Synthesis of Telechelic and Three-Arm Polytetrahydrofuran-block-amylose

Abstract

Telechelic amine terminated polytetrahydrofuran (PTHF) is prepared via cationic ring opening polymerization (CROP) of THF, initiated by trifluoromethanesulphonic anhydride (triflic anhydride). Hexamethylene tetramine (HMTA) is used as a terminating agent. The resulting HMTA terminated PTHF is hydrolyzed to result in an amine terminated PTHF. Reductive amination is carried out by reacting the PTHF with maltoheptaose resulting in maltoheptaose‐b‐PTHF‐b‐maltoheptaose. The product is prepared as a primer for the enzymatic polymerization to synthesize amylose‐b‐PTHF‐b‐amylose. In addition, a three‐arm PTHF is prepared via CROP of THF. The initiator is synthesized in situ by the reaction of triflic anhydride and triethanol amine. The resulting amine terminated three‐arm PTHF is reacted with maltoheptaose to synthesize a three‐arm PTHF‐b‐maltoheptaose which can be used for the enzymatic synthesis of three‐arm PTHF‐b‐amylose. Characterization of the products is difficult due to the amphiphilic behavior of both telechelic amylose‐b‐PTHF‐b‐amylose and three‐arm PTHF‐b‐amylose. Therefore, the analysis of the products is mainly based on attenuated total reflectance Fourier transform infrared spectroscopy.

Properties of Electrospun Nanofibers of Multi-Block Copolymers of [Poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone)]m Synthesized by Janus Polymerization

“…Both the synthesis and properties of THF-based polymers were widely reported in the literature [ 11 ]. THF can only undergo cationic ring-opening polymerization (ROP) to produce polytetrahydrofuran (PTHF), which is widely used as the soft segments in thermoplastic elastomers such as polyurethanes and polyesters due to its excellent elastomeric properties [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. Differing from random P(THF- co -CL) as a soft viscous oil obtained by cationic polymerization, multi-block copolymers of [PCL- b -P(THF- co -CL)] m are thermoplastic elastomers with high strain at break of over 1000% and moderate tensile strength of 15 MPa, where crystallized PCL segments generate hard domains and amorphous P(THF- co -CL) blocks act as soft segments [ 21 ].…”

Amylose engineering: phosphorylase‐catalyzed polymerization of functional saccharide primers for glycobiomaterials

“…Phosphorylase‐catalyzed polymerization can be used not only with bifunctional primers but also with trifunctional primers. Rachmawati et al prepared three‐armed poly(tetrahydrofuran) (PTHF)‐ b ‐maltoheptaose using a combination of cationic ring‐opening polymerization and reductive amination . The resulting polymers can be used as primers for the enzymatic synthesis of three‐armed PTHF‐ b ‐amylose.…”

“…Chemical structures and diagrams of amylose‐primer‐modified poly(ethylene glycol)s (a) and chemical structures of hydrophobic guest molecules (b). (Reprinted with permission from Ref . Copyright 2015 American Chemical Society)…”

“…Rachmawati et al prepared threearmed poly(tetrahydrofuran) (PTHF)-b-maltoheptaose using a combination of cationic ring-opening polymerization and reductive amination. 29 The resulting polymers can be used as primers for the enzymatic synthesis of three-armed PTHF-b-amylose.…”

Glyco-Nanoparticles Made from Self-Assembly of Maltoheptaose-block-Poly(methyl methacrylate): Micelle, Reverse Micelle, and Encapsulation

“…During the past decades, since the pioneer study carried out by Ziegast and Pfannemüller, increasing number of studies on block copolymers (BCPs) consisting of oligo- or polysaccharides, such as maltoheptaose, − dextran, − and amylose, − have been reported for the purpose of developing, specially, biomimetic and bioinspired nanomaterials. Thus, considering the biodegradability and biocompatibility properties exhibited by the polysaccharides, several synthetic polymers have been covalently coupled to the polysaccharides using different approach such as combinations of controlled living radical polymerizations (e.g., reversible addition–fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP)) and click-chemistry, forming saccharide hybrid block copolymers.…”