Polychloroprene

Polychloroprene is the oldest synthetic rubber. It is produced by the polymerization of 2-chloro-1,3-butadiene in a water emulsion with potassium sulfate as a catalyst  

The product is a random polymer that is vulcanized with sulfur or with metal oxides (zinc oxide, magnesium oxide etc.). Vulcanization with sulfur is very slow, and an accelerator is usually required. 

Neoprene vulcanizates have a high tensile strength, excellent oil resistance (better than natural rubber), and heat resistance. 

Neoprene rubber could be used for tire production, but it is expensive. Major uses include cable coatings, mechanical goods, gaskets, conveyor belts, and cables. 

Polychloroprene is the polymer of 2-chloro-l,3 butadiene. Emulsion polymerization produces an almost entirely trans-1,4 polymer, which is highly crystalline. Less crystalline polychloroprenes are produced by incorporating several wt.% of 2,3-dichloro-l,3 butadiene into the polymer to break up crystalline sequences. 

Irradiation of carbon-black-reinforced polychloroprene compounds produced a maximum tensile strength of 20 MPa (2,900 psi) at a dose of 20 Mrad (200 kGy), which is a value obtained typically from chemically cured compounds. The addition of 20 phr of N,N -hexamethylene-bis methacrylamide as a prorad in the above compound produced a tensile strength of 18 MPa (2,610 psi) at a dose of 7 Mrad (70 kGy). Further addition of 6 phr of hexachlo-roethane caused the deterioration of the tensile strength by 50% at the 7 Mrad (70 kGy) dose.  

When irradiating a 1 1 blend of polychloroprene and poly(butadiene-acry-lonitrile) (NBR) reinforced by 50 phr furnace black and containing 5-15 phr of tetramethacrylate of bisglycerol phtalate, the product exhibited a tensile strength of 20 MPa (2,900 psi) at a dose of 15 Mrad (150 kGy) with values of elongation at break in the range of 420-480%. These values are equal to or better than those obtained from similar compounds cured chemically.  

Irradiation of polychloroprene latexes of two different structures, one containing some sulfur and having a lower degree of branching and the other a highly branched polymer, made by mercaptane modification, showed a 

Important processing methods vulcanization, dip coating, coating, sheeting, calendering, extrusion 

Typical fillers carbon black, zinc oxide, magnesium oxide in EMI shielding field silver plated aluminum, silver plated nickel, silver coated glass spheres, silver plated copper, silver, nickel and carbon black 

Typical concentration range carbon black - 20-40 wt%, zinc oxide - 3-4 wt%, magnesium oxide -2-3 wt%, calcium carbonate, clay silica - 10-70 wt% 

Auxiliary agents lubricants, surfactants, waxes, oils 

Special methods of incorporation processing history has an essential et fect on conductivity amount of shear imposed and mixing causes the fracture of secondary carbon aggregates increased temperature during mixing may preferentially form rubber-carbon bonds rather than the carbon-carbon bonds required for conductivity vulcanization temperature may affect recovery of broken connections between carbon-carbon bonds 

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ELASTOMERS,SYNTHETIC - POLYCHLOROPRENE] (Vol8) -thioglycolic acids in [THIOGLYCOLIC ACID] (Vol24)... 

The synthesis in 1928 of polychloroprene or Neoprene, which has found much use in high strength elastomeric adhesives. 

Most elastomers can be made iato either opea-ceUed or closed-ceUed materials. Natural mbber, SBR, nitrile mbber, polychloroprene, chlorosulfonated polyethylene, ethylene—propylene terpolymers, butyl mbbers, and polyacrylates have been successfuUy used (4,111,112). 

Latex mbber foams are generally prepared in slab or molded forms in the density range 64—128 kg/m (4—8 lbs/fT). Synthetic SBR latexes have replaced natural mbber latexes as the largest volume raw material for latex foam mbber. Other elastomers used in significant quantities are polychloroprene, nitrile mbbers, and synthetic i j -polyisoprene (115). 

Other Accelerators. Amine isophthalate and thiazolidine thione, which are used as alternatives to thioureas for cross-linking polychloroprene (Neoprene) and other chlorine-containing polymers, are also used as accelerators. A few free amines are used as accelerators of sulfur vulcanization these have high molecular weight to minimize volatility and workplace exposure. Several amines and amine salts are used to speed up the dimercapto thiadiazole cure of chlorinated polyethylene and polyacrylates. Phosphonium salts are used as accelerators for the bisphenol cure of fluorocarbon mbbers. 

Butyl polymers are about 8—10 times more resistant to air permeabiUty compared to natural mbber and have excellent resistance to heat and steam or water. This accounts for its use in gaskets and diaphragms for hot water and steam service. In addition, butyl mbber can be compounded to have low residence properties and has found use in high damping mounts for engines, motors, and similar devices. Halobutyl mbbers can be blended with natural mbber, polychloroprene, and EPDM to greatiy enhance theh permeabiUty resistance. 

Specialty Elastomers. Polychloroprene and polysulfide mbber were the first synthetic specialty elastomers discovered. Since theh invention in the 1930s the total number of classes of synthetic mbbers has grown to almost 30. The foUowing lists standard acronyms by the International Synthetic Rubber Producers (IISRP) and the American Society for Testing and Materials (ASTM) for several specialty elastomers. 

Chloroprene Elastomers. Polychloroprene is a polymer of 2-chloro-l,3-butadiene. The elastomer is largely composed of the trans isomer. There are two basic polymer types the W-type and the G-type. G-types are made by using a sulfur-modified process W-types use no sulfur modification. As a result, G-types possess excellent processing and dynamic properties, and tend to be used in V-belts. However, they have poorer aging properties than W-types. The W-types tend to be used in appHcations requiring better aging, such as roUs and mechanical goods (see Elastomers, SYNTHETIC-POLYCm.OROPRENE). 

Antidegradants. Amine-type antioxidants (qv) or antiozonants (qv) such as the phenylenediamines (ppd) can significantly decrease scorch time. This is particulady tme in metal oxide curing of polychloroprene or in cases where the ppd had suffered premature degradation prior to cure. 

Neoprenes. Of the synthetic latices, a type that can be processed similarly to natural mbber latex and is adaptable to dipped product manufacture, is neoprene (polychloroprene). Neoprene latices exhibit poor initial wet gel strength, particularly in coagulant dipped work, but the end products can be made with high gum tensile strength, oil and aUphatic solvent resistance, good aging properties, and flame resistance. There are several types of neoprene latex, available at moderately high (ca 50 wt %) and medium soHds content. Differences in composition between the types include the polymer s microstmcture, eg, gel or sol, the type of stablizer, and the total soHds content (Table 22). 

Physical Factors. Unsatuiated elastomers must be stretched for ozone cracking to occur. Elongations of 3—5% are generally sufficient. Crack growth studies (10—18) have shown that some minimum force, called the critical stress, rather than a minimum elongation is required for cracking to occur. Critical stress values are neady the same for most unsaturated mbbers. However, polychloroprene has a higher critical stress value than other diene mbbers, consistent with its better ozone resistance. It has been found that temperature, plasticization, and ozone concentration have httie effect on critical stress values. 

Processing ndProperties. Neoprene has a variety of uses, both in latex and dry mbber form. The uses of the latex for dipping and coating have already been indicated. The dry mbber can be handled in the usual equipment, ie, mbber mills and Banbury mixers, to prepare various compounds. In addition to its excellent solvent resistance, polychloroprene is also much more resistant to oxidation or ozone attack than natural mbber. It is also more resistant to chemicals and has the additional property of flame resistance from the chlorine atoms. It exhibits good resiUence at room temperature, but has poor low temperature properties (crystallization). An interesting feature is its high density (1.23) resulting from the presence of chlorine in the chain this increases the price on a volume basis. 

Labile Chlorine Containing Monomers. Chlorine is introduced in the acryhc elastomer chain by analogy to polychloroprene (19). The monomers are characterized by the simultaneous presence of a double bond available for polymerization with acrylates and a chlorine atom ready to react easily during the vulcanization step. The general formula is as follows where R is a group that might enhance the reactivity of the double bond and/or of the vicinal chlorine atom. 

Prior to butyl mbber, the known natural and synthetic elastomers had reactive sites at every monomer unit. Unlike natural mbber, polychloroprene, and polybutadiene, butyl mbber had widely spaced olefin sites with aHyUc hydrogens. This led to the principle of limited functionahty synthetic elastomers that was later appHed to other synthetic elastomers, eg, chlorosulfonated polyethylene, siUcone mbber, and ethylene—propylene terpolymers. 

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