Rubber chain

The plateau region appears when the molecular weight exceeds Mc [(Mc)soln. for solutions], and is taken to be a direct indication of chain entanglement. Indeed the presence of a plateau may be a more reliable criterion than r 0 vs M behavior, especially in solutions of moderate concentration where viscosity may exhibit quite complex concentration and molecular weight behavior. It is postulated that when M greatly exceeds Mc, a temporary network structure exists due to rope-like interlooping of the chains. Rubber-like response to rapid deformations is obtained because the strands between coupling points can adjust rapidly, while considerably more time is required for entire molecules to slip around one another s contours and allow flow or the completion of stress relaxation. 

The corrqrlexity of the reaction heme conadered stems from the variety of radicals involved in the initiation and reinitiation steps (e. g., two different radical initiators, benzoyloxy and phenyl three different sites of attack in EPTM drains see Sect. 3.2.a), and in termination ste] vdiidr indude couplings between growing chains, rubber and solvent radicals. 

Nakajima, K., Watabe, H., and Nishi, T., Single polymer chain rubber elasticity investigated by atomic force microscopy. Polymer, 47, 2505-2510 (2006). 

The starting materials are long-chain rubbers. DIN 53001 covers the special terminology and definitions on rubbers and elastomers. ... 

When these compounds are chemically bonded to the rubber molecules, they are collectively known as abnormal groups. Based on the biosynthesis mechanism of other naturally occurring cw-polyisoprenes, there are at least two abnormal groups on the main-chain rubber molecule, namely the co-terminal i.e. initiating end) and a-terminal (terminating end) groups. 

The presence of epoxide groups on the main-chain rubber molecule was first inferred from a reduction in the molecular weight of the rubber after treating acid-hydrolysed natural rubber with periodic acid. " The amount of epoxide was later estimated by hydrogen bromide (HBr) titration and found to be in the range of 45 75mmol/kg of rubber, or 0.3-0.5% mol/mol of rubber. " ... 

Double carbon bond, e.g. ethylene there are two bonds between the carbon atoms. One is easy to break (unsaturated state), so that the molecule can join a polymer chain. Rubber, for example, has numerous ethylene bonds (see [13], p. 785, quoted in [16], p. 55 cf. [18], p. 240, footnote 42). 

As mentioned frequently the mechanical and optical response of molecules — and of their crystallites — is highly anisotropic. Depending on the property under consideration the carriers of the molecular anisotropy are the bond vectors (infrared dichroism), chain segments (optical and mechanical anisotropy), or the end-to-end vectors of chains (rubber elastic properties). For the representation of the ensuing macroscopic anisotropies one has to recognize, therefore, the molecular anisotropy and the orientation distribution of the anisotropic molecular units (Fig. 1.9.). Since these are essentially one-dimensional elements their distribution and orientation behavior can be treated as that of rods such a model had been used successfully to explain the optical anisotropy [78], and the anisotropies of thermal conductivity [79], thermal expansion or linear compressibility [80], and Young s modulus [59,... 

Synthetic carbon-chain rubbers (except butyl rubber) Polymers that can cross-link and degrade depenriing [Pg.81]

Diselenium dichloride acts as a solvent for selenium. Similarly disulphur dichloride is a solvent for sulphur and also many other covalent compounds, such as iodine. S Clj attacks rubber in such a way that sulphur atoms are introduced into the polymer chains of the rubber, so hardening it. This product is known as vulcanised rubber. The structure of these dichlorides is given below ... 

All the double bonds in rubber have the Z (or cis) con figuration A different polymer of isoprene called gutta-percha has shorter polymer chains and E (or trans) double bonds Gutta percha is a tough horn like substance once used as a material for golf ball covers ... 

Originally, vulcanization implied heating natural rubber with sulfur, but the term is now also employed for curing polymers. When sulfur is employed, sulfide and disulfide cross-links form between polymer chains. This provides sufficient rigidity to prevent plastic flow. Plastic flow is a process in which coiled polymers slip past each other under an external deforming force when the force is released, the polymer chains do not completely return to their original positions. 

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... 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Rubber processed in latex form accounts for about 10% of new mbber consumption. Rubber latex is a Hquid, oil-in-water emulsion which is used to make foam or thin-walled mbber articles. The same accelerators and antidegradants used in dry mbber are used in latex, with longer-chain versions preferred for greater oil solubiHty. To prepare these and other additives for addition to latex, they must be predispersed in water and the surface of the powder or oil droplet coated with a surface-active agent to prevent destabilization (coagulation) of the latex. 

Rubber Chemicals. Sodium nitrite is an important raw material in the manufacture of mbber processing chemicals. Accelerators, retarders, antioxidants (qv), and antiozonants (qv) are the types of compounds made using sodium nitrite. Accelerators, eg, thiuram [137-26-8J, greatly increase the rate of vulcaniza tion and lead to marked improvement in mbber quaUty. Retarders, on the other hand (eg, /V-nitrosodiphenylamine [156-10-5]) delay the onset of vulcanization but do not inhibit the subsequent process rate. Antioxidants and antiozonants, sometimes referred to as antidegradants, serve to slow the rate of oxidation by acting as chain stoppers, transfer agents, and peroxide decomposers. A commonly used antioxidant is A/,AT-disubstituted Nphenylenediamine which can employ sodium nitrite in its manufacture (see Rubber chemicals). 

In order to "cure" or "vulcanize" an elastomer, ie, cross-link the macromolecular chains (Fig. 2), certain chemical ingredients are mixed or compounded with the mbber, depending on its nature (4,5). The mixing process depends on the type of elastomer a high viscosity type, eg, natural mbber, requires powerhil mixers (such as the Banbury type or mbber mills), while the more Hquid polymers can be handled by ordinary rotary mixers, etc (see Rubber... 

Ethylene—Propylene (Diene) Rubber. The age-resistant elastomers are based on polymer chains having a very low unsaturation, sufficient for sulfur vulcanization but low enough to reduce oxidative degradation. EPDM can be depicted by the following chain stmcture ... 

Silicone Rubber. These polymers are based on chains of siUcon rather than carbon atoms, and owe thek temperature properties to thek unique stmcture. The most common types of siUcone mbbers are specifically and almost exclusively the polysdoxanes. The Si—O—Si bonds can rotate much more freely than the C—C bond, or even the C—O bond, so the siUcone chain is much more flexible and less affected by temperature (see Silicon COMPOUNDS, silicones). 

Halogenated Butyl Rubber. Halogenation at the isoprene site ia butyl mbber proceeds by a halonium ion mechanism leading to a double-bond shift and formation of an exomethylene alkyl haUde. Both chlorinated and brominated mbber show the predominate stmcture (1) (>80%), by nmr, as described eadier (33,34). Halogenation of the unsaturation has no apparent effect on the isobutylene backbone chains. Cross-linked samples do not crystallize on extension due to the chain irregularities introduced by the halogenated isoprene units. 

Polymerization processes are characterized by extremes. Industrial products are mixtures with molecular weights of lO" to 10. In a particular polymerization of styrene the viscosity increased by a fac tor of lO " as conversion went from 0 to 60 percent. The adiabatic reaction temperature for complete polymerization of ethylene is 1,800 K (3,240 R). Heat transfer coefficients in stirred tanks with high viscosities can be as low as 25 W/(m °C) (16.2 Btu/[h fH °F]). Reaction times for butadiene-styrene rubbers are 8 to 12 h polyethylene molecules continue to grow lor 30 min whereas ethyl acrylate in 20% emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within hmits. Initiators of the chain reactions have concentration of 10" g mol/L so they are highly sensitive to poisons and impurities. 

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