Poly methacrylate from

Fig. 1.18 Poly(itaconates) as compared to only one carbonyl in poly-(methacrylates). (From ref. [122])...

Deschenaux, R. Turpin, F. Guillon. D. Ferrocene-containing themiotropic side-chain liquid-crystalline poly-methacrylate from a mesomorphic trisubstituted ferrocene monomer. Macromolecules 4997. 30. 3759-3765. 

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

This potential reflects itself in the titration curves of weak polyacids such as poly(acrylic acid) and poly(methacrylic acid) [32]. Apparent dissociation constants of such polyacids change with the dissociation degree of the polyacid because the work to remove a proton from the acid site into the bulk water phase depends on the surface potential of the polyelectrolyte. 

Stigter, D, Kinetic Charge of Colloidal Electrolytes from Conductance and Electrophoresis. Detergent Micelles, Poly(methacrylates), and DNA in Univalent Salt Solutions, Journal of Physical Chemistry 83, 1670, 1979. 

The endopolygalacturonase obtained from a Kluyveromyces marxianus culture broth was purified through the addition of specifically designed core-shell microspheres consisting of an inner polystyrene core and an outer shell constituted by a poly(methacrylic acid-co-ethylacrylate) statistical copolymer. These microspheres were previously found very effective in purifying the pectinlyase within a commercial pectinase sample [15]. 

Figure 22 Insulin release rate (normalized to mg/hr per 160 mg device) from insulin-loaded matrix of polyethyloxazolin-poly(methacrylic acid) complex with the application of step-function electric current in 0.9% saline solution (mean from three measurements). ( ) Current on (5mA) (O) current off. (From Ref. 47.)...

Philippova and Starodubtzev have also extensively studied the complex-ation behavior of polyacids and PEG, especially, the system of crosslinked of poly(methacrylic acid) and linear poly(ethylene glycol) (Philippova and Starodubtzev, 1995 Philippova et al., 1994). They observed that decreasing the molecular weight of PEG from 6000 to 1500 resulted in its slower diffusion into the swollen network of PMAA, and a drastic decrease in both the stability and equilibrium composition of the intermacromolecular complex. Analysis of dried polymer networks of PMAA with absorbed PEG chains by FT-IR spectroscopy revealed the presence of two types of hydrogen bonded structures (1) dimers of methacrylic acid at absorption frequency of 1700 cm-1 and (2) interpolymer complexes of PMAA and PEG at 1733 cm-1. In addition, they also suggested as a result of their studies, that the hydrogen bonded dimer of PMAA forms preferentially to the intermacromolecular complex between the PMAA network and PEG chains. 

Other efforts based on the macromonomer approach to homopolymers having dendritic side chains, include the work of Draheim and Ritter on acrylate and methacrylate derived structures having dendritic chiral side chains based on L-aspartic esters [17a], and of Xi and coworkers with poly(methacrylate) structures containing very small benzyl ether dendritic side-chains [17b]. Unfortunately, both of these approaches met with limited success due to a significant drop in degree of polymerization (DP) when the size of the dendron used as pendant group in the macromonomers increased from G-l to G-2. 

In a more simple and cheap way, silver clusters can be prepared in aqueous solutions of commercially available polyelectrolytes, such as poly(methacrylic acid) (PM A A) by photo activation using visible light [20] or UV light [29]. Ras et al. found that photoactivation with visible light results in fluorescent silver cluster solutions without any noticeable silver nanoparticle impurities, as seen in electron microscopy and from the absence of plasmon absorption bands near 400 nm (F = 5-6%). It was seen that using PMAA in its acidic form, different ratios Ag+ MAA (0.15 1-3 1) lead to different emission bands, as discussed in the next section (Fig. 12) [20]. When solutions of PMAA in its sodium form and silver salt were reduced with UV light (365 nm, 8 W), silver nanoclusters were obtained with emission band centered at 620 nm and [Pg.322]

Figure 1. 40 MHz H NMR spectrum of isotactic (a) and syndiotactic (b) poly(methyl methacrylate). From ref. (54) Copyright John Wiley Sons.

The vast majority of commercial polymers based on the vinyl group (H2C=CHX) or the vinylidene group (H2C=CX2) as the repeat unit are known by their source-based names. Thus, polyethylene is the name of the polymer synthesized from the monomer ethylene poly(vinyl chloride) from the monomer vinyl chloride, and poly(methyl methacrylate) from methyl methacrylate. 

From the viewpoint of sales volume, all other members of the acrylic family constitute a small fraction of the total. However, many of them are useful specialty products. Polyacrylamide (XLIV), poly(acrylic acid) (XLV), and poly(methacrylic acid) (XLVI) and some of their copolymers are used in various applications that take advantage of their solubility in water. Poly(acrylic acid) and poly(methacrylic acid) are used as thickening agents (water... 

As a medium strength liquid (Table 16.1), THF is commonly used also in the coupled methods of polymer HPLC. It promotes desorption of medium polar polymers such as poly(acrylate)s and poly(methacrylate)s including poly(methyl methacrylate) from the nonmodified silica gel. Other strong(er) solvents widely used in the coupled polymer HPLC methods are acetonitrile that exhibits high UV transparency, and dimethyl formamide. The latter solvent readily decomposes into amine and formic acid and its strength may differ from batch to batch. 

As explained in Sections 16.3.4, 6.4.1, and 16.4.2, SEC is a nonabsolute method, which needs calibration. The most popular calibration materials are narrow molar mass distribution polystyrenes (PS). Their molar mass averages are determined by the classical absolute methods—or by SEC applying either the absolute detection or the previously calibrated equipment. The latter approach may bring about the transfer and even the augmentation of errors. Therefore, it is recommended to apply exclusively the certified well-characterized materials for calibrations. These are often called PS calibration standards and are readily available from numerous companies in the molar mass range from about 600 to over 30,000,000g moL. Their prices are reasonable and on average (much) lower than the cost of other narrow MMD polymers. Other available homopolymer calibration materials include various poly(acrylate)s and poly(methacrylate)s. They are, similar to PS, synthesized by anionic polymerization. Some calibration materials are prepared by the methods of preparative fractionation, for example, poly(isobutylene)s and poly(vinylchloride)s. 

Kwon and coworkers described solid polyelectrolyte complex systems which dissolve rapidly in response to small electric currents. The solid doses were based on poly(ethyl oxazoline) and poly(methacrylic acid) with a repeating unit stoichiometry of 1 1. Insulin was released in response to slight electric currents due to electrically induced polymer dissolution [380]. In similar work Kwon and coworkers [381] studied release of edrophonium chloride and hydrocortisone from poly(2-acrylamido-2-methylpropane sulfonate-co-n-butyl methacrylate). An on/oflf mechanism of the edrophonium chloride release was observed and was attributed to ion exchange of solute and hydroxonium ion. The cationic solute release was assisted by electrostatic forces, whereas release of the neutral hydrocortisone solute was only affected by swelling and deswelling. 

Seki and Tirrell [436] studied the pH-dependent complexation of poly(acrylic acid) derivatives with phospholipid vesicle membranes. These authors found that polyfacrylic acid), poly(methacrylic arid) and poly(ethacrylic acid) modify the properties of a phospholipid vesicle membrane. At or below a critical pH the polymers complex with the membrane, resulting in broadening of the melting transition. The value of the critical pH depends on the chemical structure and tacticity of the polymer and increases with polymer hydro-phobicity from approximately 4.6 for poly(acrylic acid) to approximately 8 for poly(ethacrylic acid). Subsequent photophysical and calorimetric experiments [437] and kinetic studies [398] support the hypothesis that these transitions are caused by pH dependent adsorption of hydrophobic polymeric carboxylic acids... 

The hemocompatibility of poly(amido-amine) polyelectrolyte complexes was recently studied by Xi, Zhang and coworkers [499, 500]. The poly(amido-amine) was based on piperazine and methylene bisacrylamide, and the polyelectrolyte complexes were obtained from the reaction of poly(amido-amine) with alginic acid, carboxymethyl cellulose or poly(methacrylic acid). Complexes of polyamido-amine and alginic acid with a 1 2 ratio gave the best hemocompatibility. Finally, the blood compatibility of polyelectrolyte complexes based on anionic and cationic cellulose derivatives were studied by Ito et al. [338], In vivo, good blood compatibility of complexes formed from quaternary hy-droxyethyl cellulose reacted with carboxymethyl cellulose and cellulose sulfate was observed. 

FIGURE 11.5 Degradation of N-a-benzoyl-l-arginine ethyl ester by trypsin. All three carboxyl containing polymers have antitrypsin activity, but the activity of trypsin in the presence poly(ethylene glycol) modified poly(methacrylic acid) is not greatly reduced. (Adapted from Madsen and Peppas 1999.)... 

Gregor et al66 reported the Cu-complex formation of poly(methacrylic acid) (PMA) resins crosslinked with 1% or 9% divinylbenzene. The formation constants of the Cu complexes with the resins were smaller than that of noncrosslinked PMA. The stepwise formation constants decreased from Ki to KA in the resin system, which was the opposite of the noncrosslinked PMA system. The rigidity of the polymer-ligand chain was considered to hinder chelate formation. Formation constants of the PMA resin were also reported by Gustafson era/.67. The formation constant of the noncrosslinked PMA decreased for various metal ions ... 

Poly(/ -acetamidostyrene) (V) is prepared from p-nitrobenzyl bromide as shown in Scheme 6. Homopolymer V has very little solubility in common organic solvents and thus it is difficult to use attempts at increasing the solubility of V by incorporation of up to 40% styrene units in copolymers such as Va do not result in any significant improvement in solubility. Polyfphenyl methacrylate) (VI) and poly(methacryl anilide) (VII) are prepared from the corresponding monomers according to literature procedures (19-20). 

Figure 2. Infrared spectra of atactic poly(a,a-dimethylbenzyl methacrylate)s unexposed (A) and exposed(B) to electron-beam, isotactic poly (a,a-dimethylbenzyl methacrylate) exposed(C) and poly(methacrylic acid)(D). Exposure charge density 1.6 x 10-4 C/cm2, film thickness 0.5 pm, prebake at 142° C. Reproduced with permission from Ref. 2. Copyright 1983, "Springer...

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