] (5) adding of an appropriate catalyst quenching reagent to the solution of the step (4); [0216] (6) adding of an appropriate catalyst scavenging reagent to the solution of the step (5); [0217] (7) recovery of the solid scavenged catalyst from the solution of the step (6); [0218] (8) recovery of the modified polymer from the solution of the step (7).

[0219] FIG. 3 illustrates a third variant of the process of the solution with the steps of: [0220] (1) providing a polymer in a solvent system adapted to maintain the polymer in a dissolved state; [0221] (2) adding of a first modification reagent; [0222] (3) adding of a second (third, fourth, etc.) modification reagent; [0223] (4) adding of an appropriate catalyst to the solution of the step (3); [0224] (5) reacting of said modification reagents with the polymer until the reaction is completed; [0225] (6) adding of an appropriate catalyst scavenging reagent to the solution of the step (5); [0226] (7) recovery of the solid scavenged catalyst from the solution of the step (6); [0227] (8) recovery of the modified polymer from the solution of the step (7).

[0228] FIG. 4 illustrates a fourth variant of the process of the solution with the steps of: [0229] (1) providing a polymer in a solvent system adapted to maintain the polymer in a dissolved state; [0230] (2) adding of a first modification reagent; [0231] (3) adding of a second (third, fourth, etc.) modification reagent; [0232] (4) adding of an appropriate catalyst to the solution of the step (3); [0233] (5) reacting of said modification reagents with polymer until the reaction is completed; [0234] (6) adding of an appropriate catalyst quenching reagent to the solution of the step (5); [0235] (7) adding of an appropriate catalyst scavenging reagent to the solution of the step (6); [0236] (8) recovery of the solid scavenged catalyst from the solution of the step (7); [0237] (9) recovery of the modified polymer from the solution of the step (8).

[0238] FIG. 5 illustrates a fifth variant of the process of the solution with the steps of: [0239] (1) providing a polymer in a solvent system adapted to maintain the polymer in a dissolved state; [0240] (2) adding of a first modification reagent; [0241] (3) adding of a second (third, fourth, etc.) modification reagent; [0242] (4) adding of an appropriate catalyst to the solution of the step (3); [0243] (5) reacting of said modification reagents with polymer until the reaction is completed; [0244] (6) adding of an appropriate catalyst quenching reagent to the solution of the step (5); [0245] (7) adding of an appropriate catalyst scavenging reagent to the solution of the step (6); [0246] (8) recovery of the solid scavenged catalyst from the solution of the step (7); [0247] (9) exchange the reaction solvent with a workup solvent from the solution of the step (8); [0248] (10) recovery of the modified polymer from the solution of the step (9).

[0249] The following are non-limiting examples illustrating the process of a chemical modification of a polysulfone backbone. The following procedures provide exemplary methods for chemical modification of polysulfone backbone and other synthetic methods used in the solution. More specific methods are given below in the Examples, which refer to the General Procedure A. The choices and amount of reagents, catalysts, catalyst scavengers, temperature, reaction times, and other parameters are illustrative but are not considered limiting in any way. Other approaches are contemplated by and within the scope of the claims.

Polysulfone Chemical Modification General Procedure A.

[0250] The following procedure (in accordance to the reaction scheme of FIG. 1) provides a general method for chemical modification of the polysulfone backbone.

[0251] The required amount of polysulfone resin (Ultrason S6010 Natur, BASF SE, Ludwigshafen, Germany) was stirred overnight at room temperature in an appropriate solvent to obtain a clear solution. To each of polymer solutions, a predefined amount of a modification reagent and a catalyst were added. The resulting mixture was incubated at a predefined temperature under gentle stirring. After a certain time of incubation at said temperature, a predefined amount of a finely powdered catalyst scavenger was added to each reaction mixture and incubation was continued for a predetermined time. Then, reaction mixtures were filtrated using a filter-aid and the modified polymers were precipitated by 10 volumes of ethanol. The precipitated polymer samples were thoroughly washed with ethanol and then dried in a vacuum oven at 60? C. for at least 24 hours.

Analytical Methods.

[0252] HPLC-ESI-HRMS and ESI-HRMS were performed on an LTQ Orbitrap XL apparatus, produced by Thermo Scientific (Waltham, MA, USA) coupled to a 1200 HPLC system (Agilent Technologies, Santa Clara, CA, USA) equipped with Grom-Sil-120-ODS-4-HE C18 column (3 ?m, 2?50 mm, Grace Davison Discovery Sciences, Hollerhecke). The following standard gradient (flow rate 0.3 mL/min, solvent A: Millipore H2O+0.1 HCOOH solvent B: AcN+0.1% HCOOH) was used if not otherwise specified:

[0253] .sup.1H NMR (500 MHz) spectra were recorded on Bruker Avance III 500 MHz spectrometer using CDCl.sub.3 as the solvent and tetramethylsilane as the internal standard.

Degree of Substitution Determination.

[0254] The amount of newly introduced aminomethylene groups was measured using .sup.1H NMR integration of signals corresponding to methylene group protons. The degree of substitution (DS) was calculated using the following equation:

[00001]$\mathrm{DS}=\left(B/A\right).Math.100$ [0255] where Ais the integral number of CH.sub.3 protons on bis-phenol A unit and B is integral of methylene group protons.

##STR00020##

[0256] The average molecular weight and molecular weight distributions were measured by gel permeation chromatography (GPC) technique. An Agilent 1260 Infinity II with a set of two columns of pore sizes of PL-gel 5 ?m MIXED-D 300?7.5 mm was used to determine polymer average molecular weights and polydispersity index (PDI). THF was used as the eluent at a flow rate of 0.8 m/min, and the calibration was carried out using low polydispersity PS standards (Agilent SEC Software2.1.9.34851).

GPS Terms Definitions

[0257] M.sub.n is the number average molar mass and it is the ordinary arithmetic mean. It is determined by measuring the molecular mass of N polymer molecules, summing the masses and dividing by N, as the following equation, where Ni is number of species with molecular weight M.sub.i.

[00002]$\mathrm{Mn}=\frac{.Math.N_i.M_i}{.Math.N_i}$

M.sub.w is the number of weight average molar mass. Some properties are dependent on molecular size, so a larger molecule will have a larger contribution. The weight average molar mass is calculate by the following equation, where W.sub.i is the weight of molecules which have molecular weight M.sub.i.

[00003]$\mathrm{Mw}=.Math.{?}_i.Math.M_i=\frac{.Math.W_i.Math.M_i}{.Math.W_i}=\frac{.Math.N_i.Math.M_i^3}{.Math.N_i.Math.M_i}$

With M.sub.n and M.sub.w, it is possible to calculate polydispersity, dividing M.sub.w by M.sub.n.
M.sub.z is the Z-average molar mass and it is determined with ultracentrifugation. Melt elasticity depends on M.sub.z

[00004]$\mathrm{Mz}=\frac{.Math.N_i.Math.M_i^3}{.Math.N_i.Math.M_i^3}$

M.sub.p is the peak of the molecular weight curve.

Example 1

Synthesis of 2-(hydroxymethyl)isoindoline-1,3-dione

[0258] ##STR00021##

[0259] To a stirred suspension of isoindoline-1,3-dione (110.3 g, 0.75 mol) in distilled water was added formaldehyde solution (37 wt. % in water, 13.3M, contains 10-15% of methanol as stabilizer) and the resulting mixture was stirred for 30 min at ambient temperature. Hereafter, the resulting suspension was refluxed for two hours. After cooling overnight in a refrigerator the product was filtered with suction, washed with ice-cooled water and air-dried. Yield of crude 2-(hydroxymethyl)isoindoline-1,3-dione was 126.4 g (95.1%). Recrystallization from absolute ethyl alcohol yields 122.9 g (97.2%) of original material. The product was used for subsequent acylation as is without further characterization.

Example 2

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl acetate

[0260] ##STR00022##

[0261] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (35.4 g, 0.2 mol) was dissolved in 200 ml of pyridine. Acetic anhydride (22.5 ml, 0.24 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature and then poured into ice-cooled water. The crystalline crude (1,3-dioxoisoindolin-2-yl)methyl acetate was collected by filtration with suction, washed with ice-cooled water and air-dried. Crystallization from absolute ethyl alcohol yields 37.7 g (0.172 mol, 85.9%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl acetate. MS m/z 219.112 [M+H].sup.+ (219.196 calculated).

Example 3

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl propionate

[0262] ##STR00023##

[0263] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (35.4 g, 0.2 mol) was dissolved in 200 ml of pyridine. Propionic anhydride (30.8 ml, 0.24 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature and then poured into ice-cooled water. The crystalline crude (1,3-dioxoisoindolin-2-yl)methyl propionate was collected by filtration with suction, washed with ice-cooled water and air-dried. Crystallization from absolute ethyl alcohol water mixture yields 43.8 g (0.172 mol, 93.9%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl propionate. MS m/z 233.037 [M+H].sup.+ (233.069 calculated).

Example 4

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl isobutyrate

[0264] ##STR00024##

[0265] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (35.4 g, 0.2 mol) was dissolved in 200 ml of pyridine. Isobutyric anhydride (39.8 ml, 0.24 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature and then poured into ice-cooled water. The crystalline crude (1,3-dioxoisoindolin-2-yl)methyl isobutyrate was collected by filtration with suction, washed with ice-cooled water and air-dried. Crystallization from absolute ethyl alcohol water mixture yields 39.4 g (0.159 mol, 79.7%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl isobutyrate. MS m/z 247.031 [M+H].sup.+ (247.084 calculated).

Example 5

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl butyrate

[0266] ##STR00025##

[0267] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (35.4 g, 0.2 mol) was dissolved in 200 ml of pyridine. Isobutyric anhydride (39.4 ml, 0.24 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature and then poured into ice-cooled water. The crystalline crude (1,3-dioxoisoindolin-2-yl)methyl isobutyrate was collected by filtration with suction, washed with ice-cooled water and air-dried. Crystallization from absolute ethyl alcohol water mixture yields 42.2 g (0.171 mol, 85.3%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl isobutyrate. MS m/z 247.042 [M+H].sup.+ (247.084 calculated).

Example 6

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl pivalate

[0268] ##STR00026##

[0269] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (26.6 g, 0.15 mol) and N-methylmorpholine (19.8 ml, 0.18 mol) were dissolved in 300 ml of dichloromethane. Trimethylacetyl chloride (20.3 ml, 0.165 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute ethyl alcohol water mixture yields 34.2 g (0.172 mol, 91.5%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl pivalate. MS m/z 261.067 [M+H].sup.+ (261.100 calculated).

Example 7

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl benzoate

[0270] ##STR00027##

[0271] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (17.7 g, 0.1 mol) and N-methylmorpholine (12.1 ml, 0.11 mol) were dissolved in 200 ml of dichloromethane. Benzoyl chloride (12.8 ml, 0.11 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute isopropyl alcohol yields 20.3 g (0.078 mol, 77.7%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl benzoate. MS m/z 281.017 [M+H].sup.+ (281.069 calculated).

Example 8

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl isobutyl carbonate

[0272] ##STR00028##

[0273] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (13.3 g, 0.075 mol) and N-methylmorpholine (9.1 ml, 0.083 mol) were dissolved in 150 ml of dichloromethane. Isobutyl chloroformate (10.8 ml, 0.083 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute isopropyl alcohol water mixture yields 18.5 g (0.067 mol, 89.1%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl isobutyl carbonate. MS m/z 277.047 [M+H].sup.+ (277.095 calculated).

Example 9

Synthesis of (1,3-dioxoisoindolin-2-yl)methyl ethyl carbonate

[0274] ##STR00029##

[0275] 2-(hydroxymethyl)isoindoline-1,3-dione (Example 1) (13.3 g, 0.075 mol) and N-methylmorpholine (9.1 ml, 0.083 mol) were dissolved in 150 ml of dichloromethane. Ethyl chloroformate (7.9 ml, 0.083 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute isopropyl alcohol water mixture yields 12.5 g (0.05 mol, 66.8%) of pure crystalline (1,3-dioxoisoindolin-2-yl)methyl isobutyl carbonate. MS m/z 249.011 [M+H].sup.+ (249.064 calculated).

Example 10

Synthesis of methyl 2-(4-benzoylphenoxy)acetate

[0276] ##STR00030##

[0277] To a vigorous stirring mixture of 4-hydroxybenzophenone (60.0 g, 0.265 mol), potassium carbonate (73.25 g, 0.530 mol) in 1000 ml of acetone, methyl bromoacetate (31.47 ml, 0.331 mol) was added drop-wise but quickly. The reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was filtered through Celite pad and concentrated in vacuum. The residue was re-dissolved in 500 ml of ethylacetate and washed sequentially with 10% (v/w) sodium hydrogen sulfate, 5M solution of sodium chloride, and 1M solution of sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from methyl tert-butyl ether yields 69.8 g (0.258 mol, 97.5%) of pure crystalline methyl 2-(4-benzoylphenoxy)acetate. MS m/z 270.057 [M+H].sup.+ (270.089 calculated).

Example 11

Synthesis of 2-(4-benzoylphenoxy)acetic Acid

[0278] ##STR00031##

[0279] Crystalline methyl 2-(4-benzoylphenoxy)acetate (Example 10, 69.8 g, 0.258 mol) was dissolved in 300 ml of methanol. 350 ml of 2N sodium hydroxide was added under vigorous stirring. The resulting mixture was refluxed overnight, cooled and methanol was evaporated under reduced pressure. The aqueous phase was acidified to pH 2 by drop-wise addition of 360 ml of 2N solution of hydrochloric acid. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from absolute ethanol yields 62.7 g (0.245 mol, 89.3%) of pure crystalline 2-(4-benzoylphenoxy)acetic acid. MS m/z 256.043 [M?H].sup.? (256.074 calculated).

Example 12

Synthesis of 2-(4-benzoylphenoxy)acetamide

[0280] ##STR00032##

[0281] A solution of 2-(4-benzoylphenoxy)acetic acid (Example 11, 40.0 g, 0.156 mol) in 400 ml of anhydrous tetrahydrofuran was stirred and chilled to ?10? C. in dry ice-acetone bath. N-methylmorpholine (18.9 ml, 0.172 mol) was added, following isobutyl chloroformate (21.4 ml, 0.164 mol) giving a precipitate. After 15 min, ice-cold 1,1,1,3,3,3-hexamethyldisilazane (39.0 ml, 0.187 mol) at once and stirring was continued for 1 h at ?10? C. Then, the cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold water. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from absolute ethanol water mixture yields 36.1 g (0.141 mol, 90.6%) of pure crystalline 2-(4-benzoylphenoxy)acetamide. MS m/z 255.072 [M+H].sup.+ (255.090 calculated).

Example 13

Synthesis of 2-(4-benzoylphenoxy)-N-(hydroxymethyl)acetamide

[0282] ##STR00033##

[0283] 2-(4-benzoylphenoxy)-N-(hydroxymethyl)acetamide (25.5 g, 0.1 mol) was added to a solution consisting of 7.9 ml of formaldehyde solution (37 wt. % in water, contains 10-15% Methanol as stabilizer, 13.3M), 100 ml of water, and potassium carbonate (0.69 g, 0.005 mol). The resulting mixture was warmed in water-bath (60-80? C.) until clear solution was obtained. The water bath was removed and precipitation occurred immediately. The suspension was stirred overnight at room temperature, then extracted three times with 100 ml dichloromethane. The combined organic phase was washed sequentially with 5M solution of sodium chloride, water and dried over anhydrous magnesium sulfate. Filtration, concentration, and re-crystallization from dichloromethane/hexane give the product (19.2 g, 0.085 mol, 84.9%) as white crystals. The obtained product was used for subsequent acetylating reaction without further purification.

Example 14

Synthesis of (2-(4-benzoylphenoxy)acetamido)methyl acetate

[0284] ##STR00034##

[0285] 2-(4-benzoylphenoxy)-N-(hydroxymethyl)acetamide (Example 13) (14.3 g, 0.05 mol) and N-methylmorpholine (6.6 ml, 0.06 mol) were dissolved in 200 ml of dichloromethane. Acetyl chloride (3.9 ml, 0.055 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute ethyl alcohol water mixture yields 12.7 g (0.039 mol, 77.6%) of pure crystalline (2-(4-benzoylphenoxy)acetamido)methyl acetate. MS m/z 327.091 [M+H].sup.+ (327.111 calculated).

Example 15

Synthesis of dimethyl 5-hydroxyisophthalate

[0286] ##STR00035##

[0287] To 5-Hydroxyisophthalic acid (36.4 g, 0.2 mol) are placed in 300 ml of methanol, along 2.2 ml of concentrated sulfuric acid was added drop-wise. The resulting solution was refluxed overnight. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold water. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from methanol-water mixture yields 40.6 g (0.193 mol, 96.7%) of pure crystalline dimethyl 5-hydroxyisophthalate. MS m/z 210.011 [M+H].sup.+ (210.053 calculated).

Example 16

Synthesis of dimethyl 5-(2-(tert-butoxy)-2-oxoethoxy)isophthalate

[0288] ##STR00036##

[0289] To a vigorous stirring mixture of dimethyl 5-hydroxyisophthalate (22.7 g, 0.108 mol), potassium carbonate (29.87 g, 0.216 mol) in 500 ml of acetone, tert-butyl bromoacetate (17.3 ml, 0.119 mol) was added drop-wise but quickly. The reaction mixture was stirred at 40? C. overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was filtered through Celite pad and concentrated in vacuum. The residue was re-dissolved in 300 ml of ethylacetate and washed sequentially with 10% (v/w) sodium hydrogen sulfate, 5M solution of sodium chloride, and 1M solution of sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from methyl tert-butyl ether/hexane mixture yields 29.24 g (0.09 mol, 83.4%) of pure crystalline dimethyl 5-(2-(tert-butoxy)-2-oxoethoxy)isophthalate. MS m/z 324.087 [M+H].sup.+ (324.121 calculated).

Example 17

Synthesis of 2-(3,5-bis(methoxycarbonyl)phenoxy)acetic acid

[0290] ##STR00037##

[0291] To the stirred solution of 29.24 g dimethyl (0.09 mol) of 5-(2-(tert-butoxy)-2-oxoethoxy)isophthalate (Example 16) in 300 ml of dichloromethane, trifluoracetic acid (200 ml) was added drop-wise, with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. After completion of the reaction, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 300 ml of toluene and evaporated again to remove the last traces of trifluoroacetic acid. The precipitate was isolated by filtration, washed several times with cold methyl tert-butyl ether, and dried in vacuum at 100? C. The yield was 24.1 g (0.09 mol, 99.7%) of pure crystalline 2-(4-benzoylphenoxy)acetamide. MS m/z 268.025 [M?H].sup.? (268.058 calculated).

Example 18

Synthesis of dimethyl 5-(2-amino-2-oxoethoxy)isophthalate

[0292] ##STR00038##

[0293] A solution of 2-(3,5-bis(methoxycarbonyl)phenoxy)acetic acid (Example 17, 20.0 g, 0.075 mol) in 200 ml of anhydrous tetrahydrofuran was stirred and chilled to ?10? C. in dry ice-acetone bath. N-methylmorpholine (9.0 ml, 0.082 mol) was added, following isobutyl chloroformate (10.2 ml, 0.078 mol) giving a precipitate. After 15 min, ice-cold 1,1,1,3,3,3-hexamethyldisilazane (18.6 ml, 0.089 mol) at once and stirring was continued for 1 h at ?10? C. Then, the cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold water. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from absolute ethanol water mixture yields 36.1 g (0.141 mol, 90.6%) of pure crystalline dimethyl 5-(2-amino-2-oxoethoxy)isophthalate. MS m/z 267.012 [M+H].sup.+ (267.074 calculated).

Example 19

Synthesis of dimethyl 5-(2-((hydroxymethyl)amino)-2-oxoethoxy)isophthalate

[0294] ##STR00039##

[0295] dimethyl 5-(2-amino-2-oxoethoxy)isophthalate (Example 18, 20.0 g, 0.075 mol) was added to a solution consisting of 5.9 ml of formaldehyde solution (37 wt. % in water, contains 10-15% Methanol as stabilizer, 13.3M), 75 ml of water, and potassium carbonate (0.52 g, 0.004 mol). The resulting mixture was warmed in water-bath (60 C) until clear solution was obtained. The water bath was removed and precipitation occurred immediately. The suspension was stirred overnight at room temperature, then extracted three times with 100 ml dichloromethane. The combined organic phase was washed sequentially with 5M solution of sodium chloride, water and dried over anhydrous magnesium sulfate. Filtration, concentration, and re-crystallization from dichloromethane/hexane give the product (17.3 g, 0.058 mol, 77.6%) as white crystals. The obtained product was used for subsequent acetylating reaction without further purification.

Example 20

Synthesis of dimethyl 5-(2-((acetoxymethyl)amino)-2-oxoethoxy)isophthalate

[0296] ##STR00040##

[0297] 2-(4-benzoylphenoxy)-N-(hydroxymethyl)acetamide (Example 19, 17.8 g, 0.06 mol) and N-methylmorpholine (7.9 ml, 0.072 mol) were dissolved in 300 ml of dichloromethane. Acetyl chloride (4.7 ml, 0.066 mol) was added drop wise with keeping reaction mixture temperature at 0-5? C. Upon completion of adding, the reaction was stirred overnight at room temperature. The progress of the reaction was monitored by TLC and LC/MS. Then reaction mixture was washed sequentially with 10% (v/w) sodium hydrogen sulfate, saturated sodium chloride, saturated sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered and concentrated in vacuum. Crystallization from absolute ethyl alcohol water mixture yields 14.6 g (0.043 mol, 71.7%) of pure crystalline dimethyl 5-(2-((acetoxymethyl)amino)-2-oxoethoxy)isophthalate. MS m/z 339.023 [M+H].sup.+ (339.095 calculated).

Example 21

Synthesis of 6-(1,3-dioxoisoindolin-2-yl)hexanoic acid

[0298] ##STR00041##

[0299] A stirred mixture of 6-aminocaproic acid (65.6 g, 0.5 mol), phthalic anhydride (74.1 g, 0.5 mol), and acetic acid (115 ml) was heated to reflux for 9 h. The product that crystallized on cooling was isolated by filtration, washed several times with water, and dried in vacuum at 100? C. to obtain 124.2 g (95.1%) of -(1,3-dioxoisoindolin-2-yl)hexanoic acid that was homogeneous by LC/MS and TLC, and is used in the next step with no further purification. MS m/z 261.24 [M?H].sup.? (261.10 calculated).

Example 22

Synthesis of 6-(1,3-dioxoisoindolin-2-yl)hexanamide

[0300] ##STR00042##

[0301] A solution of 6-(1,3-dioxoisoindolin-2-yl)hexanoic acid (Example 21, 40.0 g, 0.153 mol) in 400 ml of anhydrous tetrahydrofuran was stirred and chilled to ?10? C. in dry ice-acetone bath. N-methylmorpholine (18.5 ml, 0.168 mol) was added, following isobutyl chloroformate (21.0 ml, 0.161 mol) giving a precipitate. After 15 min, ice-cold 1,1,1,3,3,3-hexamethyldisilazane (38.2 ml, 0.184 mol) at once and stirring was continued for 1 h at ?10? C. Then, the cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold water. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from absolute ethanol water mixture yields 37.2 g (0.143 mol, 93.4%) of pure crystalline 6-(1,3-dioxoisoindolin-2-yl)hexanamide. MS m/z 267.075 [M+H].sup.+ (260.116 calculated).

Example 23

Synthesis of (6-(1,3-dioxoisoindolin-2-yl)hexanamido)methyl acetate

[0302] ##STR00043##

[0303] 6-(1,3-dioxoisoindolin-2-yl)hexanamide (Example 22, 32.0 g, 0.123 mol) and paraformaldehyde (4.43 g, 0.148 mol, corresponding to formaldehyde) were dissolved in 70 ml of glacial acetic acid. To the resulting suspension, acetic anhydride (57.8 g, 0.615 mol) was added at once and reaction mixture allow to react 12 h at room temperature under gentle stirring. Then, the reaction mixture was heated at 60? C. for next 12 h. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was crystallized two times from acetone. The yield of crystalline (6-(1,3-dioxoisoindolin-2-yl)hexanamido)methyl acetate was 37.2% (15.2 g, 0.046 mol). MS m/z 332.144 [M+H].sup.+ (332.137 calculated).

Example 24

Synthesis of N-methyl-N-(perfluorobenzyl)glycine

[0304] ##STR00044##

[0305] To suspension of sarcosine (25.0 g, 0.281 mol) in 280 ml of anhydrous dichloromethane chlorotrimethylsilane (48.5 ml, 60.97 g, 0.561 mol) was added at once. The resulting suspension was refluxed 1.5 hours. Then, heating bath was replaced by ice bath and N,N-diisopropylethylamine (102.0 ml, 79.79 g, 0.617 mol was added dropwise and incubation continued during 2 hours. Then pentafluorobenzoyl chloride (32.3 ml, 51.75 g, 0.224 mol) was added dropwise and incubation continued during 2 hours. Then, the cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold 2M HCl. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from dichloroethane yields 56.8 g (0.2 mol, 71.0%) of pure crystalline N-methyl-N-(perfluorobenzyl)glycine. MS m/z 284.075 [M+H].sup.+ (284.027 calculated).

Example 25

Synthesis of N-(2-amino-2-oxoethyl)-2,3,4,5,6-pentafluoro-N-methylbenzamide

[0306] ##STR00045##

[0307] A solution of N-methyl-N-(perfluorobenzyl)glycine (Example 24, 40.0 g, 0.141 mol) in 400 ml of anhydrous tetrahydrofuran was stirred and chilled to ?10? C. in dry ice-acetone bath. N-methylmorpholine (17.1 ml, 0.155 mol) was added, following isobutyl chloroformate (19.3.0 ml, 0.161 mol) giving a precipitate. After 15 min, ice-cold 1,1,1,3,3,3-hexamethyldisilazane (35.3 ml, 0.148 mol) at once and stirring was continued for 1 h at ?10? C. Then, the cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was suspended in 200 ml of ice-cold water. The precipitate was isolated by filtration, washed several times with cold water, and dried in vacuum at 100? C. Crystallization from absolute ethanol water mixture yields 35.3 g (0.125 mol, 88.6%) of pure crystalline N-(2-amino-2-oxoethyl)-2,3,4,5,6-pentafluoro-N-methylbenzamide. MS m/z 283.061 [M+H].sup.+ (283.043 calculated).

Example 26

Synthesis of (2-(2,3,4,5,6-pentafluoro-N-methylbenzamido)acetamido)methyl acetate

[0308] ##STR00046##

[0309] N-(2-amino-2-oxoethyl)-2,3,4,5,6-pentafluoro-N-methylbenzamide (Example 25, 34.7 g, 0.123 mol) and paraformaldehyde (4.43 g, 0.148 mol, corresponding to formaldehyde) were dissolved in 70 ml of glacial acetic acid. To the resulting suspension, acetic anhydride (57.8 g, 0.615 mol) was added at once and reaction mixture allow to react 12 h at room temperature under gentle stirring. Then, the reaction mixture was heated at 60? C. for next 12 h. The progress of the reaction was monitored by TLC and LC/MS. Upon reaction completed, the reaction mixture was evaporated to dryness under reduced pressure. The resulting solid substance was crystallized two times from methyl tert-butyl ether cyclohexane mixture 2 times. The yield of crystalline (2-(2,3,4,5,6-pentafluoro-N-methylbenzamido)acetamido)methyl acetate was 65.0% (28.45 g, 0.080 mol). MS m/z 355.144 [M+H].sup.+ (355.064 calculated).

Example 27

[0310] Using of (6-(1,3-dioxoisoindolin-2-yl)hexanamido)methyl acetate as the modification reagent together with boron trifluoride etherate as the catalyst for modification of the polysulfone backbone.

##STR00047##

[0311] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0312] Experimental parameters which are common across all samples in this example:

TABLE-US-00001 Polysulfone weight, g 15 Polysulfone repeating units (PRU), mol 0.034 Solvent 1,2-dichloroethane Solvent volume, ml 100 Modification reagent (MR) (6-(1,3-dioxoisoindolin-2- yl)hexanamido)methyl acetate Catalyst (Cat) Boron trifluoride etherate Cat/MR molar ratio 2.00 Temperature, ? C. 40 Catalyst scavenger (CatSc) KF CatSc/Cat molar ratio 2.00 Incubation with CatSc, hours 6.00

Example 28

[0313] Simultaneous incorporation of two structurally different pendant functional groups using of (2-(4-benzoylphenoxy)acetamido)methyl acetate and diethyl 5-(2-((acetoxymethyl)amino)-2-oxoethoxy)isophthalate as the modification reagent together with boron trifluoride etherate as the catalyst.

##STR00048##

TABLE-US-00002 MR-1 MR-1 [00049] [00050] (2-(4-benzoylphenoxy)acetamido) dimethyl 5-(2-((acetoxymethyl)amino)- methyl acetate 2-oxoethoxy)isophthalate

[0314] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0315] Experimental parameters which are common across all samples in this example:

TABLE-US-00003 Polysulfone weight, g 1.00 Polysulfone repeating units (PRU), mmol 2.260 Solvent dichloromethane Solvent volume, ml 10 Catalyst (Cat) Boron trifluoride etherate Cat/MR molar ratio 4.00 Catalyst weight, g 0.449 Catalyst amount, mmol 3.164 Temperature, ? C. 20 Reaction time, hours 24

Example 29

[0316] Incorporation of four structurally similar pendant functional groups bearing different leaving groups using boron trifluoride acetic acid complex as the catalyst.

##STR00051##

##STR00052##

[0317] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0318] Experimental parameters which are common across all samples in this example:

TABLE-US-00004 Polysulfone weight, g 15 Polysulfone repeating units (PRU), mol 0.034 Solvent 1,2-dichloroethane Solvent volume, ml 100 MR/PRU ratio 0.60 MR amount, mol 0.0203 Catalyst (Cat) boron trifluoride acetic acid complex Cat/MR molar ratio 0.00 Catalyst weight, g 7.643 Catalyst amount, mol 0.0407 Temperature, ? C. 20 Catalyst scavenger (CatSc) KF CatSc/Cat molar ratio 4.00 CatSc amount, g 9.452 Incubation with CatSc, hours 6.00

Example 30

[0319] Comparison of the kinetics of polysulfone modification depending on the structure of leaving group using boron trifluoride acetic acid complex as the catalyst.

##STR00053##

##STR00054##

[0320] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0321] Experimental parameters which are common across all samples in this example:

TABLE-US-00005 Polysulfone weight, g 15 Polysulfone repeating units (PRU), mol 0.034 Solvent 1,2-dichloroethane Solvent volume, ml 100 MR/PRU ratio 0.60 MR amount, mol 0.0203 boron trifluoride Catalyst (Cat) acetic acid complex Cat/MR molar ratio 2.00 Catalyst weight, g 7.643 Catalyst amount, mol 0.0407 Temperature, ? C. 20 Catalyst scavenger (CatSc) KF CatSc/Cat molar ratio 4.00 CatSc amount, g 9.452 Incubation with CatSc, hours 6.00

Example 32

[0322] The dependence of the modification efficiency on the catalyst/reagent ratio.

##STR00055##

[0323] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0324] Experimental parameters which are common across all samples in this example:

TABLE-US-00006 Polysulfone weight, g 15.00 Polysulfone repeating units (PRU), mol 0.034 Solvent dichloromethane Solvent volume, ml 100 Modification reagent (MR) (2-(4-fluorophe- noxy)acetamido)methyl acetate MR/PRU ratio 0.60 MR amount, mol 0.0203 MR weight, g 4.9058 Catalyst (Cat) boron trifluoride etherate Temperature, ? C. 20

Example 35

[0325] Comparison of the different solvents.

##STR00056##

[0326] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0327] Experimental parameters which are common across all samples in this example:

TABLE-US-00007 Polysulfone weight, g 6.00 Polysulfone repeating units (PRU), mol 0.0136 Modification reagent (MR) (2-(4-chlorophe- noxy)acetamido)methyl acetate MR/PRU ratio 0.20 MR amount, mol 0.0027 MR weight, g 0.699 Catalyst (Cat) boron trifluoride etherate Cat/MR molar ratio 6.00 Catalyst amount, mol 0.0163 Catalyst weight, g 2.309 Temperature, ? C. 22 Reaction time, hours 24

Results:

[0328]

TABLE-US-00008 Incorporation Reagent/ Degree of yield Sample Reaction RU substi- Exper- ID solvent ratio tution iment Average PSU-092 Dichloromethane 0.20 0.16 82.2% 83.3% PSU-093 Dichloromethane 0.20 0.17 84.4% PSU-094 Chlorophorm 0.20 0.17 84.3% 84.6% PSU-095 Chlorophorm 0.20 0.17 85.0% PSU-096 1,2- 0.20 0.18 87.7% 87.1% Dichloroethane PSU-097 1,2- 0.20 0.17 86.5% Dichloroethane

Example 36

[0329] Incorporation of the benzophenone functionality onto polysulfone backbone.

##STR00057##

[0330] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0331] Experimental parameters which are common across all samples in this example:

TABLE-US-00009 Polysulfone weight, g 6.00 Polysulfone repeating units (PRU), mol 0.0136 Solvent dichloromethane Solvent volume, ml 40.0000 Modification reagent (MR) (2-(4-benzoylphe- noxy)acetamido)methyl acetate Catalyst (Cat) boron trifluoride etherate Cat/MR molar ratio 6.00 Temperature, ? C. 22 Reaction time, hours 24

Example 38

[0332] Incorporation of complex multivalent functionality.

##STR00058##

[0333] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0334] Experimental parameters which are common across all samples in this example:

TABLE-US-00010 Polysulfone weight, g 6.00 Polysulfone repeating 0.0136 units (PRU), mol Solvent 1,2-dichloroethane Solvent volume, ml 40 Modification reagent (MR) dimethyl 5-(2-((acetoxymethyl)amino)- 2-oxoethoxy)isophthalate Catalyst (Cat) boron trifluoride etherate Cat/MR molar ratio 6.00 Temperature, ? C. 30 Reaction time, hours 24

Example 39

[0335] Comparison of an incorporation of two different complex multivalent functionalities.

##STR00059##

##STR00060##

[0336] The method of the polysulfone modification used in this example follows the Polysulfone chemical modification General Procedure A.

[0337] Experimental parameters which are common across all samples in this example:

TABLE-US-00011 Polysulfone weight, g 6.00 Polysulfone repeating units (PRU), mol 0.0136 Solvent 1,2-dichloroethane Solvent volume, ml 40 MR/PRU ratio 0.20 Catalyst (Cat) boron trifluoride etherate Cat/MR molar ratio 6.00 Catalyst amount, mol 0.0163 Catalyst weight, g 2.309 Temperature, ? C. 30