Poly solid-state polymerization

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

Jabarin, S. A. and Lofgren, E. A., Solid state polymerization of poly (ethylene terephthalate) kinetic and property parameters, J. Appl. Polym. Sci., 5315-5335 (1986). 

Chen, S. and Chen, F Kinetics of polyesterification III Solid-state polymerization of poly(ethylene terephthalate),. /. Polym. Sci., Polym. Chem. Ed., 25, 533-549 (1987). 

Chuah, H. H., Vinson, R. W. and Ulzelmeier, C. W., The Kinetics of Poly(Propylene Terephthalate) Solid-state Polymerization in Research Awareness Bulletin, Shell Chemical Company, July 1993, Houston, TX, pp. 101-103. 

Sulfur nitride polymers [-(-S = N-)-], which have optical and electrical properties similar to those of metals, were first synthesized in 1910. These crystalline polymers, which are super-conducive at 0.25 K, may be produced at room temperature using the solid state polymerization of the dimer (S2N2). A dark blue-black amorphous paramagnetic form of poly(sulfur nitride) (structure 11.30) is produced by quenching the gaseous tetramer in liquid nitrogen. The polymer is produced on heating the tetramer to about 300°C. 

Steinbrunn and Wenz recently reported poly(amide-CD rotaxane)s 53 via a very imaginative approach [90,91]. First, the CD was threaded on to an a,co-amino acid in water to give a pseudorotaxane monomer. An NMR study showed that two CD molecules were threaded per linear molecule for 11-aminoundecanoic acid. The X-ray powder pattern indicated that these rotaxanes stacked like channels in the solid state this provided the basis for solid state polymerization at 200°C to afford polyamide 53 with m/n=2 ... 

Andrews76 gave results of the work of Reed and Martin on cis-polyisoprene specimens crystallized from a strained cross linked melt and on solid state polymerized poly-oxymethylene respectively, explaining the results by simple two phase models. He also summarized the studies of Patel and Philips775 on spherulitic polyethylene which showed that the Young s modulus increased as a function of crystallite radius by a factor of 3 up to a radius of about 13 n and then decreased on further increasing spherulite size. 

Gross, S. M. Roberts, G. W. Kiserow, D. J. DeSimone, J. M. Crystallization and Solid State Polymerization of Poly(bisphenol A carbonate) Facilitated by Supercritical C02. Macromolecules 2000, 33, 40 -5. 

The -conjugated polyselenophene named PEDOS (182) the analog of poly-3,4-ethylenedioxythiophene (PEDOT) [281], one of the most successful conductive polymers, was obtained from 3,4-ethylenedioxyselenophene (89) using different polymerization techniques. These were oxidative chemical polymerization, solid-state polymerization, transition metal-mediated polymerization, and electrochemical polymerization (Scheme 46) [293, 294], The derivatives of PEDOS having the... 

Poly diacetylenes. The polydiacetylenes (PDA s) are unique among highly conducting polymers discovered in the past years in that they can be obtained as highly perfect macroscopic single crystals.68 Upon solid-state polymerization of... 

Pofy-l-vinyluradl (poly-VUr, 10) was also obtained by a free-radical polymerization6). In this case, it should be noted that the formation of substituted dihydrouradl rings occurred via a cydopolymerization mechanism11). y-Ray induced solid-state polymerization of the monomer (9) in high concentration and at low temperature excluded cydopolymerization completely12). Poly-VUr was also prepared by a free-radical polymerization of 2-ethoxy-4-l-vinyl-pyrimidone (ii)8) or 4-ethoxy-l-vinyl-2-pyrimidone (13)iy> followed by acid hydrolysis of the resulting polymers (12) or (14) (Scheme 2). 

Fig. 3.15 Atomic force microscopy images of poly(oxy methylene) with molecular resolution (a) raw data (b) image obtained from Fourier reconstruction. The arrow indicates the polymer chain direction (image size 7x7 nm2 Reproduced with permission from [38]). Copyright 1992. American Chemical Society, (c) AFM height image and (d) corresponding autocorrelation-filtered image acquired on POM crystals obtained by solid state polymerization [39]. Reproduced with permission from [39]. Copyright 1994. The Royal Society of Chemistry...

Iyer, V.S. Sehra, J.C. Ravindranath, K. Sivaram, S. Solid-state polymerization of poly (aryl carbonates) a facile route to high-molecular-weight polycarbonates. Macromolecules 1993, 26 (5), 1186-1197. 

While some of the above discussion is in the general reedm of prognostication, some mote specific comments are appropriate. It is appeuent that em increase in both the number and types of solid-state polymerization is a desirable research objective. Here, the major initial burden lies with the chemist to design (, new reactive molecular structure and appropriately oriented monomer crystal structures. Successful development of new lattice-controlled processes resulting in the availability of well-defined fully ordered mticromolecules will readily attract the more physically and theoreticedly oriented research communities. The PDA and poly (sulfur nitride) cases bear strong witness to this point. 

The structure analyses of two special types of dlacetylene "monomers," dlyne dimers and polydiyne macromonomers, are reviewed and preliminary results on the conversion and chromic behavior of one specific system, poly(l,8-nonadlyne) (F18N) are presented. Structure analyses of these materials before and after solid state polymerization allows a qualitative understanding of the dlacetylene polymerization. Cross-polymerized P18N has been shown to display solvatochromlc and thermochromlc behavior, even though this material Is Insoluble and Infusible. Examination of Initial optical spectroscopic data of the chromic behavior as a function of conversion, as well as consideration of the chromic behavior of conventional diacetylenes, leads to a possible explanation of the chromic behavior of crosspolymerlzed P18N. 

Solid-state polymerization was performed (under an argon atmosphere) in crystals suspended in hexane, using n-butylamine (0.5 mol%) as an initiator, for 12 and 72 h at 50 and 22 °C, respectively. The gel-like product was poly(L-lactic acid)washed with dry THF and ethyl acetate until all the monomer was removed, as confirmed by infrared spectroscopy. The product in its final form was centrifuged and dried. 

Wegner, however, established that radiation-induced solid-state polymerization of BCMO leads to a polymer morphology, which is incompatible with the so-called topochemical polymerization, i.e., a process in which monomer molecules are transformed into polymer without destruction of the crystal lattice 36). Electron microscopy, X-ray analysis and electron diffraction studies, have shown that polymerization starts at the edges and imperfections of the monomer crystals and that amorphous polymer is formed initially. Further transition from the amorphous state leads to the thermodynamically unstable monoclinic p-form. Density measurements indicate that the polymer is only 45-50% crystalline. The density of the amorphous poly-BCMO is 1.368 g/cm3 the density calculated for the crystalline polymer from crystallographic data of the p-form is 1.456 g/cm3. The density of the product of the radiation-induced solid-state polymerization is 1.41 g/cm3 36). 

Dynamic mechanical and NMR investigations of crystals grown from dilute solutions for polymers other than linear polyethylene have been much less extensive. Studies have been reported for the linear polymers polyoxy methylene (3, 40, 94), poly (ethylene oxide) (3, 78), and nylon 6 (42), and the branched polymers polypropylene (40), poly-l-butene (19, 95), poly(4-methyl-l-pentene) (33), poly (vinyl alcohol) (78), and branched polyethylene (78). In addition, dielectric loss measurements have been made on crystal aggregates of poly (ethylene oxide) (23), poly (vinyl alcohol) (68), and polyoxymethylene (3) and mechanical loss measurements have been carried out on polyoxymethylene formed by solid state polymerization (94). 

Wu, D., Chen, F. and Li, R., Reaction kinetics and simulations for solid-state polymerization of poly(ethylene terephthalate), Macromolecules, 30, 6737-6742 (1997). 

Single crystals are commonly mounted on a four-circle diffractometer. This method may provide the quality of data necessary for structural refinements. However, polymer single crystals of usable sizes have been obtained only through solid-state polymerization of monomer crystals, such as in the case of poly-diacetylcnes. Oligomers and model compounds, however, have been obtained in single-crystal fonn in several cases, either from solution or from the vapour phase. 

The immediate direct quenching prevents the growth of large spher-ulites, which cause polymer brittleness and degrade mechanical properties of the solid state polymerized polymers. The method has been exemplified with poly(amide)s (PA)s and poly(butylene terephthalate) (PBT). 

B. Duh. Solid state polymerization process for foamed poly(ethylene na-phthalate). US Patent 5 478 868, assigned to Shell Oil Company (Houston, TX), December 26, 1995. 

Poly(tetramethylene adipamide) or nylon-4,6 is prepared from tetramethylene diamine and adipic acid by polymerization in an organic solvent or by melt polymerization followed by solid-state polymerization [79,80]. The polymer melts at 295°C, about 30°C above nylon-6,6. It is more sensitive to degradation and branching. The volatility of tetramethylene diamine also makes it difficult to control the balance of end groups during polymerization. Excess diamine is added to compensate the losses. Values of M as high as 32,900 have been reported. 

---