PMPS

In the synthesis of morphine, bis-cyclization of the octahydroisoqtiinolinc precursor 171 by the intramolecular Heck reaction proceeds using palladium trifluoroacetate and 1,2,2,6,6-pentamethylpiperidine (PMP). The insertion of the diene system forms the rr-allylpalladium intermediate 172, which attacks the phenol intramolecularly to form the benzofuran ring (see Section 1.1.1.3). Based on this method, elegant total syntheses of (-)- and (+ )-dihydrocodei-none and (-)- and ( + )-morphine (173) have been achieved[141]. 

Plot of pMp° - p) against p/p° (r is expressed in cm (stp)). (1) Unpromoted Fe catalyst (2) AljOj-promoted Fe catalyst (3) AI2O3-KjO-promoted Fe catalyst (4) fused copper catalyst (5) chromium oxide gel (6) silica gel. (Courtesy Brunauer, Emmett and Teller.)... 

The synthesis of isotactic polymers of higher a-olefins was discovered in 1955, simultaneously with the synthesis of isotactic PP (1,2) syndiotactic polymers of higher a-olefins were first prepared in 1990 (3,4). The first commercial production of isotactic poly(l-butene) [9003-29-6] (PB) and poly(4-methyl-l-pentene) [9016-80-2] (PMP) started in 1965 (5). 

Polybutene can be cross-linked by irradiation at ambient temperature with y-rays or high energy electrons in the absence of air. The performance of articles manufactured from polybutene is only slightly affected by ionizing radiation at doses below 30 kGy (3 Mrad) (26). PMP is also relatively stable to P-and y-radiation employed in the sterilization of medical suppHes (27). 

Gas Permeability. Crystalline PMP is relatively highly permeable to various organic and inorganic gases. Permeabilities to oxygen, nitrogen. 

Physical Properties. Table 3 Hsts physical properties of stereoregular polymers of several higher a-olefins. Crystal ceU parameters of these polymers ate available (34—36). AU. stereoregular polyolefins have helix conformations ia the crystalline state. Their densities usually range from 0.90 to 0.95 g/cm. Crystalline PMP, however, represents an exception its density is only 0.812—0.815 g/cm, lower even than that of amorphous PMP (0.835—0.840 g/cm ), thus making it one of the lowest densities among plastics. 

PMP can also crystallise in several crystalline forms (28). Form I is produced during crystallisation from the melt. This is the only crystalline form present in commercially manufactured articles. Other crystalline modifications ate formed when the polymer is crystallised from solution (28). 

Electrical Properties. AH polyolefins have low dielectric constants and can be used as insulators in particular, PMP has the lowest dielectric constant among all synthetic resins. As a result, PMP has excellent dielectric properties and alow dielectric loss factor, surpassing those of other polyolefin resins and polytetrafluoroethylene (Teflon). These properties remain nearly constant over a wide temperature range. The dielectric characteristics of poly(vinylcyclohexane) are especially attractive its dielectric loss remains constant between —180 and 160°C, which makes it a prospective high frequency dielectric material of high thermal stabiUty. 

Polymerization Processes. Isotactic PB and PMP are produced commercially in slurry processes in Hquid monomers or monomer mixtures (optionally diluted with light inert hydrocarbons) at 50—70°C. The first commercial process for PB production used a highly isospecific... 

Rheology. Both PB and PMP melts exhibit strong non-Newtonian behavior thek apparent melt viscosity decreases with an increase in shear stress (27,28). Melt viscosities of both resins depend on temperature (24,27). The activation energy for PB viscous flow is 46 kj /mol (11 kcal/mol) (39), and for PMP, 77 kJ/mol (18.4 kcal/mol) (28). Equipment used for PP processing is usually suitable for PB and PMP processing as well however, adjustments in the processing conditions must be made to account for the differences in melt temperatures and rheology. 

Analytical and test methods for the characterization of polyethylene and PP are also used for PB, PMP, and polymers of other higher a-olefins. The C-nmr method as well as k and Raman spectroscopic methods are all used to study the chemical stmcture and stereoregularity of polyolefin resins. In industry, polyolefin stereoregularity is usually estimated by the solvent—extraction method similar to that used for isotactic PP. Intrinsic viscosity measurements of dilute solutions in decahn and tetraHn at elevated temperatures can provide the basis for the molecular weight estimation of PB and PMP with the Mark-Houwiok equation, [rj] = KM. The constants K and d for several polyolefins are given in Table 8. 

Tables 4—6 Ust ASTM methods used for the characterization of PB and PMP. A number of specialized methods were developed for testing particular articles manufactured from polyolefins several of these determine the performance of PB and PMP film, including the measurement of the film s dart impact strength and tear strength. Dart impact strength is measured by dropping a heavy dart with a round tip on a stretched film. Tear resistance, which reflects the film s resistance to tear propagation, is measured with the Ehnendorf tear tester. Two values for the tear strength are usually reported, one in the machine dkection of the film and the other in the transverse dkection. Pipes manufactured from PB are tested by pressurizing them internally with water the time-to-burst failure is determined at various temperatures (46). The standard test method for haze and luminous transmittance (ASTM D1003) is used for the measurement of PMP optical characteristics.

In particular, PB and PMP are inert materials and usually present no health hazard. PMP is employed extensively for a number of medical and food packaging appHcations. Several grades conform to FDA regulations and to the health standards of other countries. Flammability of polyolefin resins is equal to that of PP, around 2.5 cm /min (ASTM D635). However, during combustion or pyrolysis, smoke, fumes, and toxic decomposition products are formed and can pose a health hazard. 

Melt-spun fiber is produced from PMP at 280°C and is drawn around three times in air at 95°C its fiber strength is 0.18—0.26 N/tex (2—3 g/den), its elongation is around 30%. Melt-spun hoUow fibers are also manufactured. PMP has one of the highest permeabiHties for gases, and many of its appHcations capitalize on this property. 

N,N-bis(4-methylphenyl)-N,iV-bis(4-ethylphenyl)-[l,l -(3,3 -dimethyl)biphenyl]-4,4 -diamine [115310-63-9] (ETPD) (8) -doped PMPS (Table 1, entry 22), hole mobihty approaching 10 cm /Vs at 2.5 x 10 V/cm was observed (48). This is the highest recorded hole mobihty for disordered organic systems. From this perceptive, it is very interesting to study the carrier mobihty of polymers heavily doped with semiconductor nanoclusters. 

Fig. 7. The field-dependence of the charge-generation efficiency of a 2.0- lm thick (0) a l.l-).tm thick ( ), and 1.8-).tm thick (A) fuUerene/PMPS film obtained with positive charging and 340-nm irradiation (A). The soHd lines are calculated from the Onsager model. The best-fit curve is obtained with Tq = 2.7 nm and = 0.85. Also plotted is the charge-generation efficiency of a fuUerene/PVK film (+) obtained with positive charging and 340-nm irradiation (B). The soHd lines are calculated from the Onsager model. The best-fit curve is obtained with = 1.9 nm and = 0.9 (13).

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