Recent progress to construct calixarene-based polymers using covalent bonds: synthesis and applications

Abstract

The combination of supramolecular chemistry and polymer sciences creates a great possibility to afford calixarene-based polymers offering unique features and applications. The enhancement of calixarene's versatility in this manner has made chemists better able to achieve different objectives in host-guest chemistry. The calixarene-based polymers can be divided into covalent polymers and supramolecular polymers regarding the interactions. Although there are several studies available on the calixarene-based supramolecular polymers, there is a paucity of studies on the calixarene-based covalent polymers. In this paper, the most recent developments and applications of the calixarene-based covalent polymers in the last two decades have been reviewed. We have particularly focused on the polymers, including those where the calixarene molecules have been used as macromonomers and polymerize through covalent bonds. Moreover, covalent polymers or solid supports functionalized with calixarenes are highlighted as well.

Scheme 1. Calix[4]arene nanosheet 3 synthesis by Sonogashira–Hagihara cross-coupling reaction.

Scheme 2. Preparation of copolymers 7 and 8.

Scheme 3. General synthesis of poly calix[4]arenes 11, 12, 13.

Scheme 4. Typical design of diazocoupling reaction of 4,4′-biphenyldiamine and C-alkylcalix[4]resorcinarenes 14.

Scheme 5. Preparation of polymer appended calix[4]amidocrown-5 18.

Scheme 6. Synthesis rout of amidoamine calix[4]resorcinarene-based polymers 21, 22.

Scheme 7. Porous calix[4]arene polymer 24 synthesis by Sonogashira–Hagihara reaction.

Scheme 8. Synthetic pathway for the preparation of polycalix[4]amide 26 and polycalix[4]arene 28.

Scheme 9. The schematic presentation of poly-calix[6]arenes 30a–c synthesis.

Scheme 10. Structure and rout of synthesis of microcapsule 33.

Scheme 11. Chemical structure of comonomers and general synthesis of copolymers 38, 39 and 40.

Scheme 12. Polymerization reaction of BCA[n] (n = 4 and 8) and BCRA[4] with ADB.

Scheme 13. Polycondensation reaction of calix[4]arene diamine 46 with optically active diacid chlorides 47.

Scheme 14. Preparation of polymers 55a–c.

Scheme 15. Preparation of polymer 59.

Scheme 16. Preparation of poly(pyridinium) 65a–b.

Scheme 17. The presentation of chiroptical polymers 68, 71.

Scheme 18. The polymerization of 1,4-diethynyl-2,5-bis(4-methylpentyloxy)benzene 72 with a bis-calix[5]arene 74.

Scheme 19. The structures of conjugated polymers 78 and 79.

Scheme 20. The structures of conjugated polymer 81.

Scheme 21. The structures of conjugated polymer 83.

Scheme 22. Chemical structure of compound 84.

Scheme 23. Polycondensation reaction of p-tert-butylcalix[4]arene derivative 85 and di hydroxyl poly(ethylene glycol).

Fig. 1. The UV spectra of the aromatic aqueous solutions before and after the extraction by CCP hydrogel.

Fig. 2. Competitive diagram between CCP and active carbon for naphthalene adsorption from gas phases.

Scheme 24. Synthesis route of the cationic polymer 88.

Scheme 25. Chemical structure of compound 89 and 90.

Scheme 26. The chemical structure of polymer 91.

Scheme 27. The synthesis route of diamino calix[4]arene derivatives as monomers.

Scheme 28. The presentation of methacrylated calix[4]arene phosphonic acids and rout of synthesis.

Scheme 29. Wang benzaldehyde resin supported calixarene–bipyridyl ligand.

Scheme 30. The target calixarene polymer 107.

Scheme 31. The synthesize route for calixarene-based Merrifield resin 111, 112.

Scheme 32. The structure of calix[4]arene-based resin 113.

Fig. 3. The percent adsorption for metal ions by modified resin 113.

Scheme 33. The synthesis route of calix[4]arene-based Merrifield resins 115, 117.

Fig. 4. Adsorption capacity of compound 115, 117 and Merrifield resin for dichromate.

Scheme 34. Pore glass and TentaGel supported calixarenes 119, 120.

Scheme 35. TentaGel supported calixarene 121.

Scheme 36. The structure of rubber chemical additives.

Scheme 37. The synthetic strategy for silica bonded calix[4]arene derivative.

Scheme 38. The synthesis of calix[n]arene-based silica polymers and immobilization of Candida rugosa lipase.

Scheme 39. Enantioselective hydrolysis reaction of racemic naproxen methyl ester by encapsulated lipases.

Scheme 40. Preparation of mesoporous hybrid materials based on calixarene.

Scheme 41. Synthesis of allyl calixarene-functionalized mesoporous silica.

Scheme 42. Structure of alanine-calix[4]arene stationary phase.

Scheme 43. General synthesis of calix[4]crown-grafted chitosan chelating polymer 145.

Scheme 44. Immobilization of calixarene derivative 147 onto cellulose and chitosan biopolymers.

Scheme 45. The representation of calixarene-functionalized polymers 150 and 151.

Scheme 46. Modification of poly acrylic acid (PAA) using calix[4]arene diamine 46.

Scheme 47. Immobilization of bifunctional calix[4]arene 157 on carbohydrate polymers.

Scheme 48. The presentation of calixarene-based functional material 160.

Reza Zadmard

Fahimeh Hokmabadi

Mohammad Reza Jalali

Ali Akbarzadeh