Copolymer feed ratio

Copolymer Feed Ratio Incorporated Intrinsic Viscosity (dL/g)... 

The copolymer feed ratio has a considerable effect on the power conversion efficiency. It increases with increasing MEH-PPV content. A max-imvun power conversion efficiency of 1.30% for a copolymer of (OCIO)-2-spiro-PFV and MEH-PPV 50 50 has been achieved. However, with a pristine MEH-PPV, a power conversion efficiency of 2.10% is found. 

Copolymer Feed ratio Incorporation Intrinsic viscosity (dLg )... 

The fraction of sequences of the length indicated below have been measured t for a copolymer system at different feed ratios ... 

Fig. 1. Copolymer composition as a function of monomer feed ratio for various reactivity ratio combiaations, designated I—V and explained ia the text...

The composition of the copolymer determines its electroluminescence efficiency. Optimal efficiency (0.3%) was achieved in system 34 when the feed ratio of monomer 4 to monomer 34 was 9 1. This represents a 30-fold improvement in luminescence efficiency relative to PPV in the same device configuration (AlALOj/polymer/Al) 58, 62. Copolymer 33 has found uses as waveguides and... 

Copolymerization occurred when the olefin had a basicity lower than that of the aldehyde (with respect to the initiator used), but sufficiently high occasionally to displace a molecule of initiator and give rise to an active species this situation produced copolymers with varying proportions of ether units in the chain, depending on the monomers feed ratio and on the olefin used. Isopropenylbenzene gave the best results with alternate copolymerization over a fairly wide range of feed ratios rt = 0.03 0.03, r2 = 0.4 0.1 (2-furaldehyde = Mj) indene produced copolymers with lower 2-furaldehyde contents. 

The existence of an azeotropic composition has some practical significance. By conducting a polymerization with the monomer feed ratio equal to the azeotropic composition, a high conversion batch copolymer can be prepared that has no compositional heterogeneity caused by drift in copolymer composition with conversion. Thus, the complex incremental addition protocols that arc otherwise required to achieve this end, are unnecessary. Composition equations and conditions for azeotropic compositions in ternary and quaternary eopolymerizations have also been defined.211,21... 

One final point should be made. The observation of significant solvent effects on kp in homopolymerization and on reactivity ratios in copolymerization (Section 8.3.1) calls into question the methods for reactivity ratio measurement which rely on evaluation of the polymer composition for various monomer feed ratios (Section 7.3.2). If solvent effects arc significant, it would seem to follow that reactivity ratios in bulk copolymerization should be a function of the feed composition.138 Moreover, since the reaction medium alters with conversion, the reactivity ratios may also vary with conversion. Thus the two most common sources of data used in reactivity ratio determination (i.e. low conversion composition measurements and composition conversion measurements) are potentially flawed. A corollary of this statement also provides one explanation for any failure of reactivity ratios to predict copolymer composition at high conversion. The effect of solvents on radical copolymerization remains an area in need of further research. 

The solvent in a bulk copolymerization comprises the monomers. The nature of the solvent will necessarily change with conversion from monomers to a mixture of monomers and polymers, and, in most cases, the ratio of monomers in the feed will also vary with conversion. For S-AN copolymerization, since the reactivity ratios are different in toluene and in acetonitrile, we should anticipate that the reactivity ratios are different in bulk copolymerizations when the monomer mix is either mostly AN or mostly S. This calls into question the usual method of measuring reactivity ratios by examining the copolymer composition for various monomer feed compositions at very low monomer conversion. We can note that reactivity ratios can be estimated for a single monomer feed composition by analyzing the monomer sequence distribution. Analysis of the dependence of reactivity ratios determined in this manner of monomer feed ratio should therefore provide evidence for solvent effects. These considerations should not be ignored in solution polymerization either. 

Thus a log-log plot of the apparent copolymer composition ratio against the monomer feed ratio should yield a straight line with slope two. In fact, a slope near two was observed for several comonomer pairs with different polarities. 

As an example, an NMR spectrum of a 1,3-dioxolane-/3-propiolactone copolymer, obtained by using a boron-fluoride catalyst, is shown in Fig. 1101. The 1,3-dioxolane (DOL) homopolymer spectrum contains two singlet peaks of area 1 2 numbered 1 and 5, whereas the spectrum of the 0-propiolactone (PL) homopolymer contains two triplet peaks of area 1 1 numbered 2 and 6. Variation of initial feed ratios disclosed that peaks 1,3 and S are associated with the DOL units and that... 

Further improvements were made by carboxylating the polystyrene anion, leading to quantitative yields39S 396. Multiblock copolymers of molecular weight 500,000 consisting of sixty segments of poly-THF and polystyrene were prepared397. The effect of the molar feed ratio of the two components is shown in Fig. 7. 

Ester-thioester copolymers were enzymatically synthesized (Scheme 7). ° The lipase CA-catalyzed copolymerization of e-caprolactone with 11-mercaptoundecanoic acid or 3-mercaptopropionic acid under reduced pressure produced the polymer with molecular weight higher than 2 x 10". The thioester unit of the resulting polymer was lower than the feed ratio. The transesterification between poly(8-caprolactone) and 11-mercaptoundecanoic acid or 3-mercaptopropionic acid also took place by lipase CA catalyst. Recently, aliphatic polythioesters were synthesized by lipase CA-catalyzed polycondensation of diesters with 1,6-hexanedithiol. ... 

Due to higher variety of possible structures, copolymers allow a better control of the HOMO LUMO levels necessary to optimize the EL properties of the PPV, compared to homopolymers. Often the optical and electronic properties in copolymers can be finely tuned by simply changing the feed ratio of comonomers (although the structure-property relationship in these systems is even more complex than in homo-PPV polymers). Using different comonomer units, various PPV-based materials with tuned optical and electronic properties have been prepared. 

The next products developed were the thermoplastics made by vinyl polymerization. Vinyl chloride, and vinyl acetate copolymers known as Vinylite, was one of the first produced by Carbide and Carbon. It had been worked on in Europe and had also been worked on by Ostromysslenski, a chemist with the U. S. Rubber Company. The Carbide chemists realized at an early date that to get a uniform composition it was necessary to adjust the feed ratios of the two monomers to get a proper combination in the reactor to give a constant composition to the product. The next major development of a vinyl product was in the development of Lucite or Plexiglas polymers, which are clear, strong plastics. 

Styrene-SQ., Copolymers. I would now like to discuss two systems which illustrate the power of C-13 nmr in structural studies. The first is the styrene-SO system. As already indicated, this is of the type in which the chain composition varies with monomer feed ratio and also with temperature at a constant feed ratio (and probably with pressure as well.) The deviation of the system from simple, first-order Markov statistics, —i.e. the Lewis-Mayo copolymerization equation—, was first noted by Barb in 1952 ( ) who proposed that the mechanism involved conplex formation between the monomers. This proposal was reiterated about a decade later by Matsuda and his coworkers. Such charge transfer com-... 

The copolymerization between two different monomers can be described using only four reactions, two homo-polymerizations and two cross-polymerization additions. Through appropriate arrangements, equations that allow copolymer composition to be determined from the monomer feed ratio are developed. 

The high electron richness of vinylferrocene as a monomer is illustrated in its copolymerization with maleic anhydride, where 1 1 alternation copolymers are formed over a wide range of monomer feed ratios and ri -2 = 0.003. Subsequently, a large number of detailed copolymerization studies have been undertaken using metal-containing vinyl monomers. 

Fig. 12 MnandPDl values data of copolymers synthesized with different comonomer feed ratios. (Reprinted with permission from [73]. Copyright (2008) John Wiley Sons, Inc.)...

Feed Ratio Mole J Wtl Raman (Wt ) ) Copolymer Ratio Elemental Analysis (Wt %)... 

The NMR analysis (21) of the chemical composition for copolymers from various monomer feed ratios at fairly low conversion are shown in Table IV. The results were then used to estimate the reactivity ratios for the diene monomers under the conditions employed. Various published methods of calculating monomer reactivity ratios have been examined. These include the once popular but now somewhat out of favor Fineman-Ross method... 

The reactivity ratios may be evaluated by performing a series of low-conversion copolymerizations at different, monomer-feed ratios, isolating the copolymer, and determining its composition. A number of mathematical analyses have been proposed in order to provide, from the experimental data, correct values for the two unknown reactivity ratios. There is some difference of opinion as to the best method for obtaining values having quantifiable errors.84,64" However, several of... 

Funt and Gray recently reinvestigated the MMA-styrene system in detail (37). An analysis of the data at various initial feed ratios with tetrahydrofuran revealed that the copolymer composition was found to vary as the square of the feed ratios, according to the relationships proposed by O Driscoll,... 

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