Crosslinked polymer Crosslinking

Film stability is a primary concern for applications. LB films of photopoly-merizable polymeric amphiphiles can be made to crosslink under UV radiation to greatly enhance their thermal stability while retaining the ordered layered structure [178]. Low-molecular-weight perfluoropolyethers are important industrial lubricants for computer disk heads. These small polymers attached to a polar head form continuous films of uniform thickness on LB deposi-... 

A different class, in between polymer lattices and polymer solutions, is tliat of microgels, consisting of weakly crosslinked polymer networks. Just as for polymer solutions, small changes in tire solvency conditions may have large... 

Next let us consider the differences in molecular architecture between polymers which exclusively display viscous flow and those which display a purely elastic response. To attribute the entire effect to molecular structure we assume the polymers are compared at the same temperature. Crosslinking between different chains is the structural feature responsible for elastic response in polymer samples. If the crosslinking is totally effective, we can regard the entire sample as one giant molecule, since the entire volume is permeated by a continuous network of chains. This result was anticipated in the discussion of the Bueche theory for chain entanglements in the last chapter, when we observed that viscosity would be infinite with entanglements if there were no slippage between chains. 

Stretching a polymer sample tends to orient chain segments and thereby facilitate crystallization. The incorporation of different polymer chains into small patches of crystallinity is equivalent to additional crosslinking and changes the modulus accordingly. Likewise, the presence of finely subdivided solid particles, such as carbon black in rubber, reinforces the polymer in a way that imitates the effect of crystallites. Spontaneous crystal formation and reinforcement... 

A cross-linked polymer has a density of 0.94 g cm" at 25°C and a molecular weight between crosslinks of 28,000. The conformation of one bond in the middle of the molecule changes from trans to gauche, and the molecule opens up by 120°. In w-butane, the trans to gauche transformation requires about 3.3 kJ mol". Estimate a value for AH of stretching based on this model, and use the law of cosines to estimate the magnitude of the opening up that results. 

Suppose the un-cross-linked polymer chain has a molecular weight M which, upon crosslinking, is divided into subchains of molecular weight M, . This means that each subchain is a fraction of the original chain. Since the crosslink... 

In the rubbery plateau, a new impediment to movement must be overcome entanglements along the polymer chain. In discussing the effects of entanglements in Chap. 2, we compared them to crosslinks. Is it any surprise, then, that rubbery behavior similar to that shown by cross-linked elastomers characterizes this region ... 

An important application of Eq. (3.39) is the evaluation of M, . Flory et al.t measured the tensile force required for 100% elongation of synthetic rubber with variable crosslinking at 25°C. The molecular weight of the un-cross-linked polymer was 225,000, its density was 0.92 g cm , and the average molecular weight of a repeat unit was 68. Use Eq. (3.39) to estimate M. for each of the following samples and compare the calculated value with that obtained from the known fraction of repeat units cross-linked ... 

Between T j, and Tg, depending on the regularity of the polymer and on the experimental conditions, this domain may be anything from almost 100% crystalline to 100% amorphous. The amorphous fraction, whatever its abundance, behaves like a supercooled liquid in this region. The presence of a certain degree of crystallinity mimics the effect of crosslinking with respect to the mechanical behavior of a sample. 

From the point of view of technology, it is convenient to classify polymers as thermosetting and thermoplastic. The former set by chemical crosslinks introduced during fabrication and hence do not change appreciably in their deformability with changes in temperature. Thermoplastics, on the other hand, soften and/or melt on heating and can therefore be altered in shape by heating... 

In the last three chapters we have examined the mechanical properties of bulk polymers. Although the structure of individual molecules has not been our primary concern, we have sought to understand the influence of molecular properties on the mechanical behavior of polymeric materials. We have seen, for example, how the viscosity of a liquid polymer depends on the substituents along the chain backbone, how the elasticity depends on crosslinking, and how the crystallinity depends on the stereoregularity of the polymer. In the preceding chapters we took the existence of these polymers for granted and focused attention on their bulk behavior. In the next three chapters these priorities are reversed Our main concern is some of the reactions which produce polymers and the structures of the products formed. 

The presence of the unsaturated substituent along this polyester backbone gives this polymer crosslinking possibilities through a secondary reaction of the double bond. These polymers are used in paints, varnishes, and lacquers, where the ultimate cross-linked product results from the oxidation of the double bond as the coating cures. A cross-linked polyester could also result from reaction (5.J) without the unsaturated carboxylic acid, but the latter would produce a gel in which the entire reaction mass solidified and is not as well suited to coatings applications as the polymer that crosslinks upon drying. ... 

To some extent each of these objections is met by the presence of either chemical or crystallite crosslinking in the polymer. Another approach which complements the former is to incorporate rings into the backbone of the chemical chain. As an example, contrast the polyesters formed between ethylene glycol and either suberic or terephthaUc acid. Structures [V] and [VI], respectively, indicate the repeat units in these polymers ... 

Haward et al.t have reported some research in which a copolymer of styrene and hydroxyethylmethacrylate was cross-linked by hexamethylene diisocyanate. Draw the structural formula for a portion of this cross-linked polymer and indicate what part of the molecule is the result of a condensation reaction and what part results from addition polymerization. These authors indicate that the crosslinking reaction is carried out in sufficiently dilute solutions of copolymer that the crosslinking is primarily intramolecular rather than intermolecular. Explain the distinction between these two terms and why concentration affects the relative amounts of each. 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Under acidic conditions, furfuryl alcohol polymerizes to black polymers, which eventually become crosslinked and insoluble in the reaction medium. The reaction can be very violent and extreme care must be taken when furfuryl alcohol is mixed with any strong Lewis acid or Brn nstad acid. Copolymer resins are formed with phenoHc compounds, formaldehyde and/or other aldehydes. In dilute aqueous acid, the predominant reaction is a ring opening hydrolysis to form levulinic acid [123-76-2] (52). In acidic alcohoHc media, levulinic esters are formed. The mechanism for this unusual reaction in which the hydroxymethyl group of furfuryl alcohol is converted to the terminal methyl group of levulinic acid has recendy been elucidated (53). 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

Cycloahphatic diamines react with dicarboxyUc acids or their chlorides, dianhydrides, diisocyanates and di- (or poly-)epoxides as comonomers to form high molecular weight polyamides, polyimides, polyureas, and epoxies. Polymer property dependence on diamine stmcture is greater in the linear amorphous thermoplastic polyamides and elastomeric polyureas than in the highly crosslinked thermo set epoxies (2—4). 

The term epoxy is familiar to nonchemists because of the widespread use of epoxy glues and resins. These are crosslinked polyether thermoplastics made from a liquid resin which is typically a mixture of bisphenol A diglycidyl ether (70) and a polymer (71 Scheme 86). The liquid resin is cured or hardened to the final resin by mixing with a crosslinking reagent, which can be an acid, a di- or poly-alcohol, or a di- or poly-amine (Scheme 86). 

Polymer-based, synthetic ion-exchangers known as resins are available commercially in gel type or truly porous forms. Gel-type resins are not porous in the usual sense of the word, since their structure depends upon swelhng in the solvent in which they are immersed. Removal of the solvent usually results in a collapse of the three-dimensional structure, and no significant surface area or pore diameter can be defined by the ordinaiy techniques available for truly porous materials. In their swollen state, gel-type resins approximate a true molecular-scale solution. Thus, we can identify an internal porosity p only in terms of the equilibrium uptake of water or other liquid. When crosslinked polymers are used as the support matrix, the internal porosity so defined varies in inverse proportion to the degree of crosslinkiug, with swelhng and therefore porosity typically being more... 

Ion-exchange resins swell in water to an extent which depends on the amount of crosslinking in the polymer, so that columns should be prepared from the wet material by adding it as a suspension in water to a tube already partially filled with water. (This also avoids trapping air bubbles.) The exchange capacity of a resin is commonly expressed as mg equiv./mL of wet resin. This quantity is pH-dependent for weak-acid or weak-base resins but is constant at about 0.6-2 for most strong-acid or strong-base types. 

In the lightly cross-linked polymers (e.g. the vulcanised rubbers) the main purpose of cross-linking is to prevent the material deforming indefinitely under load. The chains can no longer slide past each other, and flow, in the usual sense of the word, is not possible without rupture of covalent bonds. Between the crosslinks, however, the molecular segments remain flexible. Thus under appropriate conditions of temperature the polymer mass may be rubbery or it may be rigid. It may also be capable of ciystallisation in both the unstressed and the stressed state. 

It may also be argued that plasticised PVC may be considered as a thermoplastic elastomer, with the polymer being fugitively cross-linked by hydrogen bonding via the plasticiser molecules. These materials were, however, dealt with extensively in Chapter 12 and will not be considered further here. The ionomers are also sometimes considered as thermoplastic elastomers but the commercial materials are considered in this book as thermoplastics. It should, however, be kept in mind that ionic cross-linking can, and has, been used to fugitively crosslink elastomeric materials. 

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