Poly telechelic

A polymer can be considered to be a telechelic if it contains at least one reactive end group, which can react selectively to give a bond with another molecule. Depending on functionality, (which must be distinguished from the functionality of the end group itself), telechelics can be classified as mono-, di-, tri- or poly-telechelic. ... 

Ebdon and coworkers22 "232 have reported telechelic synthesis by a process that involves copolymerizing butadiene or acetylene derivatives to form polymers with internal unsaturation. Ozonolysis of these polymers yields di-end functional polymers. The a,o>dicarboxy1ic acid telechelic was prepared from poly(S-s tot-B) (Scheme 7.19). Precautions were necessary to stop degradation of the PS chains during ozonolysis. 28 The presence of pendant carboxylic acid groups, formed by ozonolysis of 1,2-diene units, was not reported. 

This strategy is used for the synthesis of three different exact-mass telechelic oligomers. GPC, NMR, and GC/MS evidence indicates that clean depolymerization chemistry occurs for all three samples. Poly( 1,4-butadiene) (38) is broken down into oligomeric units with two, three, and four repeat units using catalyst 23. Catalyst 14 is more efficient and produces even lower molecular weight oligomers, primarily one and two repeat units. When allylchlorodimethylsilane is used instead of ethylene with 14, telechelic dimers are the only product. 

A methacryl-type polyester macromonomer was synthesized by lipase PF-catalyzed polymerizahon of DDL using vinyl methacrylate as terminator ( terminator method ), in which the vinyl ester terminator was present from the beginning of the reachon (Scheme 17). In using divinyl sebacate as terminator, the telechelic polyester having a carboxylic acid group at both ends was obtained. Various non-protected thiol compounds were used as inihator or terminator for the thiol end-funchonalizahon of poly(8-CL). ... 

Boraindane 178 <1996CHEC-II(8)889> was applied to the preparation of new telechelic polymers, including poly(methylmethacrylate) and poly(trifluoroethyl acrylate) containing two reactive OH groups at the polymer chain <2004MM6260>. 

Initiators such as (306) initiate the ROP of CL to form telechelic triblock diols.478 Molecular weights approach theoretical values with polydispersities <1.3 and no significant level of transesterification was detected at up to 95% conversions. Alternative bimetallic samarium initiators have been used to synthesize aromatic, cumulene and amine/imine link-functionalized poly(lactones).479... 

Nair et al. studied the kinetics of the polymerization of MMA at 60-95 °C using N,1SP-diethyl-NjW-di(hydroxyethyl)thiuram disulfide (30a) as the thermal in-iferter [142]. The dependence of the iniferter concentration on the polymerization rate was examined. The chain transfer constant of the propagating radical of MMA to 30a was determined to be 0.23-0.46 at 60-95 °C, resulting in the activation energy of 37.6 kj/mol for the chain transfer. Other derivatives 30b-30d were also prepared and used to derive telechelic polymers with the terminal phosphorus, amino, and other functional aromatic groups [143-145]. Thermal polymerization was also investigated with the end-functional poly(St) and poly(MMA) which were prepared using the iniferter 13 [146]. 

In aqueous solvent a hydrophobic environment was constructed by using a water-soluble and hydrophobic tri-block copolymer (Scheme 7). The central block is hydrophobic and composed of the copolymer of styrene and N-vinylimidazole (PSI), to which Cu ions can coordinate. This central block was synthesized by UV-irradia-tion polymerization bytelechelic initiator of bis(4-carbomethoxy-phenyl)-disulfide. The reaction of telechelic block with poly-(ethyleneoxide) gave the block copolymer PE0-PSI-PE0. 

Taking advantage of the living character of ROMP, telechelic poly-NBE with a 4-pyridyl end group was prepared by Nomura et al. and successfully used in the homogeneous ruthenium-catalyzed catalytic reduction of 2-phenylacetaldehyde (Tab. 8.4) [45]. 

Recently, Quirk and Mathers [264] performed LASIP of isoprene on silicon wafers. A chlorodimethylsilane-functionalized diphenylefhene (DPE) was coupled onto the surface and lithiated with n-BuLi to form the initiating species. The living poly(isoprene) (PI) was end- functionalized with ethylene oxide. A brush thickness of 5 nm after two days of polymerization (9.5 nm after four days) was obtained in contrast to a polymer layer thickness of 1.9 nm by the grafting onto method using a telechelic silane functionahzed PI. 

Poly(oxytetramethylene), poly(tetrahydrofuran), may assume the state of a viscous oil, a wax, or a crystalline solid (melting range around 55 °C), depending on the molecular weight. Poly(tetrahydrofuran) telechelics prepared with two OH end groups and in molar masses of 500-4000 g/mol are used widely as soft block in segmented polyurethanes and polyesters (see Sect. 3.4.2.1). 

Figure 4.11 Solution viscosity of (a) telechelic UPy functional poly(dimethylsiloxane) and (b) a benzyl protected analog in chloroform at 20 °C. Reprinted from Cates (1987). Copyright 1987 American Chemical Society.

Mather BD, Elkins CL, Beyer FL, Long TE. Morphological analysis of telechelic ureidopyr-imidone functional hydrogen bonding linear and star-shaped poly(ethylene-co-propylene)s. Macromol Rapid Commun 2007 28 1601-1606. 

Following route A (Fig. 1), Yan Xiao et al. reported the chemoenzymatic synthesis of poly(8-caprolactone) (PCL) and chiral poly(4-methyl-8-caprolactone) (PMCL) microparticles [5]. The telechelic polymer diol precursors were obtained by enzymatic polymerization of the corresponding monomers in the presence of hexanediol. Enzymatic kinetic resolution polymerization directly yielded the (R)-and (S )-enriched chiral polymers. After acrylation using acryloylchloride, the chiral and nonchiral particles were obtained by crosslinking in an oil-in-water emulsion photopolymerization. Preliminary degradation experiments showed that the stereoselectivity of CALB is retained in the degradation of the chiral microparticles (Fig. 2). 

A reactor was charged with poly[(R)-3-hydroxybutyrate], diethylene glycol, dibutyltin dilaurate, and diglyme and then heated overnight and the telechelic hydroxylated prepolymer isolated and used without further purification. 

A low molecular weight hydroxyallyl modified telechelic PIB was used as poly(alcohol) for the synthesis of the composites. Several procedures for the synthesis have been described involving two steps and as well as single step. The synthesis is schematically shown in Figure 6.5. 

The preparation proceeds in the following way A telechelic alcohol-functional PIB is first reacted with butyllithium in order to form an alcoholate-functional PIB dianion and the latter is then reacted with hexamethylcyclotrisiloxane to generate a living poly(dimeth-ylsiloxane) chain at the end groups of the PIB. In a final step, the remaining anionic ends are capped with trimethylchlorosilane or dimethyldichlorosilane. In this way a block copolymer, is obtained. The pressure sensitive adhesive exhibits (83) ... 

SYNTHESIS AND ION-COUPLING REACTIONS OF TELECHELIC POLY(DIMETHYLSILOXANE) HAVING CYCLIC ONIUM SALT GROUPS... 

Ion-exchange and ring-opening reactions of telechelic poly(DMS) having pyrrolidinium salt groups... 

---