Other Polyterpenes

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

Natural rubber displays the phenomenon known as natural tack. When two clean surfaces of masticated rubber (rubber whose molecular weight has been reduced by mechanical shearing) are brought into contact the two surfaces become strongly attached to each other. This is a consequence of interpenetration of molecular ends followed by crystallisation. Amorphous rubbers such as SBR do not exhibit such tack and it is necessary to add tackifiers such as rosin derivatives and polyterpenes. Several other miscellaneous materials such as factice, pine tar, coumarone-indene resins (see Chapter 17) and bitumens (see Chapter 30) are also used as processing aids. 

The other class of acrylic compatible tackifiers includes those based on ter-penes. Terpenes are monomers obtained by wood extraction or directly from pine tree sap. To make the polyterpene tackifiers, the monomers have to be polymerized under cationic conditions, typically with Lewis acid catalysis. To adjust properties such as solubility parameter and softening point, other materials such as styrene, phenol, limonene (derived from citrus peels), and others may be copolymerized with the terpenes. 

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. 

The abovementioned materials can be mixed with one another. A series of other polymers and resins can also be added if the substances listed in 1 to 4 form the bulk of the material. Additional materials are PE, PP, low molecular weight polyolefins, polyterpenes (mixtures of aliphatic and cycloaliphatic hydrocarbons produced by polymerisation of terpene hydrocarbons), polyisobutylene, butyl rubber, dammar gum, glycerine and pentaerythritol esters of rosin acid and their hydration products, polyolefin resins, hydrated polycyclopentadiene resin (substance mixtures manufactured by thermal polymerization of a mixture mainly composed of di-cyclopentadiene with methylcyclopentadiene, isoprene and piperylene which is then hydrogenated). 

Hot-melt adhesives are usually used for box-sealing applications for coated paperboard products. Migration of mineral hydrocarbons from these adhesives into foods was investigated in a survey. No mineral hydrocarbons were detected but several other substances were present in the adhesives. These were proposed to be natural resins such as polyterpene resins, tall oil rosin esters, and sterol-like natural products.Examples of each of these natural products are described in ref. 13 as being used for hot-melt adhesives. 

As the PSA industry evolved, natural rubber (NR) and styrene-butadiene rubber (SBR) were the primary elastomers used. Other backbone polymers were available but were used to a lesser degree. These other elastomers include polychloroprene, butyl rubber and nitrile rubber. Traditionally, formulations containing natural rubber have made use of polyterpene resins as tackifiers, particularly beta-pinene resins. The probable structure of a beta-pinene resin is given as follows and represents the terpene class of resins. 

Let us consider further the consequences of head-tail additions. If an additional molecule of IPP is added head-to-tail to farnesyl pyrophosphate geranylgeranyl pyrophosphate, a diterpene, is obtained. The series of events outlined above can now be repeated at a higher level of complexity geranylgeranyl pyrophosphate can either be converted to other diter-penes or two molecules of geranylgeranyl pyrophosphate can be joined tail-to-tail to give 40 C bodies. In this way tetraterpenes, i.e. carotenoids, are obtained. Further head-to-tail additions of IPP lead, finally, to the polyterpenes rubber, gutta-percha, and balata. 

In formulated adhesives the resins, plasticizers, other polymers, etc., present must be protected as well as the thermoplastic rubber. Even hydrogenated rosin esters, polyterpenes, and ole-finic hydrocarbon resins are reactive and must be protected. 

Other resins which find use as tackifiers for Neoprene include polyterpene resins, hydrogenated wood rosins, rosin esters, and couma-rone-indene resins. Chlorinated rubber is used to promote metal adhesion and as an ingredient of two-component adhesives. Poly-alpha-methyl styrene is used to obtain better specific adhesion to thermoplastic rubber. The compatibility of Neoprene with resins and other polymeric materials is detailed in Ref. 11. 

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