Homopolymers, crystallization kinetic

The crystallization kinetics of bulk triglycerides and oil-in-water emulsions has been characterized by both NMR imaging and localized spectroscopy. The rate of lipid crystallization in an oil-in-water emulsion was affected by the addition of a second homopolymer (addition of trilaurin to trimyristin in this case). The addition of the second homopolymer of higher chain length was observed to slow the rate of crystallization [26]. 

Taking all the fact presented in this section into account, together with the synthesis method and fractionation results, we conclude that the purified copolymer separated from reaction products is an iPS-fo-iPP diblock copolymer consisting of iPS and iPP blocks it is definitely not a simple blend of homopolymers. On the other hand, the distinctive characteristics of the copolymers crystallization kinetics also indicate that, compared with homopolymers and the iPS-iPP blend, the purified copolymer is a true iPS-fo-iPP diblock copolymer (23). 

Typically, polymer-grade l-LA with high chemical purity and optical purity (i.e., over 98-99% l-LA and less than 1-2% d-LA) is used for commercial PLA production. When l-LA is dehydrated at high temperature into L-lactide, some l-LA may be converted into d-LA. d-LA mixed with l-LA contributes to meso-lactide (the cyclic dimer of one d-LA and one l-LA) and heteropolymer PLA (with both d-LA and l-LA units). Heteropolymer PLA exhibits slower crystallization kinetics and lower melting points than homopolymer PLA (of pure l-LA units or pure d-LA units). 

As mentioned above, PLA should be addressed as a random copolymer rather than as a homopolymer the properties of the former depend on the ratio between L-lactic acid and D-lactic acid units. A few studies describe the influence of the concentration of D-lactic acid co-units in the PLLA macromolecule on the crystallization kinetics [15, 37, 77-79]. The incorporation of D-lactic acid co-units reduces the radial growth rate of spherulites and increases the induction period of spherulite formation, as is typical for random copolymers. In a recent work, the influence of the chain structure on the crystal polymorphism of PL A was detailed [15], with the results summarized in Figure 5.13. It shows the influence of D-lactic acid units on spherulite growth rates and crystal polymorphism of PLA for two selected molar mass ranges. 

The reverse could be observed in a compatibilized blend. Because in these blends a serious decrease of the spheruhte size was observed, the authors concluded that the compatibihzer acted as a nucleating agent for the PP phase. However, due to the increase of the melt viscosity upon compatibilization, the overall crystallization kinetics was retarded. Additionally, they observed experimentally that AF (free energy for the formation of a nucleus of critical size) and (surface free energy of folding) in compatibilized blends were larger than in PA-6 homopolymer. An opposite trend was observed for the physical PA-6/EPR blends. No further investigations have been dmie to elucidate this phenomenon. 

Silphenylene-Siloxane Copolymers.—The thermal properties vctsus structure for poly(tetramethyl-p-silphenylensesiloxane) and (tetramethyl-p-silphenylene/di-methylsiloxane) block copolymers have been compared. The homopolymer has a m.p. of 160°C, heat of fusion of 54.4 J/g and Tg of —20°C. The Tg of the copolymer varies monotonically with inojeased dimethylsiloxane content, from — 20 to —123 °C. Data have been reported on the crystallization kinetics and morphology of blends of fractionated poly(tetramethyl-p-silphenylenesiloxanes). The chemical degradation of poly(tetramethyl-/ -silphenylenesiloxane/dimethyl-siloxane) block copolymers by HF has been reported. In 48% HF at 30 °C, preferential attack occurs at the Si—O bond, particularly those of the MejSi—O non-crystalline components, in copolymers containing 15, 35, and 52% poly-dimethylsiloxane. - Further data have been reported on the crystal structure and fold conformation of poly(tetramethyl-/>-silphenylenesiloxane)s, obtained from X-ray diffraction studies. ... 

A related problem of interest is when a polymer is not crystalline as prepared, but is potentially crystallizable. This situation is commonly encountered in crys-tallizable copolymers, and is also found in homopolymers. Some typical examples of this phenomenon are found in poly(styrene) synthesized by means of alfin type catalysts,(50) poly(methyl methacrylate), prepared by either free-radical or ionic methods,(39,51,52) and poly(carhonate).(53) Treatment with particular solvents or diluent at elevated temperatures can induce crystallinity in these polymers. The reason for the problem is kinetic restraints to the crystallization process. Treatment with appropriate diluents alleviates the problem. The principles involved, and the diluent requirements will he enunciated in the discussion of crystallization kinetics. For present purposes it should be recognized that the crystallizability of a polymer, particularly a copolymer, cannot be categorically denied unless the optimum conditions for crystallization have been investigated. Thus, in light of the previous discussion regarding the minimum concentration of chain units required for crystallization, and the need to have favorable kinetic conditions, the lack of crystallization in any given situation needs to be carefully assessed. 

The results of Muller et al. [103] on PPDX-fo-PCL diblock copolymers differ from those obtained previously by Bogdanov et al. [105] when they studied by DSC the crystallization kinetics of 80/20 PCL-fo-PEO diblock copolymers. In their case, the PCL block crystallized first from a homogeneous melt and the Avrami parameters K and n were found to be similar to the kinetics parameters of the isothermal crystallization of a corresponding PCL homopolymer. Significant crystallization retardation was found for the PEG block that crystallized second. The retardation was attributed to the mutual influence between the PEG constituent and the PCL crystal phase which fixes (hardened) the total copolymer structure [ 105]. In the PPDX-fo-PCL diblock copolymer case, conversely, when the PPDX block crystallizes it does so at a slower rate than a comparable PPDX homopolymer. The crystallization of the PCL block, on the other hand, strongly depends on the composition of the diblock copolymer as shown in Fig. 9. However, for D77 C23 , the overall kinetics is retarded, which could be regarded as similar to the retardation experienced by the PEG block in the 80/20 PCL-fi-PEG diblock copolymer studied by Bogdanov et al. [105] the Avrami index in both cases was also of the order of 2. 

In a similar fashion, DSC isothermal scans were recorded in order to study the crystallization kinetics of the PPDX homopolymer after melting the samples for 3 min at 150 °C and quenching them (at 80 °C/min) to the desired crystallization temperature (7(.). After the crystallization was complete, the inverse of the half -crystallization time, (i.e., the time needed for 50% relative conversion to the crystalline state [31,60]), was taken as a measure of the overall crystallization (nucleation and crystal growth) rate and its dependence on the crystallization temperature was analyzed. 

TABLE 11.8 Parameters Derived from the LH Model Fit to the Isothermal Crystallization Kinetics Data, for the Overall Isothermal Crystallization of the PA/PE Blends and Homopolymers... 

The overall crystallization kinetics of copolymers and their blends have been studied by DSC in the temperature range 1(X)-132°C [69]. For all examined blend compositions a single crystallization exotherm was observed at each T, whereas crystallization of mechanical mixtures of the copolymers showed separated exotherms of each component, thus supporting that the crystallization of melt mixed blends occurred from a homogeneous melt. The overall crystallization rate of copolymers was found to be affected by the copolymer structure and lower than that of PP homopolymer (BP < EP < PP), while the crystallization rate of the blends was intermediate between those of pure components (Fig. 10.12). The kinetics were analyzed by means of the Avrami equation (Eq. 10.14) the calculated values of the Avrami exponent for the blends, with average values of n from... 

Copolymers are macromolecules composed of two or more chemically distinct monomer units, covalently joined to form a common polymer chain [1,2], In these materials, the sequence distribution of the monomer counits plays a critical role in determining the copolymer s crystallization behavior, and consequently influences its solid-state morphology and material properties [1,2], At one extreme, different types of monomer units may be randomly incorporated into the polymer chain, resulting in a statistical copolymer. At the other extreme, blocks of homopolymer sequences of different chemical nature and chain length may be joined together to form what is known as a block copolymer. In this chapter, we wiU review the key effects of comonomer incorporation on the solid-state morphology and crystallization kinetics in both statistical and block copolymers. 

Besides its effects on morphology, comonomer sequence distribution also affects copolymer crystallization kinetics. In statistical copolymers, due to the broad distribution of crystaUizable sequence lengths, bimodal melting endotherms are typically observed. In block copolymers, the dynamics of crystallization have features characteristic of both homopolymer crystallization and microphase separation in amorphous block copolymers. In addition, the presence of order in the melt, even if the segregation strength is weak, hinders the development of the equihbrium spacing in the block copolymer solid-state structure. 

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