# US 11,999,825 B2 · End-capped poly(aryl ether sulfone) polymers, poly(aryl ether sulfone) block copolymers, and corresponding synthesis methods

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- Number: US 11,999,825 B2
- Document ID: US11999825B2
- Status: Granted
- Kind: B2
- Application number: 17/043,699
- Filed: 2019-04-24
- Published: 2021-05-13
- Granted: 2024-06-04
- Earliest claimed: 2018-04-26
- Assignees: Solvay Specialty Polymers USA, LLC
- Applicants: Solvay Specialty Polymers USA, LLC
- Inventors: Joel Pollino; Stéphane Jeol; Kelly D. Branham; Matthew Booher
- Web page: https://patentgrep.com/patent/US11999825B2

## CPC

- C08G 65/40: from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G 75/23: Polyethersulfones
- C08G 65/4056: {(I) or (II) containing sulfur (as the sulfone group C08G75/23)}
- C08L 77/02: Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08L77/10 takes precedence)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Described herein are end-capped poly(aryl ether sulfone) (“PAES”) polymers and corresponding synthesis methods. The end-capped PAES polymers are end-capped by functionalizing a PAES polymer with a halophthalic diialkyl ester end-capping agent. It was surprisingly discovered that the resulting dialkyl phthalate end-capped PAES polymers could be synthesized with significantly improved end-capping conversion rates, relative to end-capped PAES polymers directly functionalized with traditional phthalic anhydride end-capping agents. It was also surprisingly found that by heating the isopropyl phthalate end-capped PAES polymers, the polymers could be converted to the corresponding phthalic anhydride end-capped PAES polymers, yielding a more efficient synthetic route to phthalic anhydride end-capped PAES polymers.

## Claims

### Claim 1

A dialkyl phthalate end-capped poly(aryl ether sulfone) (“PAES”) polymer comprising: a recurring unit RPAES represented by the following formula:
wherein
R1 to R16 are independently selected from the group consisting of a hydrogen, 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;
T is selected from the group consisting of a bond, —CH2—; —O—; —SO2—; —S—; —C(O)—; —C(CH3)2—; —C(CF3)2—; —C(═CCl2)—; —C(CH3)(CH2CH2COOH)—; —N═N—; —RaC═CRb—; —(CH2)m—; —(CF2)m—; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof;
where in —RaC═CRb—, each Ra and Rb are independently selected from the group consisting of a hydrogen, a C1-C12-alkyl, a C1-C12-alkoxy, and a C6-C18-aryl group,
where in —(CH2)m— and —(CF2)m—, m is an integer from 1 to 6; and
at least at one end of the PAES polymer chain, a dialkyl phthalate radical represented the following formula:
wherein
R17 to R19 are independently selected from the group consisting of a hydrogen and a C1 to C18, substituted or unsubstituted, alkyl group;
A1, A2, A4, and A5, are independently selected from the group consisting of alkyl groups represented by the formula: —(CH2)nCH3, where n is an integer from 0 to 12;
A3 and A6 are independently selected form the group consisting of H and an alkyl group represented by the formula: —(CH2)n′CH3, where n′ is an integer from 0 to 12 and
R1 to R16 and T are the same as defined above with respect to recurring unit RPAES, wherein at least 75% of the PAES polymer chain ends comprise the dialkyl phthalate radical.

### Claim 2 (depends on 1)

The end-capped PAES polymer of claim 1, wherein T is selected from the group consisting of a bond, —C(CH3)2—, and —SO2—.

### Claim 3 (depends on 1)

The end-capped PAES polymer of claim 1, wherein the PAES polymer has a number average molecular weight of at most about 25,000 g/mol as measured by gel permeation chromatography (“GPC”) using methylene chloride as a mobile phase, with polystyrene standards.

### Claim 4 (depends on 1)

The end-capped PAES polymer of claim 1, wherein the PAES polymer has a number average molecular weight of at least 1,000 g/mol.

### Claim 5 (depends on 1)

A method for synthesizing the end-capped PAES polymer of claim 1, the method comprising:
reacting, in the presence of a base and solvent, an hydroxyl terminated PAES polymer comprising recurring unit RPAES and, at least at one end of the PAES polymer chain, a hydroxyl end-capping unit represented by the following formula:
with a halophthalic dialkyl ester end-capping agent represented by the following formula
where X is Cl or F.

### Claim 6 (depends on 5)

The method of claim 5, wherein the halophthalic dialkyl ester is a fluorophthalic diisopropyl ester.

### Claim 7 (depends on 5)

The method of claim 5, wherein the base is selected from the group consisting of potassium t-butoxide, sodium t-butoxide, cesium t-butoxide, sodium isopropoxide, potassium isopropoxide, cesium isopropopoxide, 1,8-diazabicycloundec-7-ene (“DBU”), 1,5-Diazabicyclo(4.3.30)non-5-ene (“DBN”), N,N-diisopropylethylamine (“DIPEA”), sodium hydride, potassium hydride, sodium metal, potassium metal, K2CO3, Na2CO3, Cs2CO3, and triethyl amine.

### Claim 8 (depends on 5)

The method of claim 5, wherein the solvent is a polar aprotic solvent having a boiling point of more than 200° C.

### Claim 9 (depends on 8)

The method of claim 8, wherein the solvent is selected from the group consisting of dimethylformamide (“DMF”), dimethylacetamide (“DMAC”), N-methylpyrrolidone (“NMP”), hexamethylphosporic triamide (“HMPA”), dimethyl sulfoxide (“DMSO”), and sulfolane.

### Claim 10 (depends on 1)

A method for synthesizing a PAES polymer end-capped with a phthalic anhydride radical at least at one end of the PAES polymer, the method comprising heating, at a temperature from about 250° C. to about 500° C., the dialkyl phthalate end-capped PAES polymer of claim 1.

### Claim 11 (depends on 1)

A method for synthesizing a PAES block copolymer, the method comprising reacting, in a melt, the end-capped PAES polymer of claim 1 with an amine end-capped polymer represented by a formula H2N—Z—NH2 or Z—NH2, where Z is selected from the group consisting of alkanes and polyolefins, polydimethylsiloxanes (“PDMS”), polyalkylene oxides (“PAO”), perfluoroelastomers, polyvinyl pyrrolidones, polyamides, poly(aryl ether sulfones), polyetherimides (“PEI”), polyimides, polyamideimides (′PAI″), and a poly(ether ether sulfones) (“PEES”).

### Claim 12 (depends on 11)

The method of claim 11, wherein the PAES block copolymer is an AB multiblock copolymer.

### Claim 13 (depends on 11)

The method of claim 11, wherein the PAES block copolymer is an ABA triblock copolymer.

### Claim 14

A PAES block copolymer, wherein the block copolymer is represented by the following formula:
wherein
R17 to R19 are independently selected from the group consisting of a hydrogen, 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;
Q is represented by the following formula:
wherein R1 to R16 are independently selected from the group consisting of a hydrogen, 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;
T is selected from the group consisting of a bond, —CH2—; —O—; —SO2—; —S—; —C(O)—; —C(CH3)2—; —C(CF3)2—; —C(CH3)(CH2CH2COOH)—; —N═N—; —RaC═CRb; —(CH2)m—; —(CF2)m—; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof;
where in —RaC═CRb—, each Ra and Rb, are independently selected from the group consisting of a hydrogen, a C1-C12-alkyl, a C1-C12-alkoxy, and a C6-C18-aryl group, and
where in —(CH2)m— and —(CF2)m—, m is an integer from 1 to 6; and
Z is selected from the group consisting of alkanes and polyolefins, polydimethylsiloxanes (“PDMS”), polyalkylene oxides (“PAO”), perfluoroelastomers, polyvinyl pyrrolidones, polyamides, poly(aryl ether sulfones) (“PAES”), polyetherimides (“PEI”), polyimides, polyamideimides (′PAI″), and a poly(ether ether sulfones) (“PEES”).

### Claim 15 (depends on 14)

The PAES block copolymer of claim 14, wherein T is selected from the group consisting of a bond, —C(CH3)2—, and —SO2—.

### Claim 16 (depends on 14)

The PAES block copolymer of claim 14, wherein Z is selected from the group consisting of polyamides, poly(aryl ether sulfones) (“PAES”), polyetherimides (“PEI”), polyamideimides (TAT″) and poly(ether ether sulfones) (“PEES”).

### Claim 17 (depends on 14)

The PAES block copolymer of claim 14, wherein Z is
a polyamide selected from the group consisting of: PA6; PA11; PA12; PA 6,6; PA6,10; PA10,10; PA10,6; PA6,12; PA12,12; PA10,12; and PA12,10, or
a semi-aromatic polyamide selected from the group consisting of PA4,T; PA5,T; PA6,T; PA8,T; PA9,T; PA10,T; PA 12,T; PA4,I; PA5,I; PA6,I; PA8,T; PA9,I; PA10,I, PA12,I; PA6,I/6,6; PA6,T/6,6; PA6,T/6,I/6,6; PAST/8T; MXD6, MXD10, PXD6 and PXD10.

### Claim 18 (depends on 14)

A polymer composition including from 1 wt. % to 30 wt. % of the PAES block copolymer according to claim 14 and from 70 wt. % to 99 wt. % of a thermoplastic polymer distinct from the PAES block copolymer.