Copolymers phase separation

Considering the competition between intrachain contraction and interchain association, we have to discuss an overlooked viscoelastic effect in the formation of stable mesoglobules in dilute solutions. Otherwise, it would be difficult to understand why copolymer chains with a high content of hydrophobic comonomers could form smaller interchain aggregates. In the micro-phase separation, copolymer chains in solutions contract and associate. The collision between contracted and associated chains would not be effective if the collision (or contact) time (rc) is much shorter than the time (re) needed to establish a permanent chain entanglement between two ap-... 

Modern polymerization techniques, such as sequential iodine transfer polymerization of fluoroalkenes [11,12], lead to novel thermoplastic elastomers (TPEs). These triblock copolymers can be produced in a process, which can be emulsion, suspension, microemulsion, or solution polymerization [13], Using pseudo-living technology or branching and pseudo-living technology, A-B-A phase separated copolymers with soft (amorphous) and hard (crystalline) domains can be produced. The hard domains can be composed from the following ... 

Microdomain size in phase-separated copolymers plays a fundamental role in determining various macroscopic physical properties in the solid state. The difference in segmental mobility between the hard and soft domains governs the physical properties of microphase-separated polyurethane elastomers [7]. In this respect, the development of structure-property relations at the molecular level which relate directly to macroscopic behavior is the focus of this sub-section. One can exploit the well-documented difference between domain mobility [7-10] and the i3C NMR chemical shift distinction between the 0 .H2 resonances in the hard and soft segments to probe the microdomain morphology of polyether-... 

In summary, Helfands NIA theory predicts molecular weight dependencies of domain size, separation and other parameters of the phase separated copolymers with the presumption of an interface of constant thickness at the-domain boundary. 

Matyjaszewski et al. [2] patented a novel and flexible method for the preparation of CNTs with predetermined morphology. Phase-separated copolymers/stabilized blends of polymers can be pyrolyzed to form the carbon tubular morphology. These materials are referred to as precursor materials. One of the comonomers that form the copolymers can be acrylonitrile, for example. Another material added along with the precursor material is called the sacrificial material. The sacrificial material is used to control the morphology, self-assembly, and distribution of the precursor phase. The primary source of carbon in the product is the precursor. The polymer blocks in the copolymers are immiscible at the micro scale. Free energy and entropic considerations can be used to derive the conditions for phase separation. Lower critical solution temperatures and upper critical solution temperatures (LCST and UCST) are also important considerations in the phase separation of polymers. But the polymers are covalently attached, thus preventing separation at the macro scale. Phase separation is limited to the nanoscale. The nanoscale dimensions typical of these structures range from 5-100 nm. The precursor phase pyrolyzes to form carbon nanostructures. The sacrificial phase is removed after pyrolysis. 

Phase-separated copolymers/stabilized blends of polymers can be pyrolyzed to form the carbon tubular morphology. There are 20 different precursor types that can lead to 20 different morphologies of product CNTs. Typical ones are spherical, cylindrical, and lamellar. 

Belfiore, L.A., Lutz, T.J., Cheng, C., Solid State NMR Detection of Molecular Level Mixing Phenomena in Strongly Interacting Polymer Blends and Phase Separated Copolymers. Plenum, New York, NY, 1991,... 

Fraai]e J G E M 1993 Dynamic density functional theory for micro-phase separation kinetics of block copolymer melts J. Chem. Phys. 99 9202... 

Chains of polybutadiene were trapped in the network formed by cooling a butadiene-styrene copolymer until phase separation occurred for the styrene, effectively crosslinking the copolymer. At 25°C the loss modulus shows a maximum which is associated with the free chains. This maximum occurst at the following frequencies for the indicated molecular weights of polybutadiene ... 

Block copolymers are closer to blends of homopolymers in properties, but without the latter s tendency to undergo phase separation. As a matter of fact, diblock copolymers can be used as surfactants to bind immiscible homopolymer blends together and thus improve their mechanical properties. Block copolymers are generally prepared by sequential addition of monomers to living polymers, rather than by depending on the improbable rjr2 > 1 criterion in monomers. 

B = 0 when x = 1/2, a condition we have already seen [Eq. (8.60)], corresponds to a critical value of x for a copolymer of infinite molecular weight. For finite molecular weights this condition is not quite a threshold for precipitation, but is close to it. Polymer-polymer contacts are sufficiently favored over polymer-solvent contacts that a chain of infinite length would undergo phase separation. 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Several parenteral microencapsulated products have been commercialized the cote materials ate polypeptides with hormonal activity. Poly(lactide— glycohde) copolymers ate the sheU materials used. The capsules ate produced by solvent evaporation, polymer-polymer phase separation, or spray-dry encapsulation processes. They release their cote material over a 30 day period in vivo, although not at a constant rate. 

Blends of poly(vinyl chloride) (PVC) and a-methylstyrene—acrylonitrile copolymers (a-MSAN) exhibit a miscibiUty window that stems from an LCST-type phase diagram. Figure 3 shows how the phase-separation temperature of 50% PVC blends varies with the AN content of the copolymer (96). This behavior can be described by an appropriate equation-of-state theory and interaction energy of the form given by equation 9. 

Copolymerizations of benzvalene with norhornene have been used to prepare block copolymers that are more stable and more soluble than the polybenzvalene (32). Upon conversion to (CH), some phase separation of nonconverted polynorhornene occurs. Other copolymerizations of acetylene with a variety of monomers and carrier polymers have been employed in the preparation of soluble polyacetylenes. Direct copolymeriza tion of acetylene with other monomers (33—39), and various techniques for grafting polyacetylene side chains onto solubilized carrier polymers (40—43), have been studied. In most cases, the resulting copolymers exhibit poorer electrical properties as solubiUty increases. 

In contrast to ionic chain polymerizations, free radical polymerizations offer a facile route to copolymers ([9] p. 459). The ability of monomers to undergo copolymerization is described by the reactivity ratios, which have been tabulated for many monomer systems for a tabulation of reactivity ratios, see Section 11/154 in Brandrup and Immergut [14]. These tabulations must be used with care, however, as reactivity ratios are not always calculated in an optimum manner [15]. Systems in which one reactivity ratio is much greater than one (1) and the other is much less than one indicate poor copolymerization. Such systems form a mixture of homopolymers rather than a copolymer. Uncontrolled phase separation may take place, and mechanical properties can suffer. An important ramification of the ease of forming copolymers will be discussed in Section 3.1. 

The observed reversal in the thermal stability of the copolymer at a critical composition, which appears to be between 30 and 40 mol% of ethylene, may be explained on the basis of the emergence of phase-separation between the nonpolar ethylene and polar vinyl chloride blocks. Although crystallization of the ethylene blocks in the copolymer is only observed when more than 70 mol% ethylene units are present, the possibility of phase-separation occurring at lower contents of ethylene units cannot be excluded. Also, round about the critical copolymer composition, the Tg of the copolymer may be reduced to a level that would facilitate separation between the unlike phases by increased molecular mobility within the polymer matrix. As has been discussed earlier, occurrence of phase-separation in the copolymer would not only make the mechanism of stabilization due... 

The appearance of any appreciable degree of phase-separation in the copolymer should be reflected in different TgS of the two phases. But Braun and coworkers [159] observed only single TgS in the reported range of 0-57.0 mol% of ethylene in the copolymer. This may constitute a criticism of the ideas put forward here. 

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