Polymer poly condensation

Polymer Poly condensation mode Conditional sign r,K ky Q, s ... 

The second category of polymerization reactions does not involve a chain reaction and is divided into two groups poly addition and poly condensation [4]. In botli reactions, tire growth of a polymer chains proceeds by reactions between molecules of all degrees of polymerization. In polycondensations a low-molecular-weight product L is eliminated, while polyadditions occur witliout elimination ... 

Among the polymeric stabilizers may be listed poly-condensed polymers based on alkyl phenols, aldehydes, and ketones of the aliphatic series, where = 1 - 8 and R,R means alkyl [24], Na, K, Ca phenolates of poly-condensed polymers [25], and also products of epichlor-ide with one or more aliphatic amines C3—C30 [26]. 

The authors found that the yield of 30-mer (a product with 5—6 linkages) was not much smaller than that of 10-mer or 12-mer. These facts indicate that the stability of the complex between the oligonucleotides and the complementary template is the most important factor in determining the extent of the condensation. The strong influences of template polymer (Poly C) are demonstrated in Fig. 9, in which the elution profile is shown of the polymerization products of (2 MeIp)6 in the presence of Poly C (B) and in their absence (A). 

Melt poly condensation The reaction is carried out in a 250-mL stainless steel vessel with nitrogen inlet and mechanical stirrer. The vessel containing T4T-dimethyl (30 g, 72.8 mmol) and ethanediol (30 g, 0.48 mol) is heated up in an oil bath at 200°C. After 15 min reaction TiO -OCaJ I7 )4 (1.5 mL of 0.1 M solution in CH2C12) is added and subsequently the temperature is gradually raised to 260°C (l°C/min). After 10 min at 260°C the pressure is reduced (15-20 mbar) for 5 min. Then the pressure is reduced further (<2.5 mbar) for 45 min. The vessel is cooled down slowly to room temperature, maintaining the low pressure. After solidification, the polymer is ground (particle size <1 mm) and subsequently dried in a vacuum oven at 80°C. 

The solubility is generally improved by the introduction of fluorine atoms into aromatic condensation polymers. Poly(carbonate)s containing hexafluoroisopropylidene units are much more soluble than Bisphenol A poly(carbonate) (3). All of the hexafluoroisopropylidene-unit-containing poly(carbonate)s become soluble in acetone, ethyl acetate, chloroform, and dimethyl sulfoxide (DMSO) in addition to the solvents of Bisphenol A poly(carbonate) (3). Colorless, transparent, and flexible films are prepared from hexafluoroisopropylidene-unit-containing poly(carbonate)s by casting or pressing. 

Hoftyzer and van Krevelen [100] investigated the combination of mass transfer together with chemical reactions in polycondensation, and deduced the ratedetermining factors from the description of gas absorption processes. They proposed three possible cases for poly condensation reactions, i.e. (1) the polycondensation takes place in the bulk of the polymer melt and the volatile compound produced has to be removed by a physical desorption process, (2) the polycondensation takes place exclusively in the vicinity of the interface at a rate determined by both reaction and diffusion, and (3) the reaction zone is located close to the interface and mass transport of the reactants to this zone is the rate-determining step. 

The chemistry of the solid-state polycondensation process is the same as that of melt-phase poly condensation. Most important are the transesterification/glycolysis and esterification/hydrolysis reactions, particularly, if the polymer has a high water concentration. Due to the low content of hydroxyl end groups, only minor amounts of DEG are formed and the thermal degradation of polymer chains is insignificant at the low temperatures of the SSP process. 

Fontana, C. M., Poly condensation equilibrium and the kinetics of catalyzed transesterification in the formation of polyethylene terephthalate, J. Polym. Sci., Part A-l, 6, 2343-2358 (1968). 

Stevenson, R. W Poly condensation rate of poly (ethylene terephthalate) - II. Antimony trioxide catalyzed polycondensation in static thin films on metal surfaces, J. Polym. Sci., PartA-1, 1, 395-407 (1969). 

Gostoli, C., Pilati, F., Sarti, G. C. and Di Giacomo, B Chemical kinetics and diffusion in poly(butylene terephthalate) solid-state poly condensation experiments and theory, J Appl. Polym. Sci., 29, 2873-2887 (1984). 

Since it is also a poly condensation polymer, the preparation of PEN from dimethyl 2,6-naphthalenedicarboxylate (NDC) is similar to the preparation of PET from dimethyl 1,4-terephthalate (DMT) by combining a diacid ester (NDC) with ethylene glycol. In view of the fact that the commercial-scale production of PEN resin starts with 2,6-NDC, the production process is similar to that used for the production of PET from DMT. There are two main steps for the process (Scheme 10.1) [11]. 

Previous work on the synthesis of TTF (tetrathiafulvalene) containing polymers has been reported by at least seven groups of researchers. Most of this work concerns condensation 6,7,8,9 polymers or polymers made from vinyl substituted TTF molecules . Without exception, the polymers produced by these methods have been largely unacceptable for subsequent physical study because of their brittle,intractable, highly insoluble nature. Only by reaction of a suitably monofunctionalized TTF derivative with the preformed polymer poly(vinylbenzylchloride) has it been found possible — to prepare soluble TTF homopolymers with more manageable physical properties. 

Production of pol3rmers through poly-substitution or poly-condensation reactions would be expected to be a natural extension of simple PTC chemistry. To a large extent this is true, but as Percec has shown. Chapter 9, the ability to use two-phase systems for these reactions has enormously extended the chemist s ability to control the structure of the polymers produced. Kellman and co-workers (Chapter 11) have also extensively studied poly-substitution displacements on perfluorobenzene substrate to produce unique polymers. 

Properties of composites obtained by template poly condensation of urea and formaldehyde in the presence of poly(acrylic acid) were described by Papisov et al. Products of template polycondensation obtained for 1 1 ratio of template to monomers are typical glasses, but elastic deformation up to 50% at 90°C is quite remarkable. This behavior is quite different from composites polyacrylic acid-urea-formaldehyde polymer obtained by conventional methods. Introduction of polyacrylic acid to the reacting system of urea-formaldehyde, even in a very small quantity (2-5%) leads to fibrilization of the product structure. Materials obtained have a high compressive strength (30-100 kg/cm ). Further polycondensation of the excess of urea and formaldehyde results in fibrillar structure composites. Structure and properties of such composites can be widely varied by changes in initial composition and reaction conditions. 

A 500-ml reaction flask was charged with the step 1 product (43.1 mmol), the poly condensate of 4,4 -dichlorobenzophenone-2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexa-fluoropropane (Mn 11,200 Da 1.80 mmol), bis(triphenylphosphine) nickel dichloride (1.35 mmol), sodium iodide (5.85 mmol), triphenylphosphine (18 mmol), and zinc (108 mmol). The mixture was dried under vacuum and then treated with 87 ml of N,N-dimethylacetamide and kept in the temperature range of 70-90°C. After 3 hours the mixture was diluted with 200 ml of V,V-dimethylacetamide and insoluble components removed by filtration. The filtrate was then added to 1.5 liters of methanol containing 10 vol% concentrated hydrochloric acid to precipitate the polymer. After collecting, the precipitate was dried to obtain 28.5 g of product having polyhydroxyl groups. 

Another cationic polymer, poly- -(4-aminobutyl)-L-glycolic) acid (PLAGA) has been shown to condense DNA efficiently and also to be less cytotoxic than PLL. PLAGA is biodegradable, not toxic to the cells, and enhances transfection in cultured cells (202). 

Biswas and Mazumdar [49, 50] reported a similar enhancement of thermal stability on metal ion incorporation for the poly-condensate PMDA-BP/BPA/M, (Fig. 2) with the following features of interest (1) With a typical metal ion incorporated in either PMDA-BP or PMDA-BPA, initial decomposition temperature of the metal-loaded polymers does not change significantly PMDA-BP (238 °C) PMDA-BPA (235 °C), PMDA-BP-Fe(III) (280 °C), PMDA-BPA-Fe(III) (290 °C), PMDA-BP-Cu(II) (265 °C), PMDA-BP-Ni(II) (265 °C), PMDA-BP-Ni(II) (263 °C), PMDA-BPA-Ni(II) (280 ° ). (2) With either PMDA-BP or -BPA, the effect of different metal ions on the stability is in the order Fe3+ > Ni2+ > Cu2+ (upto 4% decomposition) in the BPA complex, and upto 25% in the BP complex. (3) Beyond this temperature, the order in stability becomes same in either system Fe3+ > Cu2+ > Ni2+. 

Melt poly condensation is also the most popular method for other thermotropic condensation polymers, including the polyazomethines where the reaction between aromatic aldehydes or ketones and primary amines with elimination of water leads to azomethine (Schiffs base) formation 48). 

Cationic polymer is also frequently examined to increase the potential of a gene drug. Large molecular weight cationic polymers can condense pDNA more efficiently than cationic liposomes. They include poly-L-lysine (PLL), poly-L-omithine, polyethyleneimine (PEI), chitosan, starburst dendrimer and various novel synthetic polymers. These polymers can enhance the cellular uptake of pDNA by nonspecific adsorptive endocytosis. 

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