PDMAEMA methacrylate

New drug delivery systems are of great scientific and commercial interest. Amphiphilic networks composed of about 50/50 hydrophobic PIB and hydrophilic poly(2-(-dimethylamino)ethyl methacrylate) (DMAEMA) polymer segments were found to be biocompatible and to a large extent avascular (7). These PHM-PDMAEMA networks (i, in line with propositions of Weber and Stadler (2), and Sperling (J), denotes PDMAEMA chains linked by PIB chains) gave pH dependent... 

GTP was employed for the synthesis of block copolymers with the first block PDMAEMA and the second PDEAEMA, poly[2-(diisopropylamino)e-thyl methacrylate], PDIPAEMA or poly[2-(N-morpholino)ethyl methacrylate], PM EM A (Scheme 33) [87]. The reactions took place under an inert atmosphere in THF at room temperature with l-methoxy-l-trimethylsiloxy-2-methyl-1-propane, MTS, as the initiator and tetra-n-butyl ammonium bibenzoate, TBABB, as the catalyst. Little or no homopolymer contamination was evidenced by SEC analysis. Copolymers in high yields with controlled molecular weights and narrow molecular weight distributions were obtained in all cases. The micellar properties of these materials were studied in aqueous solutions. 

ABC, ACB, and BAC triblock terpolymers, where A is PMMA, B is PDMAEMA, and C is poly[hexa(ethylene glycol)methacrylate], PHEGMA, were synthesized via GTP and sequential monomer addition [89]. The polymerizations were conducted in THF using MTS and TBABB as the initiator... 

The triblock terpolymer polypropylene oxide)-h-poly[2-(dimethylami-no)ethyl methacrylate]-b-poly[oligo(ethylene glycol) methacrylate], PPO-fc-PDMAEMA-fc-POEGMA, was prepared using the PPO macroinitiator followed by the addition of CuCl, HMTETA, and DMAEMA for the polymerization of the second block and finally OEGMA for the synthesis of the final product (Scheme 54) [128]. 

Hydrogels that have the ability to respond to pH changes have been studied extensively over the years. These gels typically contain side ioni-zable side groups such as carboxylic acids or amine groups (Oppermann, 1992 Scranton et al., 1995). The most commonly studied ionic polymers include polyacrlyamide (PAAm), poly(acrylic acid) (PAA), poly(metha-crylic acid) (PMAA), poly (diethylaminoethyl methacrylate) (PDEAEMA), and poly(dimethylaminoethyl methacrylate) (PDMAEMA). 

Fig. 11 Chemical formulas of poly(acryl amide) (PAAm), poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(t-butyl acrylate) (PtBA), and poly(acrylic acid) (PAA), and poly(dimethyl aminoethyl methacrylate) (PDMAEMA)...

While the bulk behavior of polyampholytes has been investigated for some time now, studies of interfacial performance of polyampholytes are still in their infancy. There are several reasons for the limited amount of experimental work the major one being the rather complex behavior of polyampholytes at interfaces. This complexity stems from a large array of system parameters governing the interaction between the polymer and the substrate. Nearly all interfacial studies on polyampholytes reported to-date involved their adsorption on solid interfaces. For example, Jerome and Stamm and coworkers studied the adsorption of poly(methacryhc acid)-block-poly(dimethyl aminoethyl methacrylate) (PMAA-fc-PDMAEMA) from aqueous solution on sihcon substrates [102,103]. The researchers found that the amount of PMAA-fo-PDMAEMA adsorbed at the solution/substrate interface depended on the solution pH. Specifically, the adsorption increased... 

Fig. 36 Dry thickness of polyfdimethyl aminoethyl methacrylate) (PDMAEMA) on an orthogonal PDMAEMA gradient grafted on a silica substrate. Thickness was measured in a grid of 5 mm x 5 mm on the substrate. (Reproduced with permission from [117])...

The first diblock copolymer brushes synthesized in our group were made by a combination of carbocationic polymerization and ATRP (Scheme 1) [46]. Zhao and co-workers [47] synthesized diblock copolymer brushes consisting of a tethered chlorine-terminated PS block, produced using carbocationic polymerization, on top of which was added a block of either PMMA, poly(methyl acrylate) (PMA) or poly((Ar,M -dimethylamino)ethyl methacrylate) (PDMAEMA), synthesized using ATRP. The thickness of the outer poly(meth)acrylate block was controlled by adding varying amounts of free initiator to the ATRP media. It has been reported that the addition of free initiator is required to provide a sufficiently high concentration of deactivator, which is necessary for controlled polymerizations from the sur-... 

PS—polystyrene, PMMA—poly(methyl methacrylate), PMA—poly(methyl acrylate), PDMAEMA—poly((Nd f-dimethylamino)ethyl methacrylate), PDMA—poly( dimethyl-acrylamide), P(t-BA)—poly(tert-butyl acrylate), PAA—poly(acrylic acid), PPFS—poly (pentafluorostyrene), PHFA—poly(heptadecafluorodecyl acrylate)... 

The temperature optimization for the RAFT polymerization of EAA revealed an optimum reaction temperature of 70 °C. Block copolymers with a poly(methyl acrylate) (PMA), a poly(n-butyl acrylate) (PnBA), a PMMA, or a poly(A,A-dimethyl aminoethyl methacrylate) (PDMAEMA) first block and a poly(l-ethoxyethyl acrylate) (PEEA) second block were successfully synthesized in an automated synthesizer. The synthesis robot was employed for the preparation of 16 block copolymers consisting of 25 units of the first block composed of PMA (exp. 1 ), PnBA (exp. 5-8), PMMA (exp. 9-13), and PDMAEMA (exp. 13-16) and a second block of PEEA consisting of 25, 50, 75, or 100 units, respectively. The first blocks were polymerized for 3 h and a sample from each reaction was withdrawn for SEC analysis. Subsequently, EAA was added and the reactions were continued for 12 h. The molar masses and PDI values of the obtained block copolymers are shown in Fig. 15. 

Controlled free-radical polymerization methods, like atom-transfer radical polymerization (ATRP), can yield polymer chains that have a very narrow molecular-weight distribution and allow the synthesis of block copolymers. In a collaboration between Matyjaszewski and DeSimone (Xia et al., 1999), ATRP was performed in C02 for the first time. PFOMA-/)-PMMA, PFOMA-fr-PDMAEMA [DMAEMA = 2-(dimethylamino)ethyl methacrylate], and PMMA-/)-PFOA-/)-PM M A copolymers were synthesized in C02 using Cu(0), CuCl, a functionalized bipyridine ligand, and an alkyl halide initiator. The ATRP method was also conducted as a dispersion polymerization of MMA in C02 with PFOA as the stabilizer, generating a kine-... 

PDEAEMA poly(N,N-diethylaminoethyl methacrylate) PDMAEMA poly(N,N-dimethylaminoethyl methacrylate) PDMAI poly(N,N-dimethylaminoisoprene)... 

PAA = poly (acrylic acid), PMAA = poly(methacrylic acid), PI A = poly(itaconic acid), PGA = poly(L-glutamic acid), QPVP = poly(N-ethyl-4-vinyl-pyridinium bromide), PLL = poly(L-lysine), PDMAEMA = poly(2-N,N-dimethylaminoethyl methacrylate), PVBMA = poly(4-vinylbenzyl-trimethylammonium chloride), 5,6-ionene, 2,5-ionene, 10,10-ionene, 2X and 3X (see text)... 

Because LiCl-mediated anionic polymerization of methacrylates is living, the addition of a second monomer to living polymethacrylate chains expectedly results in diblock copolymers, such as PtBuA-fc/ock-PMMA , PtBAEMA-/)Zock-PMMA , PtBMA-block-VGMA , PtBAEMA-fc/ock-PtBuMA and PtBMA-/)Zock-PDMAEMA 4. 

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