1.4- Hexadiene, copolymers

Reactivity ratios for 1-hexene (M ) with 5-methyl-1,4-hexadiene CM2) copolymerization at 30 c in hexane solvent using a Et2AlCl/6-TiCl3 AA catalyst system (Al/Ti atomic ratio s 1.5) were determined. The compositions of copolymers were measured by 300 MHz 1H-NMR spectroscopy. The reactivity ratios, calculated by the Tidwell-Mortimer method, were 1.1 + 0.2 for each of the two monomers. 

We showed (7) earlier that copolymers of higher a-olefins, particularly 1-hexene, with 5-methyl-1,4-hexadiene can be sulfur-cured readily and that they contain unsaturation approximating the level of the methylhexadiene charged. In view of this and the excellent durability (8) during flexing exhibited by vulcanizates of such copolymers, we were interested in determining the copolymer structure and the reactivity ratios of 1-hexene and 5-methyl-l,4-hexadiene during copolymerization. 

The NMR spectrum of the copolymer prepared from an equimolar mixture of the monomers is shown in Figure 10. In this spectrum, five well separated regions of NMR peaks were observed. The assignments of the peaks (Table III) were made by using the existing spectral information on homopolymers of 1-hexene and 5-methyl-1,4-hexadiene as well as the intensity variations among the copolymers with different monomer charge ratios. 

Figure 10. 300 MHz IH-NMR spectrum of a deuterobenzene solution of an equimolar copolymer of 5-methyl-l,4-hexadiene and 1-hexene prepared with a EttAlCl/ S-TiCl, catalyst at 0°C in pentane solvent.

MHz - H-tWR SPECTRAL DATA OF AN EQUIMOLAR COPOLYMER OF 1-HEXENE AND 5-METHYL-1,4-HEXADIENE... 

COPOLYMER COMPOSITION vs MONOMER FEED COMPOSITION FOR 1-HEXENE/5-CH3-l,4-HEXADIENE COPOLYMERIZATIONS... 

Cyclopolymerization of Nonconjugated Dienes. Cyclopolymerization is an addition polymerization that leads to introduction of cyclic structures into the main chain of the polymer. Nonconjugated dienes are the most deeply studied monomers for cyclopolymerization and for cyclocopolymerizations with alkene monomers 66 In general, (substituted and unsubstituted) dienes with double bonds that are linked by less than two or more than four atoms cannot undergo efficient cyclization and result in crosslinked materials.12 In fact, efficient cyclopolymerization processes have been described, for instance, for a,oo-dienes like 1,5-hexadiene, 2-methyl-l,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene,67 73 which lead to formation of homopolymers and copolymers containing methylene-1,3-cycloalkane units. 

Recent advances in the development of well-defined homogeneous metallocene-type catalysts have facilitated mechanistic studies of the processes involved in initiation, propagation, and chain transfer reactions occurring in olefins coordi-native polyaddition. As a result, end-functional polyolefin chains have been made available [103].For instance, Waymouth et al.have reported about the formation of hydroxy-terminated poly(methylene-l,3-cyclopentane) (PMCP-OH) via selective chain transfer to the aluminum atoms of methylaluminoxane (MAO) in the cyclopolymerization of 1,5-hexadiene catalyzed by di(pentameth-ylcyclopentadienyl) zirconium dichloride (Scheme 37). Subsequent equimolar reaction of the hydroxyl extremity with AlEt3 afforded an aluminum alkoxide macroinitiator for the coordinative ROP of sCL and consecutively a novel po-ly(MCP-b-CL) block copolymer [104]. The diblock structure of the copolymer... 

Copolymers and terpolymers of ethylene and propene, commonly known as EPM and EPDM polymers, respectively, are useful elastomers [Ver Strate, 1986], EPM and EPDM are acronyms for ethylene-propene monomers and ethylene-propene-diene monomers, respectively. The terpolymers contain up to about 4 mol% of a diene such as 5-ethylidene-2-norbomene, dicyclopentadiene, or 1,4-hexadiene. A wide range of products are available, containing 40-90 mol% ethylene. The diene, reacting through one of its double bonds, imparts a pendant double bond to the terpolymer for purposes of subsequent crosslinking (Sec. 9-2b). 

Commercial grades of ethylene-propylene copolymers (EPR) contain 60-75 mol% of ethylene to minimize crystallization. The addition of a third monomer, such as 1,4-hexadiene, dicyclopentadiene, or 5-ethylidene-2-norbornene, produces generally amorphous faster-curing elastomers. A large number of such terpolymers, referred to as EPDM, is available commercially. Their properties, performance, and response to radiation vary considerably depending on macrostructure, ethylene/propylene ratio, as well as on the type, amount, and distribution of the third monomer. 

The curable copolymer, poly(ethylene-co-l,4-hexadiene), was also prepared as illustrated below. 

With larger amount of propylene a random copolymer known as ethylene-propylene-monomer (EPM) copolymer is formed, which is a useful elastomer with easy processability and improved optical properties.208,449 Copolymerization of ethylene and propylene with a nonconjugated diene [EPDM or ethylene-propylene-diene-monomer copolymer] introduces unsaturation into the polymer structure, allowing the further improvement of physical properties by crosslinking (sulfur vulcanization) 443,450 Only three dienes are employed commercially in EPDM manufacture dicyclopentadiene, 1,4-hexadiene, and the most extensively used 5-ethylidene-2-norbomene. 

Polycarbophil. Polycarbophil [73038-24-1] (copolymer of acrylic acid and divinyl glycol (l,5-hexadiene-3,4-diol [1069-23-4])) consists of white-to-creamy white granules having a slight ester-like odor. It swells to contain a maximum of 1.5% water, but is insoluble in water and most organic solvents. It is prepared by copolymerization of acrylic acid and divinyl glycerol in a hot salt slurry using azobisisobutyronitrile as the initiator. 

Although both linear polyethene and isotactic polypropene are crystalline polymers, ethene-propene copolymers prepared with the aid of Ziegler catalysts are excellent elastomers. Apparently, a more or less random introduction of methyl groups along a polyethene chain reduces the crystallinity sufficiently drastically to lead to an amorphous polymer. The ethene-propene copolymer is an inexpensive elastomer, but having no double bonds, is not capable of vulcanization. Polymerization of ethene and propene in the presence of a small amount of dicyclopentadiene or 1,4-hexadiene gives an unsaturated heteropolymer, which can be vulcanized with sulfur in the usual way. 

Fetters and co-workers (89, 90) reported a difunctional initiator (20) from lithium and 2,4-hexadiene which, presumably, could be used for the synthesis of ABA copolymers. This initiator is not only oligomeric but also has bulky chain ends for reduced Li association and increased solubility. Although a purely hydrocarbon-soluble initiator was claimed, most of the data were based upon catalysts in benzene-amine solvents. Also, the authors mentioned that this initiator is stable at room temperature, but no detailed aging data were given. 

Random ethylene/propylene copolymers are amorphous and represent an interesting class of synthetic elastomers. The introduction of double bonds, useful for sulphur vulcanisation in the copolymer, can be achieved by copolymerisation of ethylene and propylene with non-conjugated dienes containing only one double bond capable of insertion for instance, 1,4-hexadiene, dicy-clopentadiene and 5-ethylidene-2-norbornene (endocyclic double bond)... 

Discuss the dependence of the micro structure of 2,4-hexadiene monomeric units (cis-1,4 or trans-1,4) in 2,4-hexadiene/l,3-butadiene copolymers on the composition of these copolymers (distribution of comonomers along copolymer chains). 

Of great industrial interest are the copolymers of ethene and propene with a molar ratio of 1/0.5, up to 1/2. These EP-polymers show elastic properties and, together with 2-5 wt% of dienes as third monomers, they are used as elastomers (EPDM). Since they have no double bonds in the backbone of the polymer, they are less sensitive to oxidation reactions. As dienes, ethylidenenorbomene, 1,4-hexadiene, and dicyclopentadiene are used. In most technical processes for the production of EP and EPDM rubber in the past, soluble or highly disposed vanadium components are used [69]. Similar elastomers can be obtained with metallocene/MAO catalysts by a much higher activity which are less colored [70-72]. The regiospecificity of the metallocene catalysts toward propene leads exclusively to the formation of head-to-tail enchainments. The ethylidenenor-bornene polymerizes via vinyl polymerization of the cyclic double bond and the tendency to branching is low. The molecular weight distribution of about 2 is narrow [73]. 

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