Monomers diene

Of the major metliods for living radical polymerization, NMP appears the most successful for polymerization of the diene monomers. There are a number of reports on the use of NMP of diene monomers (B, I) with TEMPO, 86 and other nitroxides. High reaction temperatures (120-135 C) were employed in all cases. The ratio of 1,2- 1,4-cis 1,4-trans structures obtained is similar to that observed in conventional radical polymerization (Section 4.3.2). 

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K. Stueben, ia E. C. Leonard, ed.. Vinyl and Diene Monomers, Part I, High Polymers Series Vol. XXIV, Wiley-Interscience, New York, 1970, Chapt. l,p. 181. 

The use of alkaU metals for anionic polymerization of diene monomers is primarily of historical interest. A patent disclosure issued in 1911 (16) detailed the use of metallic sodium to polymerize isoprene and other dienes. Independentiy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-l,3-butadiene was described (17). Interest in alkaU metal-initiated polymerization of 1,3-dienes culminated in the discovery (18) at Firestone Tire and Rubber Co. that polymerization of neat isoprene with lithium dispersion produced high i7j -l,4-polyisoprene, similar in stmcture and properties to Hevea natural mbber (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE Rubber, natural). 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

Soluble analogues of these difunctional initiators have been prepared either by addition of small amounts of weakly basic additives such as triethylamine (73) or anisole (74) which have relatively minor effects on diene microstmcture (37). Another method to solubilize these initiators is to use a seeding technique, whereby small amounts of diene monomer are added to form a hydrocarbon-soluble, oligomeric dilithium-initiating species (69,75). 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

At this point in the process, thermoplastic and chlorosulfonated polyethylene (CSPE) membranes are complete and are ready for packaging. In the case of ethylene—propylene—diene monomer (EPDM), the curing step occurs before the membrane is ready for packaging. The curing process is accomphshed by placing the membrane in a large vulcanizer where the material is heated under pressure to complete the cure. 

Fig. 1. SAE J200 Classification system for ASTM No. 3 oil where in volume swell nr = no requirement. EPDM is ethylene—propylene—diene monomer HR, butyl mbber SBR, styrene—butadiene mbber NR, natural mbber VMQ, methyl vinyl siUcone CR, chloroprene FKM, fluoroelastomer FVMQ, fluorovinyl methyl siUcone ACM, acryUc elastomers HSN, hydrogenated nitrile ECO, epichlorohydrin and NBR, nitrile mbber.

NR = natural mbbei SBR = styiene—butadiene mbbei EPDM = ethylene—piopjiene—diene monomer CSM = chlorosulfonated polyethylene and PE = polyethylene. 

Ethylene—Propylene Rubber. Ethylene and propjiene copolymerize to produce a wide range of elastomeric and thermoplastic products. Often a third monomer such dicyclopentadiene, hexadiene, or ethylene norbomene is incorporated at 2—12% into the polymer backbone and leads to the designation ethylene—propylene—diene monomer (EPDM) mbber (see Elastomers, synthetic-ethylene-propylene-diene rubber). The third monomer introduces sites of unsaturation that allow vulcanization by conventional sulfur cures. At high levels of third monomer it is possible to achieve cure rates that are equivalent to conventional mbbers such as SBR and PBD. Ethylene—propylene mbber (EPR) requires peroxide vulcanization. 

The reversible addition of sodium bisulfite to carbonyl groups is used ia the purification of aldehydes. Sodium bisulfite also is employed ia polymer and synthetic fiber manufacture ia several ways. In free-radical polymerization of vinyl and diene monomers, sodium bisulfite or metabisulfite is frequentiy used as the reduciag component of a so-called redox initiator (see Initiators). Sodium bisulfite is also used as a color preventative and is added as such during the coagulation of crepe mbber. 

Elastomers. Ethylene—propylene terpolymer (diene monomer) elastomers (EPDM) use a variety of third monomers during polymerization (see Elastomers, ethyiene-propylene-diene rubber). Ethyhdenenorbomene (ENB) is the most important of these monomers and requires dicyclopentadiene as a precursor. ENB is synthesized in a two step preparation, ie, a Diels-Alder reaction of CPD (via cracking of DCPD) with butadiene to yield 5-vinylbicyclo[2.2.1]-hept-2-ene [3048-64-4] (7) where the external double bond is then isomerized catalyticaHy toward the ring yielding 5-ethyhdenebicyclo[2.2.1]-hept-2-ene [16219-75-3] (ENB) (8) (60). 

EPM can be vulcanised radically by means of peroxides. A small amount of built-in third diene monomer in EPDM permits conventional vulcanisa tion with sulfur at the pendent sites of unsaturation. 

In consequence ethylene-propylene rubbers were introduced with a small amount (3-8%) of a third, diene, monomer which provided a cross-link site for accelerated sulphur vulcanisation. Such ethylene-propylene-diene monomer ternary copolymers are designated as EPDM rubbers. 

At one time it was widely expected that EPDM rubbers would become of significance in the tyre sector. For a variety of reasons but primarily because of the high cost of the diene monomers this expectation has not been realised. On the other hand these rubbers have become widely accepted as moderately heat-resisting materials with good weathering, oxygen and ozone resistance and they find extensive use in cars, domestic and industrial equipment. 

Table 11.17 Principal diene monomers used in manufacture...

Whilst the ASA materials are of European origin, the AES polymers have been developed in Japan and the US. The rubber used is an ethylene-propylene terpolymer rubber of the EPDM type (see Chapter 11) which has a small amount of a diene monomer in the polymerisation recipe. The residual double bonds that exist in the polymer are important in enabling grafting with styrene and acrylonitrile. The blends are claimed to exhibit very good weathering resistance but to be otherwise similar to ABS. 

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