Poly triblock

In Chapters 3 and 11 reference was made to thermoplastic elastomers of the triblock type. The most well known consist of a block of butadiene units joined at each end to a block of styrene units. At room temperature the styrene blocks congregate into glassy domains which act effectively to link the butadiene segments into a rubbery network. Above the Tg of the polystyrene these domains disappear and the polymer begins to flow like a thermoplastic. Because of the relatively low Tg of the short polystyrene blocks such rubbers have very limited heat resistance. Whilst in principle it may be possible to use end-blocks with a higher Tg an alternative approach is to use a block copolymer in which one of the blocks is capable of crystallisation and with a well above room temperature. Using what may be considered to be an extension of the chemical technology of poly(ethylene terephthalate) this approach has led to the availability of thermoplastic polyester elastomers (Hytrel—Du Pont Amitel—Akzo). 

Poly(dimethyl siloxanc) with vinyl or hydrosilanc (Si-H) chain ends have been converted to ATRP initiator ends e.g. Scheme 9.62) by hydrosilylalion, Bis-functional dimethyl siloxane polymers prepared in this way were used in polymerizations of S, MA, tsobornyl acrylate and BA to form ABA triblock copolymers. 

J.H. Grezlak, The Preparation and Physical Properties of Polyester-Poly(Methyl Methacrylates) Triblock Copolymers , TR for Jan 1— March 1, 1975, Contract N00014-67-A-0151-0011. Princeton Univ, Princeton (1975)... 

Polystyrene-Woc -polysulfone-/ /oc -polystyrene and poly(butyl acrylate)-Woc -polysulfone-/ /oc -poly(butyl acrylate) triblock copolymers were prepared using a macroinitiator.214 The hydroxyl-terminated polysulfone was allowed to react with 2-bromopropionyl bromide, an atomic transfer radical polymerization (ATRP) initiator, in the presence of pyridine. The modified macroinitiator could initiate die styrene polymerization under controlled conditions. 

Morphology of the anionically synthesized triblock copolymers of polyfp-methyl-styrene) and PDMS and their derivatives obtained by the selective chlorination of the hard segments were investigated by TEM 146). Samples with low PDMS content (12%) showed spherical domains of PDMS in a poly(p-methylstyrene) matrix. Samples with nearly equimolar composition showed a continuous lamellar morphology. In both cases the domain structure was very fine, indicating sharp interfaces. Domain sizes were estimated to be of the order of 50-300 A. 

Poly(styrene-/7-isobutylene-/ -styrene) (PS-PIB-PS), triblock copolymers can be prepared via coupling of living PS-PIB diblock copolymers in a one-pot procedure [12]. 

Kennedy J.P. and Price J.L., S3Tithesis, characterization and physical properties of poly(methyl methacrylate-b-isobutylene-b-methyl methacrylate) triblock copol3miers, Polym. Mater. Set Eng., 64, 40, 1991. 

A series of poly(ester-urethane) urea triblock copolymers have been synthesized and characterized by Wagner et al/ using PCL, polyethylene glycol, and 1,4 diisocyanatobutane with either lysine ethyl ester or putrescine, as the chain extender. These materials have shown the elongation at break from 325% to 560% and tensile strengths from 8 to 20 MPa. Degradation products of this kind of materials did not show any toxicity on cells. 

FIGURE 20.10 (a,b) Phase images of cryo-ultramicrotomed surfaces of triblock copolymer styrene and ethylene-butylene (SEES) samples of neat material and loaded with oil (40 wt%), respectively. (c,d) Phase images of film of triblock copolymer poly(methyl methacrylate-polyisobutylene-poly(methyl methacrylate) (PMMA-PIB-PMMA) immediately after spin-casting and after 3 h annealing at 100°C, respectively. Inserts in the top left and right comers of the images show power spectra with the value stmctural parameter of microphase separation. 

Based on the synthesis of polyphosphazenes and of diblock copolyphosp-hazenes by the living cationic polymerization of phosphoranimines [237,241], the triblock poly(phosphazene-ethylene oxide) copolymer XVIII was synthesized by Allcock [223]. 

Uchegbu and coworkers have studied the complexation and delivery of DNA using a unique poly(amino acid)-based polymer vesicle. A polymer of either poly (L-lysine) or poly(L-omithine) was functionalized with methoxy-poly(ethylene glycol) (mPEG) and hydrophobic palmitic acid chains to synthesize an amphiphilic triblock of either mPEG-6-poly(L-lysine)-6-palmitoyl or mPEG-Z>-poly(L-omithine)-6-palmitoyl. Vesicles formed from these polymers were complexed with DNA and showed improved transfection in vitro over poly(amino acid) complexed with DNA or DNA alone [82]. 

Wanka, G Hoffman, H Ulbricht, W, Phase Diagrams and Aggregation Behavior of Poly (oxyethylene)-Poly(oxypropylene)-Poly(exyethylene) Triblock copolymers in Aqueous Solutions, Macromolecules 27, 4145, 1994. 

Drug Release from PHEMA-l-PIB Networks. Amphiphilic networks due to their distinct microphase separated hydrophobic-hydrophilic domain structure posses potential for biomedical applications. Similar microphase separated materials such as poly(HEMA- -styrene-6-HEMA), poly(HEMA-6-dimethylsiloxane- -HEMA), and poly(HEMA-6-butadiene- -HEMA) triblock copolymers have demonstrated better antithromogenic properties to any of the respective homopolymers (5-S). Amphiphilic networks are speculated to demonstrate better biocompatibility than either PIB or PHEMA because of their hydrophilic-hydrophobic microdomain structure. These unique structures may also be useful as swellable drug delivery matrices for both hydrophilic and lipophilic drugs due to their amphiphilic nature. Preliminary experiments with theophylline as a model for a water soluble drug were conducted to determine the release characteristics of the system. Experiments with lipophilic drugs are the subject of ongoing research. 

SM O Connor, SH Gehrke, S Patuto, GS Retzinger. Fibrinogen-dependent adherence of macrophages to surfaces coated with poly(ethylene oxide)/poly(propylene oxide) triblock copolymers. Ann NY Acad Sci 831 138-144, 1997. 

A polystyrene-poly(ethylene,l-butene)-polystyrene triblock copolymer is produced by the selective hydrogenation of the corresponding triblock copolymer in which the center block consists of random placements of 1,2-poly(1,3-butadiene) and 1,4-poly (1,3-butadiene) units. 

Applying the slow and continuous monomer-addition (quasiliving) technique, we polymerized IBVE and MVE with the -DCC/ AgSbFg initiating system and defined optimum reaction conditions for the quasiliving polymerization of these monomers. Subsequent block polymerization starting poly(IBVE) quasiliving dications led to novel triblock polymers poly(aMeSt-b-IBVE-b-aMeSt) and poly-(MVE-b-IBVE-b-MVE). 

Symmetric triblock copolymers of the ABA type, where B was PTHF and A poly(2-methyl-2-oxazoline), PMeOx, were prepared by cationic polymerization with trifluoromethanesulfonic anhydride as a difunctional initiator [58]. Subsequent hydrolysis of the PMeOx blocks with HC1 in a methanol/ water mixture resulted in the formation of the corresponding polyethylen-imine blocks (Scheme 20). Samples with relatively low molecular weight distributions were obtained. 

A novel coil-rod-coil triblock copolymer, where the rod block was polyflu-orene, PF, and the coil blocks poly(2-tetrahydropyranyl methacrylate),... 

ABC, ACB, and BAC triblock terpolymers, where A is PMMA, B is PDMAEMA, and C is poly[hexa(ethylene glycol)methacrylate], PHEGMA, were synthesized via GTP and sequential monomer addition [89]. The polymerizations were conducted in THF using MTS and TBABB as the initiator... 

The triblock terpolymer polypropylene oxide)-h-poly[2-(dimethylami-no)ethyl methacrylate]-b-poly[oligo(ethylene glycol) methacrylate], PPO-fc-PDMAEMA-fc-POEGMA, was prepared using the PPO macroinitiator followed by the addition of CuCl, HMTETA, and DMAEMA for the polymerization of the second block and finally OEGMA for the synthesis of the final product (Scheme 54) [128]. 

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