Isoprene/propylene

A scheme for the alternating copolymerisation of conjugated dienes and a-olefins has been proposed in the case of isoprene/propylene copolymerisation with V-based Ziegler-Natta catalysts [209] ... 

Copolymers.—Both Monomers Vinyl. Ethylene-propylene copolymers have attracted the greatest attention,befitting their industrial importance. A variety of techniques has been used to assign the rather complex C spectra observed, including the synthesis of model oligomers and model polymers e.g. by hydrogenation of isoprene ). Propylene may add by either primary or secondary insertion, and a terpolymerization model has therefore been used to quantify the sequence distribution. Alternatively, Randall has proposed an analysis in terms of —CHa— or —CH(CHs)— units, rather than monomer residues. 

NR, natural mbber CR, chloroprene SRs, synthetic mbbers IR, natural isoprene SBR, styrene—butadiene mbber BR, butadiene EPDM, ethylene—propjiene-diene EPM, ethylene—propylene polymer HR, isobutylene—isoprene NBR, nitrile—butadiene. 

Isoprene [78-79-5] (2-methyl-1,3-butadiene) is a colorless, volatile Hquid that is soluble in most hydrocarbons but is practically insoluble in water. Isoprene forms binary azeotropes with water, methanol, methylamine, acetonitrile, methyl formate, bromoethane, ethyl alcohol, methyl sulfide, acetone, propylene oxide, ethyl formate, isopropyl nitrate, methyla1 (dimethoxymethane), ethyl ether, and / -pentane. Ternary azeotropes form with water—acetone, water—acetonitrile, and methyl formate—ethyl bromide (8). Typical properties of isoprene are Hsted in Table 1. 

Propylene Dimer. The synthesis of isoprene from propjiene (109,110) is a three-step process. The propjiene is dimeri2ed to 2-methyl-1-pentene, which is then isomeri2ed to 2-methyl-2-pentene in the vapor phase over siUca alumina catalyst. The last step is the pyrolysis of 2-methyi-2-pentene in a cracking furnace in the presence of (NH 2 (111,112). Isoprene is recovered from the resulting mixture by conventional distillation. 

Natural mbber comes generally from southeast Asia. Synthetic mbbers are produced from monomers obtained from the cracking and refining of petroleum (qv). The most common monomers are styrene, butadiene, isobutylene, isoprene, ethylene, propylene, and acrylonitrile. There are numerous others for specialty elastomers which include acryUcs, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin, ethylene—acryUc, ethylene octene mbber, ethylene—propylene mbber, fluoroelastomers, polynorbomene, polysulftdes, siUcone, thermoplastic elastomers, urethanes, and ethylene—vinyl acetate. 

A second route based on olefin disproportionation was developed by Phillips Petroleum (131). Here isobutylene reacts with propylene to form isoamylenes, which are dehydrogenated to isoprene. 2-Butene can be used in place of propylene since it also yields isoamylene and the coproduct propylene can be recycled. Use of mixed butylenes causes the formation of pentenes, giving piperjlene, which contaminates isoprene. 

Uses. /-Butyl hypochlorite has been found useful in upgrading vegetable oils (273) and in the preparation of a-substituted acryflc acid esters (274) and esters of isoprene halohydrins (275). Numerous patents describe its use in cross-linking of polymers (qv) (276), in surface treatment of mbber (qv) (277), and in odor control of polymer latexes (278). It is used in the preparation of propylene oxide (qv) in high yield with Httle or no by-products (269,279). Fluoroalkyl hypochlorites are useful as insecticides, initiators for polymerizations, and bleaching and chlorinating agents (280). 

The most important olefins used for the production of petrochemicals are ethylene, propylene, the butylenes, and isoprene. These olefins are usually coproduced with ethylene by steam cracking ethane, LPG, liquid petroleum fractions, and residues. Olefins are characterized by their higher reactivities compared to paraffinic hydrocarbons. They can easily react with inexpensive reagents such as water, oxygen, hydrochloric acid, and chlorine to form valuable chemicals. Olefins can even add to themselves to produce important polymers such as polyethylene and polypropylene. Ethylene is the most important olefin for producing petrochemicals, and therefore, many sources have been sought for its production. The following discusses briefly, the properties of these olefmic intermediates. 

Another approach for producing isoprene is the dimerization of propylene to 2-methyl-1-pentene. The reaction occurs at 200°C and about 200 atmospheres in the presence of a tripropyl aluminum catalyst combined with nickel or platinum. 

Currently, important TPE s include blends of semicrystalline thermoplastic polyolefins such as propylene copolymers, with ethylene-propylene terepolymer elastomer. Block copolymers of styrene with other monomers such as butadiene, isoprene, and ethylene or ethylene/propy-lene are the most widely used TPE s. Styrene-butadiene-styrene (SBS) accounted for 70% of global styrene block copolymers (SBC). Currently, global capacity of SBC is approximately 1.1 million tons. Polyurethane thermoplastic elastomers are relatively more expensive then other TPE s. However, they are noted for their flexibility, strength, toughness, and abrasion and chemical resistance. Blends of polyvinyl chloride with elastomers such as butyl are widely used in Japan. ... 

Standard butyl rubber, which is a copolymer of isobutylene with about 2% of isoprene vulcanises in the same manner as natural rubber but, as it only contains a small proportion of polyisoprene, the cross-link percentage is much reduced. It is therefore not possible to make ebonite from a butyl rubber. The same vulcanisation chemistry, with some modifications, applies to ethylene-propylene terpolymers and brominated butyl rubber. 

Table 2.6 summarises the main techniques and standards used for the determination of specific rubber components. ISO 9924-1 (2000) describes the use of TGA for the determination of the composition of butadiene, ethylene-propylene, butyl, isoprene and SBR rubbers. 

EPR Ethylene-propylene rubber NR Natural rubber poly isoprene... 

Conjugated dienes are among the most significant building blocks both in laboratories and in the chemical industry [1], Especially, 1,3-butadiene and isoprene are key feedstocks for the manufacture of polymers and fine chemicals. Since the discovery of the Ziegler-Natta catalyst for the polymerizations of ethylene and propylene, the powerful features of transition metal catalysis has been widely recognized, and studies in this field have been pursued very actively [2-7]. 

Monomers, such as ethylene, propylene, isobutylene, and isoprene, containing the carbon-carbon double bond undergo chain polymerization. Polymerization is initiated by radical, anionic or cationic catalysts (initiators) depending on the monomer. Polymerization involves addition of the initiating species R, whether a radical, cation, or anion, to the double bond followed by its propagation by subsequent additions of monomer... 

The isoprene units in the copolymer impart the ability to crosslink the product. Polystyrene is far too rigid to be used as an elastomer but styrene copolymers with 1,3-butadiene (SBR rubber) are quite flexible and rubbery. Polyethylene is a crystalline plastic while ethylene-propylene copolymers and terpolymers of ethylene, propylene and diene (e.g., dicyclopentadiene, hexa-1,4-diene, 2-ethylidenenorborn-5-ene) are elastomers (EPR and EPDM rubbers). Nitrile or NBR rubber is a copolymer of acrylonitrile and 1,3-butadiene. Vinylidene fluoride-chlorotrifluoroethylene and olefin-acrylic ester copolymers and 1,3-butadiene-styrene-vinyl pyridine terpolymer are examples of specialty elastomers. 

Petroleum is rarely used in the form produced at the well, but is converted in refineries into a wide range of products, such as gasoline, kerosene, diesel fuel, jet fuel, and domestic and industrial fuel oils, together with petrochemical feedstocks such as ethylene, propylene, butene, butadiene, and isoprene. Petroleum is refined, that is, it is separated into useful products (Figure 1.1 Chapter 3). 

Dimerization of propylene is also used to produce isoprene. Several steps are involved. Initially, dimerization of propylene to 2-methyl-1-pentene occurs. Then isomerization to 2-methyl-2-pentene is effected. Finally, the 2-methyl-2-pentene is pyrolyzed to isoprene and methane. Another multistep synthesis starts with acetylene and acetone. Perhaps the most attractive route involves formaldehyde and isobutylene (equation 17.42). 

Many substituents stabilize the monomer but have no appreciable effect on polymer stability, since resonance is only possible with the former. The net effect is to decrease the exothermicity of the polymerization. Thus hyperconjugation of alkyl groups with the C=C lowers AH for propylene and 1-butene polymerizations. Conjugation of the C=C with substituents such as the benzene ring (styrene and a-methylstyrene), and alkene double bond (butadiene and isoprene), the carbonyl linkage (acrylic acid, methyl acrylate, methyl methacrylate), and the nitrile group (acrylonitrile) similarly leads to stabilization of the monomer and decreases enthalpies of polymerization. When the substituent is poorly conjugating as in vinyl acetate, the AH is close to the value for ethylene. 

Other commercial copolymers which are typically random are those of vinyl chloride and vinyl acetate (Vinylite), isobutylene and isoprene (butyl rubber), styrene and butadiene (SBR), and acrylonitrile and butadiene (NBR). The accepted nomenclature is illustrated by EP, which is designated poly-ethylene-co-propylene the co designating that the polymer is a copolymer. When the copolymers are arranged in a regular sequence in the chains, i.e., ABAB, the copolymer is called an alternating copolymer. A copolymer consisting of styrene and maleic anhydride (SMA) is a typical alternating copolymer. 

Hydrogenated Diblock of Poly(Butadiene)-Poly(Isoprene) to give Polyethylene-propylene rubber. 

In the liquid phase there are many examples of ionic polymerizations of olefinic compounds induced by high energy radiation. In some, such as propylene,77 1-hexene,78 1-octene,18 and n-hexadecene-1,75 the initiating ionic species is believed to be the parent ion radical while in others such as isoprene,79 isobutylene,80 butadiene,81 and 2-methylstyrene,82 it is thought to be the carbonium ion. 

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