Solid-state studies poly

Andrews76 gave results of the work of Reed and Martin on cis-polyisoprene specimens crystallized from a strained cross linked melt and on solid state polymerized poly-oxymethylene respectively, explaining the results by simple two phase models. He also summarized the studies of Patel and Philips775 on spherulitic polyethylene which showed that the Young s modulus increased as a function of crystallite radius by a factor of 3 up to a radius of about 13 n and then decreased on further increasing spherulite size. 

Polyalkylarylsilanes, solid-state studies, 3, 605 Poly[(alkyl)(aryl)silylene]s, preferential screw sense, 3, 616 Polyamides, aromatic, 7t-complexed, 12, 362 Polyamidoferrocenylalkylthiolate—gold nanoparticles, synthesis, 6, 195—196... 

The results of a study of the relation between the oriented structure and drawn poly(e-caprolactone) specimens including CaCO particles, their dynamic mechanical properties and line shape analyses of CP MAS NMR spectra are presented. Solid state studies of C NMR study of poly(methyl acrylate) ionomer have been reported. ... 

Extension of these studies to the polymer in solution and the measurement of the attendant decrease in molar mass showed that it was the chain length which was important, not the solid-state properties. In particular the solid-state studies showed that there was a critical molar mass before mechanochemical effects could be observed (for polyethylene (PE), a degree of polymerization of about 100). In solution a similar effect was observed since the degradation of poly(methyl methacrylate) (PMMA) could not continue when the chain length reached about 4000 repeat units (Sohma, 1989a, 1989b). This was shown by a slow decrease in molar mass to the asymptotic value as shown in Figure 1 -39. 

Molecular dynamics in the solid state of poly hydroxyalkanoic acid)s studies by NMR... 

A similar rate law operates for isomerization of the cis and trans forms of [Co(en)2(ONO)2] and of [Co(en)2(ONO)(N02)] these nitrito nitro iso-merizations take place without change in configuration at the cobalt. Similarly nitrito nitro isomerization of ( + )-c/5-[Co(en)2(ONO)(N02)] occurs without loss of chirality. These stereochemical results contrast with normally observed behavior in substitution at cobalt(III). The nitrito nitro isomerization of [Co(NH3)5(ONO)], in this case generated in situ photochemically, has also been studied in poly(vinyl alcohol) media. This very viscous medium, viz. pva sheets, was used to probe the gap between water and solid state studies. The rate of isomerization in pva is similar to that in water, but about ten times faster than in the solid phase. Such a short range of reactivities is, of course, consistent with an intramolecular mechanism in all three media. ... 

Polyester chemistry is the same as studied by Carothers long ago, but polyester synthesis is still a very active field. New polymers have been very recently or will be soon commercially introduced PTT for fiber applications poly(ethylene naph-thalate) (PEN) for packaging and fiber applications and poly(lactic acid) (PLA), a biopolymer synthesized from renewable resources (corn syrup) introduced by Dow-Cargill for large-scale applications in textile industry and solid-state molding resins. Polyesters with unusual hyperbranched architecture also recently appeared and are claimed to find applications as crosstinkers, surfactants, or processing additives. 

The stability of polyanhydrides composed of the diacids sebacic acid (SA), bis( -carboxyphenoxy)methane (CPM), l,3-bis(g-carboxyphe-noxy)propane (CPP), l,6-bis( -carboxyphenoxy)hexane (CPH), and phenylenedipropionic acid (PDP), in solid state and in organic solutions, was studied over a 1-year period. Aromatic polyanhydrides such as poly(CPM) and poly(CPH) maintained their original molecular weight for at least a year in both solid state and solution (20). 

This sequence of formation of radical cation which is followed by a C—S bond scission into alkyl radical and alkyl sulfonyl cation was previously suggested by the same authors for the radiolysis of poly(olefin sulfone)s in the solid state and was confirmed by scavenger studies . Seavengers are ineffeetive in erystalline solids such as dialkyl sulfones and hence eould not be used in this study. 

The recent interest in substituted silane polymers has resulted in a number of theoretical (15-19) and spectroscopic (19-21) studies. Most of the theoretical studies have assumed an all-trans planar zig-zag backbone conformation for computational simplicity. However, early PES studies of a number of short chain silicon catenates strongly suggested that the electronic properties may also depend on the conformation of the silicon backbone (22). This was recently confirmed by spectroscopic studies of poly(di-n-hexylsilane) in the solid state (23-26). Complementary studies in solution have suggested that conformational changes in the polysilane backbone may also be responsible for the unusual thermochromic behavior of many derivatives (27,28). In order to avoid the additional complexities associated with this thermochromism and possible aggregation effects at low temperatures, we have limited this report to polymer solutions at room temperature. 

Probably most of these investigators were studying poly(dichlorophosphazene) in the partially crosslinked state. Most of this was summarized by Allcock (.9). More recently, highly purified, uncrosslinked II has been examined in the solid state (21). The unstressed polymer is amorphous at room temperature, but crystallization can be induced by cooling or stretching techniques. The glass transition temperature, measured by Torsional Braid Analysis, is -66°C (22). 

Following these early solid-state investigations, 1,907 nm EFISHG studies by Tam and co-workers on several complexes [W(CO)5L] (L = py or a 4-substituted py) quote (3 values similar to that of 4-nitroaniline (ca. 10 x 10-30 esu) and sensitive to the nature of the pyridyl substituent.67-69 These results were quickly followed by ZINDO/SCI-SOS calculations on the same series of complexes by Kanis et al.70 the first time that MO theory had been used to describe the quadratic NLO responses of metal complexes. The results of these calculations agree reasonably well with the EFISHG data, and indicate that the modest (3 responses can be traced to relatively small Ap12 values.70 Lacroix et al. obtained low 1,064 nm SHG activities by corona poling films of poly (4-vinylpyridine) and of two other related polymers functionalized with W(CO)5 centers.71... 

Crosslinked polymer networks formed from multifunctional acrylates are completely insoluble. Consequently, solid-state nuclear magnetic resonance (NMR) spectroscopy becomes an attractive method to determine the degree of crosslinking of such polymers (1-4). Solid-state NMR spectroscopy has been used to study the homopolymerization kinetics of various diacrylates and to distinguish between constrained and unconstrained, or unreacted double bonds in polymers (5,6). Solid-state NMR techniques can also be used to determine the domain sizes of different polymer phases and to determine the presence of microgels within a poly multiacrylate sample (7). The results of solid-state NMR experiments have also been correlated to dynamic mechanical analysis measurements of the glass transition (1,8,9) of various polydiacrylates. 

Local Dynamics in Polypeptides Studied by Solid State 2H NMR Side Chain Dynamics of Poly(Y-benzyl L-glutamate) and Racemic Poly(Y-benzyl glutamate)... 

Much less work has been focused on the effect of polymer structure on the resist performance in these systems. This paper will describe and evaluate the chemistry and resist performance of several systems based on three matrix polymers poly(4-t-butoxycarbonyloxy-a-methylstyrene) (TBMS) (12), poly(4-t-butoxycarbonyloxystyrene-sulfone) (TBSS) (13) and TBS (14) when used in conjunction with the dinitrobenzyl tosylate (Ts), triphenylsulfonium hexafluoroarsenate (As) and triphenylsulfonium triflate (Tf) acid generators. Gas chromatography coupled with mass spectroscopy (GC/MS) has been used to study the detailed chemical reactions of these systems in both solution and the solid-state. These results are used to understand the lithographic performance of several systems. 

Very recently, however, two papers were published by the group of Fujiki which report successful solid-state CD studies of chiral polysilanes. In the first, a helix-coil transition was described for film samples of poly[(A)-3,7-dimethyloctyl- -propylsilylene)], 113.327 This polymer has a relatively low glass transition temperature, T, which was considered critical for the observation of a helix-helix transition in the solid state, since helical inversion would be precluded if the inversion temperature, Tc, were below Ts as the segmental motion of the chain,... 

The emissive counterpart to CD is circularly polarized photoluminescence (CPPL). Where the fluorophore is chiral, then the photo-excited state can return to the ground state with emission of circularly polarized light, the direction of polarization of which depends on the relative intensities of the right-handed and left-handed emissions (/r and /L, respectively), which in turn depends on the chirality of the material, or more accurately, the chirality of the photo-excited state of the material. CPPL studies on poly silanes are extremely rare, however, due to the low CPPL intensity and rapid sample degradation in solution, and problems due to artifacts in the solid state. 

The authors [1] studied kinetics of poly (amic acid) (PAA) solid-state imidization both in the presence of nanofiller (layered silicate Na+-montmorillonite) and without it. It was found, that temperature imidization 1] raising in range 423-523 K and nanofiller contents Wc increase in range 0-7 phr result to essential imidization kinetics changes expressed by two aspects by essential increase of reaction rate (reaction rate constant of first order k increases about on two order) and by raising of conversion (imidization) limiting degree Q im from about 0,25 for imidization reaction without filler at 7 i=423 K up to 1,0 at Na -montmorillonite content 7... 

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