Deuterated poly methyl

FIGURE 10.11 Zimm plot of SANS data from hydrogenous and deuterated poly(methyl methacrylate) (PMMA) samples. (From Kirste et al., Polymer 16, 120, 1975. With permission.)... 

Using FRES and others techniques, Wang and Composto investigated wetting and phase separation in polymer blend films composed of deuterated poly(methyl methacrylate) (d-PMMA) and poly(styrene-raw-acrylonitrile) (h-SAN) at the critical concentration [176-180]. This blend is characterized by a lower critical solution temperature (LCST) behavior with Tlcst 160 °C and 0d-PMMA 0.5 [180]. In this... 

Fig. 16. Spectra of optically active deuterated poly(methyl thiiranes) obtained by anionic initiator with sodium. Optical activity of initial monomer (A) = -20° (neat, dm) (B) af/ = -10° (neat,...

P.B. Smith (Dow Chemical Company, Midland, Michigan) Some of the deuterium NMR work on your system has been done by Vega [A.J. Vega, ACS Polym. Prepr., 22(2), 282-283 (1981)] on deuterated poly(methyl methacrylate). Dr. Cowie mentioned in this talk [J.M.G. Cowie, contribution in this volume] that the polymer chain backbone was very stiff and that as you locked up the pendant methyl group the calculated data agreed more closely with the experimental data. I believe that Vega found that even at room temperature the pendant methyl group didn t rotate. 

Figure 7.4 Diffusion-controlled domain growth in phase-separating blends with and without nanoparticles, (a) Experimental data on phase separation dynamics in deuterated poly (methyl methac late) (dPMMA)/s1yrene-ac lonitrile (SAN) thin films, as a function of nanoparticle surface chemist and loading [47] (b) Langevin dynamics calculations of domain...

The same type of addition—as shown by X-ray analysis—occurs in the cationic polymerization of alkenyl ethers R—CH=CH—OR and of 8-chlorovinyl ethers (395). However, NMR analysis showed the presence of some configurational disorder (396). The stereochemistry of acrylate polymerization, determined by the use of deuterated monomers, was found to be strongly dependent on the reaction environment and, in particular, on the solvation of the growing-chain-catalyst system at both the a and jS carbon atoms (390, 397-399). Non-solvated contact ion pairs such as those existing in the presence of lithium catalysts in toluene at low temperature, are responsible for the formation of threo isotactic sequences from cis monomers and, therefore, involve a trans addition in contrast, solvent separated ion pairs (fluorenyllithium in THF) give rise to a predominantly syndiotactic polymer. Finally, in mixed ether-hydrocarbon solvents where there are probably peripherally solvated ion pairs, a predominantly isotactic polymer with nonconstant stereochemistry in the jS position is obtained. It seems evident fiom this complexity of situations that the micro-tacticity of anionic poly(methyl methacrylate) cannot be interpreted by a simple Bernoulli distribution, as has already been discussed in Sect. III-A. 

Nuclear Magnetic Resonance (NMR) - NMR spectra of cellulose nitrate-g-poly(methyl methacrylate) and cellulose nitrate were recorded in deuterated acetone using Perkin-Elmer-R-32 (90 MHz). 

Using poly (methyl methacrylate), PMMA, perdeuterated PMMA, and polystyrene, it was found that absorptive losses are very low (<0.1 dB/cm) at wavelengths between 0.5 and 1.0 m, and that losses due to C-H overtones can be made lower than 0.1 dB/cm between 1 and 2 m by deuteration. ... 

Another type of dependence of effective interfacial width wD on film thickness D was observed [130] for immiscible mixture of deuterated polystyrene (dPS) and poly(methyl methacrylate) (PMMA) (at T TC) an increase, from wd=1.8(4) nm for a dPS layer thickness D=6 nm to wd(D=100 nm)=2.5(4) nm, follows the logarithmic dependence wD°clnD (intrinsic interfacial width w= 1.5 nm). This may reflect [6,224] long range forces acting from the external interfaces on the internal interface Ie(x,y). On the contrary, the relation wd D1/2 found for random olefines [121] corresponds [6,224] to short range forces. We note also that capillary waves in dPS/PMMA system were observed [130] already for the thickness-to-intrinsic width ratio D/w<85 ... 

Figure 3. NMR spectra of poly(methyl methacrylate-co-methacrylic acid) obtained by (1) plasma-initiated polymerization and (2) thermal polymerization in 0.2% deuterated pyridine.

Figures 3.7 and 3.8 shows the frequency dependencies of Ti and NOE measured for the CH2 (rrr) carbon of poly(methyl methacrylate) (PMMA) in a deuterated chloroform solution at 55°C [10]. Different curves indicate the simulated results obtained by using the box-type distribution, log- distribution, 2r and 3t models described above. As is clearly seen in Fig.

The reductive desulfonylation of a-sulfonyl esters with tin hydrides only succeeds with n-deficient heterocyclic sulfones (Eq. 104).175 These sulfones are inert under standard procedures using Al/Hg or Na/Hg, but undergo facile C-S cleavage with tin hydrides. Substitution of //-liu3Snl) for n-Bu3SnH gives access to a-deuterated esters.58 A catalytic version of the reaction is carried out with substoichiometric amounts of tributyltin chloride and an excess of poly(methyl-hydrosiloxane) (PMHS) in the presence of potassium fluoride. This method has been employed for the synthesis of 2-fluoroalkanoates (Eq. 105).58... 

Figure 7.16 shows the neutron reflectivity determined by Anastasiadis et al.15 with a sample in which a thin film of a diblock copolymer was deposited on a silicon substrate. The diblock copolymer, of molecular weight 100,000, consists of a block of deuterated polystyrene joined to a block of hydrogenous poly(methyl methacrylate) of about equal length and is therefore expected to organize itself into a lamellar... 

Atactic poly(methyl methacrylate) Atactic polystyrene Butyl-rubber Chlorinated polyethylene Deuterated high density polyethylene Ethylene butylacrylate Elastomeric copolymer from ethylene and ethyl acrylate Elastomeric terpolymer from ethylene, propylene and a non-conjugated diene Elastomeric ethylene-propylene... 

SUN Sun, S.F., Light scattering studies of deuterated polystyrene-poly(methyl methacrylate) diblock copolymers in 1,4-dioxane solutions, Makromol. Chem., Rapid Commun., 4,203,1983. 

H NMR spectra were recorded on Briiker ACP 400 or DPX 400 spectrometers using deuterated solvents obtained from CEA or Aldrich. Polymerization kinetics, followed by NMR, were recorded using the Briiker built-in kinetics software. Molecular mass analyses were carried out by gel permeation (size exclusion) chromatography on a Polymer Laboratories system. THF was the eluent at 1.0 mL min with a PL-gel 5 jim (50 X 7.5 mm) guard column, two PL-gel 5 pm (300 x 7.5 mm) mixed-C columns with a refractive index detector. Samples were compared against narrow standards of poly(methyl methacrylate), A/p = 200 to 1.577 x 10 g mol , obtained from Polymer Laboratories, except for methyl methacrylate dimer, trimer, and tetramer which were prepared by catalytic chain transfer polymerization at the University of Warwick. 

Figure 4.15. The interfacial width between a thin deuterated polystyrene film and poly(methyl methacrylate), measured by neutron reflectometry. The d-PS relative molecular masses were 244 000 (+), 387 000 ( ), 641 000 ( ) and 400 000 (O and A) and the PMMA relative molecular masses were 365 000 (+, , and O) and 333 000 (A). After Sferrazza et al. (1997).

Notes The values of A, B, and C and thus of y are based on a reference volume Vre/ = 0.1 nm Polymer notation A d- label preceding the polymer acronym indicates a per-deuterated polymer partially deuterated polymers are labeled as dy, df, etc., for selective deuteration of 3, 4, etc., hydrogens. Numbers in subscripted parentheses after the polymer name indicate the primary comonomer fraction, e.g., SPB(6s) is a saturated polybutadiene with 66 mol% butadiene Polymer acronyms P2VP poly(2-vinyl pyridine), P4MS poly(4-methylstyrene), PBMA poly(n-butyl methacrylate), PCHA poly(cyclohexyl acrylate), PEB poly(ethyl butylene), PIB polyisobutylene, PI polyisoprene, PMMA poly(methyl methacrylate), PPMA poly(n-pentyl methacrylate), PP polypropylene, HHPP head-to-head polypropylene, PS polystyrene, PVME poly(vinyl methyl ether), PXE poly(2,6-dimethyl-l,4-phenylene oxide), SPB saturated polybutadiene, SPI saturated polyisoprene... 

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