Poly isotactic polymers

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

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). 

Figure 2.10 Maps of conformational energy of various isotactic polymers as function of backbone torsion angles 0i and 02 (a) Isotactic polystyrene, (b) polypropylene, (c) poly(l-butene), and (d) poly(4-methyl-l-pentene). Succession of torsion angles. .. 0i020i02 [s(M/N) symmetry] has been assumed. Isoenergetic curves are reported every 10 (a,c,d) or 5 (b) kJ/mol of monomeric units with respect to absolute minimum of each map assumed as zero.

Data concerning the chain conformations of isotactic polymers are reported in Table 2.1. In all the observed cases the torsion angles do not deviate more than 20° from the staggered (60° and 180°) values and the number of monomeric units per turn MIN ranges between 3 and 4. Chains of 3-substituted polyolefins, like poly(3-methyl-l-butene), assume a 4/1 helical conformation (T G )4,45,46 while 4-substituted polyolefins, like poly(4-methyl-1-pentene), have less distorted helices with 7/2 symmetry (T G )3.5-39 When the substituent on the side group is far from the chain atoms, as in poly(5-methyl-1-hexene), the polymer crystallizes again with a threefold helical conformation (Table 2.1). Models of the chain conformations found for the polymorphic forms of various isotactic polymers are reported in Figure 2.11. 

In the crystal structures of many other isotactic polymers, with chains in threefold or fourfold helical conformations, disorder in the up/down positioning of the chains is present. Typical examples are isotactic polystyrene,34,179 isotactic poly(l-butene),35 and isotactic poly(4-methyl-l-pentene).39,40,153,247... 

The ORD and CD curves of optically active polymers containing chromo-phoric groups show that the chromophores can be asymmetrically perturbed by the chirality of the substituents and of the main chain conformation. This is the case with poly( ec-butyl vinyl ketone) (377), which presents a Cotton effect at 292 nm, its intensity being greater in the prevalently isotactic polymer than in the atactic polymer. 

The same type of addition—as shown by X-ray analysis—occurs in the cationic polymerization of alkenyl ethers R—CH=CH—OR and of 8-chlorovinyl ethers (395). However, NMR analysis showed the presence of some configurational disorder (396). The stereochemistry of acrylate polymerization, determined by the use of deuterated monomers, was found to be strongly dependent on the reaction environment and, in particular, on the solvation of the growing-chain-catalyst system at both the a and jS carbon atoms (390, 397-399). Non-solvated contact ion pairs such as those existing in the presence of lithium catalysts in toluene at low temperature, are responsible for the formation of threo isotactic sequences from cis monomers and, therefore, involve a trans addition in contrast, solvent separated ion pairs (fluorenyllithium in THF) give rise to a predominantly syndiotactic polymer. Finally, in mixed ether-hydrocarbon solvents where there are probably peripherally solvated ion pairs, a predominantly isotactic polymer with nonconstant stereochemistry in the jS position is obtained. It seems evident fiom this complexity of situations that the micro-tacticity of anionic poly(methyl methacrylate) cannot be interpreted by a simple Bernoulli distribution, as has already been discussed in Sect. III-A. 

A polymerization of a bulky methacrylate ester (e.g. trityl methacrylate) using an optically active anionic initiator can give an isotactic polymer, poly 1-methyl-1-[(trityloxy)carbonyl]ethylene of high optical activity owing to the formation of helical polymer molecules with units of predominantly one chirality sense. 

Eukae R, Fuji T et al (1994) Biodegradation of poly(vinyl alcohol) with high isotacticity. Polym 1 26 1381-1386... 

The all-trans-all-isotactic and all-trans-all-syndiotactic structures for the 1,4-polymerization of 1,3-pentadiene are shown in Fig. 8-6. In naming polymers with both types of stereoisomerism, that due to cis-trans isomerism is named first unless it is indicated after the prefix poly. Thus, the all-trans-all-isotactic polymer is named as transisotactic l,4-poly(l,3-penta-diene) or isotactic poly( -3-methylbut-l-ene-l,4-diyl). 

Optically active polymers are rarely encountered. Most syndiotactic polymers are optically inactive since they are achiral. Most isotactic polymers, such as polypropene and poly(methyl methacrylate), are also inactive (Sec. 8-la-l). Optically active polymers have been obtained in some situations and these are discussed below. 

The carbonyl stretching band in the infrared spectrum of isotactic poly (a,a-dimethylbenzy 1 methacrylate) prebaked at 142°C for 1 hr indicated the formation of a small amount of acid group during the prebake, while the atactic polymer showed no change in the spectrum at this temperature. This may be the reason why the isotactic polymer showed a lower 7-value than the atactic polymer (Table III). 

Huels and Mobil developed technologies473 to manufacture isotactic poly (1-butene), a less important and more expensive polymer by Ziegler-Natta catalysts. The Mobil process474 is carried out in excess 1-butene and produces highly isotactic polymer. The Huels technology475 is a slurry operation and requires removal of the atactic isomer. 

A very important field of polymerization, stereospecific polymerization, was opened in 1955. In this year, Natta and his coworkers (1—3) polymerized a-olefins to crystalline isotactic poly-a-olefins with the Ziegler catalyst, and Pruitt and Baggett (4,5) polymerized dl-propylene oxide to crystalline polypropylene oxide, which was later identified as an isotactic polymer by Price and his coworkers (6,7). Since then, a large number of compounds including both unsaturated and cyclic compounds were polymerized stereospecifically and asymmetrically. Development of the stereospecific polymerization stimulated... 

In spite of the similarity of the structure of the monomer units the two corresponding isotactic polymers crystallize in two different chain conformations tiie helix of poly-3-methyl-l-butene contains four monomer units per turn (4/1) with a chain repeat of 6.85 A the helix of poly-4-methyl-l-pentene contains 3.5 units per turn (7/2) and has a repeat of 13.85 A. The copolymers tend to crystallize. Their chain conformation and cross sectional area in the crystal lattice are analogous to those of the homopolymer corresponding to the predominant comonomer. For 4-methyl-l-pentene contents higher than 50% some evidence exists that the system simultaneously contains both chain conformations. 

Poly a-methyl styrene is also reported to have a predominantly syndiotactic structure as prepared with butyllithium in cyclohexane (11). Sakurada and co-workers (90) have suggested that there is the possibility of error in the N. M. R. band assignments and that the polymer may be predominantly isotactic. It is difficult to assess the validity of this claim without details of the crystallization of the supposedly isotactic polymer. 

The optical rotatory dispersion of poly-(+)-l-methyl-benzyl-methacry ate has been measured between 320 and 230 raft. The optical activity for polymer and model has values of the same sign and of the same order of magnitude, but the isotactic polymer seems to have a larger [M] than the syndiotactic and the atactic polymers [K. J. Liu, J. S. Lignowski, R. Ullman ACS Polymer Preprints, 6, 904 (1965)]. Optically active N-methyl-N-methylbenzyl-acrylamide and N-(n-propyl)-N-methylbenzyl-acrylamide have been polymerized by Kaiser and Schulz and the optical rotation dispersion between 589 raft and 365 raft has been... 

The intramolecular interaction energy was calculated for five isotactic polymers, namely, isotactic polypropylene, poly(U-methyl-l-pentene), poly(3-methyl-1-butene), polyacetaldehyde, and poly(methyl methacrylate) (23). The molecular structures of the first four polymers have already been determined by x-ray analyses as (3/1) (2k), (7/2) (18,25.,26), (U/l) (21), and (U/l) helices (28), respectively. Here (7/2) means seven monomeric units turn twice in the fiber identity period. For isotactic poly(methyl methacrylate) (29), a (5/l) helix was considered reasonable at the time of the energy calculation in 1970, before the discovering of... 

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