Glassy crystalline copolymers

A glassy/crystalline combination in the form of polystyrene/poly-(ethylene oxide), PS/PEO. This block copolymer, which has been examined in some detail in the literature, will also serve as a model system. 

At the optimum concentration of the mixture the pyroelectric coefficient reaches the value of 4 nC/cm K exceeding that observed in the famous ferroelectric crystalline copolymers PVDF-TrFE. On cooling down to the glassy state and... 

EVA (ethylene vinyl acetate) is a copolymer which is available in various compositions of ethylene and vinyl acetate. At a content of 50 vinyl acetate or more the crystallinity has been vanished completely. Give qualitatively the nitrogen permeability at room temperature for a copolymer with 10%, 50% and 90% vinyl acetate respectively and indicate the character of the polymer in terms of rubbery and glassy, crystalline and amorphous (The glass transition temperatures of the pure polymers polyethylene and polyvinyl acetate are given in table II - 5). 

The nature of the hard domains differs for the various block copolymers. The amorphous polystyrene blocks in the ABA block copolymers are hard because the glass transition temperature (100°C) is considerably above ambient temperature, i.e., the polystyrene blocks are in the glassy state. However, there is some controversy about the nature of the hard domains in the various multiblock copolymers. The polyurethane blocks in the polyester-polyurethane and polyether-polyurethane copolymers have a glass transition temperature above ambient temperature but also derive their hard behavior from hydrogen-bonding and low levels of crystallinity. The aromatic polyester (usually terephthalate) blocks in the polyether-polyester multiblock copolymer appear to derive their hardness entirely from crystallinity. 

Figure 6.5 Illustrations of nanoscale spherical assemblies resulting from block copolymer phase separation in solution are shown, along with the chemical compositions that have been employed to generate each of the nanostructures (a) core crosslinked polymer micelles (b) shell crosslinked polymer micelles (SCKs) with glassy cores (c) SCKs with fluid cores (d) SCKs with crystalline cores (e) nanocages, produced from removal of the core of SCKs (f) SCKs with the crosslinked shell shielded from solution by an additional layer of surface-attached linear polymer chains (g) crosslinked vesicles (h) shaved hollow nanospheres produced from cleavage of the internally and externally attached linear polymer chains from the structure of (g)...

Melt-processable polymer blend or copolymer in which a continuous elastomeric phase domain is reinforced by dispersed hard (glassy or crystalline) phase domains that act as junction points over a limited range of temperature, or... 

Styrene-1,3-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS) triblock copolymers are manufactured by a three-stage sequential polymerization. One possible way of the synthesis is to start with the polymerization of styrene. Since all polystyrene chains have an active anionic chain end, adding butadiene to this reaction mixture resumes polymerization, leading to the formation of a polybutadiene block. The third block is formed after the addition of styrene again. The polymer thus produced contains glassy (or crystalline) polystyrene domains dispersed in a matrix of rubbery polybutadiene.120,481,486... 

This article reviews recent developments in polymer thermomechanics both in theory and experiment. The first section is concerned with theories of thermomechanics of polymers both in rubbery and solid (glassy and crystalline) states with special emphasis on relationships following from the thermomechanical equations of state. In the second section, some of the methods of thermomechanical measurements are briefly described. The third section deals with the thermomechanics of molecular networks and rubberlike materials including such technically important materials as filled rubbers and block and graft copolymers. Some recent data on thermomechanical behaviour of bioelastomers are also described. In the fourth section, thermomechanics of solid polymers both in undrawn and drawn states are discussed with a special focus on the molecular and structural interpretation of thermomechanical experiments. The concluding remarks stress the progress in the understanding of the thermomechanical properties of polymers. 

Microhardness (MH), has been shown to be a convenient additional technique to detect accurately the ferro to paraelectric phase changes in these copolymers. The increase of MH as a function of VF2 polar sequences observed at room temperature is correlated with the contraction of the p-all-trans unit cell On the other hand, the fast exponential decrease of MH with increasing temperature, observed above Tc, is similar to that obtained for glassy polymers above Tg and suggests the existence of a liquid crystalline state in the high temperature paraelectric phase. This phase is characterized by a disordered sequence of conformational isomers (tg-, tg+, tt) as discussed for Condis crystals [109]. 

In this chapter, structure formation in semicrystalline diblocks containing PE, PEO and other crystalline blocks is discussed in Section 5.2. Section 5.3 is concerned with theories for the equilibrium crystallization of block copolymers, whilst Section 5.4 summarizes recent experimental work on the kinetics of crystallization. There have been few studies of crystallization in thin block copolymer films, and consequently Section 5.5 is correspondingly short. Finally, structure formation in glassy diblocks is considered in Section 5,6. 

Block copolymers of the A—B—A type where A is a thermoplast and B an elastomer can have properties at ambient temperatures which would normally be expected from a crosslinked rubber. The cause of this phenomenon are the physical crosslinks produced by the thermoplastic blocks which may be either crystalline or amorphous (glassy). Above the melting temperature of the hard phase such materials flow and can be processed by the usual thermoplastic processing techniques. 

We have further studied the synthesis of novel ABC linear triblock copolymers. Specifically, novel glassy(A)-fo-rubbery(B)-fo-crystalline(C) linear tri-... 

Similarly, a polymeric medium characterised by strong cohesion, is also obtained from di- or tri-block copolymers made by linking two or three chemically homogeneous sequences which are incompatible with one another usually, the Tg of one of the two sequences is above room temperature while it is below for the other sequence [10]. There is a phase separation glassy segments are connected to one another by amorphous segments and they play the role of ordered domains formed in semi-crystalline polymers. 

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