MCM-36 zeolites tailored with acidic ionic liquid to regulate adsorption properties of isobutane and 1-butene

Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.

ROLE AND IMPORTANCE OF RADIUS OF GYRATION OF CHAINS IN THE MELT IN THE CRYSTALIZATION OF POLY(1-BUTENE)

Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (dc), the volume occupied by the chain in the melt, i.e., the radius of gyration (Rg), plays a very important role in polymer crystallization. When dc ≤ Rg, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as dc＞Rg, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(1-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase.Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (Rg), and very good agreement is obtained.

Crystallization and Crystalline Structure of Syndiotactic Polypropylene and Syndiotactic-Poly(1-Butene) Blend

The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have been investigated by means of differential scanning calorimetry (DSC), FT-IR, and wide-angle X-ray diffraction (WAXD) analyses. The melt-crystallization behavior of the blend samples was studied by DSC on the cooling process at constant rates. Bl-50, Bl-75, and Bl-90 showed lower crystallization temperatures than the neat sPP. sPP in Bl-75 showed the lowest crystallization rate among the blend samples. Bl-90 showed a two-phase molten state, and sPP in Bl-90 crystallized via two-stepprocess. Time evolution of FT-IR spectroscopy at room temperature detected conformational transformation of the sPP polymer chain in the blend samples of Bl-50 and Bl-75. The absorption peaks intensity in the FT-IR spectra derived from the helical conformations in the crystalline phase decreased, and the planar zigzag conformations in the amorphous and mesophase phases decreased over the crystallization time. The time evolution of the WAXD profile of Bl-90 indicated that sPP in the blend accelerated the crystallization of sPB. The crystallized Bl-10, Bl-25, and Bl-50 samples showed diffraction peaks in WAXD profiles and melting endothermic peak in DSC profiles derived from only the sPP crystal. The crystallinity and melting temperature of sPP in the crystallized Bl-10, Bl-25, and Bl-50 samples were almost independent of the sPB content. Both the crystalline structure of sPP and sPB were detected in Bl-75 and Bl-90. Bl-75 showed the lowest crystallinity and melting temperature of sPP among the blend samples.

Memory Effect of Crystallization in 1-Butene/α-olefin Copolymers

The macromolecular architecture is the crucial factor in determining the arrangement of the ordering structures,which,because of the multiscale feature,may exhibit distinct melting behaviors and induce the so-called memory effect to affect the following recrystallization.Until present,the correlation between the occurrence of memory effect and the intrinsic molecular structure is still far from the comprehensive understanding.In this work,four kinds of 1-butene/α-olefin random copolymers were designed and synthesized using the(pyridyl-amino)hafnium catalyst to introduce the different branches.The branch length was precisely controlled by the specific α-olefin comonomers,which include 1-hexene,1-decene,1-tetradecene,and 1-octadecene,while the branch density was tuned by the incorporation.As expected,the incorporation of α-olefin co-units to poly(1-butene)backbone decreases the non-isothermal crystallization kinetics and the degree of crystallinity.More interestingly,the resulting linear branch can induce the occurrence of memory effect and the threshold concentration of co-units(i.e.,branch density)decreases with increasing the branch length.Based on the results of these 1-butene/α-olefin copolymers with designable branches,a direct correlation with the occurrence of memory effect and the fraction of amorphous region was established,which quantitatively indicates the degree of local segregation of the crystallized poly(1-butene)sequences by theα-olefin co-units.

Self-assisted stereospecific polymerization of unmasked polar 4-methylthio-1-butene

Stereospecific polymerization of polar olefins has always been an attractive but challenging project because the Lewis basic polar groups of monomers are usually poisonous to the Lewis acidic metal centers of the catalysts. In this contribution,thiophene-fused cyclopentadienyl scandium complexes 1-3 were successfully synthesized. Combined with alkylaluminium and organoborate, these complexes showed extremely low activity and no selectivity for 1-hexene polymerization. Surprisingly,highly stereo-selective coordination polymerization of unprotected polar 4-methylthio-1-butene has been achieved in high activity for the first time under the same polymerization conditions. High-molecular-weight(M_n=110×10~3) and perfectly syndiotactic(rrrr>99%) poly(4-methylthio-1-butene)(P(MTB)) was afforded. Thus the methylthio-group-assisted mechanism that the unmasked methylthio group promoted the polymerization through σ-π chelation to the active scandium center together with the vinyl group was proposed. Moreover, the methylsulfonyl functionalized syndiotactic poly(1-butene) was also easily prepared by the oxidation of P(MTB). These results provided a new route for the synthesis of functionalized stereo-regular polyolefins.

Copolymerization of 1-butene and 1-hexene with supported titanium catalyst

With TiCl4/MgCl2(Ti)and Al(i-Bu)3(Al)as catalysts,the thermoplastic copolymer of 1-butene(Bt)and 1-hexene(He)was synthesized successfully.The effects of Bt/He,Ti/(He+Bt),Al/Ti,temperature and reaction time on conversion,catalyst efficiency(CE),intrinsic viscosity([g])and insoluble content were studied.The copolymer was analyzed with Fourier transform-infrared(FTIR)and nuclear magnetic resonance(1H-NMR).Results showed that the optimal polymerization conditions were:He/Bt=0.25,temperature 40℃–50℃,Al/Ti=400–500,Ti/(Bt+He)=3x10-5-4x10-5,time 4 h.Intrinsic viscosity was found to increase with increasing Ti/(Bt+He)and decreasing Al/Ti and polymerization temperature.When the molar content of He,Al/Ti and polymerization temperature increased,the insoluble content in CH2Cl2 of copolymers decreased.When Ti/(Bt+He)and reaction time increased,the insoluble con-tent in CH2Cl2 of copolymers also increased.The crystal-lization and stereoregularity of poly(1-butene)decreased with the addition of He.

Dehydrogenation of n-Butane to Butenes and 1,3-Butadiene over PtAg/Al₂O₃Catalysts in the Presence of H₂

The Al2O3-supported PtAg catalysts were prepared and evaluated for the dehydrogenation of n-butane at 550°C in the presence of H2. The PtAg/Al2O3 catalyst prepared by an impregnation method using the Cl- removing Pt/Al2O3 and AgNO3 showed a higher activity and selectivity to butenes and 1,3-butadiene compared to the Pt/Al2O3 catalyst, but a large amount of coke (about 30 wt% versus the catalyst weight) was formed during the dehydrogenation. The free Ag metal on the prepared catalyst dramatically promoted the coke formation, because the dehydrogenation of 1-butene over the Ag/Al2O3 catalyst produced a large amount of coke. The Cl- addition to the Cl- free Pt/Al2O3 catalyst decreased the coke formation by the reaction of the free Ag particles and Cl to form AgCl which was inactive for the coke formation. The highest initial conversion (50.3%) was obtained with the selectivity to butenes and 1,3-butadiene (butenes = 80.2% and 1,3-butadiene = 5.9%) when the PtAg/Al2O3 catalyst modified with Cl- was used.