FUNCTIONALIZED POLY(ARYL ETHER SULFONE) COPOLYMERS

Abstract

The invention relates to a side-chain functionalized poly(aryl ether sulfone) (PAES) copolymer (P1), to the process for preparing the copolymer (P1), and to its use in the preparation of a membrane, a composite material or a coating. The copolymer (P1) comprises PAES recurring units (R.sub.P1) and PAES side-chain functionalized recurring units (R*.sub.P1).

Claims

1. A copolymer (P1) comprising: recurring units (R.sub.P1) of formula (M): ##STR00017## recurring units (R*.sub.P1) of formula (N): ##STR00018## 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 an integer from 0 to 4; T is selected from the group consisting of a bond, CH.sub.2; O; SO.sub.2; S; C(O); C(CH.sub.3).sub.2; C(CF.sub.3).sub.2; C(CCl.sub.2); C(CH.sub.3)(CH.sub.2CH.sub.2COOH); NN; 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 at least one of the following formulas (G.sub.N1) to (G.sub.N6): ##STR00019## in which W is a bond or SO.sub.2, preferably SO.sub.2; each k is independently an integer from 0 to 4; each j is independently an integer from 3 to 7; each R.sub.2 is independently selected from the group consisting of: (CH.sub.2).sub.uCOOH, with u being an integer from 1 to 5, with the proviso that when T and W are both SO.sub.2 then u is not 1 or 2, (CH.sub.2).sub.kOH, with k being an integer from 1 to 5, (CH.sub.2).sub.pNR.sub.aR.sub.b, with p being an integer from 1 to 5, and a and 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).sub.qSO.sub.3Na, with q being an integer from 1 to 5, (CH.sub.2).sub.aCOCH.sub.3, with a being an integer from 0 to 10 (CH.sub.2).sub.rSi(OCH.sub.3).sub.3, with r being an integer from 1 to 5, (CH.sub.2).sub.s(CF.sub.2).sub.tCF.sub.3, with s being an integer from 1 to 5 and t being an integer from 1 to 10, C(O)R.sub.c, with R.sub.e being a C1-C6 alkyl or H, (CH.sub.2).sub.vCH.sub.3, with v being an integer from 5 to 30, and (CH.sub.2).sub.wAr, with w being an integer from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings; and wherein the copolymer (P1) has a glass transition temperature Tg being equal to or greater than the Tg.sub.h of the homopolymer consisting essentially of the same recurring units (R.sub.P1), said glass transition temperatures being measured by differential scanning calorimetry (DSC).

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.2and C(CH.sub.3).sub.2.

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

4. The copolymer (P1) claim 1, wherein k is 0 and j is 3 in the 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 1/100 and 100/1.

6. The copolymer (P1) of claim 1, wherein the recurring units (R.sub.P1) are according to formulae (M1), (M2) or (M3): ##STR00020##

7. The copolymer (P1) of claim 1, wherein R.sub.2 in the formulas (G.sub.N1), (G.sub.N2), (G.sub.N3), (G.sub.N4), (G.sub.N5) or (G.sub.N6) is independently selected from the group consisting of: CH.sub.2COOH, (CH.sub.2).sub.2OH, (CH.sub.2).sub.2NH.sub.2, (CH.sub.2).sub.3SO.sub.3Na, (CH.sub.2).sub.3Si(OCH.sub.3).sub.3, (CH.sub.2).sub.2(CF.sub.2).sub.7CF.sub.3, CHO, (CH.sub.2).sub.9CH.sub.3, and CH.sub.2-Ph, 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 of recurring units in the copolymer (P1).

9. A process for preparing the copolymer (P1) of CLAIM 1, comprising reacting in a solvent a copolymer (P0) comprising: recurring units (R.sub.P0) of formula (M): ##STR00021## and recurring units (R*.sub.P0) of formula (P): ##STR00022## 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 an integer from 0 to 4; T is selected from the group consisting of a bond, CH.sub.2; O; SO.sub.2; S; C(O); C(CH.sub.3).sub.2; C(CF.sub.3).sub.2; C(CCl.sub.2); C(CH.sub.3)(CH.sub.2CH.sub.2COOH); NN; 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 formulas (G.sub.P1) to (G.sub.P3): ##STR00023## in which: W is a bond or SO.sub.2, preferably SO.sub.2; each k is independently selected from 0 to 4, wherein the copolymer (P0) has a glass transition temperature Tg being equal to or greater than the Tg.sub.h of the homopolymer consisting essentially of the same recurring units (R.sub.P0), said glass transition temperatures being measured by differential scanning calorimetry (DSC), with a compound of formula (I):
R.sub.2SH (I) wherein R.sub.2 is selected from the group consisting of: (CH.sub.2).sub.uCOOH, with u being an integer from 1 to 5, with the proviso that when T and W are both SO.sub.2then u is not 1 or 2, (CH.sub.2).sub.kOH, with k being an integer from 1 to 5, (CH.sub.2).sub.pNR.sub.aR.sub.b, with p being an integer 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).sub.qSO.sub.3Na, with q being an integer from 1 to 5, (CH.sub.2).sub.aCOCH.sub.3, with a being an integer from 0 to 10, (CH.sub.2).sub.rSi(OCH.sub.3).sub.3, with r being an integer from 1 to 5, (CH.sub.2).sub.s(CF.sub.2).sub.tCF.sub.3, with s being an integer from 1 to 5 and t being an integer from 1 to 10, C(O)R.sub.c, with R.sub.e being a C1-C6 alkyl or H, (CH.sub.2).sub.vCH.sub.3, with v being an integer from 5 to 30, and (CH.sub.2).sub.wAr, with w being an integer from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings, wherein the molar ratio of compound (I)/polymer (P0) varies between 0.01/100 and 100/0.01, at a temperature ranging from 10 C. and 300 C.

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

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

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

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

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

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

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

17. The process of claim 9, wherein Tg5 C.+Tg.sub.h.

Description

EXAMPLES

Raw Materials

[0171] DCDPS (4,4-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers [0172] BPA (bisphenol A), available from Covestro, U.S.A. [0173] BP (biphenol), polymer grade available from Honshu Chemicals, Japan [0174] daBPA-S (2,2-diallyl Bisphenol S), available from Toronto Research Chemicals. [0175] K.sub.2CO.sub.3 (Potassium Carbonate), available from Armand products [0176] NMP (2-methyl pyrrolidone), available from Sigma-Aldrich, U.S.A. [0177] MCB (methylchlorobenzene), available from Sigma-Aldrich, U.S.A. [0178] ADVN (2,2-azobis(2,4-dimethylvaleronitrile)), available from Miller-Stephenson Chemical Co., Inc, U.S.A. [0179] AIBN (2,2-Azobis(2-methylpropionitrile)), available from Sigma Aldrich, U.S.A.

Test Methods

GPCMolecular Weight (Mn, Mw)

[0180] Method 1: 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.

[0181] Method 2: Viscotek GPC Max (Autosampler, pump, and degasser) with a TDA302 triple detector array comprised of RALS (Right Angle Light Scattering), RI and Viscosity detectors was used. Samples were run in NMP with 0.2 w/w % LiBr at 65 C. at 1.0 mL/min through a set of 3 columns: a guard column (CLM1019with a 20 k Da exclusion limit), a high Mw column (CLM1013 exclusion of 10MM Daltons relative to Poly Styrene) and a low Mw column (CLM1011exclusion limit of 20 k Daltons relative to PS). Calibration was done with a single, mono-disperse polystyrene standard of 100 k Da. Light Scattering, RI, and Viscosity detectors were calibrated based on a set of input data supplied with the standards.Samples were prepared as 2 mg/mL in NMP/LiBr.

[0182] Viscotek's OMNISec v4.6.1 Software was used for data analysis. The number average molecular weight Mn, weight average molecular weight Mw, higher average molecular weight Mz, were reported.

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.

.SUP.1.H NMR

[0184] .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.

DSC

[0185] 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, if any) values were provided using the second heat curve unless otherwise noted.

I. Preparation of Copolymer (P0-A)

The Copolymer (P0-A) was Prepared According to Scheme 1.

[0186] The polymerization was carried out in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers 4,4-dichlorodiphenyl sulfone (143.58 g), Bisphenol A (102.73 g) and 2,2 diallyl bisphenol S (16.52 g) were added to the vessel first, followed by the addition of potassium carbonate (78.29 g), and NMP (690 g) and chlorobenzene (170 g).The reaction mixture was heated from room temperature to 190 C. using a 150 C./min heating ramp, with continuous removal of the chlorobenzene using a Dean-Stark apparatus. The temperature of the reaction mixture was maintained for around eight hours, depending upon the viscosity of the solution. The reaction was stopped by turning off the heat and diluting the reaction mixture with cold solvent. The reaction mixture was filtered, coagulated into methanol and dried at 110 C.

Characterization of Copolymer (P0-A)

[0187] GPC (Method 1): Mn=12743 g/mol, Mw=58832 g/mol, PDI=4.61 [0188] TGA: 477 C.; DSC: Tg=195 C.

[0189] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicates the incorporation of the 2,2-diallyl BPS monomer in the polymer.

II. Preparation of Copolymer (P0-B)

The Copolymer (P0-B) was Prepared According to Scheme 2.

[0190] The polymerization was carried out in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers 4,4-dichlorodiphenyl sulfone (172.29 g), 4,4 biphenol (106.13 g) and 2,2 diallyl bisphenol S (9.91 g) were added to the vessel first, followed by the addition of potassium carbonate (93.69 g), and sulfolane (570 g).The reaction mixture was heated from room temperature to 210 C. using a 150 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 stopped by removing the heat and diluting with more solvent. The reaction mixture was filtered, coagulated into methanol and dried at 110 C.

Characterization of Copolymer (P0-B)

[0191] GPC (Method 1): Mn=19251 g/mol, Mw=71960 g/mol, PDI=3.70. [0192] TGA: 505 C.; DSC: Tg=235 C.

[0193] .sup.1H NMR: spectrum was not obtained due to poor solubility in the NMR solvents.

III. Preparation of Functionalized Copolymer (P1-A) by Free Radical Reaction

[0194] The copolymer (P1-A) according to the invention was prepared according to Scheme 3.

[0195] In a 250 mL three necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 31.2 g of the copolymer (P0-A) prepared according to Section I. above (Scheme 1) was dissolved in 89 g of NMP and 3.2 g of cysteamine.HCl was added. The reaction mixture was heated to 50 C. under nitrogen then 0.8 g of ADVN was added in one portion. The reaction was continued for 24 hours after which the reaction mass was coagulated into methanol, the precipitated polymer was then washed with methanol, water and then finally with methanol and dried at 110 C. under reduced pressure.

Characterization

[0196] GPC (Method 2): Mw=152023 g/mol, Mn=50044 g/mol, PDI=3.30 [0197] DSC: Tg=206 C.; TGA: 411 C.

[0198] The quantitative estimation of the amine functionalization was analyzed by titrating the amine groups. Amine content: 295 microeq/g.

Preparation of Functionalized Copolymer (P1-B) by Free Radical Reaction

[0199] The copolymer (P1-B) according to the invention was prepared according to the Scheme 4.

[0200] In a 250 mL three necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 30 g of the copolymer (P0-B) prepared according to Section II. above (Scheme 2) was dissolved in 110 g of NMP and 3.9 g of sodium 3-mercapto-1-propanesulfonate was added. The reaction mixture was heated to 75 C. under nitrogen then 0.59 g of AIBN was added in one portion.

[0201] The reaction was continued for 24 hours after which the reaction mass was coagulated into methanol, the precipitated polymer was then washed with methanol, water and then finally with methanol and dried at 110 C. under reduced pressure.

Characterization

[0202] GPC (Method 2): Mw=342287 g/mol, Mn=75154 g/mol, PDI=4.50 [0203] DSC: Tg=234C; TGA: 517 C. [0204] Sodium content: 1337 ppm

##STR00013##

##STR00014##

##STR00015##

##STR00016##