Poly microgels

For the formation of microgels the presence of a crosslinking monomer is not always necessary. Thus, microgels have also been detected in polymers prepared with bifunctional monomers, e.g. poly(acrylonitrile-co-vinylacetate) [39], polyethylene [40],poly(vinylchloride) [41] andpoly(vinylidenefluoride) [42].Obviously, the reason for the intramolecular crosslinking with the formation of microgels are side reactions. 

The [nri] of microgel solutions decreases with increasing degree of neutralization of the carboxyl acid groups of the EUP (Fig. 19) because the emulsifier concentration increases and, accordingly, the micelles or microemulsion droplets become smaller. In this case an external emulsifier poly(oxymethylene) octylphenyl ether was added to insure complete solubilization over the whole range of neutralization. 

Values for RU differed by up to 100% with 1,4-DVB-microgels [286]. The reliability of methods for determining the RU of 1,4-DVB-microgels was checked [287] with poly(4-vinylstyrene) which was prepared by anionic polymerization of 1,4-DVB (Table 3). From these results, it can be concluded that only quantitative IR-spectroscopy is a reliable method for determining the RU of 1,4-DVB-... 

An essential prerequirement for the aggregation is the presence of different epitopes on the antigenes so that their functionality is greater than one. Reversible bridging flocculation of poly(lysine) with acrylic microgels has also been reported [376]. 

Crosslinked polymer networks formed from multifunctional acrylates are completely insoluble. Consequently, solid-state nuclear magnetic resonance (NMR) spectroscopy becomes an attractive method to determine the degree of crosslinking of such polymers (1-4). Solid-state NMR spectroscopy has been used to study the homopolymerization kinetics of various diacrylates and to distinguish between constrained and unconstrained, or unreacted double bonds in polymers (5,6). Solid-state NMR techniques can also be used to determine the domain sizes of different polymer phases and to determine the presence of microgels within a poly multiacrylate sample (7). The results of solid-state NMR experiments have also been correlated to dynamic mechanical analysis measurements of the glass transition (1,8,9) of various polydiacrylates. 

Hydrogels, 13 729-759. See also Microgels Superabsorbent polymers (SAPs) AMPS polymer, 23 721 applications for, 13 747-753 biodegradable, 13 739-742 bioerodible, 9 63 conducting, 7 524 cross-linked poly (ethylene oxide),... 

In a related application, polyelectrolyte microgels based on crosslinked cationic poly(allyl amine) and anionic polyfmethacrylic acid-co-epoxypropyl methacrylate) were studied by potentiometry, conductometry and turbidimetry [349]. In their neutralized (salt) form, the microgels fully complexed with linear polyelectrolytes (poly(acrylic acid), poly(acrylic acid-co-acrylamide), and polystyrene sulfonate)) as if the gels were themselves linear. However, if an acid/base reaction occurs between the linear polymers and the gels, it appears that only the surfaces of the gels form complexes. Previous work has addressed the fundamental characteristics of these complexes [350, 351] and has shown preferential complexation of cationic polyelectrolytes with crosslinked car-boxymethyl cellulose versus linear CMC [350], The departure from the 1 1 stoichiometry with the non-neutralized microgels may be due to the collapsed nature of these networks which prevents penetration of water soluble polyelectrolyte. 

Alakhov, V., etal., Pluronic block copolymers and Pluronic poly(acrylic acid) microgels in oral delivery of megestrol acetatd, Pharm. Pharmacol., 56, 1233, 2004. 

Bromberg, L., and V. Alakhov. 2003. Effects of polyether-modified poly(acrylic acid) microgels on doxorubicin transport in human intestinal epithelial Caco-2 cell layers. J Control Release 88 11. 

For example, surfaces comprising PNIPAM microgels were utilized for drug delivery [138], Electrostatic layer-by-layer assembly with poly(NIPAM-coacrylic acid) and poly(allylamine hydrochloride) on an amino-functionalized surface yielded thermoresponsive thin films. These were capable of a thermally regulated uptake and release of the chemotherapeutic drug doxorubicin. The films were loaded... 

The first synthesis of star polymers with a microgel core was reported by Sa-wamoto et al. for poly(isobutyl vinyl ether) (poly(IBVE)) [3,4]. In the first step, living cationic polymerization of IBVE was carried out with the HI/ZnI2 initiating system in toluene at -40 °C. Subsequent coupling of the living ends was performed with the various divinyl ethers 1-4. 

Poly(N-isopropylacrylamide) (PNIPAM) is the most studied thermosensitive polymer in aqueous media. It is soluble in water at low temperatures but becomes insoluble when the temperature is increased above a certain temperature ( 32 °C) (lower critical solution temperature), which is related to the coil-to-globule transition [64, 65]. In the case of a polymer network, a volume change occurs reversibly within a narrow temperature range. The properties of such microgels can be varied to a great extent by the introduction... 

M. Bradley, J. Ramos, and B. Vincent, Equilibrium and kinetic aspects of the uptake of poly(ethylene oxide) by copolymer microgel particles of N-isopropylacrylamide and acrylic acid, Langmuir 21, 1209-1215 (2005). 

The ODN adsorption onto cationic microgel poly(N-isopropylacrylamide) particles was reported to be dramatically affected by the salinity of the incubation medium [9] as illustrated in Fig. 6. The observed result was related to (i) the reduction in attractive electrostatic interactions between ODN molecules and the adsorbent and (ii) the drastic effect of ionic strength on the physico-chemical properties of such particles [17, 27]. In fact, the hydrodynamic size, the swelling ability, the electrokinetic properties, and the colloidal stability are dramatically affected by pH, salt concentration, and the medium temperature [27]. 

As polymeric model fillers with specific surface groups and narrow size distribution, different microgel types, e.g., poly(styrene)-microgel, PS(m), and poly(methoxy-styrene)-microgel, PMS(m), are applied. They can be prepared by emulsion polymerization techniques as described, e.g., in [48]. 

During precipitation polymerization, all ingredients are dissolved in a solvent (water) to form a homogeneous mixture in which initiation of polymerization takes place. The formed polymers are transformed into a collapsed state because the reaction temperature is far above VPTT (for example in the case of PNIPAAm) and become crosslinked by crosslinker molecules to form a colloidal polymer network or microgel. This technique has been widely used for the synthesis of thermosensitive PNIPAAm [30-35] and poly(/V-vinyl caprolactam) (PVCL) [36] microgels. 

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