Physically cross-linked polymers block copolymers

Formation of physical cross-links by the anchorage of chain ends in semicrystalline domains and production of permanent entanglements is shown in the HBIB block copolymers. No such arrangement exists for the inverted polymer HIBI. (No attempt has been made to show possible chain folding, or superstructure development of their... 

PE-PEP diblock were similar to each other at high PE content (50-90%). This was because the mechanical properties were determined predominantly by the behaviour of the more continuous PE phase. For lower PE contents (7-29%) there were major differences in the mechanical properties of polymers with different architectures, all of which formed a cubic-packed sphere phase. PE-PEP-PE triblocks were found to be thermoplastic elastomers, whereas PEP-PE-PEP triblocks behaved like particulate filled rubber.The difference was proposed to result from bridging of PE domains across spheres in PE-PEP-PE triblocks, which acted as physical cross-links due to anchorage of the PE blocks in the semicrystalline domains. No such arrangement is possible for the PEP-PE-PEP or PE-PEP copolymers (Mohajer et al. 1982). 

The situation is quite different with block copolymers. As an example we again take a copolymer of styrene and butadiene, but now as a three-block copolymer, SBS. The incompatibility of polystyrene and polybutadiene now results in a phase separation, which is enabled by the circumstance that the blocks can live their own life . The polystyrene chain ends clog together into PS domains, which lie embedded in a polybutadiene matrix. These glassy domains act as physical cross-links, so that the polymer has the nature of a thermoplastic rubber. The glass-rubber transitions of PS and BR both remain present in between these two temperatures the polymer is in a, somewhat stiffened, rubbery condition (see Figure 3.8). This behaviour is dealt... 

Albertsson and coworkers [240-244] carried out extensive research to develop polymers in which the polymer properties are altered for different applications. The predominant procedure is ring-opening polymerization which provides a way to achieve pure and well defined structures. They have utilized cyclic monomers such as lactones, anhydrides, carbonates, ether-lactones. The work involved the synthesis of monomers not commercially available, studies of polymerization to form homopolymers, random and block copolymers, development of cross-linked polymers and polymer blends, surface modification in some cases, and characterization of the materials formed. The characterization is carried out with respect to the chemical composition and both chemical and physical structures, the degradation behavior in vitro and in vivo, and in some cases the ability to release drug components from microspheres prepared from the polymers. 

In contrast, thermoplastic elastomers vulcanize by a physical cross-linking, that is, by formation of hard domains in a soft matrix. Here, hard and soft refer to glass transition temperatures relative to application temperatures. The properties of these thermoplastic elastomers follow directly from their structures. All thermoplastic elastomers (TPEs, plastomers) are copolymers with long sequences of hard and soft blocks. They can be block polymers, segment polymers, or graft polymers. 

A typical triblock copolymer may consist of about 150 styrene units at each end of the macromolecule and some 1,000 butadiene units in the center. The special physical properties of these block copolymers are due to inherent incompatibility of polystyrene with polybutadiene or polyisoprene blocks. Within the bulk material, there are separations and aggregations of the domains. The polystyrene domains are dispersed in continuous matrixes of the polydienes that are the major components. At ambient temperature, below the Tg of the polystyrene, these domains are rigid and immobilize the ends of the polydiene segments. In effect they serve both as filler particles and as cross-links. Above Tg of polystyrene, however, the domains are easily disrupted and the material can be processed as a thermoplastic polymer. The separation into domains is illustrated in Fig. 6.4. 

Thermoplastic IPN Polymer alloy, containing two or more polymers in a co-continuous network form, each physically cross-linked. The cross-linking originates in crystallinity, ion cluster formation, presence of hard blocks in copolymers, etc. 

A physical bond that joins two or more chains together. They may arise from crystalline portions of a semicrystalline polymer, the glassy or crystalline portion of a block copolymer, or the ionic portion of an ionomer. The physical cross-link forces are affected by the temperature. 

A process in which melted plastic is injected into a mold cavity, where it cools and takes the shape of the cavity. Bosses, screw threads, ribs, and other details can be integrated, which allows the molding operation to be accomplished in one step. The finished part usually does not require additional work before assembling. Any IPN in which the individual polymers are thermoplastic. The polymers may contain physical cross-links as in ionomers where ionic clusters join two or more chains together. Nowadays, phase-separated polymeric systems, e.g., block and graft copolymers or thermoplastic polyurethanes, are frequently considered thermoplastic IPNs. 

Block copolymers are useful in many applications where a number of different polymers are connected together to yield a material with hybrid properties. For example, thermoplastic elastomers are block copolymers containing a rubbery matrix (polybutadiene or polyisoprene) containing glassy hard domains (often polystyrene). The block copolymer, a kind of polymer alloy, behaves as a rubber at ambient conditions, but can be molded at high temperatures because of the presence of the glassy domains that act as physical cross-links. In solution, attachment of a water-soluble polymer to an insoluble polymer leads to the formation of micelles in amphiphilic block copolymers. The presence of micelles leads to structural and flow characteristics of the polymer in solution, that differ from either parent polymer. 

Thermoplastic IPNs. These materials utilize physical cross-links rather than chemical cross-links. Thus, the materials may be made to flow at elevated temperatures. As such, they are hybrids between polymer blends and IPNs. Such cross-links may involve block copolymers, ionomers, and/or semicrystallinity. 

Block copolymers were first produced from vinyl monomers using free radically initiated polymerization processes but the full potential of block polymeric materials was not realized until the discovery of the polyurethanes. The polyurethanes,in common with segmented polyesters, were often soluble in simple solvents but in the solid state were physically cross-linked by virtue of the two-phase morphology of these materials. It was the development of living polymerizations which permitted, for the first time, the efficient synthesis of block polymers from vinyl monomers, particularly non-polar monomers. Structures of the type A-B, A-B-A, A-B-C and others could readily be achieved (where A, B, and C represent chemically distinct polymeric units) and it was Milkovich who demonstrated the importance of the tri-block structure in order to achieve good physical properties. 

Gelation in polymers may be brought about in several ways temperature changes, particularly important in protein gelation formation polymerization with cross-links phase separation in block copolymers ionomer formation or even crystallization. Such materials are usually thermoreversible for physical cross-links, or thermoset through the advent of chemical cross-Unks. Of course, there must be at least two cross-link sites per chain to induce gelation. A major... 

Presently, some hybrid polyblends, such as the thermoplastic apparent interpenetrating polymer networks (AIPNs), call for a broader view, hi contrast to traditional IPNs, in thermoplastic AIPNs the components are cross-linked by means of physical, instead of chemical, bonds. These physical bonds are glassy domains of block copolymers, ionic clusters in ionomers, or crystalline domains in semicrystalline polymers. The components of thermoplastic AIPNs are capable of forming physical networks and are characterized by mutual penetration of phases. Thermoplastic AIPNs are intermediate between mixtures of linear polymers and true IPNs because they behave like chemically cross-Unked polymers at relatively low temperatures, but as thermoplastics at elevated temperature [208]. The blends based on combinations of physically cross-Unked polymer and Unear polymer, or physicaUy cross-Unked polymer and chemically cross-Unked (thermoset) polymer, where the physically cross-Unked polymer network constitutes the continuous phase and the other component disperses into domains, will also exhibit the properties of thermoplastic compositions. 

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