Piperylenes

The first resins to be produced on a commercial scale were the coumarone—indene or coal-tar resins (1) production in the United States was started before 1920. These resins were dominant until the development of petroleum resins, which were estabHshed as important raw materials by the mid-1940s. Continued development of petroleum-based resins has led to a wide variety of aHphatic, cyclodiene, and aromatic hydrocarbon-based resins. The principal components of petroleum resins are based on piperylenes, dicyclopentadiene (DCPD), styrene, indene, and their respective alkylated derivatives. 

Aliphatic C-5—C-6. Aliphatic feedstreams are typically composed of C-5 and C-6 paraffins, olefins, and diolefins, the main reactive components being piperylenes cis-[1574-41 -0] and /n j -l,3-pentadiene [2004-70-8f). Other main compounds iaclude substituted C-5 and C-6 olefins such as cyclopentene [142-29-OJ, 2-methyl-2-butene [513-35-9] and 2-methyl-2-pentene [625-27-4J. Isoprene and cyclopentadiene maybe present ia small to moderate quaatities (2—10%). Most steam cracking operatioas are desigaed to remove and purify isoprene from the C-5—C-6 fraction for applications ia mbbers and thermoplastic elastomers. Cyclopentadiene is typically dimerized to dicyclopentadiene (DCPD) and removed from C-5 olefin—diolefin feedstreams duriag fractionation (19). 

Blends of piperylenes and amylenes (mixed 2-methyl-1-butene and 2-methyl-2-butene) or UOP propylene dimers can be adjusted to produce softening points of 0—100°C and weight average molecular weights of <1200 (32,33). Careful control of the diolefin/branched olefin ratio is the key to consistent resin properties (34). 

Due to the fact that BF is a weaker Lewis acid than AlCl, stmcturaHy distinct resins are obtained upon the respective polymerization of a piperylenes-2-methyl-2-butene system with the two different Lewis acids. Much lower levels of branched olefin are required to achieve a softening point of <40° C with the BF catalyzed system (33,36). In fact, due to its weaker acidity, BF is not useful for producing high softening point resins based on C-5 hydrocarbon feeds. 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Although most aromatic modified C-5 resins are typically higher softening point resins, certain appHcations, such as adhesives, require lower softening points. Copolymerization of a C-8—C-10 vinyl aromatic fraction with piperylenes in the presence of a C-4—C-8 mono-olefin chain-transfer stream yields resins with softening points ranging from 0—40°C (44). A particular advantage of these Hquid resins is the fact that they eliminate the need for plasticizers or oils in some pressure sensitive adhesive appHcations. 

Other natural product-based resins also became widely used, such as the light colored Lewis acid oligomerized products of terpenes such as a-pinene, p-pinene, and limonene. These natural product resins are relatively expensive, however, and formulators now often use the newer, less expensive synthetic resins in present day natural rubber PSAs. These are termed the aliphatic or C-5 resins and are Lewis acid oligomerized streams of predominately C-5 unsaturated monomers like cis- and /rawi-piperylene and 2-methyl-2-butenc [37]. These resins are generally low color products with compatibility and softening points similar to the natural product resins. Representative products in the marketplace would be Escorez 1304 and Wingtack 95. In most natural rubber PSA formulations, rubber constitutes about 100 parts and the tackifier about 75-150 parts. 

Acyclic C5. The C5 petroleum feed stream consists mainly of isoprene which is used to produce rubber. In a separate stream the linear C5 diolefin, piperylene (trans and cis), is isolated. Piperylene is the primary monomer in what are commonly termed simply C5 resins. Small amounts of other monomers such as isoprene and methyl-2-butene are also present. The latter serves as a chain terminator added to control molecular weight. Polymerization is cationic using Friedel-Crafts chemistry. Because most of the monomers are diolefins, residual backbone unsaturation is present, which can lead to some crosslinking and cyclization. Primarily, however, these are linear acyclic materials. Acyclic C5 resins are sometimes referred to as synthetic polyterpenes , because of their similar polarity. However, the cyclic structures within polyterpenes provide them with better solvency power and thus a broader range of compatibility than acyclic C5s. 

Less reactive dienes such as cyclohexadiene can be employed efficiently, giving the adduct in 90% yield in 93% ee. Acyclic dienes such as piperylene, 2,4-hexadiene, and 1-phenylbutadiene also react with the acryloyloxazolidinone derivative to afford Diels-Alder cycloadducts in high optical yields (Scheme 1.38, Table 1.17). 

The classic method for controlling stereochemistry is to perform reactions on cyclic substrates. A rather lengthy but nonetheless efficient example in the prostaglandin field uses bicyclic structures for this purpose. Bisacetic acid derivative S is available in five steps from Diels-Alder reaction of trans-piperylene and maleic anhydride followed by side-chain homologation. Bromolactonization locks the molecule as bicyclic intermediate Esterification, reductive dehalogen-... 

Reduction of azirine-2-phosphonates 99 (Scheme 3.32) with NaBH4 in ethanol exclusively gave ris-aziridine-2-phosphonates 100 in 81-82 % yield [86, 87]. A Diels-Alder reaction between azirine-2-phosphonate 101 and trans-piperylene 102... 

Ahern and Gokel (1979) briefly mention that (jE -arenediazocyanides also react with a variety of dienes (cyclopentadiene, cyclohexadiene, butadiene, ( )-piperylene, etc.) in a [4+ 2]-cycloaddition reaction with formation of tetrahydropyridazines (Scheme 6-31). Here the two azo nitrogen atoms of the diazocyanide react as a dieneophile in a bis-aza Diels-Alder reaction. 

Conjugated dienes Butadiene 1,3-cyclohexadiene Piperylene Phenylbutadienes... 

Strong effects of the catalyst on the regioselectivity have been observed in the cycloadditions of a variety of heterocyclic dienophiles. Some results of the BF3-catalyzed reactions of quinoline-5,8-dione (21) and isoquinoline-5,8-dione (22) with isoprene (2) and (E)-piperylene (3) [25], and of the cycloadditions of 4-quinolones (23a, 23b) as well as 4-benzothiopyranone (23c) with 2-piperidino-butadienes, are reported [26] in Scheme 3.8 and Equation 3.2. The most marked... 

An example of stereocontrol by high pressure is given by the regio- and diastereoselective synthesis of hydrophenanthrenones [18] which are useful intermediates for synthesizing diterpenes and steroids, by EtAlCli-catalyzed cycloadditions of heteroannular bicyclic dienone 50 with (E)-piperylene (24) and 2,3-dimethyl-1,3-butadiene (51) (Scheme 5.4). 

Table 6.8 reports the relative reaction rates of Diels-Alder reactions of 2,5-dimethylbenzoquinone with tran -piperylene in different lithium salt solutions. The data show that the reaction rate depends on the concentration of LT and that in 4.0m LT-AC and 4.0m LT-DE the rate accelerations are comparable to that exhibited in 5.0m LP-DE and 5.0m LP-AC. 

Table 6.8 Relative reaction rates of Diels-Alder reactions of 2,6-dimethylbenzoquinone with Jrawi -piperylene in LiC104 (LP) and LiNTf2 (LT) in acetone (AC) and diethyl ether (DE)...

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