Structure in copolymers

Gurovich E (1995) Why does an electric-field align structures in copolymers Phys Rev Lett 74(3) 482-485... 

In its turn, location of vinyl groups in 1,3- or 1,5-position in OVCS induces clearly determinable regularity. In all considered cases, PFOS viscosity is higher, when two vinyl groups are located in 1,5-position of tetrameric ring. This is apparently associated with disposition of vinyl groups more suitable for hydrosilylation and formation of more symmetrical structure in copolymers Ns 1-3 (structure XV). 

This calls for an essential fine-tuning of the semi-empirical thermodynamic and kinetic process models on the basis of plant data. The resulting models thus become plant-specific. Consequently, there is room for improvement of such high pressure plant models and processing recepies, where the attention will be focused mainly on polymer aspects such as the interplay between the complex kinetics in copolymer chemistry and the chemical composition and chain structure in copolymers and/or in the blend, the thermodynamic implications of the polarity of monomer, (co)polymers and solvents. 

Gurovich, E., On microphase separation of block copolymers in an electric field four universal classes. Macromolecules, 27, 7339-7362 (1994) Gurovich, E., Copolymers under a monomer orienting field. Macromolecules, 27, 7063-7066 (1994) Gurovich, E., Why does an electric field align structures in copolymers Phys. Rev, Lett., 74, 482-485 (1995). 

Polymers of chloroprene (structure [XII]) are called neoprene and copolymers of butadiene and styrene are called SBR, an acronym for styrene-butadiene rubber. Both are used for many of the same applications as natural rubber. Chloroprene displays the same assortment of possible isomers as isoprene the extra combinations afforded by copolymer composition and structure in SBR offsets the fact that structures [XIIll and [XIV] are identical for butadiene. 

Figure 3.8. Schematic representation of the polystyrene domain structure in styrene-butadiene-styrene triblock copolymers. (After Holden, Bishop and Legge )...

Materials containing the above structure in the polymer chain may be made from copolymers of methacrylic acid and methacrylonitrile. Ammonia-producing additives (such as urea and ammonium hydrogen carbonate) are added to the... 

It may not be appropriate to compare the thermal stability characteristics of VC/VAc copolymer to that of a VC homopolymer (PVC). The copolymerization would involve different kinetics and mechanism as compared to homopolymerization resulting structurally in quite different polymers. Hence, copolymerization of VC with VAc cannot be regarded as a substitution of chlorines in PVC by acetate groups. To eliminate the possibility of these differences Naqvi [45] substituted chlorines in PVC by acetate groups, using crown ethers (18-crown-6) to solubilize potassium acetate in organic solvents, and studied the thermal stability of the modified PVC. Following is the mechanism of the substitution reaction ... 

Random copolymers are similar to PEO but when the regular helical structure of the chains is demolished, the crystallinity is also destroyed. One of the simplest and most successful amorphous host polymers is an oxyethylene- oxymethylene structure in which medium length but statistically variable EO units are interspersed with methylene oxide groups. First described in 1990 [37], aPEO has the general structure... 

As has been described in Chapter 4, random copolymers of styrene (St) and 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) form a micelle-like microphase structure in aqueous solution [29]. The intramolecular hydrophobic aggregation of the St residues occurs when the St content in the copolymer is higher than ca. 50 mol%. When a small mole fraction of the phenanthrene (Phen) residues is covalently incorporated into such an amphiphilic polyelectrolyte, the Phen residues are hydrophobically encapsulated in the aggregate of the St residues. This kind of polymer system (poly(A/St/Phen), 29) can be prepared by free radical ter-polymerization of AMPS, St, and a small mole fraction of 9-vinylphenanthrene [119]. 

IUPAC recommendations suggest that a copolymer structure, in this case poly(methyl methacrylate-co-styrene) or copoly(methyl methacrylate/slyrene), should be represented as 1. The most substituted carbon of the configurational repeat unit should appear first. This same rule would apply to the copolymer segments shown in Section 7.1. However, as was mentioned in Chapter I, in this book, because of the focus on mechanism, we have adopted the more traditional depiction 2 which follows more readily from the polymerization mechanism. 

Any understanding of the kinetics of copolymerization and the structure of copolymers requires a knowledge of the dependence of the initiation, propagation and termination reactions on the chain composition, the nature of the monomers and radicals, and the polymerization medium. This section is principally concerned with propagation and the effects of monomer reactivity on composition and monomer sequence distribution. The influence of solvent and complcxing agents on copolymerization is dealt with in more detail in Section 8.3.1. 

Star molecules containing branches made of two blocks have also been prepared by these methods102 103. Recently it was shown that such star-block copolymers exhibit very interesting so-called double-diamond structures in the bulk owing to segregation due to incompatibility between chemically unlike blocks 104. ... 

Hashimoto T., Shibayama M., and Kawai H., Ordered structure in block copolymer solution. 4. Scaling rules on size of fluctuations with block molecular weight, concentration temperature in segregation and homogeneous regimes. Macromolecules, 16, 1093, 1983. 

Rate of hydration of the polymeric materials has been shown to be an important consideration in regard to drug release. Gilding and Reed (24) demonstrated that water uptake increases as the glycolide ratio in the copolymer increases. The extent of block or random structure in the copolymer can also affect the rate of hydration and the rate of degradation (25). Careful control of the polymerization conditions is required in order to afford reproducible drug release behavior in a finished product. Kissel (26) showed drastic differences in water uptake between various homopolymers and copolymers of caprolactone, lactide, and glycolide. 

Mortensen, K Brown, W Norden, B, Inverse Melting Transition and Evidence of Three-Dimensional Cubatic Structure in a Block-Copolymer Micellar System, Physical Review Letters 68, 2340, 1992. 

Diblock copolymers consist of contiguous sequences of two different covalently bound monomer units, arranged in an -A-A-A-B-B-B-B- structure. In an appropriate solvent, the diblock copolymers spontaneously self-assemble into micelles with cores which are essentially pure in one component and a diameter... 

Recent developments have allowed atomic force microscopic (AFM) studies to follow the course of spherulite development and the internal lamellar structures as the spherulite evolves [206-209]. The major steps in spherulite formation were followed by AFM for poly(bisphenol) A octane ether [210,211] and more recently, as seen in the example of Figure 12 for a propylene 1-hexene copolymer [212] with 20 mol% comonomer. Accommodation of significant content of 1-hexene in the lattice allows formation and propagation of sheaf-like lamellar structure in this copolymer. The onset of sheave formation is clearly discerned in the micrographs of Figure 12 after crystallization for 10 h. Branching and development of the sheave are shown at later times. The direct observation of sheave and spherulitic formation by AFM supports the major features that have been deduced from transmission electron and optical microscopy. The fibrous internal spherulite structure could be directly observed by AFM. 

The polybutadienes prepared with these barium t-butoxide-hydroxide/BuLi catalysts are sufficiently stereoregular to undergo crystallization, as measured by DTA ( 8). Since these polymers have a low vinyl content (7%), they also have a low gl ass transition temperature. At a trans-1,4 content of 79%, the Tg is -91°C and multiple endothermic transitions occur at 4°, 20°, and 35°C. However, in copolymers of butadiene (equivalent trans content) and styrene (9 wt.7. styrene), the endothermic transitions are decreased to -4° and 25°C. Relative to the polybutadiene, the glass transition temperature for the copolymer is increased to -82°C. The strain induced crystallization behavior for a SBR of similar structure will be discussed after the introduction of the following new and advanced synthetic rubber. 

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