Methylstyrene block polymers

The precipitated silica (J. Crosfield Sons) was heated in vacuo at 120° for 24h. before use. Two grades of surface areas 186 and 227 m g l (BET,N2), were used during this project. Random copolymers, poly(methyl methacrylates) and polystyrene PS I were prepared by radical polymerization block polymers and the other polystyrenes were made by anionic polymerization with either sodium naphthalene or sodium a methylstyrene tetramer as initiator. The polymer compositions and molecular weights are given in Table I. 

Like certain combinations of metallic elements which show degrees of mutual solubility, so organic polymer blocks show varying tendencies to "alloy" in the solid state. The synthesis and properties of block polymers is a developing science which leads to important materials and engineering applications.(65) In this section we describe the preparation of a BAB block terpolymer of f-methylstyrene and styrene.(66) Sodium atoms are used to initiate polymerization in liquid tetrahydrofuran solutions of monomer cooled... 

DON Dondos, A., Investigations on conformations of styrene-a-methylstyrene block copolymers in dilute solution, JPo/y/w. Sci. Polym. Lett., 9, 871, 1971. 

The polydispersity of polymers prepared in this way is usually very low for example, a value MJM of 1.05 was found for a sample of poly(a-methylstyrene). Living polymers can also be used for the preparation of block copolymers after the consumption of the first monomer, a second anionically polymerizable monomer is added which then grows onto both ends of the initially formed block. By termination of the living polymer with electrophilic compotmds the polymer chains can be provided with specific end groups for example, living polystyrene reacts with carbon dioxide to give polystyrene with carboxylic end groups. 

In this paper we describe the preparation and the properties of the title triblock with a low vinyl-1,2 (or 3,4 in the case of polyisoprene) polydiene center block. Two different solvent systems were used as the media of polymerization. In the first system, the polydiene center block was prepared in cyclohexane. Alpha-methylstyrene (AMS) and a polar solvent tetrahydrofuran (THF) were then added. This was followed by a slow and continuous styrene addition to complete the end block preparation. In the second system, AMS itself was used as the solvent with no other solvent added. The second solvent system enabled us to use several different polymerization schemes. The center block could be prepared first to form a tapered or untapered triblock. The end block copolymer also could be prepared first and then the diblock and then coupled to form a tri- or a radial block polymer. Instead of coupling, more styrene could be added to complete the triblock. All these different routes of preparation were used in this work. 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Indeed, cumyl carbocations are known to be effective initiators of IB polymerization, while the p-substituted benzyl cation is expected to react effectively with IB (p-methylstyrene and IB form a nearly ideal copolymerization system ). Severe disparity between the reactivities of the vinyl and cumyl ether groups of the inimer would result in either linear polymers or branched polymers with much lower MW than predicted for an in/mcr-mediated living polymerization. Styrene was subsequently blocked from the tert-chloride chain ends of high-MW DIB, activated by excess TiCU (Scheme 7.2). 

The most prevalent approach to achieve long-lasting and nonstaining ozone protection of rubber compounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The ozone-resistant polymer must be used in sufficient concentration (minimum 25 phr) and must also be sufficiently dispersed to form domains that effectively block the continuous propagation of an ozone-initiated crack through the diene rubber phase within the compound. Elastomers such as ethylene-propylene-diene terpolymers, halogenated butyl mbbers, or brominated isobutylene-co-para-methylstyrene elastomers have been proposed in combination with NR and/or butadiene rubber. 

Hyperbranched polymers have also been prepared via living anionic polymerization. The reaction of poly(4-methylstyrene)-fo-polystyrene lithium with a small amount of divinylbenzene, afforded a star-block copolymer with 4-methylstyrene units in the periphery [200]. The methyl groups were subsequently metalated with s-butyllithium/tetramethylethylenediamine. The produced anions initiated the polymerization of a-methylstyrene (Scheme 109). From the radius of gyration to hydrodynamic radius ratio (0.96-1.1) it was concluded that the second generation polymers behaved like soft spheres. 

So far, there have been only few reports about the synthesis of amphipolar polymer brushes, i.e. with amphiphilic block copolymer side chains. Gna-nou et al. [115] first reported the ROMP of norbornenoyl-endfunctionalized polystyrene-f -poly(ethylene oxide) macromonomers. Due to the low degree of polymerization, the polymacromonomer adopted a star-like rather than a cylindrical shape. Schmidt et al. [123] synthesized amphipolar cylindrical brushes with poly(2-vinylpyridine)-block-polystyrene side chains via radical polymerization of the corresponding block macromonomer. A similar polymer brush with poly(a-methylstyrene)-Wocfc-poly(2-vinylpyridine) side chains was also synthesized by Ishizu et al. via radical polymerization [124]. Using the grafting from approach, Muller et al. [121, 125] synthesized... 

Few examples of the homogeneous diblock-incompatible homo-polymer behavior have been reported. One that has received considerable attention is the system polystyrene-poly-a-methylstyrene (2). Block copolymers of styrene and a-methylstyrene exhibit a single loss peak in dynamic experiments (2,3) and have been shown to be thermorheologi-cally simple (4) hence they are considered to be homogeneous. Mechanical properties data on these copolymers also has been used to validate interesting extensions of the molecular theories of polymer viscoelasticity (2,3,4). 

Block copolymers are sometimes prepared with several different kinds of polymers. For example, Fielding-Russell and Pillar (48) synthesized poly (a-methylstyrene-b-butadiene-b-styrene). 

Block copolymer chemistry provides a convenient means of incorporating the oxygen-RIE-resistant polysiloxane moiety into a high-Tg, radiation-sensitive polymer (20). The flow characteristics of the resist are determined by the unit with higher Tg, and problems associated with phase separation are minimized because of block copolymerization. Specifically, block copolymers of dimethylsiloxane and chlorinated p-methylstyrene exhibit good sensitivity, resolution, and thermal properties and low rates of erosion during O2 RIE. 

Ishizu et al.194 synthesized hyperbranched macromolecules that resemble dendrimers. The synthetic approach involved the preparation of poly(4-methyl-styrene-b-PS-b-poly(4-methylstyrene) triblock copolymer by using naphthalene lithium as difunctional initiator. The 4-methyl groups of the terminal blocks were metalated with s-BuLi/tetramethylethylenedi-amine (TMEDA) complex in a molar ratio of 1 2. After removal of the excess s-BuLi by repeated precipitation of the living polymer and transfer of supernatant solution to another flask under high vacuum conditions, the polymer was dissolved in THF and was used as the initiator of a-methylstyrene at —78 °C. After the polymerization of a-methylstyrene, a small amount of 4-methylstyrene was added. The procedure of metalation of the a-methyl groups and polymerization of a-methylstyrene can be repeated many times to form a dendritic type hyperbranched polymer (Scheme 99). The characterization of the inter-... 

Block copolymers constituted so that the hard A blocks show increased glass temperatures might be expected to show better ultimate tensile properties than comparable block copolymers of a lower Tg in the glassy phase (12). This is demonstrated in the present system by substituting the major portion of the polystyrene in the present system for poly (a-methylstyrene). A short length of polystyrene is included at each chain end of the hard block to facilitate the second step of the synthesis and to give a more stable polymer. The effect of replacing... 

---