Poly molar mass

As stated in Section I, columns should be selected so the low molar mass portions of the samples in question can be sufficiently separated from the elution interval of the system peaks. This task cannot always be accomplished, e.g., dimethylacetamide often replaces dimethylformamide as a GPC eluent the analyzed, mostly polar, samples require a neutral salt (e.g., FiBr) (7). The calibration is usually carried out with poly(methylmethacrylate) standards... 

In this stage of the investigation, poly(methyl methacrylates) (PMMAs) were selected as the polymeric probes of intermediate polarity. Polymers of medium broad molar mass distribution and of low tacticity (14) were a gift of Dr. W. Wunderlich of Rohm Co., Darmstadt, Germany. Their molar masses ranged from 1.6 X 10" to 6.13 X 10 g-mol. For some comparative tests, narrow polystyrene standards from Pressure Co. (Pittsburgh, PA) were used. 

There have been very few examples of PTV derivatives substituted at the vinylene position. One example poly(2,5-thienylene-1,2-dimethoxy-ethenylene) 102 has been documented by Geise and co-workers and its synthesis is outlined in Scheme 1-32 [133]. Thiophene-2,5-dicarboxaldehyde 99 is polymerized using a benzoin condensation the polyacyloin precursor 100 was treated with base to obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102, which is soluble in solvents such as chloroform, methanol, and DMF. The molar mass of the polymer obtained is rather low (M = 1010) and its band gap ( ,.=2.13 eV) is substantially blue-shifted relative to PTV itself. Despite the low effective conjugation, the material is reasonably conductive when doped with l2 (cr=0.4 S cm 1). 

Hie most representative member of this class of polyesters is the low-molar-mass (M 1000-3000) hydroxy-terminated aliphatic poly(2,2/-oxydiethylene adipate) obtained by esterification between adipic acid and diethylene glycol. This oligomer is used as a macromonomer in the synthesis of polyurethane elastomers and flexible foams by reaction with diisocyanates (see Chapter 5). Hydroxy-terminated poly(f -caprolactonc) and copolyesters of various diols or polyols and diacids, such as o-phthalic acid or hydroxy acids, broaden the range of properties and applications of polyester polyols. 

The rigid and soft blocks used in polyesteredier diermoplastic elastomers (polyesteretlier TPEs) are typically PBT and poly(oxyteti amethylene) (PTMO), respectively, witii block number-average molar mass varying between 1000 and 3000. They are obtained by the melt reaction between dimethyl terephthalate, butanediol, and dihydroxy-terminated PTMO in the conditions typical of a PBT syndiesis. 

At constant PBT/PTMO composition, when the molar mass of PTMO block is >2000, partial crystallization of the polyether phase leads to copolymer stiffening. The properties of polyesterether TPEs are not dramatically different when PTMO is replaced by polyethers such as poly(oxyethylene) (PEO) or poly(oxypropylene). PEO-based TPEs present higher hydrophilicity, which may be of interest for some applications such as waterproof breathable membranes but which also results in much lower hydrolysis resistance. Changing PBT into a more rigid polymer by using 2,6-naphthalene dicarboxylic acid instead of terephthalic acid results in compounds that exhibit excellent general properties but poorer low-temperature stiffening characteristics. 

The reported molar masses of polyesters obtained by enzymatic catalysis are relatively low, generally below 8000, except for polymers recovered by precipitation.336 This procedure results in the elimination of a soluble fraction consisting of low-molar-mass linear and cyclic oligomers.336 An Mw as high as 46,400 has thus been reported for a poly(tetramethylene decanedioate) obtained... 

High-Molar-Mass Poly(tetramethylene octanedioate) by Diester—Diol Reaction... 

A typical Ziegler-Natta catalyst is the complex prepared from titanium tetrachloride and triethylaluminium. It is fed into the reaction vessel first, after which ethylene is added. Reaction is carried out at low pressures and low temperatures, typically no more than 70 °C, with rigorous exclusion of air and moisture, which would destroy the catalyst. The poly(ethylenes) produced by such processes are of intermediate density, giving values of about 0.945 g cm. A range of relative molar masses may be obtained for such... 

This polymer, which has the structure [—CH2CH(CH3)—] arose as a commercial material following the work of Natta on catalysts for the preparation of high relative molar mass polymers from alkenes. Following his work on the polymerisation of ethylene, Natta showed in 1954 that it was possible to prepare analogous polymers of propylene. Commercial exploitation followed rapidly, and poly (propylene) was first marketed in 1957. 

Polyurethanes are thermoset polymers formed from di-isocyanates and poly functional compounds containing numerous hydroxy-groups. Typically the starting materials are themselves polymeric, but comprise relatively few monomer units in the molecule. Low relative molar mass species of this kind are known generally as oligomers. Typical oligomers for the preparation of polyurethanes are polyesters and poly ethers. These are usually prepared to include a small proportion of monomeric trifunctional hydroxy compounds, such as trimethylolpropane, in the backbone, so that they contain pendant hydroxyls which act as the sites of crosslinking. A number of different diisocyanates are used commercially typical examples are shown in Table 1.2. 

The polymer in natural rubber consists almost entirely of ci -poly(isoprene) (1.6). The molecules are linear, with relative molar mass typically lying between 300 000 and 500 000. The macromolecular nature of rubber was established mainly by Staudinger in 1922, when he hydrogenated the material and obtained a product that retained its colloidal character, rather than yielding fragments of low relative molar mass. 

At the bottom of the tower, the high molar mass poly(styrene) is extruded, granulated, and cooled prior to packaging. 

The main polymers used as thickeners are modified celluloses and poly(acrylic acid). Several different modified celluloses are available, including methyl-, hydroxypropyl methyl-, and sodium carboxymethyl-cellulose and their properties vary according to the number and distribution of the substituents and according to relative molar mass of the parent cellulose. Hence a range of materials is available, some of which dissolve more readily than others, and which provide a wide spread of possible solution viscosities. Poly(acrylic acid) is also used as a thickener, and is also available in a range of relative molar masses which give rise to give solutions of different viscosities. 

Experimental values of the molar mass exponent close to 2 have been obtained. For example, for poly(methyl methacrylate), a value of 2.45 has found (see P. Prentice, Polymer, 1983, 24, 344—350). As with values of selfdiffusion coefficient, this has been regarded as close enough to 2 for reptation to be considered a good model of the molecular motion occurring at the crack tip. 

In a typical hip replacement operation, the top of the thigh bone is removed and a cavity is drilled along the direction of the long axis of the remaining bone. A metal prosthesis is placed in this cavity and secured in place with PMMA cement. In the pelvic girdle a plastic cup is fitted to act as the seat of the new, smaller hip joint. This cup is made of ultra-high molar mass poly (ethylene) and is also secured in place with PMMA cement. The components of an artificial hip joint are shown in Figure 10.1. 

Another widely used surgical procedure is knee replacement. In this operation the natural components of the knee joint are replaced with an artificial femoral component made of metal that interfaces with a tibial plateau made of ultra-high molar mass poly(ethylene). Implantation of these joints is becoming more widespread, though the demand for them is not as great as for hip replacement. 

For some polymers, like polystyrene or poly(methyl methacrylate), narrow standards of known molar mass and small polydispersity are commercially available, which can be used for calibration. Unfortunately, such standards are not available for all polymers and then the obtained true molar masses of a specific polymer might differ by a factor of two from the value obtained by calibration with, e.g., polystyrene [30] (see Section 9.1). This problem can be resolved by the so-called universal calibration, which is based on the finding that the retention volume of a polymer is a single-valued function of the hydrodynamic volume of the polymer, irrespective of its chemical nature and... 

Figure 16 SEC molar mass distribution of poly(p-phenylene) P3 in THF after universal calibration based on Equations (31) (dashed) and (36) (dotted) and with polystyrene calibration (solid line). 

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