Full‐range kinetic study on bulk syndiotactic polymerization of styrene with homogeneous metallocene catalysis

By choosing a proper agitator and reinforcing its stirring shear, powdery syndiotactic polystyrene (sPS) is prepared in a bulk precipitation process with two homogeneous metallocene catalyst systems [Cp*TiX₃/MAO/TIBA (X = Cl or OPhOMe)]. A full‐range kinetics study of the heterogeneous polymerization is performed in detail to produce this kind of powdery sPS in an industrial process. A typical curve of conversion versus time takes an S shape and an obvious acceleration phenomenon occurs in the middle stage of the polymerization, although the polymer–monomer gel is avoided. The viscous‐average molecular weight of sPS goes through a peculiar increasing–decreasing–increasing change during the bulk polymerization process. These phenomena are viewed in terms of the two‐phase polymerization mechanism and the overheating in particles during polymerization. The influence of the metallocene catalyst type and concentration, MAO/Ti ratio, triisobutyl aluminum (TIBA)/Ti ratio, and polymerization temperature on the polymerization kinetics are investigated. TIBA has dual effects on the polymerization. A small amount of TIBA in the catalyst system promotes polymerization, but more TIBA leads to a low molecular weight sPS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2635–2643, 2002     

Novel monotitanocene and methylaluminoxane catalyst for syndiospecific polymerization of styrene

Syndiotactic polystyrene (sPS) was synthesized with a novel monotitanocene complex of η⁵‐pentamethylcyclopentadienyltri‐4‐methoxyphenoxy titanium [Cp*Ti(OC₆H₄OCH₃)₃] activated by methylaluminoxane (MAO) in different polymerization media, including heptane, toluene, chlorobenzene, and neat styrene. In all cases bulk polymerization produced sPS with the highest activity and molecular weight. Solution polymerization produced much better activity in heptane than in the other solvents. Using a solvent with a higher dipole moment, such as chlorobenzene resulted in lower activity and syndiotacticity because of the stronger coordination of solvent with the Ti(III) active species, which controlled syndiospecific polymerization of styrene. With bulk polymerization at a higher polymerization temperature the Cp*Ti(OC₆H₄OCH₃)₃–MAO catalyst produced sPS with high catalytic activity and molecular weight. The external addition of triisobutylaluminum (TIBA) to the Cp*Ti(OC₆H₄OCH₃)₃–MAO system catalyzing styrene polymerization led to significant improvement of activity at a lower Al:Ti molar ratio, while the syndiotacticity and molecular weight of the yields were little affected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1243–1248, 2001     

Preparation of syndiotactic polystyrene/montmorillonite nanocomposites via in situ intercalative polymerization of styrene with monotitanocene catalyst

Syndiotactic polystyrene (sPS)/montmorillonite nanocomposites were prepared via in situ intercalative coordination polymerization using mono‐(η⁵‐pentamethylcyclopenta‐ dienyl) tribenzyloxy titanium [Cp*Ti(OBz)₃] complex activated by methylaluminoxanes (MAO) and triisobutylaluminum (TIBA). The influences of polymerization conditions, such as the weight ratio of montmorillonite and styrene, temperature, and monomer concentration, on the preparation of sPS/montmorillonite nanocomposites was investigated. The intercalation spacing in the nanocomposites, as well as the exfoliation of the montmorillonite interlayers, was characterized with wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM). The dispersibility of the nanoscale elements depended on the polymerization conditions and the surfactant treatment. The crystallizability and thermal properties of these nanocomposites were determined by differential scanning calorimetry (DSC) analysis and thermogravimetric analysis (TGA). Experimental results indicated that the degree of crystallinity of the sPS nanocomposite increased with increasing montmorillonite content and with higher T_g and thermal decomposition temperature than pure sPS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1412–1417, 2005     

In-situ generation of a well-dispersed multiwall carbon nanotube/syndiotactic polystyrene composite using pentamethylcyclopentadienyltitanium trimethoxide anchored to multiwall carbon nanotubes

A well-dispersed multiwall carbon nanotube (MWCNT)/syndiotactic polystyrene (sPS) composite was prepared by simple in-situ polymerization of styrene using pentamethylcyclopentadienyltitanium(IV) trimethoxide (Cp*Ti(OMe)₃) attached to the shortened and functionalized MWCNT (f-MWCNT). The attachment of Cp*Ti(OMe)₃ to the f-MWCNT was confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy, and energy dispersive X-ray spectroscopy. Cp*Ti(OMe)₃ attached to pristine MWCNT in the presence of methylaluminoxane (MAO) did not produce PS, whereas Cp*Ti(OMe)₃ attached to f-MWCNT showed a high catalytic activity for the syndiospecific polymerization of styrene under the same polymerization conditions. Obtained sPS showed a narrow molecular weight distribution (PDI ≈ 2), a high SI value (≥90%), and a high melting point (≈272 °C). Scanning electron microscopy and transmission electron microscopy images showed that MWCNT strands were well dispersed in the MWCNT/sPS composite. Such composites had greatly improved thermal stability compared to normal sPS polymers.     

Synthesis and characterization of elastoplastic poly(styrene‐co‐ethylene) using novel mono(η5‐cyclopentadienyl) titanium and modified methylaluminoxane catalysts

Elastoplastic poly(styrene‐co‐ethylene) with high molecular weight was synthesized using novel mono(η⁵‐pentamethylcyclopentadienyl)tribenzyloxy titanium [Cp*Ti(OBz)₃] complex activated with four types of modified methylaluminoxanes (mMAO) containing different amounts of residual trimethylaluminum (TMA). The ideal mMAO, used as a cocatalyst for the copolymerization of styrene with ethylene, contains TMA approaching to 17.8 wt %. The oxidation states of the titanium‐active species in different Cp*Ti(OBz)₃/mMAO catalytic systems were determined by the redox titration method. The results show that both active species may exist in the current system, where one [Ti(IV)] gives a copolymer of styrene and ethylene, and the second one [Ti(III)] only produces syndiotactic polystyrene (sPS). Catalytic activity, compositions of copolymerization products, styrene incorporation, and copolymer microstructure depend on copolymerization conditions, including polymerization temperature, Al/Ti, molar ratio, and comonomers feed ratio. The copolymerization products were fractionated by successive solvent extractions with boiling butanone and tetrahydrofuran (THF). The copolymer, chiefly existing in THF‐soluble fractions, was confirmed by ¹³C‐NMR, GPC, DSC, and WAXD to be an elastoplastic copolymer with a single glass transition temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1851–1857, 1999     

Syndiospecific styrene polymerization with CpTiCl3/MAO: Effects of the order of reactant addition on polymerization and polymer properties

Syndiospecific styrene (St) polymerization, catalyzed by the CpTiCl₃/methylaluminoxane (MAO) system, was investigated using two different activation procedures. The polymerization parameters included polymerization time, temperature (～25–100°C), ratio of [Al]/[Ti] (～100–1000), and catalyst precursor concentration (～0.5–10.0 × 10^?4 mol Ti/L). It was found that adding reactants in the order of (CpTiCl₃ + MAO) + St (Injection of Styrene mode) gave much higher monomer conversion rates, higher weight‐average molecular weights, and narrower molecular weight distributions than for the (St + MAO) + CpTiCl₃ (Injection of Catalyst mode). The former also yielded significantly higher syndiotacticity fractions. Differential scanning calorimetry measurements showed multiple peaks exhibiting polymorphism in crystalline syndiotactic polystyrene samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1449–1455, 2004     

Nascent morphology of syndiotactic polystyrene synthesized over silica-supported metallocene catalyst

The nascent morphology of semi-crystalline syndiotactic polystyrene (sPS) polymerized over silica-supported pentamethyl cyclopentadienyl titanium trimethoxide (Cp^∗Ti(OCH₃)₃) catalyst in a liquid slurry polymerization has been investigated under various reaction conditions. The scanning electron microscopic analysis of nascent polymers reveals that sPS molecules grow as long nanofibrils of 30-50 nm diameter and X-ray diffraction analysis shows the co-crystalline phases including both sPS and low molecular weight guest molecules of monomer and diluent. The energy dispersive X-ray spectroscopy also shows that the disintegration of silica primary particles occurs during the polymerization as evidenced by the uniform dispersion of silicon and aluminum in a polymer particle. The fibrous growth of the polymer inside a polymer particle leads to the shape replication of the original silica particles.     

Synthesis and characterization of polybutadiene with monotitanocene/methylaluminoxane catalyst

Butadiene was polymerized using a monotitanocene complex of η⁵‐pentamethylcyclopentadienyltribenzyloxy titanium [Cp*Ti(OBz)₃] in the presence of four types of modified methylaluminoxanes (mMAO), which contained different amounts of residual trimethylaluminum (TMA). The titanium oxidation states in Cp*Ti(OBz)₃/mMAO and Cp*Ti(OBz)₃/mMAO/triisobutylaluminum (TIBA) catalytic systems were determined by redox titration method. The effects of various oxidation states of titanium active species on butadiene polymerization were investigated. It was found that Ti(III) active species is more effective for preparing polybutadiene with high molecular weight. The addition of TIBA to the Cp*Ti(OBz)₃/mMAO system could reduce a greater number of Ti(IV) complexes to Ti(III) species and lead to significant increases of polymerization activity and molecular weight of polymer, whereas the polybutadiene microstructure was only slightly changed. On the basis of microstructure and property characterization by FTIR, ¹³C‐NMR, DSC, and WAXD, all resultant polymers were proved to be amorphous polybutadiene with mixed 1,2; cis‐1,4; and trans‐1,4 structures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2494–2500, 2004     

An activated neodymium‐based catalyst for styrene polymerization

Coordination polymerization of styrene with a ternary catalyst system composed of catalyst neodymium tricarboxylate (Nd), co‐catalyst Al(i‐Bu)₃ (Al) and chlorinating agent trichloroethane (Cl) was carried out in cyclohexane. The effects of the catalyst system preparation procedure and of the reaction conditions on catalytic activity, molecular weight and molecular weight distribution of the resultant polymers were investigated. The catalytic activity depended mainly on the molar ratios of Al/Nd and of Cl/Nd and on the ageing temperature and polymerization temperature. High polymerization conversion and high catalytic activity could be obtained at high Al/Nd ratios and/or at high ageing temperature. The catalyst system exhibited high activity of 8.32 × 10⁴ g polystyrene (mol Nd h)^?1 at 50 °C. The molecular weight of the polymers obtained reached high weight‐average (M_w) values (M_w = 4.35 × 10⁵ g mol^?1) when Al/Nd = 8, but relatively low values (6000–11 000 g mol^?1) at high Al/Nd ratios. Copyright © 2005 Society of Chemical Industry     

Polystyrene with half-titanocene/MAO catalysts: Influence of 2,6-diisopropylphenol

Styrene polymerization was carried out by a simple half-titanocene complex [cyclopentadienyltitanium trichloride] (CpTiCl₃) and pentamethyl [cyclopentadienyltitanium trichloride] (Cp*TiCl₃) combined with methylaluminoxane (MAO) as a cocatalyst. The effects of addition of 2,6-diisopropylphenol on the catalytic activity of the above catalytic systems and the microstructure of the resulting polymer were investigated. The results of the above experiments showed that the addition of the 2,6-diisopropylphenol changed the catalytic performance of the above catalytic systems, in terms of catalytic activity of the metal complexes and microstructure, molecular weight and molecular weight distribution of polystyrene synthesized. The yields of polystyrene of the above polymerization reactions indicated that the 2,6-diisopropylphenol enhanced the catalytic activity of both the CpTiCl₃/MAO and Cp*TiCl₃/MAO catalyst systems. Further Soxhlet extraction of the polymer was conducted by boiling acetone for 6 h to get pure syndiotactic polystyrene. The microstructure of polystyrene obtained by the above polymerization reactions was investigated by ¹³C NMR, GPC and DSC. Results indicated the formation of syndiotactic polystyrene in the absence of phenol and in low concentration of phenol. On the other hand, in the presence of excess phenol, the polystyrene produced was found to be completely atactic in nature. The appearance of monomodal peaks and narrow polydispersity in the GPC results of polystyrenes obtained in all the above polymerizations indicated that the polymerization was only coordination in nature.     

Characterization and properties of sPS/PET/SsPS‐K engineering plastic alloys

The compatibility, crystallization behavior, and mechanical properties of syndiotactic polystyrene (sPS)/polyester (PET)/potassium salt of sulfonated syndiotactic polystyrene (SsPS‐K) were investigated. DMA results showed that all the alloys showed one T_g and the half‐peak width of the sPS/PET/SsPS‐K alloys became narrower compared with that of sPS/PET alloys, which decreased with an increasing content of the SsPS‐K ionomer. The results of DSC showed that the T_m of sPS and PET of the alloys was similar to those of the pure materials and did not change with the content of the SsPS‐K ionomer, while the initial crystallization temperature (T₀) and crystallization temperature at peak (T_p) increased. The crystallization velocity of PET increased with an increasing content of SsPS‐K. The TMA results showed that the alloys could retain the perfect heat proof property of sPS. SEM micrographs showed that the addition of SsPS‐K could reduce the PET domain dimension and enhance the adhesion between the PET domains and the matrix. With an increasing content of SsPS‐K, the PET domain dimension was reduced continuously and dispersed more evenly. The ternary alloys had better mechanical properties and significantly higher unnotched Izod impact strength than those of the alloys without SsPS‐K. When the weight ratio of sPS/PET/SsPS‐K was 85/15/4, the impact strength reached a maximum of 11.5 kJ/m², which was about three times that of pure sPS, and still had a higher tensile strength, flexural strength, and storage modulus, which were 38.8, 54.2, and 1.55 × 10⁴ MPa, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 656–661, 2002     

The synthesis of high molecular weight polybutene‐1 catalyzed by Cp★ Ti(OBz)3/MAO

A new stereoregular polybutene‐1 was synthesized with a novel catalyst precursor η⁵‐pentamethyl cyclopentadienyl titanium tribenzyloxide (CpTi(OBz)₃) and methylaluminoxane (MAO). The effects of polymerization conditions on the catalytic activity, molecular weight and stereoregularity of the products were investigated in detail. It was found the catalyst exhibited highest activity of 91.2 kgPB mol Ti⁻¹ h⁻¹ at T = 30 °C, Al/Ti = 200. The catalytic activity and molecular weight were sensitive to the Al/Ti (mole/mole), polymerization temperature; they also depended on the Ti concentration. The molecular weight of the products increased with decreasing temperature. The structure and properties of the polybutene‐1 were characterized by ¹³C NMR, GPC, DSC and WAXD. The result showed the microstructure of polybutene‐1 extracted by boiling heptane was stereoregular, whereas the ether‐soluble fraction was atactic. The molecular weight of polybutene‐1 was over one million g mol⁻¹ and its molecular weight distribution ( M _w/ M _n) was from 1.1 to 1.2. © 2001 Society of Chemical Industry     

Atom transfer radical polymerization of styrene initiated by bromoacetylated syndiotactic polystyrene macroinitiator

Atom transfer radical polymerization of styrene was conducted with bromoacetylated syndiotactic polystyrene as macroinitiator and copper bromide combined with N,N,N′,N′,N′‐pentamethyldiethylenetriamine as catalyst. A two‐stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was functionalized in the side phenyl rings with acetyl groups using the Friedel–Crafts reaction; second, the acetyl groups were converted to bromoacetyl groups by an acid‐catalyzed halogenation reaction. The initiator was found to be active in the polymerization of styrene, leading to the production of graft chains with well‐defined structure. The molecular weight and molecular weight distribution of the graft chains were determined using gel permeation chromatography after cleaving from the sPS backbone using peroxide acid oxidation followed by hydrazine‐catalyzed hydrolysis. The results indicated that the polymerization process was characteristic of a ‘living’ nature. Copyright © 2007 Society of Chemical Industry     

Physical transitions and nascent morphology of syndiotactic polystyrene in slurry polymerization with embedded CpTi(OMe)3/methyl aluminoxane catalyst

The physical transitions and nascent morphology of syndiotactic polystyrene (sPS) synthesized over heterogeneized embedded Cp^*Ti(OMe)₃/MAO catalyst in n-heptane slurry polymerization have been investigated. The homogeneous metallocene catalyst is heterogenized by embedding active titanium sites into an sPS prepolymer phase. At low styrene concentrations, the reaction mixture is well-dispersed slurry of sPS particles and at high styrene concentrations, swollen sPS particles form aggregates that become a wet powder phase. For a wide range of styrene concentrations, no global gelation occurs with the embedded catalyst. Complex nascent morphology of sPS polymers is also presented. Scanning electron microscopic images show that spherical as well as irregular-shaped microparticles, films, and fibers are formed and that particle generation and growth mechanisms are different from that of heterogeneously catalyzed α-olefin polymerization processes.     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Grafted syndiotactic polystyrene synthesized via melting graft copolymerization used as a compatibilizer for immiscible syndiotactic polystyrene/polyadimide 66 blends

A new grafted syndiotactic polystyrene (g‐sPS), to be used as a compatibilizer for syndiotactic polystyrene (sPS)/polyadimide 66 blends, was prepared by the melting graft copolymerization of sPS and monomers composed of itaconic acid and dibutyl maleate with dicumyl peroxide as an initiator. The resulting g‐sPS possessed a side‐chain structure identified by IR spectra, and the results of mechanical testing show that a good impact strength and tensile strength were obtained for g‐sPS at a 7.16‐phr addition of monomer with a 3:1 proportion of dibutyl maleate and itaconic acid. Differential scanning calorimetry and scanning electron microscopy analysis indicated that the g‐sPS maintained a high glass‐transition temperature and a crystalline structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1659–1666, 2005     

Geometrically Constrained Polymerization of Styrene Over Heterogeneous Catalyst Layer in Silica Nanotube Reactors

Styrene has been polymerized to syndiotactic polystyrene (sPS) over a layer of heterogeneous Cp*Ti(OCH₃)₃/MAO catalyst immobilized onto the surfaces of silica nanotube reactor (SNTR) arrays of 60–200 nm in diameter. The polymer produced in the SNTR arrays has been found to have the molecular weights much larger than the polymers synthesized by a liquid slurry polymerization over silica-supported catalysts. A dynamic reactor model that consists of diffusion and reaction terms has been derived and solved to quantify the kinetics of styrene polymerization in a single nanotube reactor. The two-site kinetic model applied to the silica nanotube reactor model shows that the experimentally observed high polymer molecular weight can be fitted if the chain transfer rate constants for monomer and β-hydride elimination are reduced significantly. The simulation results suggest that the presence of dense crystalline sPS nanofibrils filling the nanotubes constrain the molecular movements of polymer chain ends in the proximity of catalyst sites to limit the chain transfer reactions. POLYM. ENG. SCI., 60:700–709, 2020. © 2020 Society of Plastics Engineers     

Polymerization of styrene using novel bispyrazolylimine dinickel (II)/methylaluminoxane catalytic systems

The polymerization of styrene with a series of bispyrazolylimine dinickel (II) complexes of bis‐2‐(C₃HN₂(R₁)₂‐3,5)(C(R₂) = N(C₆H₃(CH₃)₂‐2,6)Ni₂Br₄ (complex 1 : R₁ = CH₃, R₂ = Ph; complex 2 : R₁ = CH₃, R₂ = 2,4,6‐trimethylphenyl; complex 3 : R₁ = R₂ = Ph; complex 4 : R₁ = Ph, R₂ = 2,4,6‐trimethylphenyl) in the presence of methylaluminoxane (MAO) was studied. The influences of polymerization parameters such as polymerization temperature, Al/Ni molar ratio, reaction time, and catalyst concentration on catalytic activity and molecular weight of the polystyrene were investigated in detail. The influence of the bulkiness of the substituents on polymerization activity was also studied. All of the four catalytic systems exhibited high activity (up to 10.50 × 10⁵ gPS/(mol Ni h)) for styrene polymerization and provide polystyrene with moderate to low molecular weights (M_w = 4.76 × 10⁴–0.71 × 10⁴ g/mol) and narrower molecular weight distributions about 2. The obtained polystyrene was characterized by means of FTIR, ¹H‐NMR, and ¹³C‐NMR techniques. The results indicated that the polystyrene was atactic polymer. The analysis of the end groups of polystyrene indicated that styrene polymerization with bispyrazolylimine dinickel complexes/MAO catalytic systems proceeded through a coordination mechanism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Syndiospecific Polymerization of Styrene Using Half-Titanocene Catalyst Covalently Supported on MgCl<Subscript>2</Subscript>/AlEt<Subscript>n</Subscript>(OEt)<Subscript>3-n</Subscript>

The novel half-titanocene catalyst bearing reactive functional amino group, η⁵-pentamethylcyclopentadienyltri(p-amino-phenoxyl) titanium [Cp^∗Ti(p-OC₆H₄NH₂)₃], was easily synthesized by the reaction of η⁵-pentamethylcyclopentadienyltrichloride titanium (Cp^∗TiCl₃) with p-amino phenol in the presence of triethyl amine (NEt₃). Cp^∗Ti(p-OC₆H₄NH₂)₃ covalently anchored on MgCl₂/AlEt_n(OEt)_3-n support obtained from the reaction of triethylaluminium (AlEt₃) with the adduct of magnesium chloride (MgCl₂) and ethanol (EtOH), has been investigated and used to catalyze syndiospecific polymerization of styrene. Influences of the support structure, cocatalyst, and the molar ratio of Al in methylaluminoxane (MAO) and Ti (Al_MAO/Ti) on catalytic activity, syndiotacticity and molecular weight of the resultant polystyrene were investigated. Compared with the corresponding Cp^∗Ti(p-OC₆H₄NH₂)₃ homogeneous catalyst, a considerable increase in activity and molecular weight of syndiotactic polystyrene (sPS) was observed for the Cp^∗Ti(p-OC₆H₄NH₂)₃-MgCl₂/AlEt_n(OEt)_3-n supported catalyst even at a relatively low Al_MAO/Ti ratio of 50, and the kinetics of polymerization was stable during the reaction process.     

Pre‐melting temperature effect on the isothermal melt crystallization and multiple melting behavior of syndiotactic polystyrene

This work examined how pre‐melting temperature (T_max) affects the isothermal melt crystallization kinetics, the resulting melting behavior and crystal structure of syndiotactic polystyrene (sPS) by using differential scanning calorimetry (DSC), polarized light microscopy (PLM) and the wide angle X‐ray diffraction (WAXD) technique. Experimental results indicated that raising T_max decreased the nucleation rate and the crystal growth rate of sPS. The Avrami equation was also used to analyze the overall crystallization kinetics. The Avrami exponent n and rate constant K were determined for different T_max specimens at various crystallization temperatures (T_c's). Our results indicated that the nucleation type of sPS is T_max and T_c dependent as well. Evaluation of the activation energy for the isothermal crystallization processes revealed that it increases from 375 kJmol^?1 to 485 kjmol ^?1 with an increase of T_max. From the melting behavior study, we believe that the T_max and T_c‐dependent multiple melting peaks are associated with different polymorphs as well as recrystallized crystals formed during heating scans. Moreover, the percentage content of α form in the crystals formed under different crystallization conditions was estimated through WAXD experiments.