Successive self-nucleation and annealing in the solvated state of ethylene copolymers

Summary Simultaneous TG/DSC and high temperature X-ray diffraction studies were performed on the system SrCO₃-Fe₂O₃ in an atmosphere of CO₂ from room temperature to 1300°C. SrCO₃ decomposes and reacts simultaneously with the Fe₂O₃ beginning around 850°C. A transient iron rich phase is formed initially, which soon diminishes to yield a mixture of perovskite SrFeO_3-x and the iron rich phase Sr₄Fe₆O₁₃. Upon cooling the perovskite phase predominantly orders into the brownmillerite structure Sr₂Fe₂O₅. There does not appear to be a Hedvall effect associated with the first order phase transformation in SrCO₃ at 927°C.     

Early detection of degradation in a semi-crystalline polyolefin by a successive self-nucleation and annealing technique

Samples taken from a black pipeline liner that became fragile while in service were analyzed by a Successive Self-Nucleation and Annealing (SSA) technique. Two types of polyethylene, Low-Density Polyethylene (LDPE) and Linear Low-Density Polyethylene (LLDPE) were aged in air, at several temperatures, and changes in the molecular structure were followed simultaneously by infrared and calorimetric techniques. Samples with and without antioxidants were prepared, aged, and evaluated for the same oxidative treatments. The LDPE type was chosen to be identical to the black LDPE originally used for making the pipeline liner. Oxidative reactions of LDPE and LLDPE were quantified via carbonyl group concentrations measured by FTIR. Changes in the crystallization behavior of the original and aged polymers, and of the black pipeline liner, were monitored via the SSA technique. Changes of the fraction of lamellae of specific thickness in the crystallized polymer could be correlated linearly with the formation of carbonyls, and thus this calorimetric method is proposed to be suitable as a tool for early quantitative monitoring of LDPE degradation.     

Application of successive self-nucleation and annealing to study the stereo-defects distribution of biaxially oriented polypropylene

The stereo-defects distribution of polypropylene of the two industry biaxially oriented polypropylene （BOPP） samples T28FE and F28SO with different processing properties was studied through successive self-nucleation and annealing （SSA） technique. It was found that there were more medium isotactic components in sample F28SO, and the isotactic sequence length of polypropylene of sample F28SO was shorter and the isotactic sequence length distribution of polypropylene of sample F28SO was broader, which could be processed well at high-speed orientation during the processing of BOPP films. This result indicates that the isotactic sequence length distribution of polypropylene is related to the processing speed during preparing BOPP films, and the stereo-defects distribution of polypropylene has an important influence on its processing ability.     

Use of the successive self-nucleation and annealing technique to characterize <Superscript>60</Superscript>Co gamma irradiated HDPEs

The application of the Successive Self-nucleation and Annealing (SSA) thermal fractionation technique can yield detailed information of the structural changes induced in linear polyethylene by irradiation. The production of tertiary carbons during the crosslinking reactions can be equivalent to the structural heterogeneity present in branched polyethylenes since in both cases interruption of the linear crystallizable sequences occurs, and these are structural differences that can be easily detected by thermal fractionation. We demonstrate how correlations between melting point and short chain branching content employed for branched polymers can be useful to characterize the distribution of chain heterogeneity produced by crosslinking. As the radiation dose is increased and the crosslinking content also increases, the distribution of chain heterogeneity gets broader as detected by SSA. When the results are coupled with morphological observations made by transmission electron microscopy, valuable information on the morphological changes produced by crosslinking can also be ascertained, since the distribution of lamellar thicknesses substantially broadens with crosslinking. Such a broad distribution can also be predicted from SSA by simple calculations performed employing a modified version of the Gibbs–Thomson equation and is expected on the basis of random crosslinking reactions.     

Determination of chemical heterogeneity of copolymers by gel-permeation chromatography

Summary The determination of the chemical heterogeneity of copolymers has been carried out by means of gel-permeation chromatography (GPC). Consequently mixtures of different homopolymers with the same relative molecular masses have been fractionated. Although maximum chemical non-uniformity appears, non-uniform effects obtained from the GPC are negligible. It is seen that for copolymers a GPC separation only occurs when the chemical composition of the copolymer changes simultaneously with the degree of polymerisation. We have established that, in a few cases, minute chemical heterogeneity is evident from the GPC curves, but not in the bulk which obeys the kinetics of copolymerisation.     

Electronic structure of random copolymers

The electronic structure of random copolymers (RCP) is theoretically investigated by the single-site coherent potential approximation. The results are also compared with those by the band calculation for the corresponding ordered system. In the A_{1 –x} B _x binary RCP, a strong reduction in the system band gap (E _g(A_1–x B _x )) is found in the dilute B region when the system has the relation ofE _g(A)>E _g(B). This dependence is caused by the asymmetric quenching in the density-of-states (DOS) singularity at the band-edge states. The gap-opening mechanism and the asymmetric quenching are discussed by focusing on the role of the spatial dimension on the electronic structure of the random system, and the theoretical treatment is finally applied to the calculation of the joint DOS for the Si-Ge RCP system.     

Characterization of semicrystalline random copolymers by small-angle neutron scattering

A new method is introduced to determine the degree of partitioning of noncrystallizable comonomer units (B units) between the two phases of a semicrystalline random copolymer. The method is based on the comparison of the intensities of small-angle neutron and x-ray scattering (SANS and SAXS, respectively). By this technique two quantities can be evaluated: the difference Δρ of the mass densities between the crystalline and the disordered regions, and the concentration fluctuations of the B units in the two phases. It is found that SANS is very sensitive to the presence of small amounts of B units if their scattering length is sufficiently different from that of the A units. This will be the case for copolymers with B units, in which a hydrogen is substituted by another atom. But in addition it can also be achieved generally by deuteration of the comonomer units. So a wide range of copolymer systems can be studied by this method. The capability of the method was proved by measurements on chlorinated polyethylene and on 1,3,5-trioxane–1,3-dioxolane copolymers. Both copolymers are distinguished by a random distribution of the co-units. The results show that even at relatively low concentrations x_B of the comonomer units a remarkable fraction of the B units is incorporated into the crystalline A phase and that this fraction rises if x_B is increased.     

Photodegradation of some ethylene-norbornene random copolymers

We investigated the photodegradation of specific ethylene-norbornene random copolymers (ENRC) - a group of substances which has been attracting much attention in recent years. ENRCs having various contents of norbornene were studied. After irradiation, each sample was separated into chloroform-insoluble and soluble portions. The chloroform-insoluble portion was weighed and analyzed by FTIR. The chloroform-soluble portion was analyzed by size elimination chromatography (SEC), FTIR and ¹H NMR. The yield of the chloroform-insoluble portion increased with increased irradiation time. Formyl, formate, acyl, hydroxy groups and a carbon-carbon double bond were formed by photo-irradiation. Apparently, hydrogen atoms bound to the tertiary and secondary carbon atom in the parent ENRCs are abstracted. From these results, it is suggested that auto-oxidation results from photo-irradiation of the ENRCs. In ENRCs with similar stereoregularity, the degree of photodegradation increases with increasing norbornene content.     

Calculation of composition heterogeneity of block and graft copolymers

The composition heterogeneity has been calculated for some block and graft copolymers. General relationships have been derived for a model of the poly(A-g-B) or poly-(A-b-B) type fulfilling the assumption of random grafting. Numerical results have been calculated for special cases of particular interest. These include a copolymer having independent molecular weight contributions from units of species A and B (a special case of which is a block copolymer) and a graft copolymer where the grafting is not accompanied by crosslinking or degradation side reactions and no homopolymer B is formed. Two other model systems represent the effects of the presence or absence of both homopolymers. For the above models, the dependence of the composition heterogeneity on the structure-determining parameters (average number of grafts in the molecule, polydispersity index of the molecular weight of the backbone and graft) is discussed. The heterogenities thus calculated are in many cases comparatively low. The composition heterogeneity of the system is in most cases increased by the presence of homopolymers.     

Surface hydrophobicity of fluorinated block copolymers enhanced by supercritical carbon dioxide annealing

Supercritical carbon dioxide (scCO2) annealing enhances the hydrophobicity of the surfaces of asymmetric perfluorinated block copolymers. X-ray photoelectron spectroscopy (XPS) and contact angle measurement reveal that the surface domains of the fluorinated block (PF) of poly[styrene-block-4-(perfluorooctylpropyloxy)styrene] (PS-PF) become thicker than those annealed in a vacuum. Consequently, the contact angles of water on the surfaces of PS-PF block copolymers significantly increase after the scCO2 annealing compared to those annealed in a vacuum. The surface hydrophobicity enhanced by the scCO2 annealing is related to the thickness of the surface PF domain and the conformation of the PF block.     

Composition of fullerene-containing styrene-diallyl isophthalate copolymers

The effect of fullerene C₆₀ on the composition of macromolecules in the free-radical copolymerization of styrene with diallyl isophthalate is estimated. It is shown that the maximum amount of C₆₀ is contained in the high-molecular-mass fraction of the products. Constants in the Kuhn-Mark-Houwink equation are determined for the fullerene-containing copolymer synthesized from an equimolar mixture of monomers.     

Adsorption of random copolymers on disordered surfaces

Monte Carlo simulations are used to study adsorption of random heteropolymers on disordered substrates. The adsorbent surface is modelled as an impenetrable wall with the random distribution of sites characterised by short-ranged segment-specific interactions with the polymer. Spatial fluctuations in the interaction strength are described as a Gaussian process with zero mean and variance σ₁ which is proportional to the site/segment potential, and to the loading of sites on the surface. In all cases, a moderate depletion in the polymer density is observed at small surface loading. Upon increasing σ₁ the polymer begins to adsorb on the surface. At a certain threshold loading, we observe a sharp second adsorption transition followed by gradual saturation. The transition is interpreted in terms of pattern matching; i.e. the heteropolymers accomodate themselves at surface domains with site distributions that match the configuration and the sequence of the chain when the sequence and surface site distributions are related in a special way. Distinct peaks in heat capacity and compressibility observed at the adsorption transition point to a first order process envisaged in earlier replica/mean-field analysis. These results suggest that random heteropolymers with designed sequence statistics can ‘recognise’ multifunctional disordered surfaces due to statistical pattern-matching.     

Viscoelastic properties of styrene-co-methyl methacrylate random copolymers

Viscoelastic properties of styrene-co-methyl methacrylate random copolymers have been determined over a temperature range covering the glass transition, the rubbery plateau, and the terminal zone and compared with polystyrene and polymethyl methacrylate homopolymers. Nonlinear behavior was observed in the variations of most of the physical and rheological characteristics with the methyl methacrylate content in the copolymer. Results are interpreted in terms of the rupture of polar-polar intermolecular interactions between ester groups due to the presence of styrene units.     

One-step multifunctionalization of random copolymers via self-assembly

A novel methodology for random copolymer functionalization based on a noncovalent, one-step, multifunctionalization strategy has been developed. Random copolymers possessing both palladated-pincer complexes and diaminopyridine moieties (hydrogen-bonding entities) have been synthesized using ring-opening metathesis polymerization. Noncovalent functionalization of the resultant copolymers is accomplished via (1) directed self-assembly, (2) multistep self-assembly, and (3) one-step orthogonal self-assembly. This system shows complete specificity of each recognition motif for its complementary unit, with no observable changes in the association constants regardless of the degree of functionalization.     

Stereochemical heterogeneity of biodegradable poly(L‐lactide) homopolymer as revealed by temperature rising elution fractionation and successive self‐nucleation/annealing thermal fractionation

Commercial poly(L ‐lactide) is typically heterogeneous in chain structure due to the existence of a small amount of D ‐lactyl units that are produced by the racemization reactions during the synthesis. In this article, the stereochemical heterogeneity of two commercial poly(L ‐lactide) was investigated with temperature rising elution fractionation (TREF) and successive self‐nucleation/annealing (SSA) thermal fractionation. For both samples, three fractions were collected and characterized with rotatory power analysis and DSC. The fractions show distinct optical purity and DSC results, which reflect the structure differences among them directly. After SSA treatment, the observation of multiple endotherms for each physically separated fraction confirms the fractionated sample contains a heterogeneous intermolecular and intramolecular distribution of defects. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Interaction of ethylene oxide-propylene oxide copolymers with ionic surfactants studied by calorimetry: random versus block copolymers

The present study used calorimetric techniques to follow the interaction of random and block ethylene oxide (EO)-propylene oxide (PO) copolymers with ionic surfactants. Features such as the intensity of the interaction (evaluated through their critical aggregation concentrations) and the profile of the isothermal titration calorimetry (ITC) curves were comparatively analyzed for random and block copolymers with similar composition (number of EO and PO units). Random copolymers displayed an interaction similar to that observed with other hydrophilic homopolymers with the additional characteristic that the intensity of the interaction increased with the increase in the copolymer hydrophobicity (as determined by its PO content), revealing that these copolymers display an intermediate behavior between PEO and PPO. For nonaggregated block copolymers (unimers) with large enough EO blocks (molar mass above 2000 g mol-1), ITC curves revealed that the anionic surfactant sodium dodecylsulfate (SDS) interacts with the PO and EO blocks almost independently, being more favorable with the PO block, which controls the critical aggregation concentration (cac) value. Effects of temperature and of the nature of the ionic surfactants on their interaction with these copolymers were found to agree with the previously reported trends.     

Chemical heterogeneity in emulsion copolymers of carboxylic monomers

Copolymer latices of butylacrylate (BA) with acrylic and methacrylic acid (AA and MAA) were prepared by batch type emulsion polymerization, and, for comparison, copolymers with identical monomer composition were prepared by batch type solution polymerization.The distribution of the carboxylic monomers in the latex particles and the serum was studied by density gradient and sedimentation experiments with the analytical ultracentrifuge. Dynamic mechanical measurements of films of these copolymers were used to determine the storage and loss moduli as a function of temperature. From these measurements the position and extension of the glass transition range on the temperature scale is obtained. For heterogeneous emulsion copolymers with two glass transition temperatures the distribution of the carboxylic monomer units in the different copolymer phases can be determined. Electron microscopy of ultra thin cross-sections of stained films gave further insight into the film morphology.The combination of the results obtained with the different methods gives rise to the following clues: In the BA/AA latices about 40% (by weight) of the total AA used in the recipe are found in the serum as a water soluble polymer, about 50% are found to increase the glass transition temperatureT _g of the bulk of the BA copolymer and, therefore, are thought to be incorporated into the interior of the latex particles, and the remaining 10% are, conclusively, located on the particle surface.In the BA/MAA latices no water soluble copolymer could be detected in the serum, about 90% of the MAA used is found in the bulk of the copolymer, and about 10% form a second hard phase on the surface of the latex particles.Dynamic mechanical measurements on the copolymer latex films show at least two phases with different glass transition temperatures: the bulk of the copolymer with a relatively low content of (M)AA units and a glass transition range at low temperatures, and a second (M)AA rich phase with a highT _g.The latter phase forms a honeycomb-like structure surrounding the packed latex particles. That results in a three-dimensional network of polymer with a highT _g extending throughout the latex film. In spite of the fact that this phase is built from a small fraction of the total copolymer only, it has a very pronounced influence on the performance behaviour of latex films.Dedicated to Professor Dr. R. Manecke on the occasion of his 70th birthday.     

Enhancement of mechanical properties of triblock copolymers by random copolymer middle blocks

Symmetric styrene-b-styrene-co-butadiene-b-styrene (S-SB-S) tri-block copolymers with varying middle and outer block composition have been studied. We report our findings based on a systematic variation of the effective interaction parameter (χ) by adjusting the composition of the random copolymer in the middle block and of the outer blocks (in terms of PS-chain length) which allows us to explore the χ-parameter space with regard to molecular architecture more thoroughly than in SBS triblock copolymers. A variation in the S/B middle block composition or in the PS outer block content leads to a change in phase behaviour and morphology simultaneously accompanied by significant changes in mechanical properties, varying from elastomeric to thermoplastic property profile. Despite high PS contents of 55-75 wt.% these S-SB-S triblock copolymers reveal high strain at break values between 650% and 350% which is in striking contrast to the conventional SBS triblock copolymers where only about 10% strain at break have been reported to be achieved with similar PS-content (∼75 wt.%).