PDMS+benzene

The above values are applicable only in the limiting case of infinite dilution. The interaction parameter varies with the volume fraction of polymer network as has been demonstrated for the PDMS-benzene system by Flory (47) and PDMS-methyl ethyl ketone, PDMS-methyl isobutyl ketone, PDMS-ethyl-n-butyl ketone, and PDMS-diisobutyl ketone by Shiomi et al. (48). Theoretically calculated and experimentally observed values of X as a function of volume fraction of polymer are given for PDMS in alkanes, aromatic hydrocarbons, and dimethyl siloxane oligomers by Gottlieb and Herskowitz (49). In the case of PDMS-alkanes, x was practically independent of the volume fraction of polymer. 

Ashworth and Price (1986) provide values of / and volume fraction of the solvent, 0y, for the poly(dimethylsiloxane) (PDMS) - benzene system at 303 K. 

Figure 3.79 presents the data of x calculations by Equation 66 for the (network PDMS) + benzene system at 25 C. The concentration dependence x — x( 2) practically coincides with the data of osmotic pressure measurements in linear PDMS solution in benzene (Flory and Shih, 1972). 

Synthesis of comb (regular graft) copolymers having a PDMS backbone and polyethylene oxide) teeth was reported 344). These copolymers were obtained by the reaction of poly(hydrogen,methyl)siloxane and monohydroxy-terminated polyethylene oxide) in benzene or toluene solution using triethylamine as catalyst. All the polymers obtained were reported to be liquids at room temperature. The copolymers were then thermally crosslinked at 150 °C. Conductivities of the lithium salts of the copolymers and the networks were determined. 

Over the last decade, the chemistry of the carbon-carbon triple bond has experienced a vigorous resurgence [1]. Whereas construction of alkyne-con-taining systems had previously been a laborious process, the advent of new synthetic methodology based on organotransition metal complexes has revolutionized the field [2]. Specifically, palladium-catalyzed cross-coupling reactions between alkyne sp-carbon atoms and sp -carbon atoms of arenes and alkenes have allowed for rapid assembly of relatively complex structures [3]. In particular, the preparation of alkyne-rich macrocycles, the subject of this report, has benefited enormously from these recent advances. For the purpose of this review, we Emit the discussion to cychc systems which contain benzene and acetylene moieties only, henceforth referred to as phenylacetylene and phenyldiacetylene macrocycles (PAMs and PDMs, respectively). Not only have a wide... 

Another limitation of the traditional Cu-mediated cyclooligomerization reaction is generation of differentially substituted PDMs. In the above case, the substitution pattern in the starting o-diethynylbenzene must be maintained on each and every benzene moiety in the oligomeric mixture of PDMs that is produced. Thus, it is impossible to prepare less symmetric systems like 100 via this route. With the intramolecular synthetic approach, however, it should be possi-... 

Fig. 41. 0(Q)/Q2 vs. Q for different dilute solutions under -conditions PDMS/d-bromo-benzene, T = 357 K x PS/d-methylcyclohexane T = 341 K O PS/d-cyclohexane T = 311 K...

Under good solvent conditions the dynamics of semi-dilute solutions was investigated by NSE using a PDMS/d-benzene system at T = 343 K and various concentrations 0.02 c < 0.25. The critical concentration c as defined by (112) is 0.055. 

Fig. 60. Crossover from single-chain to many-chain relaxation at T = 343 K. Lineshape analysis for PDMS/d-benzene at c = 5 and 18% double logarithmic plot of — ln/S(Q,t)/S(Q,0) vs. t/s. (Reprinted with permission from [116]. Copyright 1982 J. Wiley and Sons, Inc., New York)...

Figure 1. Mc from equilibrium swelling in benzene vs. concentration of A 4 endlinking agent in divinyl—PDMS, Mn = 11,500.

Triacetone triperoxide (TATP) is a powerful explosive manufactured in clandestine laboratories and used by terrorists. As TATP subHmes easily, analysis was performed by SPME trapping of its vapor, using polydimethylsiloxane/divinyl benzene (PDMS/DVB) fiber, followed by desorption into a GC/MS injector [10]. Figure 6 shows the TIC, mass chromatogram and the El mass spectmm of headspace from a debris sample containing TATP [11]. The El mass spectmm contains a molecular ion at m/z 222 and several fragment ions. In the chemical ionization mass spectmm of TATP [12], the m or ions were at m/z 223 (100%), 222 (20%), 133 (20%), 117 (40%), 115 (20%), 103 (75%) and 100 (50%). 

SPME Fiber. A 65 pm poly(dimethylsiloxane)/divinyl benzene (PDMS/DVB) fiber coating (Supelco, Bellefonte, PA) was used in this method. This fiber coating was selected for its ability to retain the derivatizing agent and for its affinity for the PFBOA-aldehyde oxime (7). 

The SPMB fiber was coaled with 65 pm poly(dir tathyi-siloxane)/divinyl benzene (PDMS/DVB SPME). 

Unambiguous A 65 pm poly(dimethylsiloxane)/divinyl benzene (PDMS/... 

We have shown that living polydlmethylslloxanes (PDMS) can be prepared by adding the [211] cryptand to benzene solutions of D3 after reaction with n-butyllithium, at 25°C, as can be seen from the results of Table IV. The propagation reaction is much faster with [211] than with THF. 

In order to elucidate this point, viscosity measurements of living and deactivated PDMS solutions were performed In toluene, with Li+ + [211] as counterion. As no significant change was observed, It can be deduced that the fraction of aggregates Is negligible (< 1% for [C] 10 mole. " ). Moreover, conductance measurements made on model sllanolates In THF Indicate that the fraction of free Ions Is very low. In our system (benzene) we conclude therefore that the contribution to the reactivity from free ions can be neglected. Thus the main Ionic species are cryptated ion pairs, and... 

GPC diagrams of the PDMS obtained from D3 with Ll+ + [211] as counterion in benzene show that the proportion of oligomers is very low. However, Mw/Mn values corresponding to high yields of conversion are nearly equal to 2. 

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