Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

Abstract

Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymer, a method of using triptycene-based ladder polymers, a structure incorporating triptycene-based ladder polymers, a method of gas separation, and the like.

Description

[0001] Cross References to Related Applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 61 / 859,800, filed July 30, 2013, entitled "TRIPTYCENE-BASEDL ADDER MONOMERS AND POLYMERS, METHODSOFMAKINGEACH, ANDMETHODSOFUSE," the entirety of which is incorporated herein by reference. Background technique

[0003] Gas separation is an emerging technology and the market is growing rapidly, including applications such as air separation to enrich oxygen or nitrogen, as well as removal of acid gases and recovery of hydrocarbons from natural gas streams. The economics of membrane-based separation systems depend on the gas permeability (thickness and pressure normalized flux) and selectivity (preferential permeation of one gas over another) of the materials used. Unfortunately, there is often a trade-off between these two main parameters, such that increased air permeability is accompanied by decreased selectivity, and vice versa. This leads to a...

Examples

preparation example Construction

[0031] Before examples of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, this disclosure is not limited to particular materials, reagents, reaction materials, preparation methods, etc., as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It is also possible in this disclosure that steps may be carried out in a different order which is logically feasible.

[0032] It must be noted that nouns used in the specification and appended claims include plural references. Thus, for example, reference to "a support" includes a plurality of supports. In this specification and the appended claims, various terms will be referred to, which shall be defined to have the following meanings unless it is obvious that the contrary meaning is meant.

[0033] definition:

[0034] The term "substituted" means that any...

example

[0070] Having now described some embodiments of the disclosure, the examples generally describe some additional embodiments. While embodiments of the present disclosure have been described with reference to the examples and corresponding text, it is not intended that the embodiments of the present disclosure be limited to these descriptions. On the contrary, the intention is to cover all alternatives, modifications, and equivalents as included within the spirit and scope of the embodiments of this disclosure.

example 1

[0072] Scheme (1): Synthetic pathway of A-B monomer

[0073]

[0074] Scheme 1. Synthetic pathway for 9,10-dialkyltriptycene-based A-B monomers

[0075] Reagents and conditions: (i) diazonium salts of anthranilic acid or substituted anthranilic acid, 1,2-propylene oxide, CH 2 Cl 2 , reflux; (ii) 0.25MHNO 3 , AcOH and CH 2 Cl 2 (1:1,v:v), 5 minutes; (iii) 4,5-difluoro-1,2-diaminobenzene, ethanol, reflux, 6 hours; (iv) BBr 3 、CH 2 Cl 2 ,2 hours.

[0076] where Ar is a substituted or unsubstituted aromatic moiety and, R 1 and R 2 Is aryl, alkyl (R 1 = R 2 or R 1 ≠R 2 ) halogen or hydrogen.

[0077] Scheme (2) Synthetic pathway of novel ladder polymers

[0078]

[0079] Scheme 2: Self-condensation reaction of A-B monomers to form ladder polymers with inherent microporosity.

[0080] Specific examples of ladder polymers prepared from 9,10-disubstituted A-B monomers:

[0081]

[0082]

[0001] Cross References to Related Applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 61 / 859,800, filed July 30, 2013, entitled "TRIPTYCENE-BASEDL ADDER MONOMERS AND POLYMERS, METHODSOFMAKINGEACH, ANDMETHODSOFUSE," the entirety of which is incorporated herein by reference. Background technique

[0003] Gas separation is an emerging technology and the market is growing rapidly, including applications such as air separation to enrich oxygen or nitrogen, as well as removal of acid gases and recovery of hydrocarbons from natural gas streams. The economics of membrane-based separation systems depend on the gas permeability (thickness and pressure normalized flux) and selectivity (preferential permeation of one gas over another) of the materials used. Unfortunately, there is often a trade-off between these two main parameters, such that increased air permeability is accompanied by decreased selectivity, and vice versa. This leads to a...

Examples

preparation example Construction

[0031] Before examples of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, this disclosure is not limited to particular materials, reagents, reaction materials, preparation methods, etc., as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It is also possible in this disclosure that steps may be carried out in a different order which is logically feasible.

[0032] It must be noted that nouns used in the specification and appended claims include plural references. Thus, for example, reference to "a support" includes a plurality of supports. In this specification and the appended claims, various terms will be referred to, which shall be defined to have the following meanings unless it is obvious that the contrary meaning is meant.

[0033] definition:

[0034] The term "substituted" means that any...

example

[0070] Having now described some embodiments of the disclosure, the examples generally describe some additional embodiments. While embodiments of the present disclosure have been described with reference to the examples and corresponding text, it is not intended that the embodiments of the present disclosure be limited to these descriptions. On the contrary, the intention is to cover all alternatives, modifications, and equivalents as included within the spirit and scope of the embodiments of this disclosure.

example 1

[0072] Scheme (1): Synthetic pathway of A-B monomer

[0073]

[0074] Scheme 1. Synthetic pathway for 9,10-dialkyltriptycene-based A-B monomers

[0075] Reagents and conditions: (i) diazonium salts of anthranilic acid or substituted anthranilic acid, 1,2-propylene oxide, CH 2 Cl 2 , reflux; (ii) 0.25MHNO 3 , AcOH and CH 2 Cl 2 (1:1,v:v), 5 minutes; (iii) 4,5-difluoro-1,2-diaminobenzene, ethanol, reflux, 6 hours; (iv) BBr 3 、CH 2 Cl 2 ,2 hours.

[0076] where Ar is a substituted or unsubstituted aromatic moiety and, R 1 and R 2 Is aryl, alkyl (R 1 = R 2 or R 1 ≠R 2 ) halogen or hydrogen.

[0077] Scheme (2) Synthetic pathway of novel ladder polymers

[0078]

[0079] Scheme 2: Self-condensation reaction of A-B monomers to form ladder polymers with inherent microporosity.

[0080] Specific examples of ladder polymers prepared from 9,10-disubstituted A-B monomers:

[0081]

[0082]

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