Thermal gelation

Analysis of variance for each dependent variable showed that in almost all cases, R2 coefficients higher than 0.83 were obtained (Table 2), which means that models were able to explain more than 83% of the observed responses. For the rate of gelation, thermal hysteresis and hardness, the lack of fit test was not significant. For Tge, and Tm, the lack of fit was significant, which means that the model may not have included all appropiate function of independent variables. According to Box and Draper,13 we considered the high coefficients R2 as evidence of the applicability of the model. 

Other examples illustrating the effect of substituent distribution on properties include (/) enzymatic stabiUty of hydroxyethjlceUulose (16,17) (2) salt compatibihty of carboxymethylceUulose (18,19) and (J) thermal gelation properties of methylceUulose (20). The enzymatic stabUity of hydroxyethylceUulose is an example where the actual position of the substituents within the anhydroglucose units is considered important. Increasing substitution at the C2 position promotes better resistance toward enzymatic cleavage of the polymer chain. Positional distribution is also a factor in the other two examples. 

Properties. MethylceUulose [9004-67-5] (MC) and its alkylene oxide derivatives hydroxypropylmethylceUulose [9004-65-3] (HPMC), hydroxyethylmethylceUulose [9032-42-2] (HEMC), and hydroxybutyknethylcellulose [9041-56-9] (HBMC) are nonionic, surface-active, water-soluble polymers. Each type of derivative is available in a range of methyl and hydroxyalkyl substitutions. The extent and uniformity of the methyl substitution and the specific type of hydroxyalkyl substituent affect the solubifity, surface activity, thermal gelation, and other properties of the polymers in solution. 

The commercial polymers are of comparatively low molecular weight (M = 25 000-60 000) and whilst being essentially linear may contain a few branches or cross-links arising out of thermal oxidation. Exposure to ultraviolet light causes a rapid increase in gel content, whilst heating in an oven at 125°C causes gelation only after an induction period of about 1000 hours. Eor outdoor applications it is necessary to incorporate carbon black. The polymers, however, exhibit very good hydrolytic stability. 

This reaction is reported to proceed at a rapid rate, with over 25% conversion in less than 0.001 s [3]. It can also proceed at very low temperatures, as in the middle of winter. Most primary substituted urea linkages, referred to as urea bonds, are more thermally stable than urethane bonds, by 20-30°C, but not in all cases. Polyamines based on aromatic amines are normally somewhat slower, especially if there are additional electron withdrawing moieties on the aromatic ring, such as chlorine or ester linkages [4]. Use of aliphatic isocyanates, such as methylene bis-4,4 -(cyclohexylisocyanate) (HnMDI), in place of MDI, has been shown to slow the gelation rate to about 60 s, with an amine chain extender present. Sterically hindered secondary amine-terminated polyols, in conjunction with certain aliphatic isocyanates, are reported to have slower gelation times, in some cases as long as 24 h [4]. 

In conclusion, the self-condensation of 2-furaldehyde promoted by heat occurs with the formation of di- and trifurylic intermediates. The functionality of the growing chain increases after each oligomerization step until gelation and precipitation of the resin occurs. Thus, the process is non-linear from the onset since the condensation product 4 possesses three sites for further attack, namely the free C-5 position and the two formyl groups. It is interestering to note that while the polycondensation of 2-furfuryl alcohol is essentially linear and cross-linking is due to side reactions, the thermal resinification of 2-furaldehyde is intrinsically non-linear and gel formation occurs at earlier conversions. 

One of the simplest ways to prepare a chitin gel is to treat chitosan acetate salt solution with carbodiimide to restore acetamido groups. Thermally not reversible gels are obtained by AT-acylation of chitosans N-acetyl-, N-propionyl- and N-butyryl-chitosan gels are prepared using 10% aqueous acefic, propionic and bufyric acid as solvents for treatment with appropriate acyl anhydride. Both N- and 0-acylation are found, but the gelation also occurs by selective AT-acylation in the presence of organic solvents. 

The property of thermal, reversible gelation is obtained by the addition of water-soluble proteins and protein degradation products to an aqueous solution of poly (vinyl alcohol) 2). Protein products such as albumin, gelatin, glue, a-amino acids, and their condensation products—diketopiperazines—may be used. A typical formulation for the preparation of a thermally reversible gel is ... 

CaCl2 formed wide but relatively short strands without forming apparent continuous network structures in most cases (Fig. 6.13D). For i-carra-geenan, the addition of or Ca formed localized networks through side-by-side aggregation between helices, which was consistent with the thermal hysteresis between sol-to-gel and gel-to-sol transitions. However, this interhelical aggregation was not necessarily a prerequisite for gelation. 

The glass transition involves additional phenomena which strongly affect the rheology (1) Short-time and long-time relaxation modes were found to shift with different temperature shift factors [93]. (2) The thermally introduced glass transition leads to a non-equilibrium state of the polymer [10]. Because of these, the gelation framework might be too simple to describe the transition behavior. 

Thermal gelation, 13 73 Thermal gel stabilization, 23 71 Thermal generation, of Ag+ intermediate complexes, 19 355... 

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