Polymers, cross-linked

Suppose a monomer A (functionality 2) is mixed with a small proportion of monomer B (functionality 4) then, assuming the conditions are correct, a cross-linked network will be produced. Four linear chains of A will meet at each B cross-link. For example, suppose styrene (functionality 2) 

6 Monomer A (functionality 2) yields a linear homopolymer when polymerized, but when polymerized with a small amount of monomer B (functionality 4) it yiMs a aoss-linked copolymer. 

The entire network will consist of chains of A units meeting at B aoss-Unks as indicated in Hgure 1.6. The proportion of B will, of course, determine the tightness of the cross-link network. The polymerization of other 

We are interested in the application of porous polymers for the preparation of adsorbents [191,192], ion exchangers [193,194], and membranes [60,198,199]. For these applications, cross-linked polymers are fundamentally applied. 

The Physical Chemistry of Materials Energy and Environmental Applications 

More concretely, we are interested in highly cross-linked, permanently porous polymers. These materials, which have a permanent porous structure produced during their synthesis and preserved in the dry state [203], are employed in a broad variety of applications [204] as adsorbents and ion exchangers [191-194], 

The inner porous morphology of these resins is distinguished by interconnected channels that form a porous network, which pervades the rigid, significantly cross-linked polymer matrix [205], These materials are often synthesized by suspension polymerization [206], where a polymerization mixture which includes a cross-linking monomer, a functional comonomer or comonomer, an initiator, and a porogenic agent is polymerized. 

As common examples of monomers used for the production of resins, methacrylate and styrene can be mentioned, where the cross-linkers are ethylene dimethacrylate (EDMA) or divinyl benzene (DVB), respectively [205], The most important resins of this type are the poly(styrene-divinyl benzene) type or Amberlite resins, as well as the Wofatit and Lewatit [192] types. These materials have been widely applied as adsorbents [191,192,207] and as ion exchangers [193,194,208], 

As indicated above, multifunctional monomers, instead of merely forming branches, can link main chains together to such an extent that the molecules are transformed into network type structures, known as cross-linked polymers, as shown in Fig. 3.3. This is especially likely if one of the monomers has a functionality of four, such as divinylbenzene. These cross-linked networks can be two-dimensional, but most often are three-dimensional. 

The vast majority of polymers used in packaging are thermoplastics, and most have a linear or nearly linear structure. Important packaging polymers with a branched structure include low density polyethylene and ethylene vinyl acetate. 

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Note that in the compound (CH3)2Si(OH)2 the silicon atom can hold two OH groups, unlike carbon. It is this property that makes the existence of silicones possible. By variation of the compounds and conditions of hydrolysis, straight chains, rings and cross-linked polymers are obtained, for example ... 

Two classes of micron-sized stationary phases have been encountered in this section silica particles and cross-linked polymer resin beads. Both materials are porous, with pore sizes ranging from approximately 50 to 4000 A for silica particles and from 50 to 1,000,000 A for divinylbenzene cross-linked polystyrene resins. In size-exclusion chromatography, also called molecular-exclusion or gel-permeation chromatography, separation is based on the solute s ability to enter into the pores of the column packing. Smaller solutes spend proportionally more time within the pores and, consequently, take longer to elute from the column. 

In a cross-linked polymer, the junction units are different kinds of monomers than the chain repeat units, so these molecules might be considered to be still another comonomer. While the chemical reactions which yield such cross-linked substances are copolymerizations, the products are described as cross-linked rather than as copolymers. In this instance, the behavior due to cross-linking takes precedence over the presence of an additional type of monomer in the structure. 

Some commercially important cross-linked polymers go virtually without names. These are heavily and randomly cross-linked polymers which are insoluble and infusible and therefore widely used in the manufacture of such molded items as automobile and household appliance parts. These materials are called resins and, at best, are named by specifying the monomers which go into their production. Often even this information is sketchy. Examples of this situation are provided by phenol-formaldehyde and urea-formaldehyde resins, for which typical structures are given by structures [IV] and [V], respectively ... 

Polymers with the mechanical and chemical properties we have discussed in this section are called elastomers. In the next couple of sections we shall examine the thermodynamic basis for elasticity and then apply these ideas to cross-linked polymer networks. 

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... 

The four regions of behavior shown by the polymers in Fig. 3.9 are fairly typical of high molecular weight un-cross-linked polymers. Let us examine the four regions of behavior, this time in terms of what is happening at the molecular level ... 

In addition to the set of Voigt elements, a Maxwell element could also be included in the model. The effect is to include a contribution given by Eq. (3.69) to the calculated compliance. This long time flow contribution to the compliance is exactly what we observe for non-cross-linked polymers in Fig. 3.12. 

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 ... 

It has been hypothesized that cross-linked polymers would have better mechanical properties if interchain bridges were located at the ends rather than the center of chains. To test this, low molecular weight polyesters were synthesizedf... 

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. 

We might be tempted to equate the forces given by Eqs. (9.61) and (3.38) and solve for a from the resulting expression. However, Eq. (3.38) is not suitable for the present problem, since it was derived for a cross-linked polymer stretched in one direction with no volume change. We are concerned with a single, un-cross-linked molecule whose volume changes in a spherically symmetrical way. The precursor to Eq. (3.36) in a more general derivation than that presented in Chap. 3 is... 

Fig. 25. Schematic representation of imprinting (a) cross-linking polymerization ia the presence of a template (T) to obtain cavities of specific shape and a defined spatial arrangement of functional groups (binding sites. A—C) (b) cross-linked polymer prepared from the template monomer and ethylene...

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

Chemical Stabilization. The chemistry of the system determines both the rate at which the polymer phase is formed and the rate at which it changes from a viscous fluid to a dimensionally stable cross-linked polymer phase. It also governs the rate at which the blowing agent is activated, whether it is due to temperature rise or to insolubilization in the Hquid phase. 

Cross-linked macromolecular gels have been prepared by Eriedel-Crafts cross-linking of polystyrene with a dihaloaromatic compound, or Eriedel-Crafts cross-linking of styrene—chloroalkyl styrene copolymers. These polymers in their sulfonated form have found use as thermal stabilizers, especially for use in drilling fluids (193). Cross-linking polymers with good heat resistance were also prepared by Eriedel-Crafts reaction of diacid haUdes with haloaryl ethers (194). 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

Polycarbonates. Currently, all audio CDs (CD-AD), all CD-ROM, and the biggest fraction of substrate disks for WORM and EOD worldwide are manufactured from a modified bisphenol A—polycarbonate (BPA-PC) (3). In 1991, some 1.3 x 10 compact disks were produced, equivalent to an annual amount of about 35,000 t BPA-PC. WORM and EOD disks are manufactured mainly from BPA-PC for sizes of 5.25 in. and below, and glass for larger form factors (eg, 12 in.), partially also from BPA-PC, and in some cases from aluminum or from cross-linked polymers (epoxy resins) (190). 

For substrates of WORM and EOD(PCR) disks the industry in the future wants polymers that have a markedly improved resistance to heat softening compared to BPA-PC and, if possible, a lower water absorption and lower birefringence, but otherwise maintain the good characteristics in toughness, production, and cost (194). This goal is being approached in different ways further modification of BPA-PC, newly developed polymers, improvement of the processing characteristics of uv-curable cross-linked polymers, and development of special copolymers and polymer blends, eg,... 

Table 10 compares the values of different experimental uv-curable cross-linked polymers with those of BPA-PC for the most important properties of substrate materials (220). In spite of this remarkable progress in the development of fast curing cross-linked polymers, BPA-PC and, to a small extent, glass are still the materials of choice for substrates for optical data storage. 

Duromers (cross-linked polymers) based on highly reactive resins with short setting times. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Fig. 26. Qualitative compatison of substrate materials for optical disks (187) An = birefringence IS = impact strength BM = bending modulus HDT = heat distortion temperature Met = metallizability WA = water absorption Proc = processibility. The materials are bisphenol A—polycarbonate (BPA-PC), copolymer (20 80) of BPA-PC and trimethylcyclohexane—polycarbonate (TMC-PC), poly(methyl methacrylate) (PMMA), uv-curable cross-linked polymer (uv-DM), cycHc polyolefins (CPO), and, for comparison, glass.

P—H is a polymei with covalently attached hydrogen, L is the initiating radical, and P—P is a cross-linked polymer. Cross-linking is a commercially... 

Membranes made by interfacial polymerization have a dense, highly cross-linked interfacial polymer layer formed on the surface of the support membrane at the interface of the two solutions. A less cross-linked, more permeable hydrogel layer forms under this surface layer and fills the pores of the support membrane. Because the dense cross-linked polymer layer can only form at the interface, it is extremely thin, on the order of 0.1 p.m or less, and the permeation flux is high. Because the polymer is highly cross-linked, its selectivity is also high. The first reverse osmosis membranes made this way were 5—10 times less salt-permeable than the best membranes with comparable water fluxes made by other techniques. 

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