Polymerization conditions

Polymerization conditions are of course an important determinant of these structural variations and inhomogeneities. For example, in a series of simple experiments. 

Structural Aspects Morphology and Fiber/Film Processing 

CPs that are more (or less) crosslinked can also be obtained via selective fractionation of the de-doped, soluble form this method was for instance applied to P(ANi) via fractionation, by Gel Permeation Chromatography (GPC), of P(ANi) solutions in NMP [299], with solubility of the various fractions in NMP being a measure of the degree of crosslinking. 

A large number of experimental conditions to obtain polymers have been developed. 

The recognition and material properties of MIPs are strongly dependent on the polymerization conditions. Variation of the polymerization temperature solvent, template, and monomer concentrations and cross-linker percentage attenuates the fidelity of the imprinting process by changing the structure and stability of the prepolymerization complex as well as the templated binding sites. The noncovalent imprinting 

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Aqueous Dispersions. The dispersion is made by the polymerization process used to produce fine powders of different average particle sizes (58). The most common dispersion has an average particle size of about 0.2 p.m, probably the optimum particle size for most appHcations. The raw dispersion is stabilized with a nonionic or anionic surfactant and concentrated to 60—65 wt % soHds by electrodecantation, evaporation, or thermal concentration (59). The concentrated dispersion can be modified further with chemical additives. The fabrication characteristics of these dispersions depend on polymerization conditions and additives. 

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Vlayl fluoride undergoes free-radical polymerization. The first polymerization iavolved heating a saturated solutioa of VF ia tolueae at 67°C uader 600 MPa (87,000 psi) for 16 h (24). A wide variety of ioitiators and polymerization conditions have been explored (25—27). Examples of bulk (28,29) and solution (25,28,30,31) polymerizations exist however, aqueous suspension or emulsion methods are generally preferred (26,32—40). VF volatiflty dictates that moderately high pressures be used. Photopolymerizations, usually incorporating free-radical initiators, are also known (26,28,29,35). 

The conversion of aromatic monomers relative to C-5—C-6 linear diolefins and olefins in cationic polymerizations may not be proportional to the feedblend composition, resulting in higher resin aromaticity as determined by nmr and ir measurements (43). This can be attributed to the differing reactivity ratios of aromatic and aHphatic monomers under specific Lewis acid catalysis. Intentional blocking of hydrocarbon resins into aromatic and aHphatic regions may be accomplished by sequential cationic polymerization employing multiple reactors and standard polymerization conditions (45). 

Hydrocarbon resins based on CPD are used heavily in the adhesive and road marking industries derivatives of these resins are used in the production of printing inks. These resins may be produced catalyticaHy using typical carbocationic polymerization techniques, but the large majority of these resins are synthesized under thermal polymerization conditions. The rate constants for the Diels-Alder based dimerization of CPD to DCPD are weU known (49). The abiHty to polymerize without Lewis acid catalysis reduces the amount of aluminous water or other catalyst effluents/emissions that must be addressed from an environmental standpoint. Both thermal and catalyticaHy polymerized DCPD/CPD-based resins contain a high degree of unsaturation. Therefore, many of these resins are hydrogenated for certain appHcations. 

Processes for HDPE with Broad MWD. Synthesis of HDPE with a relatively high molecular weight and a very broad MWD (broader than that of HDPE prepared with chromium oxide catalysts) can be achieved by two separate approaches. The first is to use mixed catalysts containing two types of active centers with widely different properties (50—55) the second is to employ two or more polymerization reactors in a series. In the second approach, polymerization conditions in each reactor are set drastically differendy in order to produce, within each polymer particle, an essential mixture of macromolecules with vasdy different molecular weights. Special plants, both slurry and gas-phase, can produce such resins (74,91—94). 

Depending on the final polymerization conditions, an equilibrium concentration of monomers (ca 8%) and short-chain oligomers (ca 2%) remains (72). Prior to fiber spinning, most of the residual monomer is removed. In the conventional process, the molten polymer is extmded as a strand, solidified, cut into chip, washed to remove residual monomer, and dried. In some newer continuous processes, the excess monomer is removed from the molten polymer by vacuum stripping. 

Kinetics. Details of the kinetics of polymerization of THF have been reviewed (6,148). There are five main conclusions. (/) Macroions are the principal propagating species in all systems. (2) With stable complex anions, such as PF , SbF , and AsF , the polymerization is living under normal polymerization conditions. When initia tion is fast, kinetics of polymerizations in bulk can be closely approximated by equation 2, where/ is the specific rate constant of propagation /is time [I q is the initiator concentration at t = 0 and [M q, [M and [M are the monomer concentrations at t = 0, at equiHbrium, and at time /, respectively. 

A low temperature catalytic process has been reported (64). The process involves the divalent nickel- or zero-valent palladium-catalyzed self-condensation of halothiophenols in an alcohol solvent. The preferred halothiophenol is -bromothiophenol. The relatively poor solubiHty of PPS under the mild reaction conditions results in the synthesis of only low molecular weight PPS. An advantage afforded by the mild reaction conditions is that of making telecheHc PPS with functional groups that may not survive typical PPS polymerization conditions. 

For some apphcations, eg, foam mbber, high soHds (>60%) latices are requited. In the direct process, the polymerization conditions are adjusted to favor the production of relatively large average particle-size latices by lowering the initial emulsifier and electrolyte concentration and the water level ia the recipe, and by controlling the initiation step to produce fewer particles. Emulsifier and electrolyte are added ia increments as the polymerization progresses to control latex stabiUty. A latex of wt% soHds is obtained and concentrated by evaporation to 60—65 wt % soHds. 

The position of the equiUbrium depends on a number of factors, such as concentration of siloxane units and the nature of substituents on the sihcon, but is independent of the starting siloxane composition and the polymerization conditions (81,82). For a hulk polymerization of dimethyl siloxane, the equihbrium concentration of cycHc oligomers is approximately 18 wt % (83). The equiHbrium mixture of cyclosiloxanes is composed of a continuous population to at least but D, D, and make over 95 wt % of the total cycHc fraction (84). 

The physical piopeities of poly(vinyl alcohol) aie highly coiielated with the method of piepaiation. The final piopeities are affected by the polymerization conditions of the parent poly(vinyl acetate), the hydrolysis conditions, drying, and grinding. Further, the term poly(vinyl alcohol) refers to an array of products that can be considered copolymers of vinyl acetate and vinyl alcohol. 

Although reactivity ratios indicate that VP is the more reactive monomer, reaction conditions such as solvent polarity, initiator type, percent conversion, and molecular weight of the growing radical can alter these ratios (138). Therefore, depending on polymerization conditions, copolymers produced by one manufacturer may not be identical to those of another, especially if the end use appHcation of the resin is sensitive to monomer sequence distribution and MWD. 

In all of the ethylene polymerization processes, the catalyst is sensitive to feed impurities and is poisoned by most polar compounds. Many of the properties of the polymer are determined by polymerization conditions, but catalyst composition and condition are critical determinants as well. 

Similarly, it is often impossible, or at least very difficult, to experimentally determine the characteristics of a measurement system under the conditions where it is used. It is certainly possible to fill an emulsion polymerization reactor with water and determine the dynamic-characteristics of the temperature measurement system. However, it is not possible to determine these characteristics when the reactor is filled with the emulsion under polymerization conditions. 

We have found that in the system of presulfate initiator, the PVAc latexes are not dissolved transparently in the methanol-water mixture [8], and in the system of HPO initiator, the extraction of the polymer from the PVAc latex films with acetone greatly depends on the polymerization condition [9]. These results suggest that if a polymerization method can be found in which the grafting polymerization of VAc onto PVA is controlled to the minimum, a large portion of PVAc in the latex film will have a chance of extraction with solvents. In this Chapter, the preparations of the unique porous films from the PVAc latexes containing PVA as a protective colloid by an extraction of the PVAc particles with acetone and the characteristic properties of the porous films are summarized. 

Polymerization conditions Heating time to the polymerization temperature (min) ... 

Preparation of uniform seed particles Soapless emulsion polymerization is usually preferred for the preparation of uniform seed particles since this technique provides emulsifier-free, larger, and highly uniform micropheres relative to those that can be obtained by the conventional emulsion recipes including emulsifiers and various additives. The size of uniform seed particles with the soapless emulsion procedure is in the range of 0.6-1.2 tm depending on the polymerization conditions [75,108]. 

The SCB distribution (SCBD) has been extensively studied by fractionation based on compositional difference as well as molecular size. The analysis by cross fractionation, which involves stepwise separation of the molecules on the basis of composition and molecular size, has provided information of inter- and intramolecular SCBD in much detail. The temperature-rising elution fractionation (TREE) method, which separates polymer molecules according to their composition, has been used for HP LDPE it has been found that SCB composition is more or less uniform [24,25]. It can be observed from the appearance of only one melt endotherm peak in the analysis by differential scanning calorimetry (DSC) (Fig. 1) [26]. Wild et al. [27] reported that HP LDPE prepared by tubular reactor exhibits broader SCBD than that prepared by an autoclave reactor. The SCBD can also be varied by changing the polymerization conditions. From the cross fractionation of commercial HP LDPE samples, it has been found that low-MW species generally have more SCBs [13,24]. 

The MWD is the ratio of Mw Mn and is called the polydispersity index. This largely varies from one grade of polymer to the other, depending on the polymerization conditions and the type of catalyst used. Figure 14 shows different types of MWD for the polymers. 

Polymerization of butadiene and of isoprene confronts us with still another configurational problem. The addition may take place in either the 1,2 or 1,4 positions (with an additional possibility of 3,4 addition in the case of isoprene), and, moreover, in the 1,4 addition the new unit may acquire a cis or a trans configuration. It is known that by proper choice of a catalyst and by judicious adjustment of polymerization conditions processes can be developed which yield polymers of high stereospecificity, namely all 1,4 cis, all 1,4 trans, all 1,2 isotactic, or all 1,2 syndiotactic polymers. 

In catalytic polymerization the reactivity of the propagation center depends on the catalyst composition. Therefore, the dependence of the molecular structure of the polymer chain mainly on the catalyst composition, and less on the experimental conditions, is characteristic of catalytic polymerization. On the other hand, in polymerization by free-radical or free-ion mechanisms the structure of a polymer is determined by the polymerization conditions (primarily temperature) and does not depend on the type of initiator. 

The shape of the kinetic curves depends on the catalyst type and polymerization conditions (ethylene pressure, temperature, concentration of inhibitors in reaction medium) (89, 97, 98). The types of the kinetic curves obtained. at ethylene polymerization under various conditions are presented in Fig. 1. 

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