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Home Focus Chemicals

Molecular-weight polymer selection

17. February 2019
in Chemicals
Industry Process Food Beverage

Researchers at Kanaza­wa Uni­ver­si­ty report in Nature Com­mu­ni­ca­tions that a crys­tal of mol­e­cules known as pillar[5]arenes can form a host–guest com­pound with poly(ethylene oxides) poly­mers. The effect can be used to select poly­mers with dif­fer­ent mol­e­c­u­lar weights and end groups.

When poly­mers are con­fined into one-dimen­sion­al (1D) chan­nels, they behave dif­fer­ent­ly. Their dynam­ics changes, and they may chem­i­cal­ly bind to the sur­round­ing chan­nel. A team of researchers led by Tomo­ki Ogoshi from Kanaza­wa Uni­ver­si­ty has now shown that such 1D con­fine­ment, pro­vid­ed by a mol­e­c­u­lar crys­tal of so-called acti­vat­ed pillar[5]arenes, can be used to selec­tive­ly cap­ture dif­fer­ent types of polymers.

The sci­en­tists stud­ied host–guest bind­ing (‘com­plex­a­tion’) between acti­vat­ed pillar[5]arenes (abbre­vi­at­ed ‘P5’) and poly(ethylene oxide) poly­mers (abbre­vi­at­ed ‘PEO’). P5 is a mol­e­cule con­sist­ing of 5 iden­ti­cal organ­ic units fea­tur­ing a ben­zene ring, with a pen­tag­o­nal shape. The monomer­ic build­ing block of PEO is O‑CH2-CH2; PEOs with 100 or more monomers can eas­i­ly be synthesized.

Host–guest com­plex­a­tion was achieved by first melt­ing PEO at 80°C, and then immers­ing the P5 mol­e­cules acti­vat­ed by dry­ing sol­vates into the melt. By means of nuclear mag­net­ic res­o­nance (NMR) spec­troscopy mea­sure­ments, Ogoshi and col­leagues were able to show that PEO mol­e­cules were tak­en up by the P5 struc­ture. X‑ray dif­frac­tion exper­i­ments showed that the crys­tal struc­ture of the P5 mol­e­cules had changed into a net­work fea­tur­ing channels.

The researchers then looked at what hap­pened with a mix­ture of PEOs con­sist­ing of var­i­ous num­bers of monomers. The num­ber of build­ing blocks affects the weight — the more monomers, the heav­ier the poly­mer. Ogoshi and col­leagues dis­cov­ered that the heav­ier PEOs were tak­en up in larg­er quan­ti­ties, show­ing that the P5 host can select PEOs with high mass frac­tion from a poly­dis­perse mix­ture. By means of com­put­er sim­u­la­tions, it was pos­si­ble to attribute this find­ing to an increased bind­ing ener­gy for the larg­er (heav­ier) PEOs.

The sci­en­tists also inves­ti­gat­ed the effect of the PEO’s end group. The fastest PEO uptake was observed for methoxy end groups (O‑CH3), for which an equi­lib­ri­um state was reached after 3 min­utes. For OH and NH2 end groups, the times to reach equi­lib­ri­um were 10 and 20 min­utes, respec­tive­ly. Uptake for PEO with COOH as the end group was slow.

The obser­va­tion by Ogoshi and col­leagues that P5 crys­tals can per­form high mass frac­tion­a­tion from poly­mer mix­tures with a broad mol­e­c­u­lar-weight dis­tri­b­u­tion is impor­tant because, quot­ing the sci­en­tists, “high-mol­e­c­u­lar-weight poly­mers gen­er­al­ly exhib­it supe­ri­or char­ac­ter­is­tics such as increased ther­mal sta­bil­i­ty, improved mechan­i­cal prop­er­ties, and high­er crys­tallini­ty com­pared with low-mol­e­c­u­lar-weight polymers.”

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