Polystyrene repeating unit

The absorption spectrum observed in the pulse radiolysis of solid films of polystyrene is shown in Figure 5. The absorption spectrum around 540 nm is also very similar to the absorption spectrum of polystyrene excimer observed in irradiated polystyrene solutions in cyclohexane as reported previously (2,3). The absorption with the maximum at 410 nm was reported previously and was assigned to anionic species (13,14). The longer life absorptions, attributed to triplet excited polystyrene repeat units and nonidentifiable free radicals, were observed in a wave length region < 400 nm. The absorption spectrum of CMS films obtained in pulse radiolysis showed a peak around 320 nm and a very broad absorption around 500 nm as shown in Figure 6. 

Figure 1.1. Calculation of glass transition temperature Tg and density p at room temperature of polystyrene as an example of the application of group contribution techniques, (a) The structure of a polystyrene repeat unit, (b) Fonnal breakdown of this structure into two "groups", (c) Each group makes a contribution to the molecular weight M of the repeat unit, to the "molar glass transition function" Yg, and to the amorphous molar volume V [3a], M, Yg and V arc sums of these contributions ...

Monomers are generally simple organic molecules from which the polymer molecule is made. The strucmre of the repeating unit of a polymer is essentially that or closely related to that of the monomer molecule(s). The formula of the polystyrene repeating unit (II) is thus seen to be essentially the same as that of the monomer styrene CH2 =CH-C6H5. 

To synthesize polyethylene a double carbon bond in the starting material ethylene (CH2=CH2) breaks to allow attachment to other ethylene molecules resulting in a high molecular weight material or macromolecule. Other polymers which are formed by a similar process include polystyrene (repeat unit or monomer is styrene), polypropylene (monomer propene), poly (methyl methacrylate) where the monomer is methyl methacryalate, 1,4-polybutadiene (monomer is buta-1,3-diene) and 1,4-polyisoprene (monomer is isoprene) which has the same formula as natural rubber. Detaik of how polymers are prepared and processed are presented in Chapter 3. 

A still more intricate pattern of potential energy may be expected if the repeat units of the polymer chain carry other substituents, such as the phenyl groups in polystyrene, but these examples establish the general method for quantitatively describing the effects of steric hindrance on rotation. 

We ve seen on several occasions in previous chapters that a polymer, whether synthetic or biological, is a large molecule built up by repetitive bonding together of many smaller units, or monomers. Polyethylene, for instance, is a synthetic polymer made from ethylene (Section 7.10), nylon is a synthetic polyamide made from a diacid and a diamine (Section 21.9), and proteins are biological polyamides made from amino acids. Note that polymers are often drawn by indicating their repeating unit in parentheses. The repeat unit in polystyrene, for example, comes from the monomer styrene. 

Repeating unit of polymer chain including solvation Mn of samples not irradiated based on GPC in NMP with polystyrene standards, or by NMR end-group analysis if so indicated Measured net G value after cesium-137 irradiation corrected relative to Fricke dosimeter... 

Fig. 20. Plot of the exponent ras a function of the chain lengths between two branching points. Open symbols results by Colby et al. [118,119] for branched polyesters. The variation of this length was achieved by co-condensation of trifunctional monomers with increasing fraction of bifunctional units. Filled symbols refer to polydicyanurates (N Nj ), anhydride cured phenyl monoglycidyl ether with a small fraction of bisphenol A diglyci-dylether as crosslinker (N=8Nj ) and end-functionalized 3-arm polystyrene stars crosslinked by diisocyanate (N 40 N ). N denotes the number of repeating units between two branching points...

Among the uncommon stmctures of stereoregular polymers determined in recent times, is that of isotactic polystyrene first observed by Keller and coworkers in crystalline gels (185) and later studied by Corradini et al. (186). In this case too, a highly stretched helix [ (6/1)] is observed, with unit height h = 5.1 A and imit twist t = 60°. The repeating unit contains two independent monomer units with rotation angles close to 180°. 

Numerous polymers autooxidize to form peroxides. These compositionally, and thus calorimetrically, ill-defined products may be considered polymeric peroxides. However, one well-defined polymeric peroxide is that of polystyrene with the repeat unit —CHa-CH(CeH5)-0-0-. Through a combination of combustion and reaction calorimetry (chain degradation to benzaldehyde and formaldehyde), a solid phase enthalpy of formation of this species was found to be 27 21 kJ mol . Much the same procedure was used to determine the enthalpy of degradation for the polyperoxide polymers of 2-vinylnaphthalene and the isomeric 1- and 2-propenylnaphthalene to form the related acylnaphthalene and formaldehyde. Numerically, the reaction enthalpy values for these last three polyperoxides were —206+4, —222 + 8 and —222 + 10 kJmol, to be compared with the aforementioned polystyrene with a value of —209 + 8 kJ mol. However, in the absence of enthalpy of formation data for the decomposition products in the naphthalene case, we hesitate to derive enthalpies of formation for these three species. ... 

Thermoplastic Polymers. Most thermoplastic polymers are used in high-volume, widely recognized applications, so they are often referred to as commodity plastics. (We will elaborate upon the distinction between a polymer and a plastic in Chapter 7, but for now we simply note that a plastic is a polymer that contains other additives and is usually identified by a variety of commercial trade names. There are numerous databases, both in books [1] and on the Internet [2], that can be used to identify the primary polymer components of most plastics. With a few notable exceptions, we will refer to most polymers by their generic chemical name.) The most common commodity thermoplastics are polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) and polystyrene (PS). These thermoplastics all have in common the general repeat unit -(CHX-CH2)-, where -X is -H for PE, -CH3 for PP, -Cl for PVC, and a benzene ring for PS. When we discuss polymerization reactions in Chapter 3, we will see that all of these thermoplastics can be produced by the same type of reaction. 

Chlorination. Chlorination conditions were varied to give a series of polymers with a range of chlorination for each base polymer. The degree of chlorination varied between 0.5 (15% w/w Cl) and 2.5 (44% w/w Cl) per monomer unit. Samples with approximately one chlorine per repeat unit (23.3% w/w Cl) were prepared in order to compare their lithographic performance with that of polychloromethylstyrene and chloromethylated polystyrene. 

In the first approach, a maleimide-functionalized polystyrene of 40 repeat units (P DI = 1.04) was covalently coupled to the sulfur atom of a reduced disulfide bridge on the surface of the lipase B from Candida antarctica (CALB) (Figure 6.11a) [33]. TEM studies of the reaction mixture in water/THF revealed well-defined enzyme fibers with a length of several micrometers. The fibers consisted of bundles of rods, of which the smallest had diameters between 25 and 30 nm. These diameters were in... 

The third approach made use of the streptavidin-biotin couple to connect enzymes to hydrophobic polymer tails (Figure 6.11c) [36]. In the first step of the self-assembly, two biotin-functionalized polystyrene chains (90 repeat units, PDI =... 

The total number of cross-links per gram is directly proportional to radiation dose. Either RSMW or JRg(Mw)2/3 should be independent of initial molecular weight, depending on whether all repeating units or only those near the surface of the coils have equal probabilities for intermolecular cross-link formation. Complete coil collapse is clearly ruled out by the results. Moreover, detailed calculations (46) show that a trend in the product RgMw due to systematic differences in intramolecular cross-linking, should be observed even for only partially collapsed random coils. If the coil radii in bulk polystyrene were reduced by even as much... 

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