Polymers polymeric matrix

D. J. Morantz and J. W. Wigley, The contrasting phosphorescence decay kinetics of diacetyl and aromatic ketone phosphors in polymeric matrices, Polymer Communication 26, 170-171 (1985). 

The well known complexing properties of macrocyclic compounds towards metal ions have led to their incorporation into polymeric matrices. Polymer-supported crown ethers have many advantages, such as easy handling and recoverability when used for the removal of the toxic metal ions from the environment. Crown ether-, calixarene-, calixcrown- and cyclodextrin- based polymers have been recently receiving attention as the new polymers and may be processed into materials suitable as the extractant (solvent extraction), collector (ion flotation) or the ion carrier (transport across liquid membranes or ion selective electrodes). 

Depending on the nature of the particles embedded in the polymeric matrix, polymer-inorganic hybrid membranes can be divided into two nonexclusive groups mixed matrix membranes (MMMs) and nanocomposite membranes (NCMs). 

In order to avoid particle aggregation during the polymerization process, grafting techniques offer an excellent possibility for direct covalent linking of the particles and the polymeric matrix. Polymers can either be grafted to or from the nanoparticle surfaces. If polymers should be grafted to the nanopartide surface, polymers will be end-capped with functional groups (Scheme 1). 

Also semiconductor nanoparticles can be prepared in the presence of their polymeric matrix. Polymers with functional groups such as hydroxyl, carboxyl, or amines can form complexes with different metal salts. Subsequent treatment with, for example, H2S gas results in sulfide nanoparticles. Only recently Shen et al. used cadmium acrylate ionomers to form ion cluster, copolymerized with methyl methacrylate, and obtained highly transparent CdS/PMMA nanocomposites... 

Ion-exchange resins are categorized by the nature of functional groups attached to a polymeric matrix, by the chemistry of the particular polymer in the matrix, and by the porosity of the polymeric matrix. There are four primary types of functionaHty strong acid, weak acid, strong base, and weak base. Another type consists of less common stmctures in specialty resins such as those which have chelating characteristics. 

There are several approaches to the preparation of multicomponent materials, and the method utilized depends largely on the nature of the conductor used. In the case of polyacetylene blends, in situ polymerization of acetylene into a polymeric matrix has been a successful technique. A film of the matrix polymer is initially swelled in a solution of a typical Ziegler-Natta type initiator and, after washing, the impregnated swollen matrix is exposed to acetylene gas. Polymerization occurs as acetylene diffuses into the membrane. The composite material is then oxidatively doped to form a conductor. Low density polyethylene (136,137) and polybutadiene (138) have both been used in this manner. 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

Conducting polymer composites have also been formed by co-electrodeposition of matrix polymer during electrochemical polymerization. Because both components of the composite are deposited simultaneously, a homogenous film is obtained. This technique has been utilized for both neutral thermoplastics such as poly(vinyl chloride) (159), as well as for a large variety of polyelectrolytes (64—68, 159—165). When the matrix polymer is a polyelectrolyte, it serves as the dopant species for the conducting polymer, so there is an intimate mixing of the polymer chains and the system can be appropriately termed a molecular composite. 

It is precisely the loosening of a portion of polymer to which the authors of [47] attribute the observed decrease of viscosity when small quantities of filler are added. In their opinion, the filler particles added to the polymer melt tend to form a double shell (the inner one characterized by high density and a looser outer one) around themselves. The viscosity diminishes until so much filler is added that the entire polymer gets involved in the boundary layer. On further increase of filler content, the boundary layers on the new particles will be formed on account of the already loosened regions of the polymeric matrix. Finally, the layers on all particles become dense and the viscosity rises sharply after that the particle with adsorbed polymer will exhibit the usual hydrodynamic drag. 

The model for a filled system is different. The filler is, as before, represented by a cube with side a. The cube is coated with a polymer film of thickness d it is assumed that d is independent of the filler concentration. The filler modulus is much higher than that of the d-thick coat. A third layer of thickness c overlies the previous one and simulates the polymeric matrix. The characteristics of the layers d and c are prescribed as before, and the calculation is carried out in two steps at first, the characteristics of the filler (a) - interphase (d) system are calculated then this system is treated as an integral whole and, again, as part of the two component system (filler + interphase) — matrix. From geometric... 

Moreover, the interaction of the surface of the fillter with the matrix is usually a procedure much more complicated than a simple mechanical effect. The presence of a filler actually restricts the segmental and molecular mobility of the polymeric matrix, as adsorption-interaction in polymer surface-layers into filler-particles occurs. It is then obvious that, under these conditions, the quality of adhesion can hardly be quantified and a more thorough investigation is necessary. 

The analysis of an unknown number of unknown additives in unknown concentration in an unknown polymeric matrix is a demanding task for the analytical chemist for a variety of circumstances (Table 2.1). Primary analytical needs include the identification of the additives, the quantification of the additive levels, and the examination of additive stability. Obviously, the experimental analytical conditions must be such that no measurable polymer degradation or additive loss occurs during analysis. 

In direct insertion techniques, reproducibility is the main obstacle in developing a reliable analytical technique. One of the many variables to take into account is sample shape. A compact sample with minimal surface area is ideal [64]. Direct mass-spectrometric characterisation in the direct insertion probe is not very quantitative, and, even under optimised conditions, mass discrimination in the analysis of polydisperse polymers and specific oligomer discrimination may occur. For nonvolatile additives that do not evaporate up to 350 °C, direct quantitative analysis by thermal desorption is not possible (e.g. Hostanox 03, MW 794). Good quantitation is also prevented by contamination of the ion source by pyrolysis products of the polymeric matrix. For polymer-based calibration standards, the homogeneity of the samples is of great importance. Hyphenated techniques such as LC-ESI-ToFMS and LC-MALDI-ToFMS have been developed for polymer analyses in which the reliable quantitative features of LC are combined with the identification power and structure analysis of MS. 

Because these types of polymeric matrix systems are the simplest to design and the easiest to obtain approval by the Food and Drug Administration, they have been the most extensively studied in the past two decades. Numerous polymers have been evaluated for these types of drug delivery systems and although it would be impractical to present each of these polymers and its specific application to drug delivery, this chapter will review in general the types of polymers used as matrices for drug delivery (1-4). 

In principle, the interaction of small molecules within a swollen polymer is one of the easiest situation to be proven, due to the large difference in size of species involved. Changes in the small molecule diffusivity will occur as a result of specific interactions between the diffusant and the polymeric matrix. 

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