A series of linear poly glycidol copolymers, tethering with both alkene and hydroxyl groups, were prepared by a combination of anionic ring-opening polymerization （ROP） using specific reactions of ethoxy ethyl glycidyl ether （EEGE） and allyl glycidyl ether （AGE） firstly, and subsequently removal of the protection group of glycidol in EEGE to achieve the linear copolymer pendant with both hydroxyl groups and double bonds. The EEGE/AGE monomer reactivity ratio is measured to be 3.30/1.13. The chemical compositions of the as-synthesized polymers were characterized by tH NMR and GPC, and the glass transition temperatures （Tg） of as-synthesized polymers were determined by DSC. The final copolymers have abundant double bonds and hydroxyl as side groups. Furthermore, the ratio of the double bonds to hydroxyl groups can be controlled by the ratio of the starting materials in a wide range.
Two triblock polymers, tetraaniline-block-poly（N-isopropyl acrylamide）-block-poly（hydroxyethyl acrylate） （TA-b-PNIPAM-b-PHEA） and TA-b-PHEA-b-PNIPAM, were synthesized with unambiguous structure by a two step method. The difference of these two diblock polymers is the connection order of carboxyl group to block, e.g., carboxyl group to PNIPAM block for PNIPAM-b-PHEA and to PHEA block for PHEA-b-PNIPAM. Secondly, block tetraaniline was linked to the diblock polymer through amidation to yield the corresponding triblock copolymer. Both of them have almost the identical chemical compositions. The only difference is the connection order of each block in the triblock polymers. When they were self-assembled at 45℃ in a suitable solution, both of their aggregates have spherical shape with slight defects on their surface with the average diameter of about 400 nm. However, when their aggregate dispersion was cooled down to 20 ℃, only TA-b-PHEA-b-PNIPAM＇s morphology changed, forming worm-like aggregates with the diameter of about 100-200 nm transformed from spherical ag- gregates. Both amphiphilic property and position of each block in this triblock copolymer are very essential for this morphology transformation. Since the worm-like aggregates presented here by our group have hollow structure in- side, its controlled release properties for doxorubicin were evaluated. Drug release experiment indicated that along with the temperature changes, the rearrangement of the intermediate layer structure caused morphology change in aggregate, thus accelerating the speed of drug release.
