Synthetic polymers condensation polymerization

Braided Synthetic Nonabsorbable Sutures. Braided synthetic nonabsorbable sutures are made by melt-spinning thermoplastic polymers into fine filaments (yams), and braiding them, with or without a core, to form multifilament sutures in a range of sizes. Nylon-6,6 [32131 -17-2] (7) is a polyamide produced by the condensation polymerization of adipic acid and 1,6-hexanediamine. 

Condensation polymers, which are also known as step growth polymers, are historically the oldest class of common synthetic polymers. Although superseded in terms of gross output by addition polymers, condensation polymers are still commonly used in a wide variety of applications examples include polyamides (nylons), polycarbonates, polyurethanes, and epoxy adhesives. Figure 1.9 outlines the basic reaction scheme for condensation polymerization. One or more different monomers can be incorporated into a condensation polymer. 

The early, independent work of Starks, Markosa and Brandstrom from ca. 1965-1969, brought into focus with Starks classical paper in 1971, showed PTC to be potent and versatile synthetic tool.[1-4] Since that time, the well-documented investigations of PTC have been massive and vigorous.[5-7] In polymer chemistry PTC was effectively exploited first in anionic addition polymerization and more recently has been extended to condensation polymerization.[5,8-9] However, until a very few years ago, the use of solid-liquid PTC systems in polycondensation has for the most part escaped this intensive scrutiny. Consequently, some time ago we began a rather broad study into the use of solid-liquid PTC to effect polycondensations.[10]... 

Nearly all synthetic polymers are synthesized by the polymerization or copolymerization of different "monomers." The chain growth process may involve the addition chain reactions of unsaturated small molecules, condensation reactions, or ringopening chain-coupling processes. In conventional polymer chemistry, the synthesis of a new polymer requires the use of a new monomer. This approach is often unsatisfactory for Inorganic systems, where relatively few monomers or cyclic oligomers can be Induced to polymerize, at least under conditions that have been studied to date. The main exception to this rule is the condensation-type growth that occurs with inorganic dl-hydroxy acids. 

Many naturally occurring and some synthetic polymers are produced by condensation reactions, many of which are described kinetically by the term stepwise polymerization. A high fractional conversion is required to form linear polymers such as polyesters, nylons. 

A high molecular weight organic compound, natural or synthetic, whose structure can be represented by a repeated small unit, the monomer (e.g., polyethylene, isoprene and cellulose). Synthetic polymers are formed by the addition or condensation polymerization of monomers. If two or more different monomers are involved, a copolymer is obtained. Some polymers can be rubbers and some can be plastics. Plastics which are also high polymers can include both natural, or synthetic products but exclude rubber whether natural or synthetic. At some stage in its manufacture every plastic is capable of flowing under heat and pressure into the desired final shape. 

The synthesis of optically active polymers is an important area in macromolecular science, as they have a wide variety of potential applications, including the preparation of CSPs [31-37]. Many of the optically active polymers with or without binding to silica gel were used as CSPs and commercialized [38]. These synthetic polymers are classified into three groups according to the methods of polymerization (1) addition polymers, including vinyl, aldehyde, isocyanide, and acetylene polymers, (2) condensation polymers consisting of polyamides and polyurethanes, and (3) cross-linked gels (template polymerization). The art of the chiral resolution on these polymer-based CSPs is described herein. 

Polymers are large molecules (macromolecules) that consist of one or two small molecules (monomers) joined to each other in long, often highly branched, chains in a process called polymerization. Both natural and synthetic polymers exist. Some examples of natural polymers are starch, cellulose, chitin (the material of which shells are made), nucleic acids, and proteins. Synthetic polymers, the subject of this chapter, include polyethylene, polypropylene, polystyrene, polyesters, polycarbonates, and polyurethanes. In their raw, unprocessed form, synthetic polymers are sometimes referred to as resins. Polymers are formed in two general ways by addition or by condensation. 

We focus our attention in this experiment on synthetic polymers and the basic mechanism by which some of them are formed. The two most important types of reactions that are employed in polymer manufacturing are the addition and condensation polymerization reactions. The first is represented by the polymerization of styrene and the second by the formation of nylon. 

Synthetic polymers are grouped into two categories addition polymers and condensation polymers. A condensation polymerization occurs when a polymer... 

Carbonaceous materials (CMs) are sometimes also named polymeric carbons. They are mostly prepared by thermal decomposition of organic precursors. One strategy is pyrolysis of gaseous or vaporized hydrocarbons at the surface of heated substrates, a second is heating (pyrolysis) of natural or synthetic polymers, both in an inert atmosphere. The latter is of special interest, and according to Miyabayashi et al. [374], precursors such as condensed polycyclic hydrocarbons, polymeric heterocyclic compounds, phenol-formaldehyde resins, polyacrylonitrile or polyphenylene are heated to 300-3000 °C for 0.15-20 h. Sometimes, a temperature/time profile is run. The temperature range must be divided into two domains, namely... 

Many important fibers, including cotton and wool, are naturally occurring polymers. The first commercially successful synthetic polymers were made not by polymerization reactions but through the chemical regeneration of the natural polymer cellulose, a condensation polymer of the sugar glucose that is made by plants ... 

The synthetic scheme used for the preparation of the LC polymers reported here involves the random copolymerization of both aromatic and aliphatic components as shown in Fig. 1. Both the diol and hydroquinone components can react with nearly equal probability with the diacid chloride component. We therefore have three factors which can contribute to inhomogeneity in this polymer system (i) the polydispersity of chain length expected in a condensation polymerization, (ii) the distribution of diol and hydroquinone components in the polymer chain, and (iii) the presence of methyl substituents and bromine substituents on the hydroquinone and terephthalate groups, respectively, means that many isomeric structures are also possible. 

Monomers can be joined by means of two principal methods to form polymers, and these methods are used as the broad basis for classification of synthetic polymers. The first of these, condensation, or step-growth polymerization, involves the use of functional group reactions such as esterification or amide formation to form polymers. When each of the molecules involved has only one functional group then the reaction between a carboxylic acid and an alcohol gives an ester (Eq. 20.3). In this equilibrium reaction water removal will help drive the reaction to the right. 

In contrast with the usually slow progress of condensation polymerization the second major classification, addition, or vinyl-type polymerizations, usually proceed very rapidly, so rapidly that they are referred to as chain reaction polymerizations. This method of producing synthetic polymers uses the potential dual functionality present in a carbon-carbon double bond. The process is initiated by the use of radical or charged initiator species to form new sigma bonds from the carbon-carbon double bonds of the monomer, to link the monomer units (Eq. 20.6). 

Addition polymerization is usually such a rapid process that only monomer and final polymer chains are present. Very little of the active material in the system is oligomeric, that is, consisting of only a small number of linked monomer units en route to polymer, at any one point in time. Also, in addition polymerization the whole monomer molecule adds to form polymer. No small molecule is lost in the process. Further details of the polymerization processes involved and the structural properties of the products obtained from addition polymerization are discussed in Chaps. 22 and 23. This chapter will focus on the background theory of synthetic polymers, and condensation, or step-growth, polymerization. 

Several of the most effective polymeric delivery systems were polyamidoamine den-drimers (220) and polyethyleneimines (PEI) (221). Being non-biodegradable, these synthetic polymers posed a potential toxicity to cell therefore, biodegradable polypeptides like PLL and protamine were used for condensation and delivery of gene, but they had limited efficacy in transfection (222, 223). They were usually used with cationic lipids to obtain enhanced transfection activity (178,201). Among the biodegradable polymers, chitosan... 

Synthetic polymers are used in a number of areas of life and range from the nylon used in various articles of clothing to the polyvinyl chloride (PVC) used in plumbing and other applications. Synthetic polymerization of organic monomers can take place by addition polymerization or by step-growth (condensation) polymerization. Polystyrene is a common product of addition polymerization, and nylon is a common product of step-growth polymerization. 

Many efforts have been made to base polymers on furfural made from pentoses.159 The polymers may be useful, but tend to have lower thermal stability than the usual synthetic polymers. Polyesters based on furfural were mentioned earlier. The acid-catalyzed polymerization of furfuryl alcohol is used in foundry cores.160 Furfural has been condensed with cardanol (m-pentadecadienylphenol) from cashew nut shell oil in the presence of other phenols to produce polymeric resins.161 Cardanol and hydrogenated cardanol have been polymerized with horseradish peroxidase to soluble polymers in up to 85% yield.162 Plasticizers that are effective in polyvinyl chloride, such as (12.31), have been made from furfural.163... 

Stepwise Polymerization. Although condensation polymers account for only about one-fourth of synthetic polymers (bulkwise), most natural polymers are of the condensation type. As shown by Carothers in the 1930s 2, ), the chemistry of condensation polymerizations is essentially the same as classic condensation reactions that result in the synthesis of monomeric amides, urethanes, esters, etc. the principle difference is that the reactants employed for polymer formation are bifunctional (or higher) instead of monofunctional. Although more complicated situations can occur, we will consider only the kinetics of simple polyesterification. The kinetics of most other common condensations follow an analogous pathway. 

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