Cross-links, in polymers

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Dimercapto-l,3,4-thiadiazole derivatives, accelerated by amines, are used to cross-link chlorinated polyethylene. Polyisobutylene containing brominated i ra-methylstyrene cure functionahty can be cross-linked in polymer blends with dimercapto-1,3,4-thiadiazole derivatives accelerated with thiuram disulfides. Trithiocyanuric acid is suggested for use in polyacrylates containing a chlorine cure site and in epichlorohydrin mbbers. 

Fig. 6.2. How Young s modulus increases witl) increasing density of covalent cross-links in polymers, including rubbers above tbe glass temperature. Below To, be modulus of rubbers increases markedly because tbe Van der Waals bonds take hold. Above Tq they melt, and the modulus drops.

Bases like water or ammonia [33] have been found to enhance cross-linking in polymers like PP and ethylene-propylene elastomers. The mechanism of action of various indirect cross-link promoters is reported in the literature [77-81]. 

Explain the role of the photochemical reactions of carbonyl compounds in the photoinitiated polymerisation of vinyl monomers and cross-linking in polymers. 

In practice, the emission anisotropy of luminescent molecules in solution is considered to be proportional to the viscosity of the medium, except in the case where structural reasons arise, for instance helix-coil transition, cross-linking in polymer systems etc... (18-21). Therefore, if there is only the effect in viscosity, the mobility of the marker must be higher in the case of the compact complex system which have a very low viscosity. 

A. Led with. Photochemical cross-linking in polymer-based systems, Dev. Polym. 3, 55 (1982). W. L. Dining, Polymerization of unsaturated compounds by photocycloaddition reactions, Chem. Revs. 83, 1 (1983). 

The effects of these parameters and cross-linking in polymer cable insulations, aged in radiation and thermal enviromnents, were investigated. The results were then used to recommend standards for an OIT methodology suited for practical use, including the nuclear power industiy. Techniques to estimate error in (O.l.T.) thermograms interpretation and reproducibility were also developed (Mason and Reynolds 1997). 

Although not true topological knots, the cross-links in polymer entanglements, which behave as gels on sufficiently short timescales, are also topological in nature. 

Table 3. Radiation Chemical Yields of Chain Scission and Cross-linking in Polymers Irradiated in Inert Atmosphere ...

A novel approach for solid-state NMR characterisation of cross-linking in polymer blends from the analysis of polarisation transfer dynamics is... 

Used industrially to cross-link hydroxylic polymers, polyethyleneimine. Possesses some carcinogenic properties. Polyethyleneimine is a hygroscopic liquid used in paper manufacture to confer wet strength and in textiles, alkylated derivatives also form useful polymers. 

If the concentration of junction points is high enough, even branches will contain branches. Eventually a point is reached at which the amount of branching is so extensive that the polymer molecule becomes a giant three-dimensional network. When this condition is achieved, the molecule is said to be cross-linked. In this case, an entire macroscopic object may be considered to consist of essentially one molecule. The forces which give cohesiveness to such a body are covalent bonds, not intermolecular forces. Accordingly, the mechanical behavior of cross-linked bodies is much different from those without cross-linking. 

The physical properties of the final foam can be varied broadly by controlling the degree of cross-linking in the final polymer as well as the stmcture... 

Two other important commercial uses of initiators are in polymer cross-linking and polymer degradation. In a cross-linking reaction, atom abstraction, usually a hydrogen abstraction, occurs, followed by termination by coupling of two polymer radicals to form a covalent cross-link ... 

In the case of phenoHcs, it is possible to make linear thermoplastic polymers called novolaks, but this is done by reaction of less than one mole of formaldehyde with one mole of phenol the resulting resin has a large excess of free phenol. Usually in appHcation hexamethylene tetramine (HEXA) is added to the novolak. When heated, the HEXA breaks down into ammonia and formaldehyde and enters the reaction to form a light degree of cross-links in the final product. 

Solubility. Cross-linking eliminates polymer solubiUty. Crystallinity sometimes acts like cross-linking because it ties individual chains together, at least well below T. Thus, there are no solvents for linear polyethylene at room temperature, but as it is heated toward its (135°C), it dissolves in a variety of aUphatic, aromatic, and chlorinated hydrocarbons. A rough guide to solubiUty is that like dissolves like, ie, polar solvents tend to dissolve polar polymers and nonpolar solvent dissolve nonpolar polymers. 

Miscellaneous Curing Reactions. Other functional groups can react with the thiol terminal groups of the polysulfides to cross-link the polymer chains and build molecular weight. For example, aldehydes can form thioacetals and water. Organic and inorganic acids or esters can form thioesters. Active dienes such as diacrylates can add to the thiols (3). Examples of these have been mentioned in the Hterature, but none have achieved... 

For all three diallyl phthalate isomers, gelation occurs at nearly the same conversion DAP prepolymer contains fewer reactive allyl groups than the other isomeric prepolymers (36). More double bonds are lost by cyclisation in DAP polymerisation, but this does not affect gelation. The heat-distortion temperature of cross-linked DAP polymer is influenced by the initiator chosen and its concentration (37). Heat resistance is increased by electron beam irradiation. 

Multifunctional Hydroxy, Mercapto, and Amino Compounds. These are used to cross-link halogenated polymers. Depending on the labihty of the halogen, the cross-linking agents can be capped to reduce reactivity or used in combination with accelerators to increase the rate of reaction. Benzoyl capping is common with hydroxy and mercapto compounds forming the carbamate by reaction with one equivalent of carbon dioxide is used with diamines. 

Synthesis of Silicone Monomers and Intermediates. Another important reaction for the formation of Si—C bonds, in addition to the direct process and the Grignard reaction, is hydrosdylation (eq. 3), which is used for the formation of monomers for producing a wide range of organomodified sihcones and for cross-linking sihcone polymers (8,52—58). Formation of ether and ester bonds at sihcon is important for the manufacture of curable sihcone materials. Alcoholysis of the Si—Cl bond (eq. 4) is a method for forming silyl ethers. HCl removal is typically accomphshed by the addition of tertiary amines or by using NaOR in place of R OH to form NaCl. 

The mineral talc is extremely soft (Mohs hardness = 1), has good sHp, a density of 2.7 to 2.8 g/cm, and a refractive index of 1.58. It is relatively inert and nonreactive with conventional acids and bases. It is soluble in hydroduoric acid. Although it has a pH in water of 9.0 to 9.5, talc has Lewis acid sites on its surface and at elevated temperatures is a mild catalyst for oxidation, depolymerization, and cross-linking of polymers. 

Hyperbranched polyurethanes are constmcted using phenol-blocked trifunctional monomers in combination with 4-methylbenzyl alcohol for end capping (11). Polyurethane interpenetrating polymer networks (IPNs) are mixtures of two cross-linked polymer networks, prepared by latex blending, sequential polymerization, or simultaneous polymerization. IPNs have improved mechanical properties, as weU as thermal stabiHties, compared to the single cross-linked polymers. In pseudo-IPNs, only one of the involved polymers is cross-linked. Numerous polymers are involved in the formation of polyurethane-derived IPNs (12). 

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