Preparation of telechelic oligomers by controlled thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene)

It was found that telechelic isotactic oligo(1-butene) and telechelic oligo(propylene-ran-1-butene) could be isolated as nonvolatile oligomers from polymer residues resulting from the thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene), respectively. Their structures were determined by ¹H and ¹³C NMR with attention being paid to their reactive end groups. The maximum average number of terminal vinylidene groups per molecule (f_TVD) was 1.8, indicating that about 80 mol% were α,ω-diene oligomers having two terminal vinylidene groups. This useful new telechelic oligomer had a lower polydispersity than the original polymer, in spite of its lower molecular weight and T_m. The composition of end groups of nonvolatile oligomers obtained by thermal degradation of poly(propylene-ran-1-butene) could be explained by the differences in bond dissociation energy and activation energy of elementary reactions during thermal degradation, based on the monomer composition of the original polymer.     

Phase behavior of blends of linear low density polyethylene and poly(ethene-propene-1-butene)

The aim of this work was the study of blends of linear low density polyethylene (LLDPE) and an ethene-propene-1-butene terpolymer (t-PP). Two types of polyethylene were used to prepare the blends: an ethene-co-1-hexene (LLDPE(H)) copolymer and an ethene-co-1-octene (LLDPE(O)) copolymer. These copolymers present similar comonomer contents, molar mass, molar mass distribution and catalyst systems, but differ in their comonomer distribution. The blends were obtained through mechanical mixing using a single screw extruder at different compositions: 20, 40, 50, 60 and 80 wt.% of LLDPE. From DSC measurements two separated melting and crystallization peaks were observed and dynamic mechanical analysis showed two glass transitions indicating that LLDPE/t-PP blends are immiscible in amorphous and crystalline phases in the solid state. X-ray diffraction showed that the unit cell parameters of both polymers in the blends remain unchanged independent of the composition of the blend.     

Microhardness-structure correlation of iPP/EPR blends: influence of molecular weight and EPR particle content

The influence of molecular weight on the mechanical properties of isotactic poly(propylene) (iPP) and iPP blended with ethylene-propylene copolymers has been investigated by means of the microhardness technique. The hardness (H) of iPP is shown to slightly decrease with increasing molecular mass, within the range of molecular weights investigated. The H-decrease is correlated to a loss of crystallinity as the average molecular weight increases. On annealing, the mechanical properties are enhanced as a consequence of an increase in both, the degree of crystallinity and the crystalline lamellar thickness. A value of H ^∞ _c for iPP crystals of infinite thickness in the α-form is proposed for the first time. The inclusion of EPR particles in the iPP matrix softens the material. This result could be explained in terms of an increase in the basal surface free energy of the iPP crystals with increasing amount of rubber content. Received: 2 February 1998 Accepted: 11 May 1998     

Differential scanning calorimetry,small‐angle X‐ray scattering,and wide‐angle X‐ray scattering on homogeneous and heterogeneous ethylene‐α‐copolymers

The objective of this work was to use both X‐ray and differential scanning calorimetry techniques in a comparative study of the lamellar and crystalline structures of heterogeneous and homogeneous ethylene‐α‐copolymers. The samples differed in the comonomer type (1‐butene, 1‐hexene, 1‐octene, and hexadecene), comonomer content, and catalyst used in the polymerizations. Step crystallizations were performed with differential scanning calorimetry, and the crystallinity and lamellar thicknesses of the different crystal populations were determined. Wide‐angle X‐ray scattering was used to determine crystallinities, average sizes of the crystallites, and dimensions of the orthorhombic unit cell. The average thickness, separation of the lamellae, and volume fractions of the crystalline phase were determined by small‐angle X‐ray scattering (SAXS). The results revealed that at densities below 900 kg/m³, polymers were organized as poorly organized crystal bundles. The lamellar distances were smaller and the lamellar thickness distributions were narrower for the homogeneous ethylene copolymers than for the heterogeneous ones. Step‐crystallization experiments by SAXS demonstrated that the long period increased after annealing. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1860–1875, 2001     

Anionic copolymers of caprolactam with laurolactam (nylon 6/12 copolymers)—I. Preparation and general properties

Copolyamides of high mol.wt were obtained by the anionic copolymerisation of ?-caprolactam with ω-laurolactam at 180°C, using a sodium caprolactamate-N-phenylcarbamoylcaprolactam initiator activator system. The proportions of co-units in the copolymers were close to those in the comonomer feeds. The copolymers were crystalline and substantially fully hydrogen-bonded over the whole range of compositions, except at 50/50 mole% ratio, each displayed only one crystalline phase corresponding to that of the major component. T_m and density measurements indicated a crystallinity minimum at 50 60 mole% NH(CH₂)₅CO unit content. The properties of the copolyamides were consistent with random copolymeric structures.     

Crystallinities of copolymers of ethylene and 1-alkenes

Random copolymers of ethylene with 1-butene, 1-octene, and 1-octadecene have been prepared using a homogeneous vanadium-based catalyst system. Comonomer contents determined by ¹³C-NMR analysis of polymer solutions are in the range 1–10 mol%. Crystallinities were estimated by means of density measurements, x-ray diffraction, differential scanning calorimetry, laser Raman spectroscopy, and CPMAS ¹³C-NMR spectroscopy. The results are compared with those obtained for heterogeneous copolymers of ethylene containing 1–4 mol% 1-butene. As the comonomer content is increased, the crystallinity decreases. The dimension perpendicular to the 110 plane in orthorhombic crystallites decreases linearly with crystallinity. This decrease in crystallite size is accompanied by an increase in the size of the orthorhombic unit cell. For copolymers containing large amounts of 1-octene and 1-octadecene, a second crystalline form appears. Differences in estimates of crystallinity are discussed in terms of looser packing in highly branched copolymers and the extent to which the second crystalline form participates in the phase structure.     

Costereosymmetric α-olefin copolymers

Copolymerization of propylene and 1-butene with highly stereospecific three-component coordination catalysts produced multiblock crystalline copolymers having stereo-regular sequences of both propylene and 1-butene. Copolymers containing from 3 to about 80% 1-butene had two DTA melting points which were attributable to polypropylene and poly-1-butene crystallinity. Those containing from 18 to about 70% 1-butene had x-ray diffraction patterns showing peaks characteristic of polypropylene and form I poly-1-butene, but form II poly-1-butene crystallinity was never observed. The multiblock copolymer structure observed is also supported by the fact that the product of the reactivity ratios is greater than unity. The composition distributions of low-conversion and continuously prepared copolymers were similar and relatively broad. For example, copolymers containing an average of 12% 1-butene had species containing from 5–30% 1-butene. High-conversion copolymers had an even broader composition distribution due to the gradual increase of the 1-butene concentration in the comonomer mixture as the copolymerization proceeded. The absence of homopolymers was demonstrated by fractionation. The ability to detect homopolymers was proved by the fact that a mixture of stereoregular polypropylene and poly-1-butene were readily separated. Increasing the amount of 1-butene tended to decrease those properties dependent upon crystallinity such as hardness, tensile strength, stiffness, density, and melting point, but tended to improve significantly the impact strength, low temperature properties, and clarity of molded objects. These duocrystalline copolymers retained a much higher level of properties than that observed for random copolymers prepared with less stereospecific coordination catalysts.     

Co- and terpolymerization of ethylene with 1-butene and 1-decene by using Cp2ZrCl2-methylaluminoxane catalyst

Copolymerizations of ethylene/1-butene, and ethylene/1-decene and terpolymerization of ethylene/1-butene/1-decene were carried out in n-heptane with various concentrations of comonomer in the feed. Cp₂ZrCl₂-methylaluminoxane (MAO) was used as catalyst. When comonomers were added into the ethylene polymerization, the activity of the catalyst increased significantly and continued to do so as the concentration of the comonomer was increased. At the same time as the comonomer concentration and catalyst activity increased, the molecular weight and crystallinity of the polymers decreased. An important reason for the activity enhancement may, therefore, be that the comonomer takes part in the activation of catalytic centers, decreasing the activation energy required for monomer to insert into the active centers. Use of Cp₂ZrCl₂-MAO catalyst allowed the preparation of ethylene/1-decene copolymers containing 20 wt % of 1-decene. © 1993 John Wiley & Sons, Inc.     

Comparison of semicrystalline ethylene–styrene and ethylene–octene copolymers based on comonomer content

The structure and properties of homogeneous copolymers of ethylene and styrene (ES) and ethylene and octene (EO) were compared. Semicrystalline copolymers presented a broad spectrum of solid‐state structures from highly crystalline, lamellar morphologies to the granular, fringed micellar morphology of low‐crystallinity copolymers. The combined observations from density, thermal behavior, and morphology with primarily atomic force microscopy revealed that the crystalline phase depended on the amount of comonomer but was not strongly affected by whether the comonomer was styrene or octene. This was consistent with the exclusion of both comonomers from the crystal. However, ES and EO showed strong differences in the amorphous phase. ES had a much higher β‐relaxation temperature than EO, which was attributed to restrictions on chain mobility imposed by the bulky phenyl side group. The deformation behavior of ES and EO exhibited the same trends with comonomer content, from necking and cold drawing typical of a semicrystalline thermoplastic to uniform drawing and high recovery characteristic of an elastomer. Aspects of deformation behavior that depended on crystallinity, such as yielding and cold drawing, were determined primarily by comonomer content. However, the difference in the β‐relaxation temperature resulted in much higher strain hardening of ES than EO. This was particularly evident with low‐crystallinity, elastomeric copolymers. A classification scheme for semicrystalline copolymers based on comonomer content, previously developed for EO, was remarkably applicable to ES. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1578–1593, 2001     

Compatibility mechanisms between EVA and complex impact heterophasic PP-EPx copolymers as a function of EP content

Compatibility mechanisms between EVA and complex heterophasic iPP-EPx copolymers have been studied as a function of EP content. Systematic studies were made in order to characterize the thermal, morphological and mechanical behavior, before and after blending a series of PP-EPx/EVA concentrations. Multiple melting, proportional to the EP content, was observed for the neat copolymers and an explanation was given for its evolution in terms of rejection-like secondary crystallization. After blending with EVA, the generation of a single T_g was taken as an indication of compatibility between both polymers. A morphological transition toward compatibility was first determined at 20 wt.% EVA which was in correlation with a morphological change from isolated spherical domains to interconnected voids. A second morphological transition from interconnected voids to fibrous crystals was observed above 40 wt.% EVA. This last transition marked the beginning of compatibility. Overall, the evolution of blends was explained in terms of the nature of the complex heterophasic copolymers. Tensile mechanical studies were also consistent with morphological changes. Increases in the x content in EPx and in EVA concentration worked in favor of impact resistance.     

Morphologies, crystallinity and dynamic mechanical characterizations of polypropylene/polystyrene blends compatibilized with PP-g-PS copolymer: Effect of the side chain length

PP-g-PS copolymers were synthesized with the same polypropylene (PP) backbones and various side chain lengths of PS sequences via reactive comonomer p-allyltoluene (p-AT) by Ziegler–Natta copolymerization and the subsequent living anionic graft-polymerization. ¹H NMR characterized that the PP-g-PS copolymer had grafted 3.15 side chains per 1000 carbons in the PP backbones and the length of PS sequences varied in the range of 25.8–309.9 units. PP/PS blends with the PP-g-PS copolymer as compatibilizer (wt. 75/25/5) were prepared and characterized by SEM, WAXD and DMA to investigate the morphologies, crystallinity and glass transition temperatures of the PP/PS blends. All the results pointed out that the average side chain length (GL) of the graft copolymer (GL is from 25.8 to 309.9) made great effects of the PP/PS blends, such as the PS dispersed phase, the crystallinity of the PP component and the two glass transition temperatures of the blends, which showed the same trend with the increase of the GL. Overall, only with a suitable average side chain length, the PP-g-PS copolymer could achieve optimal compatibilizing efficiency of the PP/PS blends.     

Effects of ultrahigh molecular weight polyethylene and mould temperature on morphological evolution of isotactic polypropylene at micro-injection moulding condition

The effects of ultrahigh molecular weight polyethylene (UHMWPE) and mould temperature (T_mould) on an isotactic polypropylene (iPP) matrix moulded via micro-injection were investigated via polarized light microscopy, scanning electron microscopy, differential scanning calorimetry, wide-angle X-ray diffraction and small-angle X-ray scattering. Results showed that the complex viscosity of the system increased significantly when the UHMWPE content was more than 5%; however, this viscosity decreased when the UHMWPE content was less than 5%. In addition, the addition of UHMWPE increased the onset of crystallisation temperature and the relative crystallinity of the β-form crystals in micro-injection moulded specimens. Moreover, the UHMWPE phase induced the formation of fan-shaped β crystals in iPP/UHMWPE blends. When mould temperature was 50 °C, the degree of orientation of microparts increased and the crystalline structures were highly compact. However, the relative crystallinity of the β-phase form (K_β) was lower than those prepared at 130 °C T_mould. Most importantly, well-oriented, bundle-like β crystals have been discovered for the first time in 5 wt.% UHMWPE/iPP blends obtained at 130 °C T_mould owing to the “orientation-maintenance” and “shear-amplification” effects of UHMWPE.     

Formation and morphology of cellulose acetate butyrate (CAB)/polyolefin and CAB/polyester in situ microfibrillar and lamellar hybrid blends

Cellulose acetate butyrate (CAB)/iPP (isotactic polypropylene), CAB/HDPE (high density polyethylene), CAB/PET (poly ethylene terephthalate), CAB/PTT (poly trimethylene terephthalate), CAB/PBT (poly butylenes terephthalate) and CAB/IPET-PEG (poly(ethylene terephthalate-co-isophthalate)-poly(ethylene glycol)) in situ microfibrillar and lamellar hybrid blends at a weight ratio of 80/20 were prepared by melt extrusion. Microfibrillar and lamellar hybrid morphologies of CAB/polyolefin and CAB/polyester blends under different force fields were investigated. The formation process of in situ microfibrillar and lamellar hybrid blends were analyzed and proposed.     

Crystallization and enzymatic degradation of novel poly(ε-caprolactone-co-propylene succinate) copolymers

A series of novel poly(ε-caprolactone-co-propylene succinate) P(CL-co-PSu) copolymers having low propylene succinate content and high molecular weight were synthesized following a combinatory scheme of ring opening and polycondensation reactions, in an attempt to obtain copolymers of sufficient performance and increased biodegradation rates. Enzymatic hydrolysis of the copolymers was studied in the presence of mixture of Rhizopus delemar and Pseudomonas cepacia lipases. Much higher hydrolysis rates, comparing to neat PCL, were proved by both mass loss measurements and scanning electron microscopy (SEM) observations of the degraded film surfaces. Thermodynamics of cocrystallization and wide-angle X-ray diffraction (WAXD) patterns were investigated to estimate the extent of comonomer cocrystallization. Results of the study showed that comonomer inclusion may hold, though the molar fraction of the comonomer in the PCL crystals is lower than in the bulk. This means that not only the observed decrease of the degree of crystallinity from about 48% for PCL to about 29% for the P(CL-co-PSu) 75/25 favours enzymatic hydrolysis, but also the enrichment of the amorphous phase in the fast degrading propylene succinate units plays its role. The non-isothermal crystallization rates of the copolymers, like the melting points, decreased substantially when the propylene succinate content exceeded 8 mol%. The activation energy of crystallization was calculated using the isoconversional method of Friedman, over the whole range of crystallization temperatures. An increase was found in the activation energy with increasing the comonomer content in the copolymers also proving the reduced symmetry along the copolymer chains due to the presence of comonomer units.     

用钛系载体高效催化剂进行乙烯-丙烯-1-丁烯三元共聚合的研究 Ⅱ.共聚物的结构表征

通过各种表征手段对用TiCl_4,Ti(OBu)_4/MgCl_2/EB/φSiCl_2/AlEt_3催化剂合成的乙丙丁三元共聚物进行了剖析。发现在一定组成范围内,三元共聚物不含庚烷不溶物。DSC和WAXD分析检测不到结晶相。用~(13)C-NMR技术表征了在相同条件下合成的乙丙、乙丁及丙丁三组二元共聚物的序列分布。结果表明,乙丙和乙丁共聚物的序列结构可用一级Markov分布描述。丙丁共聚物则服从Bernoulli分布,用~(13)C-NMR方法计算了乙丙丁三元共聚物的化学组成,并初步考察了共聚物硫化胶的力学性能。     

Effects of stereo-defect distribution on the crystalline morphology and tensile behavior of isotactic polypropylene prepared by compression molding process

In this study, the aggregation morphology, tensile behavior, and morphology evolution during the tensile test of two isotactic polypropylene (iPP) samples with similar molecular weight and average isotacticity but different uniformities of stereo-defect distribution are investigated by differential scanning calorimetry (DSC), two-dimensional wide angle X-ray diffraction (2D-WAXD), and scanning electronic microscopy (SEM). The results revealed that the uniformity of stereo-defect distribution of iPP determines the crystalline structure and aggregation morphology, and further influences the tensile behavior and morphology evolution during the tensile test. For PP-A with less uniform stereo-defect distribution, its ability of crystallization is stronger compared with PP-B, resulting in smaller spherulite sizes, higher melting point and degree of crystallinity, and narrower distribution of lamellar thickness of the compression molding specimens. During the tensile test, mainly the inter-spherulite deformation takes place at the early stage for deformation, which further results in drastic deformation of lamellar and high degree of reorientation at the strain increases, exhibiting higher yield strength and elastic modulus, and lower elongation at break compared with PP-B; for PP-B with more uniform stereo-defect distribution, larger spherulite sizes, lower melting point and degree of crystallinity in its compression molding sample are observed. During the tensile test, intra-spherulite deformation mainly takes place, which can disperse the tensile stress more uniformly. As the strain increases, lower degree of crystalline destruction and reorientation of the crystallites take place. The yield strength and elastic modulus of PP-B is lower than PP-A, and its elongation at break is higher.     

Phase morphology of iPP/aPS/SEP blends

Supermolecular structure and phase morphology of the ternary isotactic polypropylene/atactic polystyrene/poly(styrene-b-ethylene-co-propylene) (iPP/aPS/SEP) compression molded blends with 100/0, 90/10, 70/30, and 50/50 iPP/aPS weight ratios and with different amounts of added SEP compatibilizer were studied by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). SEP significantly reduced the size of dispersed aPS particles that enabled better spherulitization in the iPP matrix. Furthermore, iPP spherulites in ternary blends with 90/10 iPP/aPS weight ratio became larger in comparison with the pure iPP. TEM revealed that the SEP formed continuous interface layer around the dispersed aPS particles even when only 2.5 wt.% of SEP was added. Particle size distribution was distinctly bimodal. When the SEP content was increased to 10 wt.%, joining together smaller and bigger aPS and SEP particles formed dispersed aggregates. Additionally, both amorphous components (aPS and SEP) influenced crystallization process of iPP matrix and so modified, to some extent, its final supermolecular structure. SEP compatibilizer did not significantly affect crystallite orientation. The increase of crystallite sizes, which was more affected by the addition of aPS than by the addition of SEP, seemed to be influenced by the solidification effect rather than by the phase morphology of the blends.     

The influence of side branches on the structure of crystalline phase in ethylene-1-alkene copolymers

The influence of side branches on the unit cell dimensions in ethylene-1-alkene copolymers was investigated both at room temperature as well as during heating of the samples up to melting. Time resolved X-ray diffraction investigations revealed that in the case of ethylene-1-octene copolymers with low and moderate comonomer content, the transversal expansion of the unit cell occurs due to the limited thickness of lamellae, however the samples with higher comonomer content (above 5 mol %) exhibit distinctly larger expansion resulting from the stresses imparted on the basal surfaces of crystals by the excluded branches. At high temperatures, independently on the thermal expansion, an additional increase of the unit cell volume occurs, caused probably by a penetration of the end-parts of side branches, residing near the crystals surface, into the surface cells. Similar phenomenon is observed for ethylene-1-butene copolymer. On contrary, the ratio of the average unit cell volume in ethylene-1-propene copolymer to the unit cell volume in linear polyethylene at the same temperature, decreases starting from about 50 °C. Such a behavior is a new confirmation of a partial inclusion of methyl branches into the crystalline phase. Most probably, when the temperature increases, the volume of included branch becomes a decreasing fraction of the thermally expanding unit cell volume.     

Classification of homogeneous ethylene-octene copolymers based on comonomer content

Ethylene-octene copolymers prepared by Dow's INSITE™ constrained geometry catalyst technology present a broad range of solid-state structures from highly crystalline, lamellar morphologies to the granular morphology of low crystallinity copolymers. As the comonomer content increases, the accompanying tensile behavior changes from necking and cold drawing typical of a semicrystalline thermoplastic to uniform drawing and high recovery characteristic of an elastomer. Although changes in morphological features and tensile properties occur gradually with increasing comonomer content, the combined body of observations from melting behavior, morphology, dynamic mechanical response, yielding, and large-scale deformation suggest a classification scheme with four distinct categories. Materials with densities higher than 0.93 g/cc, type IV, exhibit a lamellar morphology with well-developed spherulitic superstructure. Type III polymers with densities between 0.93 and 0.91 g/cc have thinner lamellae and smaller spherulites. Type II materials with densities between 0.91 and 0.89 g/cc have a mixed morphology of small lamellae and bundled crystals. These materials can form very small spherulites. Type I copolymers with densities less than 0.89 g/cc have no lamellae or spherulites. Fringed micellar or bundled crystals are inferred from the low degree of crystallinity, the low melting temperature, and the granular, nonlamellar morphology. © 1996 John Wiley & Sons, Inc.     

Side-chain crystallinity. II. Heats of fusion and melting transitions on selected copolymers incorporating n-octadecyl acrylate or vinyl stearate

The heats of fusion and the melting transitions of the crystallinity present in the side chains were determined for selected copolymers incorporating n-octadecyl acrylate or vinyl stearate. A major purpose of this investigation was to ascertain the effect of interrupting the long ordered 18-carbon side chains by randomly interspersed amorphous side chains of various lengths. For this purpose the lower acrylate homologs (C₁ through C₈ and including oleyl, C₈) were copolymerized over the composition range with n-octadecyl acrylate. It was found that simple dilution of the crystalline component (from comonomer b) by the amorphous component (from comonomer a) governed the decline in the heats of fusion and the fraction of crystallinity present. High crystallization rates were encountered because equilibrium crystallinity was nearly achieved for most of the copolymers. Melting point depression was less than theory in copolymers having short amorphous comonomer side chain lengths, but approached the theoretical depression as these side chains became very long. Thus the outer methylene sequences (the crystalline sequences) of the fatty co-units could bridge the smaller amorphous a units, giving rise to larger crystal sizes than theory specified. Main-chain stiffness, when present in the melt, had a small effect on the distribution of crystallite sizes but exhibited a much larger influence in preventing the attainment of equilibrium crystallinity, especially at high amorphous comonomer compositions. However, crystallinity was still high compared with that of copolymers described in the literature crystallizing through their main-chain units. When long blocks of crystalline segments were present (as in compositionally heterogeneous vinyl stearate copolymers), melting point depression was small and followed the theoretical probability sequence function.