Sample polymers

In the following data acquisition, the same 163 standard polymer samples used in the former edition were adopted as a set of representative ones utilized in versatile fields, which include representative synthetic polymers [a) polyolefins (homopolymers) (001— 007), b) vinyl polymers with ethylene units (copolymers) (008—015), c) vinyl polymers with styrene units (016—028), d) vinyl polymers with styrene derivatives (029—035), e) acrylate-type polymers (036—049), f) chlorine-containing vinyl polymers (050-059), g) fluorine-containing vinyl polymen (060—066), h) the other vinyl polymers (067—070), i) diene-type elastomers (071—081), j) polyamides (082-090), k) polyacetals and polyethers (091—095), 1) thermosetting polymers (096—106), m) polyimides and polyamide-type engineering plastics (107—114), n) polyesters (115—126), o) the other engineering plastics with phenylene skeletons (127—138), p) sificone polymers (139—143), and q) polyurethanes (144—147)] along with some natural polymers [r) cellulose-type polymers (148-155) and s) the other some natural polymers (156-163)]. 

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The so-called peak power delivered by a pulsed laser is often far greater than that for a continuous one. Whereas many substances absorb radiation in the ultraviolet and infrared regions of the electromagnetic spectrum, relatively few substances are colored. Therefore, a laser that emits only visible light will not be as generally useful as one that emits in the ultraviolet or infrared ends of the spectrum. Further, witli a visible-band laser, colored substances absorb more or less energy depending on the color. Thus two identical polymer samples, one dyed red and one blue, would desorb and ionize with very different efficiencies. 

The terminal groups of a polymer chain are different in some way from the repeat units that characterize the rest of the molecule. If some technique of analytical chemistry can be applied to determine the number of these end groups in a polymer sample, then the average molecular weight of the polymer is readily evaluated. In essence, the concept is no different than the equivalent procedure applied to low molecular weight compounds. The latter is often included as an experiment in general chemistry laboratory classes. The following steps outline the experimental and computational essence of this procedure ... 

Next let us consider the differences in molecular architecture between polymers which exclusively display viscous flow and those which display a purely elastic response. To attribute the entire effect to molecular structure we assume the polymers are compared at the same temperature. Crosslinking between different chains is the structural feature responsible for elastic response in polymer samples. If the crosslinking is totally effective, we can regard the entire sample as one giant molecule, since the entire volume is permeated by a continuous network of chains. This result was anticipated in the discussion of the Bueche theory for chain entanglements in the last chapter, when we observed that viscosity would be infinite with entanglements if there were no slippage between chains. 

Stretching a polymer sample tends to orient chain segments and thereby facilitate crystallization. The incorporation of different polymer chains into small patches of crystallinity is equivalent to additional crosslinking and changes the modulus accordingly. Likewise, the presence of finely subdivided solid particles, such as carbon black in rubber, reinforces the polymer in a way that imitates the effect of crystallites. Spontaneous crystal formation and reinforcement... 

Our objectives in this section are twofold to describe and analyze a mechanical model for a viscoelastic material, and to describe and interpret an experimental procedure used to study polymer samples. We shall begin with the model and then proceed to relate the two. Pay attention to the difference between the model and the actual observed behavior. 

Returning to the Maxwell element, suppose we rapidly deform the system to some state of strain and secure it in such a way that it retains the initial deformation. Because the material possesses the capability to flow, some internal relaxation will occur such that less force will be required with the passage of time to sustain the deformation. Our goal with the Maxwell model is to calculate how the stress varies with time, or, expressing the stress relative to the constant strain, to describe the time-dependent modulus. Such an experiment can readily be performed on a polymer sample, the results yielding a time-dependent stress relaxation modulus. In principle, the experiment could be conducted in either a tensile or shear mode measuring E(t) or G(t), respectively. We shall discuss the Maxwell model in terms of shear. 

As we did in the case of relaxation, we now compare the behavior predicted by the Voigt model—and, for that matter, the Maxwell model—with the behavior of actual polymer samples in a creep experiment. Figure 3.12 shows plots of such experiments for two polymers. The graph is on log-log coordinates and should therefore be compared with Fig. 3.11b. The polymers are polystyrene of molecular weight 6.0 X 10 at a reduced temperature of 100°C and cis-poly-isoprene of molecular weight 6.2 X 10 at a reduced temperature of -30°C. 

The bead and spring model is clearly based on mechanical elements just as the Maxwell and Voigt models were. There is a difference, however. The latter merely describe a mechanical system which behaves the same as a polymer sample, while the former relates these elements to actual polymer chains. As a mechanical system, the differential equations represented by Eq. (3.89) have been thoroughly investigated. The results are somewhat complicated, so we shall not go into the method of solution, except for the following observations ... 

The preceding example of superpositioning is an illustration of the principle of time-temperature equivalency. We referred to this in the last chapter in connection with the mechanical behavior of polymer samples and shall take up the... 

Suppose a bulk-crystallized polymer sample is observed in an optical microscope with the sample placed between Polaroid filters oriented at right angles to each other. In the absence of any sample, the light would be attenuated owing to the 90° angle between the vectors describing the light transmitted by the two filters. With a crystalline sample of polymer in place, however, a display like... 

Howardt describes a model system used to test the molecular weight distribution of a condensation polymer The polymer sample was an acetic acid-stabilized equilibrium nylon-6,6. Analysis showed it to have the following end group composition (in equivalents per 10 g) acetyl = 28.9,... 

Hven fractionated polymer samples are generally polydisperse, which means that the molecular weight determined from intrinsic viscosity experiments is an average value. The average obtained is the viscosity average as defined by Eqs. (1.20) and (2.40) as seen by the following argument ... 

Evaluate M and B for each of the five runs on this polymer sample and comment on the following points ... 

Below about 0.75 T, polymers are brittle (Fig. 23.9). Unless special care is taken to avoid it, a polymer sample has small surface cracks (depth c) left by machining or abrasion, or caused by environmental attack. Then a tensile stress tr will cause brittle failure if... 

A further feature of anionic polymerisation is that, under very carefully controlled eonditions, it may be possible to produee a polymer sample which is virtually monodisperse, i.e. the molecules are all of the same size. This is in contrast to free-radical polymerisations which, because of the randomness of both chain initiation and termination, yield polymers with a wide molecular size distribution, i.e. they are said to be polydisperse. In order to produce monodisperse polymers it is necessary that the following requirements be met ... 

Gels made in this way have virtually no usable porosity and are called Jordi solid bead packings. They can be used in the production of low surface area reverse phase packings for fast protein analysis and in the manufacture of hydrodynamic volume columns as well as solid supports for solid-phase syntheses reactions. An example of a hydrodynamic volume column separation is shown in Fig. 13.2 and its calibration plot is shown in Fig. 13.3. The major advantage of this type of column is its ability to resolve very high molecular weight polymer samples successfully. 

The selection of the right gel-permeation chromatography (GPC) column or column combination for a special task is a multistage procedure. First, a decision about the type of column has to be made according to the polymer samples in question ... 

There are different reasons to discard a column a column can be damaged by irreversible adsorption of reactive polymer samples. Small amounts of styrene oligomers are known to permanently elute from styrene-divinylbenzene materials with tetrahydrofuran as the eluent, which means a continuous shear degradation of the separation material and consequently a decrease of the packing quality this observation is very important if fractions are collected and used for further analyses, e.g., for the determination of infrared (IR) spectra. One can presume that similar effects are present with other organic materials too. 

The latest trend is to smaller beads in smaller columns, as this saves eluent and shortens the time for a chromatographic analysis. This argument can be correct if only one suitable detector is used. However, these modern small columns are not optimal for a combination of detectors. So-called multiple detection is a combination of some detectors with different measurement principles (differential refractometer, spectral photometer, light-scattering detector, on-line viscometer) behind the last column, mostly in series, seldom in a branched ( parallel ) order. In this way, the tedious preparative fractionation of a polymer sample can often be avoided. 

A more difficult criterion to meet with flow markers is that the polymer samples not contain interferents that coelute with or very near the flow marker and either affect its retention time or the ability of the analyst to reproducibly identify the retention time of the peak. Water is a ubiquitous problem in nonaqueous GPC and, when using a refractive index detector, it can cause a variable magnitude, negative area peak that may coelute with certain choices of totally permeated flow markers. This variable area negative peak may alter the apparent position of the flow marker when the flow rate has actually been invariant, thereby causing the user to falsely adjust data to compensate for the flow error. Similar problems can occur with the elution of positive peaks that are not exactly identical in elution to the totally permeated flow marker. Species that often contribute to these problems are residual monomer, reactants, surfactants, by-products, or buffers from the synthesis of the polymer. 

In industry and academia the need often arises to isolate portions of a polymer sample, whether it be to separate low molecular weight material from a sample or to actually fractionate the polymer across its molecular weight distribution. If gram quantities of isolated polymer are needed, true preparative chromatography equipment and techniques are usually necessary. 

When a dilute solution of a polymer (c << c ) is equilibrated with a porous medium, some polymer chains are partitioned to the pore channels. The partition coefficient K, defined as the ratio of the polymer concentration in the pore to the one in the exterior solution, decreases with increasing MW of the polymer (7). This size exclusion principle has been used successfully in SEC to characterize the MW distribution of polymer samples (8). 

A narrow pore size distribution is essential to HOPC. To separate polymer samples with various average molecular weights, users need to prepare columns packed with porous materials of a uniform but different pore size, e.g., 10, 13, 18, and 24 nm. In contrast, a broader pore size distribution is common in a SEC column. A need to analyze a wide range of molecular weights (over many decades) by a single set of columns has spread the use of these columns. 

Each of the four columns was packed with CPG00120C d = 13.0 nm). The column dimensions and experimental conditions are listed in Table 23.1. The flow rates (solution and solvent) were set to be proportional to the cross section of the column, whenever possible. The number of drops collected in each test tube was almost proportional to the cross section, especially for the initial fractions that might show a shift in M. Figure 23.9 shows chromatograms for some the fractions separated using 2.1-, 3.9-, and 7.8-mm i.d. columns. The result with the 7.8-mm i.d. column is a reproduction of Fig. 23.2 (3). Chromatograms of the fractions obtained from the 1.0-mm i.d. column overlapped with the chromatogram of the injected polymer sample (not shown). 

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