Epoxy functionalized poly(aryl ether sulfones) copolymers

Abstract

The invention pertains to a side-chain epoxy-functionalized copolymer (P1) and to the process for preparing this copolymer (P1). The present invention also pertains to the use of the copolymer (P1) in the preparation of a membrane, a composite material or a coating. The present invention also relates to a resin composition comprising at least the copolymer (P1) according to the present invention.

Claims

1. A copolymer (P1) comprising: recurring units (R.sub.P1) of formula (M): ##STR00013## recurring units (R*.sub.P1) of formula (N): ##STR00014## optionally at least 50 μeq of hydroxyl end groups, amine end groups, acid end groups or epoxy end groups, wherein each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each i is independently selected from 0 to 4; G.sub.N is selected from the group consisting of at least one of the following formulas: ##STR00015## each k is independently selected from 0 to 4; each j is independently selected from 3 to 7; T and Q are independently selected from the group consisting of a bond, —CH.sub.2—, —O—; —SO.sub.2—, —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.aC═CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen, 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.

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

3. The copolymer (P1) of claim 1, wherein Q in the formulas (G.sub.N1), (G.sub.N2) and/or (G.sub.N3) of the recurring units (R*.sub.P1) is selected from the group consisting of a bond, —SO.sub.2— and —C(CH.sub.3).sub.2—.

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

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

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

7. The copolymer (P1) of claim 1, wherein the recurring units (R.sub.P1) are according to formula (M1): ##STR00016##

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

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

10. A process for preparing copolymer (P1) comprising at least partially epoxidizing a copolymer (P0) comprising: recurring units (R.sub.P0) of formula (M): ##STR00017## recurring units (R*.sub.P0) of formula (P): ##STR00018## optionally at least 50 μeq of hydroxyl end groups, amine end groups, acid end groups or epoxy end groups, wherein each R.sub.1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each i is independently selected from 0 to 4; G.sub.P is selected from the group consisting of at least one of the following formulas: ##STR00019## each k is independently selected from 0 to 4, T and Q are independently selected from the group consisting of a bond, —CH.sub.2—, —O—; —SO.sub.2—; —S—; —C(O)—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —C(═CCl.sub.2)—; —C(CH.sub.3)(CH.sub.2CH.sub.2COOH)—; —N═N—; —R.sub.aC═CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen, 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.

11. The process of claim 11, being carried out: in the presence of a peroxy acid, or with at least one hydrogen peroxide precursor and at least one carboxylic acid or derivative thereof in the presence of water.

12. The process of claim 10, 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 in the copolymer (P0).

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

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

Description

EXAMPLES

[0132] Raw Materials

DCDPS (4,4′-dichlorodiphenyl sulfone), available from Solvay Specialty Polymers
BPA (bisphenol A), available from Covestro, U.S.A.
BP (biphenol), polymer grade available from Honshu Chemicals, Japan
daBPA (2,2′-diallyl Bisphenol), available from Sigma-Aldrich, U.S.A.
K.sub.2CO.sub.3 (Potassium Carbonate), available from Armand products
3-chloroperoxy benzoic acid, available from Sigma-Aldrich, U.S.A.
Methylene chloride, ethyl acetate, available from Sigma-Aldrich, U.S.A.
Chlorobenzene, available from Sigma-Aldrich, U.S.A.
NMP (2-methyl pyrrolidone), available from Sigma-Aldrich, U.S.A.

[0133] Test Methods

[0134] GPC—Molecular weight (Mn, Mw)

[0135] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5p mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 20 μL of a 0.2 w/v % solution in mobile phase was selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn, weight average molecular weight Mw, higher average molecular weight Mz, were reported.

[0136] Thermal Gravimetric Analysis (TGA)

[0137] 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.

[0138] .sup.1H NMR

[0139] .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.

[0140] DSC

[0141] DSC was used to determine glass transition temperatures (Tg) and melting points (Tm)-if present. DSC experiments were carried out using a TA Instrument Q100. DSC curves were recorded by heating, cooling, re-heating, and then re-cooling the sample between 25° C. and 320° C. at a heating and cooling rate of 20° C./min. All DSC measurements were taken under a nitrogen purge. The reported Tg and Tm values were provided using the second heat curve unless otherwise noted.

[0142] I. Preparation of Allyl/Vinylene-Modified PSU Copolymer (P0-A)

[0143] The functionalized PSU copolymer (P0-A) was prepared according to the Scheme 1.

[0144] The copolymerization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (287.16 g), BPA (216.88 g) and daBPA (15.76 g) are added to the vessel first, followed by the addition of K.sub.2CO.sub.3 (150.6 g), NMP (696 g).

[0145] The reaction mixture is heated from room temperature to 190° C. using a 1° C./min heating ramp. The temperature of the reaction mixture is maintained for 6 to 8 hours, depending upon the viscosity of the solution. The reaction is terminated by stopping the heating. The reaction mixture is filtered, coagulated into methanol and dried at 110° C.

[0146] The copolymer is in the form of a racemate product. Due to the presence of the base and high temperature during polymerization, the daBPA monomer racemizes during polymerization in such a way that the position of the double bond changes along the side chains. This leads to the formation of molecules differing from each other by the fact that the double bond may be at the end of the side chain or one carbon before the end of the side chain, as shown in Scheme 1.

[0147] Characterization

[0148] GPC: Mn=26,430 g/mol, Mw=143,489 g/mol, PDI=5.43

[0149] TGA: 485° C.

[0150] DSC: 182.2° C.

[0151] .sup.1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicates the incorporation of the daBPA monomer in the polymer.

[0152] II. Preparation of Epoxy Functionalized PSU Copolymer (P1-A)

[0153] The functionalized PSU copolymer (P1-A) was prepared according to the following procedure according to Scheme 2.

[0154] The epoxy functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-A (100 g) is dissolved at room temperature in dichloromethane (900 g). 3-chloroperoxybenzoic acid (11.71) was added at room temperature. The reaction is allowed to proceed for 48 hours. The reaction mixture is then filtered and coagulated in ethyl acetate. The coagulated copolymer is then washed with ethyl acetate and then dried at 110° C.

[0155] Characterization

[0156] GPC: Mw=83,273 g/mol, Mn=15,325 g/mol, PDI=5.43

[0157] TGA: 488° C.

[0158] DSC: 109° C.

[0159] .sup.1H NMR: The total absence of unsaturated groups was confirmed by the complete disappearance of a multiplet at 6.1-6.4 ppm.

[0160] FTIR: The presence of bands at ˜900 cm.sup.−1 indicates the presence of epoxy groups.

[0161] III. Preparation of Epoxy Functionalized PSU Copolymer (P1-B)

[0162] The epoxy functionalization takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P0-B (147 g) is dissolved at room temperature in dichloromethane (900 g). 3-chloroperoxybenzoic acid (56 g) was added at room temperature. The reaction is allowed to proceed for 48 hours. The reaction mixture is then filtered and coagulated in ethyl acetate. The coagulated copolymer is then washed with ethyl acetate and then dried at 110° C.

[0163] Characterization

[0164] GPC: Mn=27,443 g/mol, Mw=83,273 g/mol, PDI=3.03

[0165] TGA: 468° C.

[0166] DSC: 185° C.

[0167] .sup.1H NMR: The total absence of unsaturated groups was confirmed by the complete disappearance of a multiplet at 6.1-6.4 ppm.

[0168] FTIR: The presence of bands at ˜900 cm.sup.−1 indicates the presence of epoxy groups.

[0169] IV. Preparation of Functionalized PSU Copolymer (P2-B.sub.1)

[0170] The functionalized PSU copolymer (P2-B.sub.1) was prepared according to the following procedure according to Scheme 3.

[0171] The ring-opening reaction takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P1-B (10 g) is dissolved at room temperature in NMP (80 g). 1-hexylamine (837 mg) was added at room temperature. The reaction was heated to 80° C. and allowed to proceed overnight. The reaction mixture is then filtered and coagulated in ethyl acetate. The coagulated copolymer is then washed with ethyl acetate and then dried at 85° C. under vacuum.

[0172] Characterization

[0173] GPC: Mn=26,136 g/mol, Mw=85,736 g/mol, PDI=3.28.

[0174] TGA: This material had a distinct thermal degradation profile one at 200° C. (16.39% loss in weight which corresponds to degradation of the hexyl side-chains) and 488° C. which corresponds to the polysulfone main-chain.

[0175] DSC: 151° C.

[0176] FTIR: The presence of bands at 3,421 cm.sup.−1 (indicating —OH groups), around 2,900 cm.sup.−1 (indicating CH alkyl groups) indicate the presence of the hexyl side-chains.

[0177] V. Preparation of Functionalized PSU Copolymer (P2-B.sub.2)

[0178] The functionalized PSU copolymer (P2-B.sub.2) was prepared according to the following procedure according to Scheme 4.

[0179] The ring-opening reaction takes place in a glass reactor vessel (1 L) fitted with an overhead stirrer, nitrogen inlet. Copolymer P1-B (20 g) is dissolved at room temperature in NMP (80 g). KOH (1.4 g) dissolved in 10 g of water, was added at room temperature. The reaction was heated to 100° C. and allowed to proceed overnight.

[0180] The reaction mixture is then cooled and acidified with HCl until pH reaches 4 and then coagulated in ethyl acetate. The coagulated copolymer is then washed with ethyl acetate and then dried at 85° C. under vacuum.

[0181] Characterization

[0182] GPC: Mn=9,110 g/mol, Mw=17,255 g/mol, PDI=1.89

[0183] DSC: 1514 The resultant polymer was titrated for hydroxyl groups and the aliphatic hydroxyl content was found to be 66 μeq/g.

[0184] DSC: 154° C.

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##STR00011##

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