Crystalline polymers preparation

Highly crystalline polymers prepared at —78 °C were shown to be stereoregular. As each polymer unit contains two assymetric carbon atoms ... 

Drazic PS (1995) Liquid crystal dispersions. World Scientific, Singapore Dufresne A (2006) Comparing the mechanical properties of high performances polymer nanocomposites from biological sources. J Nanosci Nanotechnol 6 322-330 Dutta D, Weiss RA, Kristal K (1992) Blends containing liquid crystalline polymers preparation and properties of melt drawn fibers, unidirectional prepregs and composite laminates. Polym Compos 13 394-401... 

Second, in the early 1950s, Hogan and Bank at Phillips Petroleum Company, discovered (3,4) that ethylene could be catalyticaHy polymerized into a sohd plastic under more moderate conditions at a pressure of 3—4 MPa (435—580 psi) and temperature of 70—100°C, with a catalyst containing chromium oxide supported on siUca (Phillips catalysts). PE resins prepared with these catalysts are linear, highly crystalline polymers of a much higher density of 0.960—0.970 g/cnr (as opposed to 0.920—0.930 g/cnf for LDPE). These resins, or HDPE, are currentiy produced on a large scale, (see Olefin polymers, HIGH DENSITY POLYETHYLENE). 

Since 1980, mthenium tetroxide, RuO, has been used for staining a number of heterophase polymers for tern (221) it seems to be a more versatile staining agent than OsO. For instance, in SAN modified with acrylate mbber, where the mbber phase is fully saturated, an excellent contrast between the mbber and the matrix has been achieved (222). Crystalline polymers have been stained with RuO (223), and excellent cra2e stmctures have been revealed (221). The stain may be prepared by dissolving RuCl - 3H2O in aqueous sodium hypochlorite for immediate use (224). 

In tbe first attempt to prepare a two-dimensional crystalline polymer (45), Co y-radiation was used to initiate polymerization in monolayers of vinyl stearate (7). Polymerization at the air—water interface was possible but gave a rigid film. The monomeric monolayer was deposited to give X-type layers that could be polymerized in situ This polymerization reaction, quenched by oxygen, proceeds via a free-radical mechanism. 

Crystallization kinetics have been studied by differential thermal analysis (92,94,95). The heat of fusion of the crystalline phase is approximately 96 kj/kg (23 kcal/mol), and the activation energy for crystallization is 104 kj/mol (25 kcal/mol). The extent of crystallinity may be calculated from the density of amorphous polymer (d = 1.23), and the crystalline density (d = 1.35). Using this method, polymer prepared at —40° C melts at 73°C and is 38% crystalline. Polymer made at +40° C melts at 45°C and is about 12% crystalline. 

Because of its regularity it would be expected that the polymer would be capable of crystallisation. In practice, however, the X-ray pattern characteristics of crystalline polymer is absent in conventionally fabricated samples. On the other hand films which have been prepared by slow evaporation from solvent or by heating for several days at 180°C do exhibit both haziness and the characteristic X-ray diagram. The amount of crystallisation and the size of the crystallite structures decrease with an increase in the molecular weight of... 

The thermotropic aromatic main chain liquid crystalline polymers are also prepared by the phase transfer catalyzed aromatic nucleophilic polymerization [87]. Polyetherification of bis(4-chloro-3-nitrophenyl) sulfone with mesogenic aromatic diols is shown below ... 

Strong elongational deformation and use of matrix polymers whose viscosity is higher than that of TLCP phase are better to ensure uniform and fine fibril formation. But application of compatibilizing techniques to in situ composite preparation can be useful to get the most desirable products. These can reduce the high costs of the liquid crystalline polymers and expensive special engineering plastics used for the in situ composite preparation and reduce the processing cost, whereas they can increase the performance of produced in situ composites, hence, their applications, too. 

The first patent of Edwards and Robinson147 claims the condensations of pyromel-litic acid and aliphatic diamine salt to prepare polyimide. Recently, that approach has been revisited, and biphenyl tetracarboxylic and pyromellitic acids give a salt monomer by reaction with 1 mol of an aliphatic diamine (octamethylene diamine and dodecamethylene diamine). The salts were polymerized under 250 MPa at 250°C for 5 h in closed reaction vessels (Fig. 5.32) giving crystalline polymers.148 By reaction of pyromellitic tetraacid with oxydianiline, it has been possible to isolate a monomeric salt. It was polymerized under 30 MPa giving a PMDA-ODA polyimide with water elimination. 

Copolymerization of ethylene and styrene by the INSITE technology from Dow generates a new family of ethylene-styrene interpolymers. Polymers with up to 50-wt% styrene are semicrystalline. The stress-strain behavior of the low-crystallinity polymers at ambient temperature exhibits elastomeric characteristics with low initial modulus, a gradual increase in the slope of the stress-strain curve at the higher strain and the fast instantaneous recovery [67], Similarly, ethylene-butylene copolymers may also be prepared. 

Chloroacetaldehyde was prepared by heating its crystalline polymer and collecting the distillate in ether. The ethereal solution was at once reacted with the acetylenic Grignard reagent according to the procedure described above. After removal of the ether, the reaction mixture was concentrated as far as possible with a water pump. The residue at this point contained tneso-divinylacetylene dichlorohydrin, CHaCl—CHOH—C=C—CHOH—CHjCl, and probably the d,l isomer. When distillation was attempted by heating the reaction mixture strongly, it decomposed in an explosive manner. 

Three major topics of research which are based on phase transfer catalyzed reactions will be presented with examples. These refer to the synthesis of functional polymers containing functional groups (i.e., cyclic imino ethers) sensitive both to electrophilic and nucleophilic reagents a novel method for the preparation of regular, segmented, ABA triblock and (A-B)n alternating block copolymers, and the development of a novel class of main chain thermotropic liquid-crystalline polymers, i.e., polyethers. 

Many polymer-salt complexes based on PEO can be obtained as crystalline or amorphous phases depending on the composition, temperature and method of preparation. The crystalline polymer-salt complexes invariably exhibit inferior conductivity to the amorphous complexes above their glass transition temperatures, where segments of the polymer are in rapid motion. This indicates the importance of polymer segmental motion in ion transport. The high conductivity of the amorphous phase is vividly seen in the temperature-dependent conductivity of poly(ethylene oxide) complexes of metal salts. Fig. 5.3, for which a metastable amorphous phase can be prepared and compared with the corresponding crystalline material (Stainer, Hardy, Whitmore and Shriver, 1984). For systems where the amorphous and crystalline polymer-salt coexist, NMR also indicates that ion transport occurs predominantly in the amorphous phase. An early observation by Armand and later confirmed by others was that the... 

The structures of crystalline polymer-salt complexes provide insight into the structure of the more conducting amorphous materials. To date, large single crystals of polymer-salt complexes have not been prepared, but it has been possible to obtain structural information from single crystal X-ray diffraction applied to stretched oriented fibres in the PEO NaI and PEOiNaSCN systems (Chatani and Okamura, 1987 Chatani, Fujii, Takayanagi and Honma, 1990). One of the most detailed studies is of (PEO)3 NaI, Fig. 5.11(a). The sodium ion in this structure is coordinated to both the polymer and to the iodide ion and the polymer is coiled in the form of an extended helix. 

In some cases crystalline polymers show additional absorption bands in the infrared spectrum, as in polyethylene ( crystalline band at 730 cm amorphous band at 1300 cm" ) and polystyrene (bands at 982,1318, and 1368 cm" ). By determining the intensity of these bands it is possible to follow in a simple way the changes of degree of crystallinity caused, for example, by heating or by changes in the conditions of preparation. 

It was discovered by Ziegler in Germany and Natta in Italy in the 1950s that metal alkyls were very efficient catalysts to promote ethylene polymerization at low pressures and low temperatures, where free-radical polymerization is very slow. They further found that the polymer they produced had fewer side chairrs because there were fewer growth mistakes caused by chain transfer and radical recombination. Therefore, this polymer was more crystalline and had a higher density than polymer prepared by free-radical processes. Thus were discovered linear and high-density polymers. 

After Little s proposal, many researchers have pursued such an exciting system in vain. Even metallic behavior was rarely seen in doped organic polymers, gels, and actuators. As mentioned in Sect. 3.4.4, MCso with linearly polymerized Ceo" exhibited one-dimensional (M = Rb, Cs) or three-dimensional (M = K) metallic behavior [144]. Recently a doped poly aniline was reported to exhibit a metallic temperature dependence for a crystalline polymer chemical oxidation of monomers grew crystallite polyaniline [329] early doping studies on polypyrrole (PFg) and poly(3,4-ethylene-dioxythiophene)X (X = PFg, BF4, and CF3SO3) prepared by electrooxidation at low temperatures also showed a metallic temperature dependence below 10-20 K (Scheme 16) [330, 331]. 

The polarizing microscope can be used to observe morphological features of all crystalline polymers that can be prepared as thin films. Birefringence measurement is applicable to all polymers in which orientation or anisotropy can be induced. 

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