Condensation polymers polyamides

ETHYLENE We discussed ethylene production in an earlier boxed essay (Section 5 1) where it was pointed out that the output of the U S petrochemi cal industry exceeds 5 x 10 ° Ib/year Approximately 90% of this material is used for the preparation of four compounds (polyethylene ethylene oxide vinyl chloride and styrene) with polymerization to poly ethylene accounting for half the total Both vinyl chloride and styrene are polymerized to give poly(vinyl chloride) and polystyrene respectively (see Table 6 5) Ethylene oxide is a starting material for the preparation of ethylene glycol for use as an an tifreeze in automobile radiators and in the produc tion of polyester fibers (see the boxed essay Condensation Polymers Polyamides and Polyesters in Chapter 20)... 

Nylon-6, [-(CH2)5-NH-C(=0)-]n belongs to the important class of polyamide condensation polymers. Polyamides are characterised by the presence of secondary amides —NHCO— in the backbone so hydrogen bonds are fonned between neighbouring chains. These strongly influence the mechanical properties of the polymer. Nylon-6 has two crystalline forms, a and y, which differ in the conformation of the backbone in the a form it is planar and in the y form it is helical. INS studies [27] of both forms of nylon-6, including oriented samples, have been made. The amide V, VI and VII modes that involve out of plane deformations of the -NHCO- group were shown to depend on the crystal form. The assignments were supported by DFT calculations on model compounds. 

Preparation Methods for Condensation Polymers Polyamides Polyesters Polyimides Polyurethanes Polyureas Polycarbonates Polyanhydrides... 

The leader of DuPont s effort was Wallace H Carothers who reasoned that he could reproduce the properties of silk by constructing a polymer chain held together as is silk by amide bonds The neces sary amide bonds were formed by heating a dicar boxylic acid with a diamine Hexanedioic acid adipic acid) and 1 6 hexanediamme hexamethylenedi-amine) react to give a salt that when heated gives a polyamide called nylon 66 The amide bonds form by a condensation reaction and nylon 66 is an example of a condensation polymer... 

Polyesters are a second class of condensation polymers and the principles behind their synthesis parallel those of polyamides Ester formation between the functional groups of a dicarboxylic acid and a diol... 

Condensation polymer (Section 20 17) Polymer m which the bonds that connect the monomers are formed by condensa tion reactions Typical condensation polymers include poly esters and polyamides... 

Condensation polymers such as polyesters and polyamides are especially well suited to this method of molecular weight determination. For one thing, the molecular weight of these polymers is usually less than for addition polymers. Even more pertinent to the method is the fact that the chain ends in these molecules consist of unreacted functional groups. Using polyamides as an example, we can readily account for the following possibilities ... 

Comparable but equally specific considerations must be applied to other condensation polymer systems. The following example is an illustration of the application of these ideas to the molecular weight of polyamides. 

Heteroatom Chain Backbone Polymers. This class of polymers includes polyesters, which have been widely studied from the initial period of research on biodegradable polymers, polyamides, polyethers, polyacetals, and other condensation polymers. Their linkages are quite frequendy found in nature and these polymers are more likely to biodegrade than hydrocarbon-based polymers. 

In Chapter 25 it will be shown that polyesters, condensation polymers containing the repeat -COO- group, may be produced by reactions analogous to the methods used to produce polyamides as summarised in the first section of this chapter. It... 

STRATEGY (a) Look at the backbone of the polymer, the long chain to which the other groups are attached. If the atoms are all carbon atoms, then the compound is an addition polymer. If ester groups are present in the backbone, then the polymer is a polyester and the monomers will be an acid and an alcohol. If the backbone contains amide groups, then the polymer is a polyamide and the monomers will be an acid and an amine, (b) If the monomer is an alkene or alkvne, then the monomers will add to one another a Tr-bond will be replaced by new cr-bonds between the monomers. If the monomers are an add and an alcohol or amine, then a condensation polymer forms with the loss of a molecule of water. 

Most condensation polymers are formed by the reaction of a carboxylic acid with an alcohol to form a polyester or with an amine to form a polyamide. 

The name Nylon was given by the Du Pont company of America to their first synthetic condensation polymer formed by the reaction of difuncfional acids with difuncfional amines, ft had been made as part of the fundamental programme of W. H. Carothers to investigate the whole topic of polymerisation. The term has gradually been extended to other related polymers. These materials are strictly polyamides, but this term includes that otherwise distinct class of natural macromolecules, the proteins. The term nylon is retained for its usefulness in distinguishing synthetic polyamides from the broader class of such polymers. 

The most common form of step growth polymerization is condensation polymerization. Condensation polymers are generally formed from simple reactions involving two different monomers. The monomers are difunctional, having a chemically reactive group on each end of their molecules. Examples of condensation polymerization are the formation of nylon 66, a polyamide, and of poly(ethylene terephthalate), a polyester. Because condensation poly-... 

In 1929 Carothers proposed a generally useful differentiation between two broad classes of polymers condensation polymers in which the molecular formula of the structural unit (or units) lacks certain atoms present in the monomer from which it is formed, or to which it may be degraded by chemical means, and addition polymers, in which the molecular formula of the structural unit (or units) is identical with that of the monomer from which the polymer is derived. Condensation polymers may be formed from monomers bearing two or more reactive groups of such a character that they may condense intermolecu-larly with the elimination of a by-product, often water. The polyamides and polyesters referred to above afford prime examples of condensation polymers. The formation of a polyester from a suitable hydroxy acid takes place as follows ... 

Similar interchange processes may occur in other condensation polymers under suitable conditions. There is ample evidence in the literature on polyamides, and on monomeric amides as well, for the occurrence of the amine-amide interchange reaction (II)... 

Although polymers in-service are required to be resistant toward hydrolysis and solar degradation, for polymer deformulation purposes hydrolysis is an asset. Highly crystalline materials such as compounded polyamides are difficult to extract. For such materials hydrolysis or other forms of chemolysis render additives accessible for analysis. Polymers, which may profitably be depolymerised into their monomers by hydrolysis include PET, PBT, PC, PU, PES, POM, PA and others. Hydrolysis occurs when moisture causes chain scissions to occur within the molecule. In polyesters, chain scissions take place at the ester linkages (R-CO-O-R ), which causes a reduction in molecular weight as well as in mechanical properties. Polyesters show their susceptibility to hydrolysis with dramatic shifts in molecular weight distribution. Apart from access to the additives fraction, hydrolysis also facilitates molecular characterisation of the polymer. In this context, it is noticed that condensation polymers (polyesters, -amides, -ethers, -carbonates, -urethanes) have also been studied much... 

One previous synthesis of ferrocene-containing condensation polymers via interfacial methods at room temperature has been reported by Knobloch and Rauscher, who formed low molecular weight polyamides and polyesters by reacting l,l -bis(chloro-formyl)ferrocene with various diamines and diols. Further, Carraher and co-workers have utilized interfacial techniques in the formation of other types of organometallic polymers. 

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 end group functionality of condensation polymers is typically defined by the monomers employed to make these materials. An example is shown below for a common polyamide polymer, namely nylon (see Figure 2). These polymers... 

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