Effect of the comonomer content on the mechanical parameters and microhardness values in poly(ethylene‐co‐1‐octadecene) synthesized by a metallocene catalyst

Stress–strain and microhardness measurements were carried out on a series of copolymers of ethylene and 1‐octadecene with different comonomer contents in the corresponding homopolymer of ethylene, synthesized with a metallocene catalyst. The different mechanical properties, deduced from the stress–strain curves (Young's modulus, yield stress, deformation at break, and energy to break) are interpreted in terms of the crystallinity and molecular weight of the samples because these two characteristics show considerable variations with the comonomer content. The microhardness values are explained in terms of these properties, and they are also correlated with Young's moduli and yield stresses deduced from the stress–strain curves. Linear relations are found between microhardness and yield stress and between the logarithm of the microhardness and the logarithm of the elastic modulus. The properties deduced from these lines are compared with literature values. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 277–285, 2001     

Permeation measurements in ethylene‐1‐hexene,ethylene‐1‐octene,and ethylene‐1‐dodecene copolymers synthesized with metallocene catalysts

The permeation behavior of different ethylene‐1‐hexene, ethylene‐1‐octene, and ethylene‐1‐dodecene copolymers synthesized with metallocene catalysts has been analyzed. These copolymers cover a wide range of comonomer contents, so their crystallinities display rather considerable variations. The results for the permeability to oxygen of the different ethylene copolymers show that the main factor influencing the permeability is the noncrystalline fraction, although some influence of the kind of comonomer may also be present, which may be explained by the fact that when the alkyl branch of the α‐olefin is longer, there is an increase in the free volume in the amorphous and interfacial regions, causing slightly higher values of the permeability coefficient. From the results with different gases, it follows that, in general, an increase in the size of the penetrant (as expressed by its kinetic diameter or critical molar volume) leads to an increase in the solubility and a decrease in the diffusion coefficient. A wide range of permeability values is covered by these ethylene copolymers, depending basically on the crystallinity of the sample, but the permselectivity of CO₂ with respect to oxygen (and probably between other pairs of gases) does not differ very much among the different copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2174–2184, 2003     

Structural characterization and mechanical behavior of metallocenic copolymers of ethylene and 5,7-dimethylocta-1,6-diene

The relationships between structure and mechanical properties have been established in several copolymers of ethylene and 5,7-dimethylocta-1,6-diene synthesized by a metallocene catalyst. A dependence with composition and polymerization temperature has been found for different structural and mechanical parameters. The branches cannot be incorporated into the orthorhombic crystal lattice and, consequently, structural parameters such as crystallinity and crystal size are considerably affected as 5,7-dimethylocta-1,6-diene content increases in the copolymer. These structural changes influence significantly the rigidity of the copolymers and a decrease of this parameter, determined from either storage modulus or microhardness, with increasing 5,7-dimethylocta-1,6-diene molar fraction is found. The location of the different viscoelastic relaxations is also strongly dependent on composition.     

Copolymerization of ethylene with 1‐hexene over metallocene catalyst supported on complex of magnesium chloride with tetrahydrofuran

The study of ethylene/1‐hexene copolymerization with the zirconocene catalyst, bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂)/methylaluminoxane (MAO), anchored on a MgCl₂(THF)₂ support was carried out. The influence of 1‐hexene concentration in the feed on catalyst productivity and comonomer reactivity as well as other properties was investigated. Additionally, the effect of support modification by the organoaluminum compounds [(MAO, trimethlaluminum (AlMe₃), or diethylaluminum chloride (Et₂AlCl)] on the behavior of the MgCl₂(THF)₂/Cp₂ZrCl₂/MAO catalyst in the copolymerization process and on the properties of the copolymers was explored. Immobilization of the Cp₂ZrCl₂ compound on the complex magnesium support MgCl₂(THF)₂ resulted in an effective system for the copolymerization of ethylene with 1‐hexene. The modification of the support as well as the kind of organoaluminum compound used as a modifier influenced the activity of the examined catalyst system. Additionally, the profitable influence of immobilization of the homogeneous catalyst as well as modification of the support applied on the molecular weight and molecular weight distribution of the copolymers was established. Finally, with the successive self‐nucleation/annealing procedure, the copolymers obtained over both homogeneous and heterogeneous metallocene catalysts were heterogeneous with respect to their chemical composition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2512–2519, 2004     

Metallocenic copolymers of ethylene and 5,7‐dimethylocta‐1,6‐diene: Structural characterization and mechanical behavior

The relationship between the structure and mechanical properties has been established for several copolymers of ethylene and 5,7‐dimethylocta‐1,6‐diene synthesized with a metallocene catalyst. A dependence on the composition and polymerization temperature has been found. The branches cannot be incorporated into the orthorhombic crystal lattice, and consequently, structural parameters such as the crystallinity and crystal size are considerably affected as the 5,7‐dimethylocta‐1,6‐diene content increases in the copolymers. The viscoelastic relaxations have been analyzed and compared with those exhibited by high‐density polyethylene (HDPE). The β relaxation does not appear in HDPE and is exclusively seen in the copolymers. As the 5,7‐dimethylocta‐1,6‐diene content rises, the intensity of this process is increased, and its location is shifted to a lower temperature up to comonomer contents of approximately 6–8 mol % in the copolymers. On the other hand, the α mechanism associated with motion within the crystalline regions is also moved to a lower temperature and its intensity is diminished as the 5,7‐dimethylocta‐1,6‐diene molar fraction increases in the copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3797–3808, 2004     

Spatially inhomogeneous crystallinity in heterogeneous ethylene‐α‐olefin copolymers

The crystallinity development in heterogeneous ethylene‐1‐butene copolymers is compared with that in ethylene copolymers, with more bulky 1‐heptene as a comonomer. The thermal transitions of the 1‐heptene based copolymers persistently occur at higher temperatures than of the corresponding 1‐butene copolymers. The earlier crystallization onset is reflected in thicker primary crystals, which in turn are associated with the presence of longer ethylene sequences because of the inaccessibility of 1‐heptene to sterically shielded catalytic sites. In addition, the 1‐heptene based copolymers are characterized by a higher degree of primary crystallinity, whereas the 1‐butene copolymers exhibit more prominent secondary crystallization. The 1‐butene based copolymers thus have a less heterogeneous chemical composition distribution. At high comonomer contents, the highly heterogeneous nature of the 1‐heptene copolymers is emphasized by a more pronounced presence of low crystalline spherulite inclusions accomplished by the liquid–liquid phase separation of dissimilar polymeric chains before crystallization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3000–3018, 2005     

Morphology of homogeneous copolymers of ethylene and 1‐octene. II. Structural changes on annealing

Based on DSC evidence, annealing of ethylene‐1‐octene copolymers results in a gradually increasing thermal stability of the original, metastable, crystals. SAXS and WAXD were used to monitor the structural changes involved after isothermal annealing for a fixed time at step‐wise higher temperatures. A series of samples that differ in molar mass and comonomer content, ranging from 0 to 11.8 mol % 1‐octene, were cooled at two extreme rates from 150°C, i.e., a quenching into liquid nitrogen and a controlled cooling at 0.1°C per minute to room temperature. The crystallinities of the quenched linear polyethylenes (LPEs), being included in this study as reference materials, and of the quenched copolymer with a 1‐octene content of 2.1 mol % are always found to be lower than the crystallinities of the slowly cooled samples. On the other hand, higher crystallinities can be found for the quenched copolymers with a higher comonomer content compared to the slowly cooled specimens. A sequence of cocrystallization and recrystallization events is proposed to explain this contraintuitive, but reproducible experimental fact. This reasoning can also account for the steeper increase of the amorphous layer thickness of the latter slowly cooled copolymers compared to the quenched samples. All copolymers show a very moderate increase of the lamellar thickness after each heating step. Besides additional crystallization and recrystallization, lateral growth of the crystals and an increase of the crystallite density can account for the gradual increase of the thermal stability of copolymer crystals during prolonged annealing. The morphological effects observed for the LPEs confirm earlier findings. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 83–100, 1999     

Tacticity of poly‐α‐olefins from poly‐1‐hexene to poly‐1‐octadecene

A systematic study of the influence of the α‐olefin size, the catalyst stereospecificity and the reaction temperature was done on the catalytic activity and tacticity of poly‐α‐olefins from 1‐hexene to 1‐octadecene. The metallocenes used were rac‐Et[Ind₂]ZrCl₂ ( 1 ) and Me₂C[Cp(9‐Flu)]ZrCl₂ ( 2 ) to obtain isotactic and syndiotactic polyolefins. Some catalysts giving atactic polymers were also used in order to study all the possible ¹³C NMR pentades. Catalytic activities increased and isotacticity and syndiotacticity decreased with temperature, but no real trend was found with the α‐olefin size. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4744–4753, 2005     

Synthesis and characterization of materials prepared via the copolymerization of ethylene with 1‐octadecene and norbornene using a [(π‐cyano‐nacnac)Cp] zirconium complex

[3‐Cyano‐2‐(2,6‐diisopropylphenyl)aminopent‐2‐en‐4‐(phenylimine)tris (pentafluorophenyl)borate](η⁵‐C₅H₅)ZrCl₂, [(B(C₆F₅)₃‐ NC‐nacnac)CpZrCl₂], precatalyst ( 2 ) can be treated with low concentrations of methylaluminoxane (MAO) to generate active sites capable of copolymerizing ethylene with 1‐octadecene or norbornene under mild conditions. A series of poly(ethylene‐co‐octadecene) and poly(ethylene‐co‐norbornene) copolymers were prepared, and their properties were characterized by NMR, differential scanning calorimetry, and mechanical analysis. The results show that this system produced poly(ethylene‐co‐octadecene) copolymers with a branching content of about 8 mol %. However, upon increasing the comonomer concentration, a drastic reduction in the M_n of the product is observed concomitant with an increase in comonomer incorporation. This leads to a gradual decrease in Young's modulus and stress at break, indicating an increase in the “softness” of the copolymer. In the case of copolymerizations of ethylene and norbornene, the catalytic system ( 2 /MAO) shows a substantial decrease in reactivity in the presence of norbornene and generates copolymer chains in which 5–10 mol % norbornene is in blocks. We also observe that ethylene norbornene copolymers exhibit a high degree of alternating insertions (close to 50%), as determined by NMR spectroscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Fractionation of ethylene/1‐pentene copolymers using a combination of SEC‐FTIR and SEC‐HPer DSC

The short chain branching distribution (SCBD) and thermal properties of ethylene/1‐pentene copolymers were studied using SEC‐FTIR and SEC‐HPer DSC. The copolymers, synthesized with Cp₂ZrCl₂/MAO, were fractionated using size exclusion chromatography (SEC). The infrared analysis of the fractions showed that the copolymers had—on average—higher 1‐pentene concentration in the low molecular weight range. Furthermore, the thermal properties of the SEC deposits of these copolymers on a Germanium disc were studied using high performance differential scanning calorimetry (HPer DSC). Single SEC separations were used to accumulate fractions in the microgram range that were directly analyzed with regard to their thermal properties, thus allowing us to study SCBD as well as thermal behavior simultaneously. When these fractions (with masses ranging from 10–80 μg) were analyzed using HPer DSC, good melting and crystallization temperature distributions were obtained, proving that HPer DSC can be used as a complementary method to SEC‐FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2956–2965, 2007     

Comprehensive thermal analysis of random copolymers of ethylene and 1-olefins

Random copolymers of ethylene and propylene, butene-1 and hexene-1 were characterised by measurements of heat capacity in the temperature interval 140–480 K and specific volume of the melt in the temperature interval 330–490 K and in the range of pressures 27.8–100 MPa. Analysis of the composition dependences, of the degree of crystallinity, melting and glass transition temperatures, as well as of thermodynamic and thermophysical properties of the melt led to the conclusion about the microblock structure of macromolecules of all series at molar ethylene contentF ₁ > 0.8. In this range of compositions the properties of copolymers in the melt seem to be independent of the chemical nature of a comonomer, contrary to the solid state where at identical molar compositions, the degree of crystallinity diminishes and the melting temperature decreases, as the molecular structure of the comonomer becomes more complex. This effect becomes weaker asF ₁ decreases, so that in the composition rangeF ₁ < 0.8 the properties of copolymers of all series are additive.

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Zusammenfassung Durch Messungen der Wärmekapazität im Temperaturintervall 140–480 K und des spezifischen Volumens im Temperaturintervall 330–490 K und im Druckbereich 27.8–100 MPa wurden Random-Kopolymere von Ethylen und Propylen, Buten-1 und Hexen-1 charakterisiert. Die Analyse der Abhängigkeit des Kristallinitätsgrades, der Schmelz- und Glasumwandlungspunkte sowie der thermodynamischen und thermophysikalischen Eigenschaften der Schmelzen führte zu einem Schluß über die Mikroblock-Struktur von Makromolekülen aller Serien bei einem molaren Ethylengehalt vonF ₁>0.8. In diesem Zusammensetzungsintervall scheinen die Eigenschaften des Kopolymers unabhängig von der chemischen Natur des Komonomers zu sein, im Gegensatz zum festen Zustand, wo bei einer ähnlichen molaren Zusammensetzung sich der Kristallinitätsgrad verringert und die Schmelztemperatur sinkt, wenn die Molekülstruktur des Komonomers komplexer wird. Dieser Effekt wird kleiner, wennF ₁ abnimmt, so daß im Zusammensetzungsbereich mitF ₁<0.8 die Eigenschaften der Kopolymere aller Serien additiv sind.

     

Poly(ethylene terephthalate) copolymers containing 5‐tert‐butyl isophthalic units

Poly(ethylene terephthalate‐co‐5‐tert‐butyl isophthalate) copolymers, abbreviated as PET^tBI, with compositions ranging between 95/5 and 25/75, as well as the two parent homopolymers, PET and PE^tBI, were prepared from comonomer mixtures by a two‐step melt‐polycondensation. Polymer intrinsic viscosities varied from 0.4 to 0.7 dL g^?1 with weight‐average molecular weights ranging between 31,000 and 80,000. The copolymers were found to have a random microstructure with a composition according to that used in the corresponding feed. The melting temperature and crystallinity of PET^tBI decreased with the content in 5‐tert‐butyl isophthalic units, whereas the glass‐transition temperature increased from 82 °C for PET up to 99 °C for PE^tBI. Copolymerization slightly improved the thermal stability of PET. Preliminary X‐ray diffraction studies revealed that PET^tBI adopt the same crystal structure as PET with the alkylated isophthalic units probably excluded from the crystal lattice. The homopolymer PE^tBI appeared to be a highly crystalline polymer taking up a crystal structure clearly different from that of PET and PET^tBI copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 1994–2004, 2001     

Unusual features of ethylene copolymerization reactions with binary metallocene catalysts

Ethylene/1-hexene copolymers produced with MAO-activated binary metallocene catalysts, such as combinations Cp₂ZrCl₂ + (Me₅Cp)₂ZrCl₂, (Ind-H₄)₂ZrCl₂ + (Me₅Cp)₂ZrCl₂, Cp₂ZrCl₂ + Cp₂TiCl₂, etc., contain three types of components. Two of the components can be attributed to active centers derived from each individual metallocene complex, and one or two materials are produced with different types of active center. Some of the binary catalysts generate the three components in comparable proportions, whereas other catalysts produce copolymers with one dominant component, which does not resemble the copolymers produced with the individual complexes. A mechanism is proposed for the formation of the “new” copolymer materials.     

The copolymerization of propylene with higher,linear α‐olefins

Propylene was copolymerized with the linear α‐olefins 1‐octene, 1‐decene, 1‐tetradecene, and 1‐octadecene. The metallocene catalyst Me₂Si(2‐Me Benz[e]Ind)₂ZrCl₂, in conjunction with methylalumoxane as a cocatalyst, was used to synthesize the copolymers. The copolymers were characterized by ¹³C and ¹H NMR with a solvent mixture of 1,2,4‐trichlorobenzene (TCB) and benzene‐d₆ (9/1) at 100 °C. Thermal analyses were carried out to determine the melting and crystallization temperatures, whereas the molecular weights and molecular weight distributions were determined by gel permeation chromatography with TCB at 140 °C. Glass‐transition temperatures were determined with dynamic mechanical analysis. Relationships among the comonomer type and amount of incorporation and the melting/crystallization temperatures, glass‐transition temperature, crystallinity, and molecular weight were established. Moreover, up to 3.5% of the comonomer was incorporated, and there was a decrease in the molecular weight with increased comonomer content. Also, the melting and crystallization temperatures decreased as the comonomer content increased, but this relationship was independent of the comonomer type. In contrast, the values for the glass‐transition temperature also decreased with increased comonomer content, but the extent of the decrease was dependent on the comonomer type. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4110–4118, 2000     

Copolymerization of ethylene with cyclopentene or 2‐butene with half titanocenes‐based catalysts

Half titanocenes (CpCH₂CH₂O)TiCl₂ (1), (CpCH₂CH₂OCH₃)TiCl₃ (2), and CpTiCl₃ (3), activated by methylaluminoxane (MAO) were tested in copolymerization of ethylene with internal olefins such as cyclopentene. All the catalysts were able to give incorporation of cyclopentene in polyethylene matrix. ¹³C NMR analysis of obtained copolymers showed that the catalytic systems have low regiospecificity. In fact, in ethylene–cyclopentene copolymers, cyclic olefin inserts with both 1,2 and 1,3‐enchainment. X‐ray powder diffraction analysis of these copolymers confirmed that 1,2 inserted cyclopentene units are excluded from crystalline phase, whereas 1,3‐cyclopentene units are included, giving rise to expansion of unit cell of crystalline polyethylene. Titanium‐based catalysts were investigated also in the copolymerization of ethylene with E and Z‐2‐butene. Only complex (1) was able to give copolymers and ¹³C NMR analysis of products showed 2‐3, 1‐3, and 1‐2 insertion of 2‐butene. Differential scanning calorimetry analysis displayed that ethylene–cyclopentene, as well as ethylene‐2‐butene, copolymers are crystalline and their melting point decreases by increasing the comonomer content. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4725–4733, 2008     

Positron spectroscopy analysis in metallocene propylene/1‐octadecene copolymers: Parameters dependence on monoclinic and mesomorphic polymorphs

Copolymers of propylene and 1‐octadecene synthesized by a metallocene catalyst were characterized by PALS, WAXD, DSC, and density measurements. The change in the sizes and the number density of free‐volume holes as a function of the 1‐octadecene content were compared to the master laws published for copolymers of propylene with α‐olefins of shorter lengths. It was found that the samples were separated into two groups. The first set of samples obeyed the master laws while the second group deviated. This behavior was explained by the difference in the copolymer structure. The WAXD analysis confirmed the separation as well. The deviation was explained as due to the mesomorphic crystalline structure of the second group of samples, in contrast to the monoclinic one for the first group, which was a result of the relatively fast cooling from the molten state and from the high comonomer molar content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1994–2002, 2010     

α‐olefin homopolymerization and ethylene/1‐hexene copolymerization catalysed by novel ansa‐group IV complexes/MAO system

The catalytic properties of a set of ansa‐complexes (R‐Ph)₂C(Cp)(Ind)MCl₂ [R = ^tBu, M = Ti ( 3 ), Zr ( 4 ) or Hf ( 5 ); R = MeO, M = Zr ( 6 ), Hf ( 7 )] in α‐olefin homopolymerization and ethylene/1‐hexene copolymerization were explored in the presence of MAO (methylaluminoxane). Complex 4 with steric bulk ^tBu group on phenyl exhibited remarkable catalytic activity for ethylene polymerization. It was 1.6‐fold more active than complex 11 [Ph₂C(Cp)(Ind)ZrCl₂] at 11 atm ethylene pressure and was 4.8‐fold more active at 1 atm pressure. The introduction of bulk substituent ^tBu into phenyl groups not only increased the catalytic activity greatly but also enhanced the content of 1‐hexene in ethylene/1‐hexene copolymerization. The highest 1‐hexene incorporation was 25.4%. In addition, 4 was also active for propylene and 1‐hexene homopolymerization, respectively, and low isotactic polypropylene (mmmm = 11.3%) and isotactic polyhexene (mmmm = 31.6%) were obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Melting behavior of polyethylene/α‐olefin copolymers: Narrow composition distribution copolymers and fractions from Ziegler–Natta and single‐site catalyst products

The melting temperature and heat of fusion were measured for an extensive series of compositionally uniform copolymers of ethylene with butene‐1, hexene‐1, and octene‐1. Fractions and whole polymers that exhibited minimal interchain compositional heterogeneity were from commercial copolymers made with either Ziegler–Natta (ZN) or single‐site metallocene catalysts. The present results do not support recent claims that ZN and corresponding metallocene catalyst copolymers melt at significantly different temperatures, nor the implication that comonomer incorporation is “blocky” in ZN copolymers. In five of the six comonomer/catalyst systems the dependencies of the melting temperature on comonomer type and amount were scarcely distinguishable. This common behavior is the same as that for a model random copolymer, so we conclude that most ethylene/α‐olefin copolymers have random distributions of ethylene sequences. The exception in the present study is a metallocene ethylene/butene‐1 copolymer that melts at lower temperatures and apparently has perceptibly alternating sequence distributions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3416–3427, 2004     

Random propene/4‐methyl‐1‐pentene copolymers synthesized with C2 symmetric highly isospecific metallocenes

Propene (P)/4‐methyl‐1‐pentene (Y) copolymers in a wide range of composition were prepared with isospecific single center catalysts, rac‐Et(IndH₄)₂ZrCl₂ ( EBTHI ), rac‐Me₂Si(2‐Me‐BenzInd)₂ZrCl₂ ( MBI ), and rac‐CH₂(3‐^tBuInd)₂ZrCl₂ ( TBI ). ¹³C NMR analysis of copolymers and statistical elaboration of microstructural data at triad level were performed. Unprecedented and surprising results are here reported. Random P/Y copolymers were prepared with the most isospecific catalyst, TBI , that is known to prepare ethene/propene and ethene/4‐methyl‐1‐pentene copolymers with long homosequences of both comonomers, whereas longer homosequences of both comonomers were observed in copolymers from the less enantioselective metallocenes EBTHI and MBI . These findings, which are against what is acknowledged in the field, can pave the way for the preparation on a large scale of random propene‐based copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2575–2585     

Poly(ethylene terephthalate) copolymers containing 5‐nitroisophthalic units. I. Synthesis and characterization

Poly(ethylene terephthalate‐co‐5‐nitroisophthalate) copolymers, abbreviated as PETNI, were synthesized via a two‐step melt copolycondensation of bis(2‐hydroxyethyl) terephthalate and bis(2‐hydroxyethyl) 5‐nitroisophthalate mixtures with molar ratios of these two comonomers varying from 95/5 to 50/50. Polymerization reactions were carried out at temperatures between 200 and 270 °C in the presence of tetrabutyl titanate as a catalyst. The copolyesters were characterized by solution viscosity, GPC, FTIR, and NMR spectroscopy. They were found to be random copolymers and to have a comonomer composition in accordance with that used in the corresponding feed. The copolyesters became less crystalline and showed a steady decay in the melting temperature as the content in 5‐nitroisophthalic units increased. They all showed glass‐transition temperatures superior to that of PET with the maximum value at 85 °C being observed for the 50/50 composition. PETNI copolyesters appeared stable up to 300 °C and thermal degradation was found to occur in two well‐differentiated steps. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1934–1942, 2000