Process for preparing functionalized poly(aryl ether sulfones) polymers and block copolymers resulting therefrom

Abstract

Poly(aryl ether sulfones) (PAES) polymers (P1) which are functionalized with reactive functional groups on at least one end of the PAES polymer, a process for preparing the PAES polymers (P1), a process for preparing block copolymers (P2) using the functionalized poly(aryl ether sulfones) (PAES) polymers (P1) and the block copolymers (P2) obtainable by such process

Claims

1. A poly(aryl ether sulfone) (PAES) polymer (P1) comprising: recurring units (R.sub.PAES) of formula (L): ##STR00019## at least one terminal group of formula (M): ##STR00020## wherein: each R.sup.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 an independently selected 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)—; —N═N—; —R.sub.aC=CR.sub.b—, where each R.sub.a and R.sub.b, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH.sub.2).sub.m— and —(CF.sub.2).sub.m— with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof; y1 and y2 independently vary between 0 and 50, at least one of y1 or y2 being different from 0; R′ is a bond, a heteroatom, a (CH.sub.2—CH.sub.2—O).sub.n group with n varying from 1 to 16, a C5-C40 aryl group, a C3-C40 branched aliphatic group or a C3-C40 cycloaliphatic group; and X is Cl, Br or I.

2. The PAES polymer of claim 1, wherein T is selected from the group consisting of a bond, —SO.sub.2— and —C(CH.sub.3).sub.2—.

3. The PAES polymer of claim 1, wherein the PAES polymer comprises at least 50 mol. % (based on the total number of moles in the polymer) of recurring units of formula (L).

4. The PAES polymer of claim 1, wherein the PAES polymer comprises at least 50 mol. % based on the total number of moles in the PAES polymer of recurring units selected from the group consisting of formulas: ##STR00021##

5. The PAES polymer of claim 1, wherein the PAES polymer has a number average molecular weight (Mn) of less than about 25,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards.

6. The PAES polymer of claim 1, wherein the PAES polymer has a number average molecular weight (Mn) of no less than about 1,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards.

7. The PAES polymer of claim 1, wherein the PAES polymer is such that R′ is a bond, a heteroatom or a (CH.sub.2—CH.sub.2—O).sub.n group with n varying from 1 to 16.

8. The PAES polymer of claim 1, wherein the PAES polymer is such that y1 varies between 1 and 40 and y2 equals 0.

9. A process for preparing the poly(aryl ether sulfone) (PAES) polymer (P1) of claim 1, comprising reacting a poly(aryl ether sulfone) (PAES) polymer (P0) comprising: recurring units (R.sub.PAES) of formula (N): ##STR00022## and at least one terminal group of formula (P): ##STR00023## wherein: each R.sup.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 an independently selected integer from 0 to 4; W is O—R or S—R; and R is H, K, Na, Li, Cs or a NHQ, where Q is a group containing 1 to 10 carbon atoms; with a compound of formula (I)
X—(CH.sub.2).sub.y1—R′—(CH.sub.2).sub.y2—X  (I) wherein X is Cl, Br or I; y1 and y2 independently varies between 0 and 50, at least one of y1 or y2 being different from 0; R′ is a bond, a heteroatom, a (CH.sub.2—CH.sub.2—O).sub.n group with n varying from 1 to 16, a C5-C40 aryl group, a C3-C40 branched aliphatic group or a C3-C40 cycloaliphatic group; and wherein the molar ratio of compound (I)/polymer (P0) is higher than 1 optionally in the presence of a base and a polar aprotic solvent at a temperature ranging from room temperature and 250° C.

10. The process of claim 9, wherein the polymer (P0) is in the form of a phenoxide or a phenyl thiolate.

11. The process of claim 9, wherein: the solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N,Ndimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and sulfolane, and/or the base is selected from the group consisting of potassium carbonate (K.sub.2CO.sub.3), potassium tert-butoxide, sodium carbonate (CaCO.sub.3), cesium carbonate (Cs.sub.2CO.sub.3) and sodium tert-butoxide.

12. The process of claim 9, wherein the polymer (P0) is added to the compound (I) which is in a stoichiometric excess and pre-dissolved in solution.

13. A process for preparing block copolymers (P2) comprising condensing at least the PAES polymer (P1) of claim 1, with at least a block polymer, optionally sulfonated, selected from the groups consisting of: aliphatic block polymers selected from the group consisting of polyolefins, polyesters (PE), polysiloxanes, polyalkylene oxide (PAO), polyamides (PA) and polyfluoropolymers, and aromatic block polymers selected from the group consisting of poly(aryl ether sulfone) (PAES) distinct from polymer (P1), poly(aryl ether ketone) (PAEK), poly(aryl sulphide) (PAS), poly(ether imide) (PEI), polyphenylene ether (PPE), Liquid Crystalline Polyester (LCP), polycarbonate (PC) and polyamideimide (PAI), in the presence of a base and a polar aprotic solvent at a temperature ranging from 50 and 250° C.

14. The process of claim 13, wherein the condensation takes place at a temperature ranging from 70 and 120° C., in a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N,Ndimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and sulfolane, for at least 1 hour.

15. Block copolymers (P2) obtainable by the process of claim 13.

16. The process of claim 9, wherein the molar ratio of compound (I)/ polymer (P0) is higher than 5.

17. The process of claim 9, wherein reacting the PAES polymer (P0) is carried out in the presence of a base and a polar aprotic solvent at a temperature between 70 and 120° C.

Description

EXAMPLES

(1) Two functionalized PPSU polymers (P1) were prepared and characterized.

(2) One of these polymers is according to the invention, the other one is a comparative one.

(3) Molecular Weight (Mn & Mw)

(4) Gel permeation chromatography (GPC) analyses were carried out using a Waters 2695 Separations Module and a Waters 2487 Dual Wavelength Absorbance detector with methylene chloride as an eluent on two PLgel 5 μm mixed-D columns (300×7.5 mm). An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 15 μL of a 0.2 w/v % solution in mobile phase was selected. Calibration was performed with 10 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn and weight average molecular weight Mw were reported.

(5) Thermal Gravimetric Analysis (TGA)

(6) 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.

(7) DSC

(8) 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.

(9) HNMR

(10) HNMR spectra were measured using a 400 MHz Bruker spectrometer with CDCl.sub.3 as a solvent. All spectra are reference to residual proton in the solvent.

I. Synthesis of the Functionalized PPSU Polymers (P1)

Example 1—Synthesis of Octyl Bromide Terminated PPSU (PPSU Phenoxy Chain Ends Added to 1,8-Dibromooctane in Excess and Dissolved in Solution) (Inventive and Preferred Way of Component Addition)

(11) This example demonstrates the synthesis of a functionalized PPSU polymer, more precisely functionalized with two terminal molecules according to the following scheme:

(12) ##STR00015##

Formation of the KO-PPSU-OK Reactant Solution

(13) 4,4′-dichlorodiphenyl sulfone (14.34 g, 0.0499 mol), 4,4′-Biphenol (9.85 g, 0.0529 mol), K.sub.2CO.sub.3 (7.67 g, 0.0555 mol), and sulfolane (46.67 g, 30 wt % solids) were combined in a 1 L 4-neck reaction vessel equipped with a mechanical stirrer, a Dean-Stark trap (wrapped in heat tape at ˜100° C.), an internal thermometer, and a nitrogen sparge tube. The resulting mixture was then slowly heated with stirring (˜30 min) to 210° C. and held at that temperature for 3.5 hours. Following build in molecular weight, the reaction mixture was then cooled to 150° C., diluted with anhydrous NMP (about 17 g), a second charge of K.sub.2CO.sub.3 was added (7.67 g, 0.0555 mol), and the mixture was continually stirred at 150° C. This describes the formation of the KO-PPSU-OK reactant solution.

(14) Formation of the 1,8-Dibromooctane Reactant Solution

(15) Separately, in a 250 mL 3 neck round bottomed flask equipped with a mechanical stirrer and nitrogen purge 1,8-dibromooctane (32 g, 0.118 mol, 20 eq to hydroxyl/phenoxide end groups) was dissolved in NMP (16.67 g) and heated to 100° C. with continuous stirring.

(16) Reaction of KO-PPSU-OK with 1,8-Dibromooctane

(17) Subsequently, the KO-PPSU-OK reactant solution at 150° C. was slowly poured into the 1,8-dibromooctane solution stirring at 100° C. Upon complete addition of the KO-PPSU-OK to the 1,8-dibromooctane solution, the resulting mixture was heated to 150° C. and stirred at this temperature for 2 hours and then cooled to 25° C.

(18) Isolation of Final Octyl Bromide Terminated PPSU Polymer

(19) To collect the final polymer, the reaction was further diluted with NMP (13 g), filtered via pressure filtration to remove potassium salts followed by coagulation in a blender using Hot Water (500 mL). The precipitated white solid was then collected via vacuum filtration and repeatedly subjected wash/filtration cycles using hot water (3×500 mL) and was continuously extracted overnight using a Soxhlet extractor with methanol as a solvent to remove the residual 1,8-dibromooctane. The same Soxhlet procedure was repeated a second time using acetone as a solvent. Upon drying the extracted solids in a vacuum oven (110° C., 36 mmHg) for 16 h the final polymer was yielded as a white solid.

(20) Characterization of Octyl Bromide Terminated PPSU Polymer

(21) The material obtained by the aforementioned process was characterized by GPC, TGA, DSC, and HNMR. GPC was used to determine molecular weights (Mn & Mw) and polydispersity index (PDI). TGA was used to determine the decomposition onset at 5% weight loss (Tdec (5% loss)). HNMR was used to determine end group conversions and to confirm expected bond connections. DSC was used to determine glass transition temperatures (Tg) and melting points (Tm), if present.

(22) Results:

(23) Mn=10,699 g/mol

(24) Mw=21,679 g/mol

(25) PDI=2.03

(26) Tg=191° C. No Tm was detected on the first or second heat.

(27) The TGA analysis of the polymer gave a two-step decomposition profile. The first step showed a 2 wt. % loss that started at 298° C. and ended at 368° C. The second step showed a 57 wt. % loss that started at 405° C.

(28) By proton NMR, two signals were present in the final sample that proved diagnostically significant in confirming the desired structure formed. First, the CH2 groups adjacent to the bromine atom (CH.sub.2Br) were present at 3.39 ppm. Second, the CH.sub.2 groups adjacent to the newly formed alkyl aryl ether (PhOCH2) were present at 3.98 ppm. These two signals integrated 1:1 relative to one another as would be expected should the alkyl-aryl ether bond form between the alkyl halide and the polymer chain end. Further evidence of high end group conversion obtained by proton NMR was found by examining the aryl protons alpha to the OH group on the phenyl ring. These signals shifted quantitatively from 6.89 ppm to 6.95 ppm.

Example 2—Synthesis of Pentyl Bromide Terminated PPSU (1,5-Dibromopentane Added to PPSU Phenoxy Chain Ends) (Inventive and Preferred Way of Component Addition)

(29) This example demonstrates the synthesis of a functionalized PPSU polymer, more precisely functionalized with two terminal molecules according to the following scheme:

(30) ##STR00016##

(31) Formation of the KO-PPSU-OK Reactant Solution

(32) 4,4′-dichlorodiphenyl sulfone (14.34 g, 0.0499 mol, 1.00 eq), 4,4′-Biphenol (9.85 g, 0.0529 mol, 1.06 eq), K.sub.2CO.sub.3 (7.67 g, 0.0555 mol, 1.11 eq.), and sulfolane (46.67 g, 30 wt % solids) were combined in a 1 L 4-neck reaction vessel equipped with a mechanical stirrer, a Dean-Stark trap (wrapped in heat tape at ˜100° C.), an internal thermometer, and a nitrogen sparge tube. The resulting mixture was then slowly heated with stirring (˜30 min) to 210° C. and held at that temperature for 3.5 hours. Following build in molecular weight, the reaction mixture was then cooled to 150° C., diluted with anhydrous NMP (about 17 g), a second charge of K.sub.2CO.sub.3 was added (7.67 g, 0.0555 mol), and the mixture was continually stirred at 150° C. This describes the formation of the KO-PPSU-OK reactant solution.

(33) Formation of the 1,5-Dibromopentane Reactant Solution

(34) Separately, in a 250 mL 3 neck round bottomed flask equipped with a mechanical stirrer and nitrogen purge 1,5-dibromopentane (27.05 g, 0.118 mol, 20 eq to hydroxy end groups) was dissolved in NMP (16.67 g) and heated to 100° C. with continuous stirring.

(35) Reaction of KO-PPSU-OK with 1,5-Dibromopentane

(36) Subsequently, the KO-PPSU-OK reactant solution at 150° C. was slowly poured into the 1,5-dibromopentane solution stirring at 100° C. Upon complete addition of the KO-PPSU-OK to the 1,8-dibromooctane solution, the resulting mixture was allowed to stir for 2 hours at 100° C. and was then cooled to 25° C.

(37) Isolation of Final Pentyl Bromide Terminated PPSU Polymer

(38) To collect the final polymer, the reaction was further diluted with NMP (13 g), filtered via pressure filtration to remove potassium salts and then coagulated in a blender using hot water (500 mL). The precipitated white solid was then collected via vacuum filtration and repeatedly subjected wash/filtration cycles using methanol (6×500 mL) and hot water (3×500 mL). The washed solids were then dried in a vacuum oven (110° C., 36 mmHg) for 16 h to yield the final polymer as a white powder. GC-MS analysis of the solids indicated the presence of only 48 ppm residual 1,5-dibromopentane indicating the wash protocol was successful in removing the excess unreacted starting materials.

(39) Characterization of Pentyl Bromide Terminated PPSU Polymer

(40) The material obtained by the aforementioned process was characterized by GPC, TGA, DSC, and HNMR. GPC was used to determine molecular weights (Mn & Mw) and polydispersity index (PDI). TGA was used to determine the decomposition onset at 5% weight loss (Tdec (5% loss)). HNMR was used to determine end group conversions and to confirm expected bond connections. DSC was used to determine glass transition temperatures (Tg) and melting points (Tm), if present.

(41) Results:

(42) Mn=11,413 g/mol

(43) Mw=23,388 g/mol

(44) PDI of 2.05

(45) Tg=200.4° C. No Tm was detected on the first or second heat.

(46) The TGA analysis of the polymer gave a two-step decomposition profile. The first step showed a 2 wt. % loss that started at 298° C. and ended at 354° C. The second step showed a 55 wt. % loss that started at 408° C.

(47) By proton NMR, two signals were present in the final sample that proved diagnostically significant in confirming the desired structure formed. First, the CH.sub.2 groups adjacent to the bromine atom (CH.sub.2Br) were present at 3.43 ppm. Second, the CH.sub.2 groups adjacent to the newly formed alkyl aryl ether (PhOCH2) were present at 3.99 ppm. These two signals integrated 1:1 relative to one another as would be expected should the alkyl-aryl ether bond form between the alkyl halide and the polymer chain end. Further evidence of high end group conversion obtained by proton NMR was found by examining the aryl protons alpha to the OH group on the phenyl ring. These signals shifted quantitatively from 6.89 ppm to 6.95 ppm.

Example 3—Synthesis of Octyl Bromide Terminated PPSU (1,8-Dibromooctane Added to PPSU Phenoxy Chain Ends) (Inventive)

(48) This example demonstrates the synthesis of a functionalized PPSU polymer, more precisely functionalized with two terminal molecules according to the following scheme:

(49) ##STR00017##

(50) 4,4′-dichlorodiphenyl sulfone (14.34 g, 0.0499 mol, 1.00 eq), 4,4′-Biphenol (9.85 g, 0.0529 mol, 1.06 eq), K.sub.2CO.sub.3 (7.67 g, 0.0555 mol, 1.11 eq.), and sulfolane (46.67 g, 30 wt % solids) were combined in a 1 L 4-neck reaction vessel equipped with a mechanical stirrer, a Dean-Stark trap (wrapped in heat tape at ˜100° C.), an internal thermometer, and a nitrogen sparge tube. The resulting mixture was then slowly heated with stirring (˜30 min) to 210° C. and held at that temperature for 3.5 h. Following build in molecular weight, the reaction mixture was then cooled to 150° C. and diluted with anhydrous NMP (about 33 g) and K.sub.2CO.sub.3 was added (7.67 g, 0.0555 mol). Following stirring for 10 min, 1,8-dibromooctane (32 g, 0.118 mol, 20 eq to hydroxy end groups) was slowly injected via syringe and the resulting mixture was allowed to stir for 2 h at 150° C.

(51) To collect the final polymer, the reaction was further diluted with NMP (13 g) and subsequently filtered via pressure filtration to remove potassium salts followed by coagulation in a blender using Methanol (500 mL). The precipitated white solid was then collected via vacuum filtration and repeatedly subjected wash/filtration cycles using hot water (3×500 mL), methanol (3×500 mL), and acetone (2×500 mL) and was subsequently dried in a vacuum oven (110° C., 36 mmHg) for 16 h to yield the final polymer as a white solid.

(52) With respect to GPC analysis, the sample obtained gave a Mn of 14,567 g/mol, a Mw of 35,290 g/mol, and a PDI of 2.42. Compared to the molecular weight values found for example 1, the Mn was significantly higher (14,567 g/mol vs 10,699 g/mol) as was the Mw (35,290 g/mol vs 21,679 g/mol) and the PDI (2.42 vs 2.03). This suggests that significant chain extension occurred upon introducing the 1,8-dibromooctane to the phenoxy chain ends. This means a portion of the 1,8-dibromooctane reacted at both ends thereby inserting an octyl chain in the backbone. Thus, the process described in comparative example 2 alters away from placing the desired octyl bromide groups exclusively at the chain terminus of the PPSU structure.

II. Synthesis of the Block Copolymers (P2)

Example 4—Synthesis of PES-b-PPSU Using Octyl Bromide Terminated PPSU of Example 1 (Inventive)

(53) This example demonstrates the synthesis of a block copolymer comprising a PPSU-PES block copolymer using the functionalized PPSU polymer of example 1 and reacting it with an PhOK terminated PES oligomer according to the following scheme:

(54) ##STR00018##

(55) Formation of the KO-PES-OK Reactant

(56) 4,4′-dichlorodiphenyl sulfone (2.63 g, 0.0917 mol, 1.00 eq), Bisphenol-S (2.45 g, 0.00979 mol, 1.07 eq), K.sub.2CO.sub.3 (1.39 g, 0.0010 mol, 1.03 eq.), and sulfolane (11.85 g, 30 wt % solids) were combined in a 100 mL 3-neck reaction vessel equipped with a mechanical stirrer, a Dean-Stark trap (wrapped in heat tape at ˜100° C.), an internal thermometer, and a nitrogen sparge tube. The resulting mixture was then slowly heated with stirring (˜45 min) to 230° C. and held at that temperature for 4 h. Following build in molecular weight, the reaction mixture was then cooled to 150° C. and continually stirred.

(57) Formation of the Octyl Bromide Terminated PPSU (Reaction Solution

(58) Br(CH.sub.2).sub.8O-PPSU-O(CH.sub.2).sub.8Br according to Example 1 (4.67 g, 257.14 μeq/g end groups, 1:1 with respect to PES PhOK end groups) was dissolved in NMP (10.9 g, 30 wt. % solids) at 25° C. with continuous stirring.

(59) Reaction of KO-PES-OK with Br(CH.sub.2).sub.8O-PPSU-O(CH.sub.2).sub.8Br

(60) Subsequently, the KO-PES-OK solution stirring at 150° C. was injected via syringe into the Br(CH.sub.2).sub.8O-PPSU-O(CH.sub.2).sub.8Br reactant solution at 25° C. Upon complete addition, the resulting mixture was allowed to equilibrate to a temperature of 120° C. for 16 hours at which point the reaction was cooled to 25° C.

(61) Isolation of Final PES-b-PPSU Block Copolymer

(62) To collect the final block copolymer, the reaction was further diluted with NMP (8.5 g), filtered via pressure filtration to remove potassium salts and then coagulated in a blender using a 1:1 mixture of hot water/methanol (500 mL). The precipitated white solid was then collected via vacuum filtration and repeatedly subjected wash/filtration cycles using hot water (3×500 mL). The washed solids were then dried in a vacuum oven (110° C., 36 mmHg) for 16 h to yield the final polymer as a white powder.

(63) Characterization of PES-b-PPSU Block Copolymer

(64) The material obtained by the aforementioned process was characterized by GPC, TGA, DSC, and HNMR. GPC was used to determine molecular weights (Mn & Mw) and polydispersity index (PDI). TGA was used to determine the decomposition onset at 5% weight loss (Tdec (5% loss)). HNMR was used to determine end group conversions and to confirm expected bond connections. DSC was used to determine glass transition temperatures (Tg) and melting points (Tm), if present.

(65) Results:

(66) Mn=23,286 g/mol

(67) Mw=87,761 g/mol

(68) PDI of 3.30.

(69) The doubling of molecular weight (Mn) and quadrupling of Mw relative to the molecular weight of the Br(CH.sub.2).sub.8O-PPSU-O(CH.sub.2).sub.8Br produced in Example 1 confirms chain extension to form the desired PES-b-PPSU block copolymer.

(70) The DSC analysis of the block copolymer gave a single Tg=219.4° C., which was expected in view of the identical Tg values of both PPSU and PES (typical Tg=220° C.).

(71) The TGA analysis of the block copolymer gave a one-step decomposition profile. The first step showed a 56 wt. % loss that started at 403° C.

(72) By proton NMR, one signal was present in the final PPSU-PES block copolymer sample that proved diagnostically the desired structure formed. The CH.sub.2 groups adjacent to the bromine atom (CH.sub.2Br) present at 3.39 ppm in the Br(CH.sub.2).sub.8O-PPSU-O(CH.sub.2).sub.8Br sample of Example 1 completely disappeared following block copolymerization leaving only a single broad peak present at 3.97 ppm. This peak is assigned to overlapping CH.sub.2 alkyl aryl ether signals (PhOCH2-) arising from alkyl aryl ether connections made between the PES and PPSU (both PES-OCH2- and PPSU-OCH2 are at nearly identical chemical shifts).