Styrene living anionic polymerization

The earliest SIS block copolymers used in PSAs were nominally 15 wt% styrene, with an overall molecular weight on the order of 200,000 Da. The preparation by living anionic polymerization starts with the formation of polystyryl lithium, followed by isoprene addition to form the diblock anion, which is then coupled with a difunctional agent, such as 1,2-dibromoethane to form the triblock (Fig. 5a, path i). Some diblock material is inherently present in the final polymer due to inefficient coupling. The diblock is compatible with the triblock and acts... 

Though living anionic polymerization is the most widely used technique for synthesizing many commercially available TPEs based on styrenic block copolymers, living carbocationic polymerization has also been developed in recent years for such purposes [10,11], Polyisobutylene (PlB)-based TPEs, one of the most recently developed classes, are synthesized by living carbocationic polymerization with sequential monomer addition and consists of two basic steps [10] as follows ... 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

Sequential addition of different monomer charges to a living anionic polymerization system is useful for producing well-defined block copolymers. Thermoplastic elastomers of the triblock type are the most important commercial application. For example, a styrene-isoprene-styrene triblock copolymer is synthesized by the sequence... 

The fairly broad most probable distribution for the rays may be considered as an undesirable imperfection of regular stars. Corresponding measurements with much narrower arm length distributions were made later, mainly by the research groups of Fetters [20, 30, 31] and Roovers [25, 26] which were obtained by living anionic polymerization of styrene, isoprene and butadiene respective-... 

Based on this approach Schouten et al. [254] attached a silane-functionalized styrene derivative (4-trichlorosilylstyrene) on colloidal silica as well as on flat glass substrates and silicon wafers and added a five-fold excess BuLi to create the active surface sites for LASIP in toluene as the solvent. With THF as the reaction medium, the BuLi was found to react not only with the vinyl groups of the styrene derivative but also with the siloxane groups of the substrate. It was found that even under optimized reaction conditions, LASIP from silica and especially from flat surfaces could not be performed in a reproducible manner. Free silanol groups at the surface as well as the ever-present impurities adsorbed on silica, impaired the anionic polymerization. However, living anionic polymerization behavior was found and the polymer load increased linearly with the polymerization time. Polystyrene homopolymer brushes as well as block copolymers of poly(styrene-f)lock-MMA) and poly(styrene-block-isoprene) could be prepared. 

In addition to the triblock thermoplastic elastomers, other useful copolymers of styrene with a diene are produced commerically by living anionic polymerization. These include di-and multiblock copolymers, random copolymers, and tapered block copolymers. A tapered (gradient) copolymer has a variation in composition along the polymer chain. For example, S-S/D-D is a tapered block polymer that tapers from a polystyrene block to a styrene-diene random copolymer to polydiene block. (Tapered polymers need not have pure blocks at their ends. One can have a continuously tapered composition from styrene to diene by... 

Organolithum compounds (lithium alkyls) are the most valuable initiators in anionic polymerization.120168 169172-175 Since living anionic polymerization requires the fastest possible initiation, sec- or ferf-butyllithium is usually used. Lithium alkyls add readily to the double bond of styrene [Eq. (13.32)] or conjugated dienes and form free ions or an ion pair depending on the solvent ... 

As was stated above, the interpretation that the field affects the dis-sodation state of the growing chain ends was not uniquely substantiated by the experimental data, except those on copolymerizations. Thus it is interesting to investigate the field influence on much simpler systems than cationic homopolymerizations. For this purpose we have chosen living anionic systems in which only propagation steps are involved. The system first studied was a living anionic polymerization of styrene with n-butyllithium in the binary mixtures of benzene and tetrahydrofuran (17,24) and in the binary mixtures of benzene and dimethoxyethane (15). 

Table 3. Field effect on the living anionic polymerization of styrene in benzene-di-...

Ise, N., H. Hirohara, T. Makino, K. Takaya, and M. Nakayama Ionic polymerization under an electric field. XIII. living anionic polymerization of styrene in the Unary mixtures of benzene and dimethoxyethane by the three-state mechanism. Presented at the 17th Discussion Meeting of High Polymers, October, 1968, Matsuyama, Preprint p. 261. 

The first method, which is used in many instances, proceeds by anionic block copolymerization. In a first step styrene is anionically polymerized using an efficient bifunctional initiator. The polymer obtained has a well-defined molecular weight, it exhibits a rather narrow molecular weight distribution and it has carbanionic living sites at both ends of its linear chains7. ... 

Introduced as a chain-end group, the BBN group was converted to an alkoxide group, that is, -0 K+, an efficient initiator for anionic polymerization for ethylene oxide. The ring opening living anionic polymerizations of ethylene oxide were carried out with potassium alkoxide polyolefins to prepare polycthylcnc-block-poly(cthylcnc oxide) (PE-fc-PEO), poly(ethylene-co-styrene)-foZock-poly(ethylene oxide), and poly(ethylene-co-octene)-Mock-poly(ethylene oxide) (EOR-fo-PEO) [37]. 

PS macromonomers have been efficiently applied to the synthesis of well-defined polymer hybrids with controlled length of grafts. They are, in general, prepared via living anionic polymerization of styrene monomers and their treatment with vinyl compounds, such as -allyl, -undecenyl, and styryl compounds. 

There are essentially two methods used for the production of commercial FTPEs. The first is referred to as iodine transfer polymerization, which is similar to the living anionic polymerization used to make block copolymers such as styrene-butadiene-styrene (e.g., Kraton ). The difference is that this living polymerization is based on a free radical mechanism. The products consist of soft segments based on copolymers of vinylidene fluoride (VDF) with hexafluoropropylene (HFP) and... 

A knife handle made of Kraton which is a block copolymer of styrene and butadiene that is made by living anionic polymerization (Source www.knifeoutlet.com). 

FIGURE 3-34 Schematic representation of the formation of a styrene/butadiene (SBR) triblock copolymer by living anionic polymerization. 

Since shortly after its discovery by Szwarc et al. [5] in the mid-1950s, living anionic polymerization has been recognized as an ideal route to styrenic block copolymers [6]. To date, living anionic polymerization remains the only commercially important technology for SBC synthesis. The anionic polymerization of styrene and common dienes such as butadiene and isoprene satisfies the criteria outlined above, particularly when carried out in a hydrocarbon solvent and initiated by an appropriate lithium alkyl. 

The second route (87, 98) to block copolymers is the anion to Zie-gler-Natta transformation reaction. Living anionic polymerizations (polymerizations that do not terminate) of styrene and isoprene are treated with... 

The synthesis and purification of polystyrene methacryloyl macromonomers (PS-MA) in the molecular weight range Mn= 1000-2000 g mol 1 by living anionic polymerization of styrene (S), termination with ethylene oxide (EO), and subsequent reaction with methacrylic chloride has already been described in detail elsewhere [180] (see also Scheme 16). In this context it has to be emphasized that the hydroxyethyl-terminated PS-MA macromonomer precursor (PS-OH) as obtained after purification of the crude PS-OH by silica column chromatography (cyclohexane/dichloromethane 1/1 v/v) and as charged in the PS-MA synthesis still contains up to about 15 wt-% of non-functionalized polystyrene (PS-H). This PS-H impurity of the PS-MA macromonomer does not interfere with the PS-MA synthesis and the subsequent TBA/PS-MA copolymerization and is easily and conveniently removed from the resulting PTBA-g-PS graft copolymer (see below). 

A transformation method can introduce some functional groups at the junction as in B-63, which bear a fluorescent dye between the polyisoprene and polystyrene segments.375 The preparation is based on quenching the living anionic polymerization of isoprene with l-(9-phenanthryl)-l-phenylethylene followed by addition of excess a,a -dibromo-/>xylene, which affords a C—Br terminal effective for the copper-catalyzed radical polymerization of styrene. 

B-90 and B-91, respectively.390 Another route coupled with cationic ring-opening polymerizations is accomplished for polymer B-92 with the use of a hydroxyl-functionalized initiator with a C—Br terminal, where the OH group initiates the cationic polymerizations of 1,3-dioxepane in the presence of triflic acid.329 Polyethylene oxide)-based block copolymers B-93 are obtained by living anionic polymerization of ethylene oxide and the subsequent transformation of the hydroxyl terminal into a reactive C—Br terminal with 2-bromopropionyl bromide, followed by the copper-catalyzed radical polymerization of styrene.391... 

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