Thermoplastic elastomers polymer synthesis

E. Carone, L. D llario, A. Martinelli, New conducting thermoplastic elastomers. I. Synthesis and chemical characterization, Journal of Applied Polymer Science 2002, 83, 857. 

Muppalla, R. Jewrajka, S. K., Synthesis, Morphology and Properties of Poly(dimethylsiloxane)/Poly(n-butyl acrylate) mixed Soft Block-Based Copolymers A New Class of Thermoplastic Elastomer. Polymer 2012,53, 1453-1464. 

This chapter discusses synthetic polymers based primarily on monomers produced from petroleum chemicals. The first section covers the synthesis of thermoplastics and engineering resins. The second part reviews thermosetting plastics and their uses. The third part discusses the chemistry of synthetic rubbers, including a brief review on thermoplastic elastomers, which are generally not used for tire production but to make other rubber products. The last section addresses synthetic fibers. 

Phthalazinone, 355 synthesis of, 356 Phthalic anhydride, 101 Phthalic anhydride-glycerol reaction, 19 Physical properties. See also Barrier properties Dielectric properties Mechanical properties Molecular weight Optical properties Structure-property relationships Thermal properties of aliphatic polyesters, 40-44 of aromatic-aliphatic polyesters, 44-47 of aromatic polyesters, 47-53 of aromatic polymers, 273-274 of epoxy-phenol networks, 413-416 molecular weight and, 3 of PBT, PEN, and PTT, 44-46 of polyester-ether thermoplastic elastomers, 54 of polyesters, 32-60 of polyimides, 273-287 of polymers, 3... 

FIGURE 5.2 Synthesis of polyisobutylene (PIB)-based star-block thermoplastic elastomer (TPE). (From Jacob, S. and Kennedy, J.P., Adv. Polym. Sci., 146, 1, 1999.)... 

Puskas, J.E. et al. Synthesis and characterization of novel dendritic (arborescent) polyisobutylene-polystyrene thermoplastic elastomers, J. Polym. Set A, 43, 1811, 2005. 

Controlled/living radical polymerisation (CRP) is currently a fast developing area in polymer synthesis and it allows preparation of many advanced polymeric materials, including thermoplastic elastomers, surfactants, gels, coatings, biomaterials, materials for electronics and many others. 

In the 1960s, anionic polymerized solutron SBR (SSBR) began to challenge emulsion SBR in the automotive tire market. Organolithium compounds allow control of the butadiene microstructure, not possible with ESBR. Because this type of chain polymerization takes place without a termination step, an easy synthesis of block polymers is available, whereby glassy (polystyrene) and rubbery (polybutadicnc) segments can be combined in the same molecule. These thermoplastic elastomers (TPE) have found use ill nontire applications. 

The species -O-N-R in the scheme is a stable organic radical called a nitroxide, one type of radical that does not react with itself but which reacts with carbon radicals forming weak C-O-N bonds. This approach continues to develop and allows the synthesis of polymers with very narrow molar mass distributions, block copolymers, and polymers with different architectures such as highly branched materials (discussed shortly). This is but one of a limited number of techniques that show promise for producing improved thermoplastics, elastomers, and adhesives for packaging and automotive applications (Anon. 2002). 

Block copolymers are an important class of polymers used in many applications from thermoplastic elastomers to polymer-blend stabilizers. Their synthesis is most often done by ionic polymerization, which is both costly and sometimes difficult to control. However, block copolymer properties strongly depend, for example, on the exact chemical composition, block molar mass, and block yield. These parameters can be evaluated in a single experiment using copolymer GPC with multiple detection. 

Intense commercial and academic interest in block copolymers developed during the 1960s and continues today. These materials attract the attention of industry because of their potential for application as thermoplastic elastomers, tough plastics, compatibilizing agents for polymer blends, agents for surface and interface mo dification, polymer micelles, etc. Academic interest arises, primarily, from the use of these materials as model copolymer systems where effects of thermodynamic incompatibility of the two (or more) components on properties in bulk and solution can be probed. The synthesis, characterization, and properties of classical linear block copolymers (AB diblocks, ABA triblocks, and segmented (AB)n systems) have been well documented in a number of books and reviews [1-7] and will not be discussed herein except for the sake of comparison. 

Nair, J.K., Reddy, T.S., Satpute, R.S., Mukundan, T., and Asthana, S.N., Synthesis and characterization of energetic thermoplastic elastomers (ETPEs) based on 3,3-bis(azidomethyl)oxetane(BAMO)-3-azi-domethyl-3-methyloxetane (AMMO) copolymers, J. Polym. Mater. 21 (2), 205, 2004. 

One of the major areas for potential involves the synthesis of polyolefin block copolymers. A PP-EPR-PP or PE-EPR-PE block copolymer could have large potential as is or in blends with other polyolefins. PE-EPR-PE block copolymers have been synthesized via anionic polymerization of butadiene-isoprene-butadiene ABA block copolymers followed by hydrogenation [Mohajer et al, 1982 Rangarajanout et al., 1993]. These materials would have utility in hot melt adhesive formulations as well as general-purpose thermoplastic elastomer applications. Improvements on the synthesis procedures to offer viable approaches to polyolefin block copolymers could open up a new class of commercial polyolefins. In summary, several opportunities exist for new combinations of commercial blends from the list of commodity polymers. 

Rieger has recently reported another class of Ci catalysts (45) for the synthesis of stereoblock polypropylenes. However unlike the polymers formed using 42—44, polymers ranging from flexible plastics (with melting points as high as 134 °C) to thermoplastic elastomers are produced. Similar metallocenes... 

A variety of specialty polyolefins and polyolefin alloys can now be made directly in the reactor taking advantage f the new technology. Examples are the catalloy materials from Himont, which are polyolefin alloys made by synthesis and not by the conventional route of compounding. Hivalloy is a polypropylene/polystyrene alloy made by synthesis and combines the properties of both crystalline and amorphous engineering polymers. Such materials could challenge the established positions of several thermoplastic elastomers. 

The discovery of living cationic polymerization has provided methods and technology for the synthesis of useful block copolymers, especially those based on elastomeric polyisobutylene (Kennedy and Puskas, 2004). It is noteworthy that isobutylene can only be polymerized by a cationic mechanism. One of the most useful thermoplastic elastomers prepared by cationic polymerization is the polystyrene-f -polyisobutylene-(>-polystyrene (SIBS) triblock copolymer. This polymer imbibed with anti-inflammatory dmgs was one of the first polymers used to coat metal stents as a treatment for blocked arteries (Sipos et al., 2005). The SIBS polymers possess an oxidatively stable, elastomeric polyisobutylene center block and exhibit the critical enabling properties for this application including processing, vascular compatibility, and biostability (Faust, 2012). As illustrated below, SIBS polymers can be prepared by sequential monomer addition using a difunctional initiator with titanium tetrachloride in a mixed solvent (methylene chloride/methylcyclohexane) at low temperature (-70 to -90°C) in the presence of a proton trap (2,6-dt-f-butylpyridine). To prevent formation of coupled products formed by intermolecular alkylation, the polymerization is terminated prior to complete consumption of styrene. These SIBS polymers exhibit tensile properties essentially the same as those of... 

Uses Organic synthesis lacquers comonomer for alkyd resins comonomer for thermoplastic polyamides polyester hot-melt adhesives low-temp. plasticizers urethane elastomers polymer modifier in food-pkg. 

He has raieived the following awards Academy of Athens Award for Chemistry (1989), Empirikion Award for Sciences (1994), the Gre Chemists Association Award (2000), the AC, PMSEA. K. Doolittle Award (2003), the/ntenwifionPolymer Science, Japan (SPSJ, 2007), the ACS PMSE Cooperative Research Award (2010) and the ACS, Rubber Division, Chemistry of Thermoplastic Elastomers Award (2011). He was elected as a PMSE Fellow for 2004 and was the "Ralph Milkovich" Memorial Lecturer for 2006 at the University of Akron. He has Honorary D rees Doctorate Honoris Causa) fiom the University Simon Bolivar, Caracas, Venezuela (2010) and the University of loannina, Greece (2010). He has dedicate his career primarily to the synthesis and properties of model polymers and has published more than 400 papers in refereed scientific journals, three books ( litor), is the author of one book on Block Copolymers (Wiley 2003) and owns 6 patents,. 

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