Polymerization linear

The effects of the concentration of divinylbenzene on pore-size distribution and surface areas of micropores, mesopores, and macropores in monosized PS-DVB beads prepared in the presence of linear polymeric porogens have been studied (65). While the total surface area is clearly determined by the content of divinylbenzene, the sum of pore volumes for mesoforms and macropores, as well as their pore-size distribution, do not change within a broad range of DVB concentrations. However, the more cross-linked the beads, the better the mechanical and hydrodynamic properties. 

Less important methods are the self condensation of w-hydroxy acid and the ring opening of lactones and cyclic esters. In self condensation of w-hydroxy acids, cyclization might compete seriously with linear polymerization, especially when the hydroxyl group is in a position to give five or six membered lactones. 

The most important complexes with C-donors, other than organometallics, are cyanides. AgCN has a structure with Ag—C-N-Ag bonding in linear polymeric chains it dissolves in excess KCN forming K+Ag(CN)2 (digonal with Ag-C 2.13A, i[Pg.288]

Another factor in step-growth polymerizations is cyclization versus linear polymerization.1516 Since ADMET is a step-growth polymerization, most reactions are carried out in the bulk using high concentrations of the reactant in order to suppress most cyclic formation. A small percentage of cyclic species is always present but is dependent upon thermodynamic factors, typical of any polycondensation reaction. 

Striking support of this contention is found in recent data of Castro (16) shown in Figure 14. In this experiment, the polymerization (60-156) has been carried out in a cone-and-plate viscometer (Rheometrics Mechanical Spectrometer) and viscosity of the reaction medium monitored continuously as a function of reaction time. As can be seen, the viscosity appears to become infinite at a reaction time corresponding to about 60% conversion. This suggests network formation, but the chemistry precludes non-linear polymerization. Also observed in the same conversion range is very striking transition of the reaction medium from clear to opaque. 

Furthermore, formation of these products occurs with much greater ease than linear polymerization of units of six or more chain members, and they are more stable to hydrolysis or other ring-opening reactions. 

When a bidentate ligand bridges two metalloporphyrins, a linear polymeric chain is formed. This arrangement has been dubbed shish... 

It should be emphasized that the electrochemical carbonization proceeds, in contrast to all other common carbonization reactions (pyrolysis), already at the room temperature. This fact elucidates various surprising physicochemical properties of electrochemical carbon, such as extreme chemical reactivity and adsorption capacity, time-dependent electronic conductivity and optical spectra, as well as its very peculiar structure which actually matches the structure of the starting fluorocarbon chain. The electrochemical carbon is, therefore, obtained primarily in the form of linear polymeric carbon chains (polycumulene, polyyne), generally termed carbyne. This can be schematically depicted by the reaction ... 

It was assumed that linear polymeric particles are formed in the low water content solutions which show spinnability on the way of progressing hydrolysis-polycondensation reaction. In order to confirm this, the molecular weights and intrinsic viscosities of the solutions listed in Table 1 have been measured (2.). Figure 2 shows the log Mjj versus log[ri] plots. The slope of the plot a is larger than 0.5, that is, 0.75 and 0.64 respectively for solutions 1 and 2 of... 

DNA is a helical polyanion built by the union of two linear polymeric strands that are composed of sugars (deoxyribose) finked by phosphates. Each sugar contains an aromatic base (G,C,A, or T) bound to C-l of the sugar. The two strands are normally complementary so that when they combine to form the duplex, each base on one strand forms Watson-Crick hydrogen bonds with its counterpart (G with C and A with T) on the opposite... 

There are five prime factors that determine the properties of starches 1. starch is a polymer of glucose (dextrose) 2. the starch polymer is of two types linear and branched 3 the linear polymeric molecules can associate with each other giving insolubility in water 4. the polymeric molecules are organized and packed into granules which are insoluble in water and 5 disruption of the granule structure is required to render the starch polymer dispersible in water. The modification of starch takes into account these factors. 

Figure 1. Number fraction of ring structures per molecule (Nr) as a function of extent of reaction (p) for bulk, linear, and nonlinear polyurethane-forming reactions with approximately equimolar concentrations of reactive groups (r = [NCO]J [OH]0 ss 1) (2,3). Conditions O-linear polymerization, HDI + poly(ethyleneglycol) at 70°, [NCOfo — 5.111 mol/kg, [OH], = 5.188 mol/kg number-average number of bonds in chain forming smallest ring structure (v) = 25.2, and nonlinear polymerization, HDI and POP triol at 70°C, [NCO] — 0.9073 mol/kg, [OH]0 = 0.9173 mol/kg v = 115. Reproduced with permission from Ref. 5.

The reaction of dabco (l,4-diazobicyclo[2.2.2]octane) with Me2Cd yields a 1 1 adduct 197, which adopts a linear polymeric structure (Figure 34).255 The cadmium atom is coordinated by two dabco units and two methyl carbon atoms giving rise to a distorted tetrahedral environment. Finally, the organocadmium adduct 198 (Figure 35) has been isolated from the reaction of Me2Cd with Cd[(SeP-/-Pr2)2N]2.256 The solid-state structure consists of dimeric units where each methylcadmium unit is coordinated to three selenium atoms. The geometry about the cadmium center is tetrahedral with a Cd-C distance of 2.16 A, which is comparable to that observed in other cadmium alkyl complexes. 

A normal priority in both direct and template procedures is to maximize yields of the required product by choosing strategies which inhibit competing linear polymerization and other reactions. Unless special circumstances obtain, polymeric materials are often the major product when macrocyclic syntheses are attempted in the absence of appropriate conditions. 

The mechanism of crosslinking emulsion polymerization and copolymerization differs significantly from linear polymerization. Due to the gel effect and, in the case of oil-soluble initiators, monomer droplets polymerize preferentially thus reducing the yield of microgels. In microemulsion polymerization, no monomer droplets exist. Therefore this method is very suitable to form microgels with high yields and a narrow size distribution, especially if oil-soluble initiators are used. 

Controlling the size, shape and ordering of synthetic organic materials at the macromolecular and supramolecular levels is an important objective in chemistry. Such control may be used to improve specific advanced material properties. Initial efforts to control dendrimer shapes involved the use of appropriately shaped core templates upon which to amplify dendritic shells to produce either dendrimer spheroids or cylinders (rods). The first examples of covalent dendrimer rods were reported by Tomalia et al. [43] and Schluter et al. [44], These examples involved the reiterative growth of dendritic shells around a preformed linear polymeric backbone or the polymerization of a dendronized monomer to produce cylinders possessing substantial aspect ratios (i.e. 15-100) as observed by TEM and AFM. These architectural copolymers consisting of linear random... 

Crospovidone is a cross-linked homopolymer of A-vinyl-2-pyrrolidone. Acetylene and formaldehyde react to form butynediol. Hydrogenation and subsequent cyclodehydrogenation gives butyrolactone. The reaction of butyrolactone with ammonia produces pyrrolidone, which is vinylated with acetylene under pressure. The linear polymerization of the vinylpyrrolidone yields polyvinylpyrrolidone, a soluble binder, whereas the popcorn (branched) polymerization yields crospovidone, an insoluble... 

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