ABA block polymers

A number of siloxane ABA block polymers have been formed. Copolymers of dimethyl-siloxane (A)-diphenylsiloxane (B)-dimethylsiloxane (A) have been synthesized by the sequential polymerization of reactants. The diphenylsiloxane block acts as a hard block and the more flexible dimethylsiloxane blocks act as soft blocks. 

In the case of the heterophase systems resulting from the ABA block polymers, the strength is reinforced because of the ability of the plastic,... 

These studies of the ABA block polymers also help to explain the results obtained by many investigators, as described in a recent comprehensive review (4). 

As the cited paper [126] notes, the product seems to be similar to an ABA block polymer in which A consists of the DGEBA fragments and a curing agent, and B is represented by the butadiene—acrylonitrile chain of one OBDANC molecule (an oligomeric butadiene—acrylonitrile copolymer with the end carboxyl groups) with the following structure ... 

Isophthaloyl chloride has also been employed in block copolymer preparation. Poly(m-phenylene isophthalamide) and either poly-(ethylene oxide) or poly(dimethyl siloxane) block copol3miers have been prepared by terminating the former with isophthaloyl chloride and subsequently adding hydroxy terminated poly(ethylene oxide) or poly(dimethyl siloxane)(79). Block copolymers were also produced when a polyformal was capped with 1,6-hexandiol, and then heated in the presence of poly(tetramethylene terephthalate)(80). In another interesting application, polyesterpolyether block copolymers of poly-(ethylene terephthalate) and a number of polyglycols have been reported(Sl). Their synthesis involves esterification, catalyzed by zinc acetate/titanyl oxalate. ABA block polymer of 2-hydroxyethyl methacrylate and styrene was prepared by coupling -NH2 terminated PHEMA and isocyanate terminated polystyrene. The latter material was prepared by UV polymerization of styrene in the presence of bis(p-isocyanatophenyl)disulfide (82),... 

In the preparation of monohydroxypolymethyl methacrylate described in Fig. 2,2-mercaptoethanol provides the terminal hydroxyl group. Azobisisobutyronitrile (AIBN) derived initiator fragments make polymer without hydroxyl functionality, but this apparently does not interfere with the development of a high level of physical properties in the completed ABA block polymer. 

Passing, J., Mckenna, W. P., Bandyopadhyay, S., Eyring, E. M. (1984). Ultrasonic and C-13-Nmr studies on gel formation in aqueous-solutions of the Aba block polymer pluronicr F-127. Journal of Molecular Liquids, 27, 165-178. 

ABA and ) n block polymers exhibit higher melt viscosities than do AB diblock copolymers with similar molecular weights. The former two... 

If (P ) is terminated by a chain transfer to a solvent or a monomer, a graft copolymer is formed, or, if the termination is from a combination, a crosslinked network polymer is formed. If the pre-existing polymer (B) contains an end group that itself is photosensitive (or can produce a radical by interacting with photoinitiator) and in the presence of a vinyl monomer (A), block copolymer of type AB can be produced if the photosensitive group is on one end of the polymeric chain. Type ABA block copolymer can be produced if the polymer chain (B) contains a photosensitive group on both ends. 

The quantum yield of polymerization is 6.72 and for photoinitiation < / = 2.85 x 10 . The polystyrene produced with this initiator shows photosensitivity when irradiated with UV light (A = 280 nm). This polymer, which carries two photosensitive end groups of - SC(S) N(CH3)2, behaves as a telechelic polymer and it is useful for production of ABA block copolymer. 

Triblock copolymers of ABA type, where B is the central elastomeric block and A is the rigid end-block, are well-known commercially available polymers [7,8]. The chemical structures of some common TPEs based on styrenic block copolymers are given in Eigure 5.1. Synthesis of such ABA-type polymers can be achieved by three routes [9] ... 

Fig. 16 Various type of elastin-based side-chain polymers (a) ABA block copolymer produced via ATRP, (b) homopolymer produced via ATRP, (c) homopolymer produced via RAFT polymerization...

No formal termination is given in structure 5.42 because in the absence of contaminants the product is a stable macroanion. Szwarz named such stable active species living polymers. These macroanions or macrocarbanions have been used to produce block copolymers such as Kraton. Kraton is an ABA block copolymer of styrene (A) and butadiene (B) (structure 5.43). Termination is brought about by addition of water, ethanol, carbon dioxide, or oxygen. 

Difunctional initiators such as sodium naphthalene are useful for producing ABA, BABAB, CAB AC, and other symmetric block copolymers more efficiently by using fewer cycles of monomer additions. Difunctional initiators can also be prepared by reacting a diene such as /n-diisoprope ny I benzene or l,3-bis(l-phenylethenyl)benzene with 2 equiv of butyl-lithium. Monomer B is polymerized by a difunctional initiator followed by monomer A. A polymerizes at both ends of the B block to form an ABA triblock. BABAB or CABAC block copolymers are syntehsized by the addition of monomer B or C to the ABA living polymer. The use of a difunctional initiator is the only way to synthesize a MMA-styrene-MMA triblock polymer since MMA carbanion does not initiate styrene polymerization (except by using a coupling reaction—Sec. 5-4c). 

This ABA block copolymer consists of stiff polystyrene (PS) and resilient polybutadiene blocks. The domains of these TPEs have characteristic Tt values of 100 and —80 C, respectively. The polybutadiene blocks retain their flexibility at low temperatures, and the polystyrene blocks lose their stiffness when the polymer is heated above 110 C. A related thermoplastic is a transparent AB block copolymer of styrene and butadiene (K-resin). 

Polymeric steric stabilizer such as poly(vinylpyrrolidone) (PVPo),poly(acrylic acid), poly(hydroxypropyl)cellulose, etc., are used to prepare monodisperse polymer in dispersion polymerization of monomers such as alkyl acrylates and methacrylates, and styrene in polar media. AB and ABA block copolymers are a second type of steric stabilizer which can be used in dispersion polymerization. For example, the poly(styrene-h-ethylene oxide) was recently used by Winnik et al. [6] in the dispersion polymerization of styrene in methanol. 

A special type of ABA block copolymer is formed when dendrimers are used as stoppers on rotaxanes. Rotaxanes are linear polymers onto which one or several large macrocycles are threaded. In order to prevent unthreading, sufficiently bulky groups must be attached to the two ends of the rotaxane. The [G-3] po-ly(benzyl ether) dendrimer proved to be highly suited for trapping [128] (see Scheme 16). The linear polymer is made of stiff bipyridinium groups that spontaneously assemble with diparaphenylene-34-crown-10 to form the rotaxane. The dendrimers are attached via quaternation of pyridine with benzyl bromide... 

Soft blocks are composed of linear, dihydroxy poly ethers or polyesters with molecular weights between 600 and 3000. In a typical polymerization of a thermoplastic polyurethane elastomer, the macroglycol is end capped with the full amount of aromatic diisocyanate required in the final composition. Subsequently, the end-capped prepolymer and excess diisocyanate mixture reacts further with the required stoichiometric amount of monomeric diol to complete the reaction. The diol links the prepolymer segments together while excess diol and diisocyanate form short hard-block sements, leading to the (AB)n structure illustrated in Figure 1. Block lengths in (AB)n polymers are frequently much shorter than those in anionically synthesized ABA block copolymers. 

The PHEMA-fe-PMPS-fc-PHEMA amphiphilic ABA block copolymers were used to generate patterned calcium carbonate hlms with dimensions of several hundreds of microns using the photolithographic properties of the polysilane component [77]. PHEMA-fe-PMPS-fc-PHEMA was spin cast from THF solution onto glass substrates. On this polymer layer continuous hhns of calcium carbonate,... 

Termination evidently does not occur as readily in anionic polymerization of thietanes as it does in cationic polymerization. Organo-lithium initiated polymerizations of thietanes lead to living polymers, which have been used to prepare ABA block copolymers of dienes and cyclic sulphides [69, 70]. Since the anionic polymerization of thietanes proceeds via a carbanion, thietEines can initiate vinyl polymerization and their polymerization can be initiated by vinyl monomers. Kinetic parameters of such polymerizations have not yet been reported. 

The living ends of a suitable polymer may initiate polymerization of another monomer, and thus lead to the synthesis of block polymers free of homopolymers. For sample, one prepares living polystyrene then adds pure methyl methacrylate to its solution and produces in this way a block polymer of styrene and methyl methacrylate (22). Actually, it is possible to produce living polymers with two active ends which can form a block polymer containing three segments—ABA. 

In this case an ABA block copolymer is formed. The chemical structure of such a polymer is represented by formula (3)... 

From the table It appears that the Izod Impact strength Improves as the Interfacial adhesion increases. This Is also concluded In a recent publication about nylon 6.6 compounded with polyethylene-g-maleic anhydride polymer (15). Addition of more rubber In system 3 (30 %) affords hardly any addltonal Improvement In toughness, but the flexural modulus, which In ABA block copolymers Is already lower than In a dispersed rubber system, Is more than halved. 

Block copolymers between alkyl or related methacrylates (B-1,132 198,357 B-2,198 and B-3115,146,148) were prepared via the ruthenium-, copper-, and nickel-catalyzed living radical polymerizations. These block copolymers can be synthesized both via sequential living radical polymerizations and via the living radical polymerization initiated from isolated polymers. For example, the ruthenium-catalyzed sequential living radical polymerization of MMA followed by nBMA affords AB block copolymers B-1 with narrow MWDs (Mw/Mn = 1.2), which can be extended further into ABA block copolymers B-2 with similarly narrow MWDs (Mw/Mn = 1.2).198 Star block copolymers with B-1 as arm chains were similarly synthesized but with multifunctional initiators.357... 

The ABA-type block copolymers B-86 to B-88 were synthesized via termination of telechelic living poly-(THF) with sodium 2-bromoisopropionate followed by the copper-catalyzed radical polymerizations.387 A similar method has also been utilized for the synthesis of 4-arm star block polymers (arm B-82), where the transformation is done with /3-bromoacyl chloride and the hydroxyl terminal of poly(THF).388 The BAB-type block copolymers where polystyrene is the midsegment were prepared by copper-catalyzed radical polymerization of styrene from bifunctional initiators, followed by the transformation of the halogen terminal into a cationic species with silver perchlorate the resulting cation was for living cationic polymerization of THF.389 A similar transformation with Ph2I+PF6- was carried out for halogen-capped polystyrene and poly(/>methoxystyrene), and the resultant cationic species subsequently initiated cationic polymerization of cyclohexene oxide to produce... 

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