Crystal structure of nylon 12

The crystal structure of nylon 12 prepared by polymerization of dodecalactam has been determined by x-ray diffraction. Nylon 12 fiber exhibits only the γ form as its stable crystal structure. The unit cell of nylon 12 was determined with the aid of the x-ray diffraction pattern of a doubly oriented specimen. The unit cell is monoclinic with a = 9.38 Å, b = 32.2 Å (fiber axis), c = 4.87 Å and β = 121.5° and contains four repeating monomer units. The chain is planar zigzag for the most part but is twisted at the position of amide groups, forming hydrogen bonds between neighboring parallel chains. The chain conformation is similar to that of the γ form of nylon 6 proposed by Arimoto. It was deduced from the calculations that there are two chain conformations statistically coexistent according to the direction of twisting. In each conformation, hydrogen bonds are formed between parallel chains to make pleated sheetlike structures. The sheets are nearly parallel to (200) and in the sheet the directions of the neighboring chains are antiparallel, as is the case with nylon 6.     

Crystalline structure and thermal behavior of nylon‐10,14

The structure and morphology of a novel polyamide, nylon‐10,14, and its lamellar crystals from dilute solution were examined by transmission electron microscopy and wide‐angle X‐ray diffraction (WAXD). Both the electron‐diffraction pattern and WAXD data demonstrated that nylon‐10,14 adopts the structure of a triclinic lattice similar to that of the traditional nylon‐66 but with a corresponding increase of the c parameter to 3.23 nm. In addition, the thermal behavior of melt‐crystallized nylon‐10,14 was investigated by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The glass‐transition temperature of nylon‐10,14 determined by the DMA data was 46.6°C. DSC indicated that the multiple melting behavior of isothermally crystallized nylon‐10,14 probably results from the melt and recrystallization mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1422–1427, 2003     

Thermal evidences of the interaction between plasticizers and Ca salts in cement

The interactions between an organic polymer with plasticizing activity and a model surface (CaCO₃), with a surface activity similar to the cement one, have been analysed by volumetric analysis and thermal analysis: TG/DTG and DSC. The synthesized polymer has a negative link site (carboxylate) that is able to interact with the substrate and a long ethylene oxide chain that contribute to the dispersing activity. The pattern of the adsorption isotherm suggests the occurring of a step like adsorption, initially characterised by a coil conformation of PEO chain followed by a more PEO strained, linear, conformation as the amount of polymer increases. The polymer adsorption appears to modify the crystalline phase and morphology of the CaCO₃ surface as the thermal analysis puts in evidence through the CaCO₃ decomposition temperature shifts. SEM analysis confirms the morphology changes induced by polymer adsorption.     

Further studies of the preferred chain conformation of crystalline poly(vinylidene chloride)

The polymer chain conformation of crystalline poly(vinylidene chloride) (PVDC) has been the subject of controversy for the past three decades. In this study, a combination of techniques has been employed in an attempt to elucidate the preferred conformation of PVDC. Conformational models containing two monomers per translational repeat distance have been considered. Calculations of the translational repeat distance and the nonbonded Cl ?Cl contact distance between two adjacent CCl₂ groups have been performed for each of the models. By comparing these results with those derived from x-ray analysis and a theoretical estimation of the minimum nonbonded Cl ?Cl contact distance, an initial judgment of the structural feasibility of the models has been gained. A symmetry analysis has been performed for each conformational model and theoretical estimations of the polarization and intensity of the C? Cl and C? H stretching vibrations have been obtained. These results have been compared with experimental infrared and Raman spectra. It is concluded that a TXTX′ (where X and X′ are torsional angles of equal value but opposite sign) chain-conformational model for PVDC is favored.     

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1492–1506     

Novel diffraction effects in the combined wide-angle and low-angle X-ray diffraction patterns of solution-grown nylon crystals

It was shown previously that in sedimented mats of solution-grown nylon crystals the 001 wide-angle reflection due to the unit-cell period along the chain and the low-angle reflection due to the lamellar periodicity are both along the same azimuth (meridian) in the x-ray diffraction pattern.¹ Presently in photographs which contain both the wide-angle and low-angle regions a series of new meridional reflections have been observed between the low-angle and 001 reflections and between 001 and 002 reflections. This finding implies that, with the large chemical repeat distances in question, diffraction effects at low and wide angles cannot be considered in isolation as is usual in most polymer crystal studies. In particular, the new reflections promise to provide a direct diffraction approach to the structure of the chain-folded lamellae.     

Polymorphic forms of nylon 3

The crystal structure of nylon 3 was studied, and four crystalline modifications were observed. Modification I, as determined from the x-ray diffraction pattern of drawn fibers, is similar to the α crystal structure of nylon 6. The unit cell is monoclinic; a = 9.33 Å, b = 4.78 Å, (fiber identity period), c = 8.73 Å, and β = 60°. The theoretical density for nylon 3 with four monomeric units in the unit cell is 1.39 g/cm³, and the observed density is 1.33 g/cm³. The space group is P2₁. The nylon 3 chains are in the extended planar zigzag conformation. Although other odd-numbered nylon form triclinic or pseudohexagonal crystals when oriented, drawn nylon 3 crystals are monoclinic. In addition to modification I, modifications II, III, and IV were studied. Lattice spacings of modifications II and III are equal to those of modification I. However x-ray diffraction intensities are different. Infrared spectra of those forms indicate an extended planar zigzag conformation of the chains. Modification IV is thought to correspond to the so-called smectic hexagonal form. No γ crystals were found, and it appears that polyamide chains with short sequences of methylene groups cannot form crystals of this type.     

Regular,adjacent reentry folding in single crystals of a liquid crystal polymer crystallized from the nematic state

Folded chain single crystals 35 Å thick have been grown from the liquid crystal state of an aromatic-aliphatic azomethine ether polymer (AZMEP-n) having a 10-carbon flexible segment (n = 10). Electron diffraction has permitted refinement of the triclinic unit cell. The molecular axes lie at an ca. 65° angle to the lamella normal and fold every third chemical repeat distance. For AZMEP-1 and -8 extended chain lamellae are formed; for AZMEP-7 both folded and extended chain lamellae are found. The observations of folded chain lamallae are in agreement with prior suggestions from our laboratory of chain folding in the liquid crystalline state in thin films. © 1992 John Wiley & Sons, Inc.     

Thermal degradation of aliphatic polyamides studied by field ionization and field desorption mass spectrometry

The aliphatic polyamides nylon 6.6, 6.9, 6.10, 6.12, 12.6, 12.10, and 12.12 of the diamine dicarboxylic acid-type were pyrolyzed in the ion source of a double-focusing mass spectrometer and the thermal degradation products were recorded by field ionization (FI) and field desorption (FD) mass spectrometry (MS). In the FI mode, several series of thermal degradation products differing in the number of polymer repeating units were detected up to 1000 Daltons. The main products were oligomers and, in addition, protonated dinitriles and various protonated nitriles are formed in large amounts except for nylon 6.6 and nylon 12.6. These two polymers form, in contrast to all other samples, large amounts of protonated amides and diamines. The technique employed allows distinction between oligomers already present in the original polymer and oligomers formed by thermal fission of bonds in the polymer chain. Reaction mechanisms are given that explain the products observed. High resolution experiments and accurate mass measurements were performed to confirm the proposed structures. In the FD mode, cationized oligomers (attached mostly to a sodium cation) were observed below 200°C with the dimers being the base peak for most samples. In contrast to the FI results, the monomers were only detected at very low intensities. Similarly, only weak signals for additional thermal degradation products were registered except for nylon 12.6. At higher temperatures the FD mass spectra gave protonated and doubly protonated oligomers in the high mass range up to 2000 Daltons, which resulted in complementary structural information about the polymers.     

Structures for monodisperse oligoamides. A novel structure for unfolded three-amide nylon 6 and relationship with a three-amide nylon 6 6

Three-amide oligomers of nylon 6 and nylon 6 6 have been investigated using electron microscopy (imaging and diffraction), X-ray diffraction, and computational modeling. A new crystal structure has been discovered for the three-amide oligomer of nylon 6. This material crystallizes from chloroform/dodecane solutions into an unfolded crystal form that has progressively sheared hydrogen bonding in two directions between polar (unidirectional) chains. This structure is quite different from the usual room temperature α-phase structure of chain-folded nylon 6 crystals, in which alternatingly sheared hydrogen bonding occurs between chains of opposite polarity in only one direction. The occurrence of this new structure illustrates the extent to which progressively sheared hydrogen bonding is preferred over alternatingly sheared hydrogen bonding. Indeed, the progressive hydrogen bonding scheme occurs in the three-amide nylon 6 material even though it requires a disruption to the lowest potential energy all-trans conformation of the chain backbone, and requires all the chains in each hydrogen-bonded layer to be aligned in the same direction. We believe the presence of chain folding, which necessarily incorporates adjacent chains of opposite polarity into the crystal structure, prevents the formation of this new crystal structure in the nylon 6 polymer. In contrast, the three-amide nylon 6 6 crystal structure is analogous to the polymeric nylon 6 6 α-phase structure, found in both fibers and chain-folded crystals, and consists of progressive hydrogen-bonded sheets which stack with a progressive shear. In both structures, the molecules (≈ 3 nm in length) form smectic C-like layers with well-orchestrated stacking of 2.2 nm to form a three-dimensional crystal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2849–2863, 1998     

Structure and morphology of nylon 46 lamellar crystals: Electron microscopy and energy calculations

A detailed electron microscopy study of the structure and morphology of lamellar crystals of nylon 46 obtained by crystallization from solution has been carried out. Electron diffraction of crystals supported by X‐ray diffraction of their sediments revealed that they consist of a twinned crystal lattice made of hydrogen‐bonded sheets separated 0.376 nm and shifted along the a‐axis (H‐bond direction) with a shearing angle of 65°. The interchain distance within the sheets is 0.482 nm. These parameters are similar to those previously described for nylon 46 lamellar crystals grown at lower temperatures. A combined energy calculation and modeling simulation analysis of all possible arrangements for the crystal‐packing of nylon 46 chains, in fully extended conformation, was performed. Molecular mechanics calculations showed very small energy differences between α (alternating intersheet shearing) and β (progressive intersheet shearing) structures with energy minima for successive sheets sheared at approximately 1/6 c and 1/3 c. A mixed lattice composed of a statistical array of α and β structures with such sheet displacements was found to be fully compatible with experimental data and most appropriate to describe nylon 46 lamellar crystals. Annealing of the crystals at temperatures closely below the Brill transition induced enrichment in β structure and increased chain‐folding order. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 41–52, 2000     

Dispersion and distribution of organically modified montmorillonite in nylon‐66 matrix

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with an alkyl ammonium surfactant pretreated montmorillonite (MMT). The thermal stability of the organic MMT powders was measured by thermogravimetric analysis. The decomposition of the surfactant on the MMT occurred from 200 to 500 °C. The low onset decomposition temperature of the organic MMT is one shortcoming when it is used to prepare polymer nanocomposites at high melt‐compounding temperatures. To provide greater property enhancement and better thermal stability of the polymer/MMT nanocomposites, it is necessary to develop MMT modified with more thermally stable surfactants. The dispersion and spatial distribution of the organic MMT layers in the nylon‐66 matrix were characterized by X‐ray diffraction. The organic MMT layers were exfoliated but not randomly dispersed in the nylon‐66 matrix. A model was proposed to describe the spatial distribution of the organic MMT layers in an injection‐molded rectangular bar of nylon‐66/organic MMT nanocomposites. Most organic MMT layers were oriented in the injection‐molding direction. Layers near the four surfaces of the bar were parallel to their corresponding surfaces; whereas those in the bulk differed from the near‐surface layers and rotated themselves about the injection‐molding direction. The influence of the spatial distribution of the organic MMT on crystallization of nylon‐66 was also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1234–1243, 2003     

Commensurate and incommensurate hydrogen bonds. An exercise in crystal engineering.

Ureas characteristically form one-dimensional hydrogen-bonded alpha-networks with a repeat distance of about 4.60 A. Oxamides form similar alpha-networks with a longer 5.05 A repeat distance. The urea of glycine and the oxamide of glycine were each cocrystallized with a series of four bipyridines, including two urea derivatives and two oxamide derivatives. This series of eight cocrystals was studied by X-ray diffraction in order to see what would happen when molecules that would normally form alpha-networks with incommensurate distances were forced into the same crystal. The two all-urea crystals and the two all-oxamide crystals contained the expected alpha-networks with repeat distances in accordance with normal urea or oxamide values. Four of the crystals were mixed, containing both oxamide and urea molecules. Three consisted of two-dimensional beta-networks with alternating parallel urea and oxamide subnetworks. The repeat distances averaged 4.87 A, a value close to the value expected for oxamides, but shorter than any previously observed examples. In the fourth mixed crystal, the urea alpha-network formed with a normal urea repeat distance, but the oxamide network did not form, the oxamide adopting an unusual molecular conformation that maximizes intramolecular hydrogen bonds instead.     

13C-NMR Sequence Analysis. 23. Synthesis and NMR Spectroscopic Characterization of Polyoxamides with Alternating and Random Sequences of Aliphatic Diamines

Three classes of polyoxamides were prepared: homopolymers derived from α-, ω-diaminoalkanes, and 4,4′-diaminodiphenyl-methane, copolymers with an alternating sequence of two different aliphatic diamines and copolymers with a random sequence of two different diamines. For their syntheses a new class of monomers, the diamine bisoxamide diethyl esters, were prepared from α,ω-diamines and oxalic acid chloride ethyl ester. The 22.63 MHz ¹³C-NMR spectra of the polyoxamide solution in fluorosulfonic acid permitted sequence analysis because the carbonyl signals are sensitive to the nature of the neighboring diamine units. In contrast, 9.12 MHz ¹⁵N-NMR spectra did not give any sequence information. The thermal stability of the polyoxamides was investigated, but differential scanning calorimetry did not give useful information on the crystallinity of the polyoxamides because of their thermal degradation.     

An investigation of the smectic-isotropic transition in a side-chain liquid crystal polymer by synchrotron radiation x-ray diffraction

In this work we have used synchrotron x-radiation diffraction to follow in real-time the isotropic-smoetic phase transition of a side-chain liquid crystalline polymer. The analysis of the x-ray data indicated that the transition occurs within a very narrow biphasic region. As the transition takes place, the size of the smectic regions, as indicated by the width of the diffraction peaks, changed only very slightly before impingement, suggesting a two-dimensional growth pattern. A thermal investigation of the polymer paralleling the x-ray experiments was undertaken and a kinetic analysis applied to the resulting data. Qualitative agreement with a disk-like growth of the smectic regions was found. We have shown that the overall kinetics of the isotropic-smectic transition of a side-chain polymer can be studied by x-ray diffraction permitting the evaluation of several structural parameters. © 1993 John Wiley & Sons, Inc.     

Structures of X 34‐nylons in chain‐folded lamellae and gel‐spun fibers

Structural studies and morphological features of a new family of linear, aliphatic even–even, X 34‐nylons, with X = 2, 4, 6, 8, 10, and 12, are investigated with X‐ray diffraction and electron microscopy. Solution‐grown crystals were obtained by isothermal crystallization from N,N‐dimethylformamide solutions. The thickness of lamellar‐like crystals was orders of magnitude less than the chain lengths of the polymer samples used, implying that the chains fold to form chain‐folded lamellae. The results bear a close resemblance, with the noticeable exception of 2 34‐nylon, to those reported for nylon 6 6 and other even–even nylon chain‐folded lamellar crystals. The basic structure of the straight‐stem lamellar core is similar to that of the classic nylon 6 6 triclinic α structure, and the chains tilt ≈42° relative to the lamellar normal. In the case of 2 34‐nylon, the structure resembles the 2 Y nylon series, and the chain tilt angle reduces to 36.6°. These combined results suggest that, even with a relatively low frequency of amide units along the backbone of these molecules, hydrogen bonding is still the dominant element in controlling the behavior, structure, and properties of these polymers. In addition, gels were prepared in concentrated sulfuric acid, and gel‐spun fibers were studied using X‐ray diffraction. The data are interpreted in terms of a modified nylon triclinic α structure that bears a resemblance to the structure of even–even nylons at elevated temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2685–2692, 2002     

CONFORMATION AND CHAIN PACKING STRUCTURES OF POLY (ρ-PHENYLEN BENZOBISTHIAZOLE) BY MOLECULAR SIMULATION*

The conformation, the chain packing stabilization and the unit cell modeling of poly(p-phenylene benzobisthiazole) have been investigated by using molecular simulation techniquein the present work. A coupling behaviour of σ-bond rotations at either side of the pheny-lene ring or the heterocyclic ring was found surely to exceed a length of the repeat unit ofthe polymer chain. For a single chain model, the stable torsion angle of the repeat resultedat 14°. In the crystalline cell minimization, the dihedral angle along the polymer chaincould even be stabilized in various values. It therefore indicates that the intermolecularinteraction does play a considerable role for this polymer forming the conformation. Ac-cording to cohesive energies calculated for these unit cell models, the torsion angle in themost stable crystalline cell is 0°. When the chains packing together, there exist so manyenergy stable wells along the chain axis 0.35--0.36nm apart from neighbouring chains.Most of the unit cells have quite closed cohesive energies. These factors thus cause thedifficulty of forming an unique perfect crystalline structure of the polymer. The presentstudy suggested a number of reasonable unit cells, and the most stable crystalline structurefor this polymer that is monoclinic, non-primitive unit cell.     

X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

Crystal structure and morphology of biaxially oriented polyamide 12 films

The structural and morphological characteristics of biaxially oriented polyamide 12 films are described on the basis of the results from differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), polarized FT‐IR spectroscopy, and small angle X‐ray scattering (SAXS). The WAXD patterns of the oriented polyamide 12 films indicated only the monoclinic γ crystal with little dimensional changes of its unit cell depending on the stretching conditions. The crystallographic angles (α = γ = 90°, β = 121°) that were determined via the WAXD patterns confirmed the monoclinic symmetry of the γ crystal. Annealing the films stretched at 115 °C in boiling 20% formic acid solution did not result in structural changes of the crystalline unit cell. The chain‐axis repeat distance of 31.9 Å for the γ crystal was experimentally obtained with (0 26 0) planes. It was shortened as compared with that of all‐trans conformation. For films having primary orientation to MD, normals to the basal plane of folded‐chain lamellae were parallel to MD (primary stretch direction) resulting in two‐point SAXS patterns. Growth in long spacing with an increase of stretch temperature was discovered. Annealing the films induced further elongation in long spacing. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1189–1200, 2002     

Structure of poly(N-methyl laurolactam)

The structure of poly(N-methyl laurolactam) has been studied in the solid state and in solution. In oriented, annealed monofilaments, the chain exhibits a distorted extended planar zigzag conformation. Upon orientation, an increase in crystallinity and a slight shift of the large d spacing in the diffraction pattern to a higher value is observed. In the crystalline regions of the polymer, the amide groups are proposed to have the anti conformation, whereas the amorphous regions may consist of both the syn and anti forms. Differential scanning calorimetry and thermal mechanical analysis showed multiple melting endotherms which probably result from partial melting and reorganization of small, imperfect crystallites. In solution, nuclear magnetic resonance spectroscopy showed the presence of a conformational equilibrium of the syn and anti amide groups in the polymer chains. The effect of thermal and mechanical treatments on certain infrared group frequencies of the amide moieties was studied and correlated with other pertinent analytical data.