Functionally terminated polymer

In comparison to Ba-Mg-Al polymerizations, the preparation of block copolymers and functionally terminated polymers has not been successful with Ba-Li initiators. Chain transfer to toluene in Ba-Li systems is considered to be responsible for this behavior. 

Functionally terminal polymers are valuable material intermediates. The di- and polyfunctional varieties (telechelic polymers) have found theoretical (e.g., model network) and commercial (e.g., liquid rubber) applications (1, ). On the other hand, macromolecules with a functional group at one chain end (semitelechelic polymers) have been used to prepare novel macromolecular monomers (Macromers ), as well as block and graft copolymers ( -8). 

Synthesis of functional Terminal Polymers. Mono-and di- terminal -OH and - polydienes were prepared according to our published procedures (13.14). Star -OH polydienes were synthesized analogously except that ethyl 6-1ithiohexyl acetaldehyde acetal was used as the initiator and trichloromethylsilane as the joining agent. 

Model networks of known structure can be prepared by end-linking functionally-terminated polymer chains [3, 4, 157]. Because of the nature of this network formation process, the molecular weight of the starting chains becomes the critically important molecular weight between cross-links, Mc. Control of Mc and its... 

Besides some particular cases such as ozonolysis2,3) or ring-opening polymerization of ketene-acetal type monomers4), the hydroxytelechelic polymers can be synthesized also by anionic polymerization. This process leads to polymers with smaller polydispersity and to a theoretical functionality of two free-radical polymerizations are easier to carry out, cheaper and, therefore, of industrial importance. Several reviews deal with the synthesis of functionally terminated polymers s>6 7, while this paper concerns only radical processes leading to hydroxytelechelic polymers. 

Supercritical fractionation was investigated for the special-purpose polymers of both the diol and triol of a glycidyl azide polymer and a hydroxy-terminated polybutadiene. Hydroxy polybutadiene is used on a large scale as an ingredient in plastic bonded explosive (PBX) propellant formulations the hydroxy functionality of the polybutadiene reacts with an isocyanate functionality of another prepolymer to form a urethane. In the polysiloxanes section we referred to functionally terminated polymers as macromonomers in the terminology of the urethane industry, however, isocyanate-terminated polyester polymers are normally referred to as prepolymers in their reaction to form the urethane, even though the prepolymers are typically between 1,000 and 10,000 molecular weight. 

Model silicone networks, i.e., those prepared by end-linking of functionally terminated polymer chains, have been extensively utilized to explain the influence of molecular structure on mechanical properties. An important number of studies have been focused on the contribution of elastically active chains and trapped entanglements to equilibrium properties [1-7]. In contrast, very little work has been done to explain the influence of network structure on non-equilibrium properties [8], and the contribution of some of the main structural parameters to viscoelastic properties has been poorly explored. A few qualitative studies have shown in the past that pendant chains have a strong influence on relaxation properties, but the type of contribution was not clearly understood [9]. 

Many examples exist where a polymerization has been continued by ATRP. V" Often the procedure involves functionalization of a hydroxy-terminated polymer with bromoisobutyroyl (BriBBr, 314) or bromoisopropionoyl (BriPBr, 315) bromide. Examples include polyethylene oxide)044,646 and polypropylene... 

In many cases, these cyclic siloxanes have to be removed from the system by distillation or fractionation, in order to obtain pure products. On the other hand, cyclic siloxanes where n = 3 and n = 4 are the two most important monomers used in the commercial production of various siloxane polymers or oligomers via the so-called equilibration or redistribution reactions which will be discussed in detail in Sect. 2.4. Therefore, in modern silicone technology, aqueous hydrolysis of chloro-silanes is usually employed for the preparation of cyclic siloxane monomers 122> more than for the direct synthesis of the (Si—X) functional oligomers. Equilibration reactions are the method of choice for the synthesis of functionally terminated siloxane oligomers. 

Terminal-functionalized polymers such as macromonomers and telechelics are very important as prepolymer for construction of functional materials. Single-step functionalization of polymer terminal was achieved via lipase catalysis. Alcohols could initiate the ring-opening polymerizahon of lactones by lipase catalyst. The lipase CA-catalyzed polymerizahon of DDL in the presence of 2-hydroxyethyl methacrylate gave the methacryl-type polyester macromonomer, in which 2-hydroxyethyl methacrylate acted as initiator to introduce the methacryloyl group quanhtatively at the polymer terminal ( inihator method ).This methodology was expanded to the synthesis of oo-alkenyl- and alkynyl-type macromonomers by using 5-hexen-l-ol and 5-hexyn-l-ol as initiator, respechvely. 

Anionic polymerization in suitable systems allows the preparation of polymers with controlled molecular weight, narrow molecular weight distributions and functional termination. The functional termination of a living anionic polymerization with a polymerizable group has been used frequently in the preparation of macromonomers (4). Our research has encompassed the anionic homo and block copolymerizations of D- or hexamethyl cyclotrisiloxane with organolithiums to prepare well defined polymers. As early as 1962 PSX macromonomers were reported in the literature by Greber (5) but the copolymerization of these macromonomers did not become accepted technique until their value was demonstrated by Milkovich and... 

The molybdenum initiators also allow for functionalization of the polymer end groups. The use of appropriately substituted alkylidene ligands553,554 and functionalized termination agents555 have both been described. A more convenient approach using chain transfer agents has also been developed, initially with substituted cyclopentenes,509 and then with 1,3-dienes and styrenes.556... 

Even though the short oligosaccharide segment made of seven units may not be considered as a true polymer chain, the chemistry devised by them should be easily applicable to longer saccharidic chains. Liu and Zhang used the Michael reaction for coupling a dextran (Dex) with an amino-functionalized terminal and acrylolyl end-capped PCL [146]. Sun et al. also synthesized Dex-b-PCL by disulfide bond formation [147]. 

Terpyridine moieties have been introduced as a terminal unit of macromolecules. In a subsequent procedure the two-step self-assembly process based on Rum/Run chemistry was used for polymers end-capped with the 2,2/ 6/,2 -terpyridine ligand. More precisely, the terpyridine-functionalized polymers were complexed with RUCI3 to selectively form a mono-complex. In a further step, this mono-complex was reacted under reducing conditions with other uncomplexed 2,2/ 6/,2/-terpyridine-terminated polymer blocks in order to form an asymmetrical AB ruthenium(II) frzs-complex. 

Functionalization of these reactive anionic chain ends can be achieved by a variety of methods all based on the general concepts of carbanion chemistry. For example, reaction with C02 or succinnic anhydride leads to the carboxy terminated derivatives [10], while hydroxy-terminated polymers can be easily obtained by reaction with ethylene oxide (Scheme 3) [11]. In select functionalization reactions, such as alkylation with p-vinyl benzyl chloride, the nucleophilicity of the carbanionic species may be necessary and this can be achieved by reaction of the chain end with 1,1-diphenylethene followed by functionalization [12,13]. 

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