Phase transition temperatures polymers

Although the properties of specific polymer/wall systems are no longer accessible, the various phase transitions of polymers in confined geometries can be treated (Fig. 1). For semi-infinite systems two distinct phase transitions occur for volume fraction 0 = 0 and chain length N oo, namely collapse in the bulk (at the theta-temperature 6 [26,27]) and adsorp-... 

In a fundamental sense, the miscibility, adhesion, interfacial energies, and morphology developed are all thermodynamically interrelated in a complex way to the interaction forces between the polymers. Miscibility of a polymer blend containing two polymers depends on the mutual solubility of the polymeric components. The blend is termed compatible when the solubility parameter of the two components are close to each other and show a single-phase transition temperature. However, most polymer pairs tend to be immiscible due to differences in their viscoelastic properties, surface-tensions, and intermolecular interactions. According to the terminology, the polymer pairs are incompatible and show separate glass transitions. For many purposes, miscibility in polymer blends is neither required nor de-... 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Taken together, the experimental observations reported in the previous sections suggest that the formation of colloidally stable particles heated above their phase-transition temperature may be a universal phenomenon, taking place not only in aqueous polymer solutions, but also in solutions of polymers that can undergo a coil-globule transition in organic solvents. 

After polymerizing, the phase behavior changes dramatically. The phase transition temperatures return to values very close to those observed in the pure FLC. The interactions which lower the transitions in monomer/FLC systems are not significant in polymer/FLC systems. Similar results are observed in HDDA/FLC systems. The only notable exception is that the monomer saturation concentration occurs at a significantly lower concentration (5 wt%). 

Polyion complex technique [40] is a unique method for immobilization of bilayer membranes with polymers. Water-insoluble complex is precipitated as the polyion complex when an aqueous solution of the charged bilayer membrane is mixed with a water solution of the counter charged polyelectrolyte. Stoichiometric ion pair formation is often found. Aging of the precipitate in a hot mixture kept above phase transition temperature of the bilayer membrane completes the ion exchange reaction [41], Chloroform solution of the polyion complex is washed by water several times to remove water soluble components [42]. 

Yoshida, R., Sakai, K., Okano, T., and Sakurai, Y. Modulating the phase transition temperature and thermo-sensitivity in iV-isopropylacrylamide copolymer gels, J. Biomater. Set Polymer Ed., 1994, 6, 585-598. 

The phase transition was traced by monitoring the transmittance of a 500 nm light beam on a Spectronic 20 spectrophotometer (Baush Lomb). The concentration of the aqueous polymer solution was 5 wt%, and the temperature was raised from 15 to 70°C in 2° increments every 10 min. To observe their pH/temperature dependence, the phase transitions of polymers in citric-phosphate buffer solution versus temperature at two pH values (4.0 and 7.4) were measured. 

Polymeric phospholipids based on dioctadecyldimethylammonium methacrylate were formed by photopolymerization to give polymer-encased vesicles which retained phase behavior. The polymerized vesicles were more stable than non-polymerized vesicles, and permeability experiments showed that vesicles polymerized above the phase transition temperature have lower permeability than the nonpolymerized ones [447-449]. Kono et al. [450,451] employed a polypeptide based on lysine, 2 aminoisobutyric acid and leucine as the sensitive polymer. In the latter reference the polypeptide adhered to the vesicular lipid bilayer membrane at high pH by assuming an amphiphilic helical conformation, while at low pH the structure was disturbed resulting in release of the encapsulated substances. 

Further progress in the field of conformational phase transition in polymer gels, especially in polyelectrolyte gels, was achieved in the paper by Tanaka [4]. He investigated the swelling of polyacrylamide (PAA) networks, which were crosslinked by N,AT-methylenebisacrylamide (BAA), in the mixtures of water and acetone. When the quality of the solvent was made poorer (this happened when the concentration of acetone was increased or the temperature was lowered) shrinking of the samples was observed. Tanaka showed that at certain... 

Aqueous dispersions of polymerizable lipids and surfactants can be polymerized by UV irradiation (Fig. 18). In the case of diacetylenic lipids the transition from monomeric to polymeric bilayers can be observed visually and spectroscopically. This was first discussed by Hub, 9) and Chapman 20). As in monomolecular layers (3.2.2) short irradiation brings about the blue conformation of the poly(diacetylene) chain. In contrast, upon prolonged irradiation or upon heating blue vesicles above the phase transition temperature of the monomeric hydrated lipid the red form of the polymer is formed 23,120). The visible spectra of the red form in monolayers and liposomes are qualitatively identical (Fig. 19). 

In contrast, the phase transition of polymeric liposomes is retained if the polymer chain is more flexible or located on the surface of the vesicles instead within the hydrophobic core. Polymerized vesicles of methacrylamide (29) show a phase transition temperature which is slightly lower than the one for the corresponding monomeric vesicles (Fig. 26). This can be explained by a disordering influence of the polymer chain on the head group packing 15). 

Methacryloylic lipid (5) is polymerizable in the hydrophobic part of the molecule. The phase transition temperature of the polymeric vesicle is again lowered compared to the non-polymerized vesicle (Fig. 27). The difference between the phase transition temperatures of monomer and polymer is somewhat larger than in the case of acrylamide (29). This might indicate that a saturated polymer chain in the hydrophobic core of a membrane decreases membrane order to a higher extent than a polymer chain on the membrane surface 15). 

Miscibility of a natural lipid (DMPC) and the monomeric and polymeric lecithin analogue (26) was studied in large unilamellar vesicles using freeze-fracture electron microscopy and photobleaching by H. Gaub 100>. Before polymerization the two lipids appear miscible at all compositions in the fluid state and at DMPC concentrations at or below 50 mol/o in the solid state. After polymerization a two-dimensional solution of the polymer in DMPC is obtained at T > T (T phase transition temperature of polymeric 26) while lateral phase segregation into DMPC-rich domains and patches of the polymer is observed T < T. The diameter of the polymerized lipid domains was found to average 400 A. 

Figure la shows a general schematic illustration of the stimuli-responsive phase transition of a polymer system from the state X to the state Y. In the absence of external stimulation, the polymer system changes the state at a temperature Ta. We assume that the phase transition temperature will rise to Tb in the presence of external stimulation. Then, if the external stimulation is applied to the system at T (T, < T < Tb), the state will change from Y to X isothermally at a certain value of the external stimulation, Ca as shown in Fig. lb. This principle is useful for constructing efficient stimuli-responsive polymers. 

Consequently, the stimulation alters the phase transition temperature from Ta of polymer-A to Tb of polymer-B. 

Table 10. Phase transition temperatures of linear and crosslinked l.c. side chain polymers...

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