TEM studies on single crystal structure of syndiotactic poly(propene-co-butene-1)s

Themorphologies and structures of single crystals of syndiotactic poly(propene-co-1-butene) (PPBU) with 1-butene contents of 2.6, 4.2, 9.9, 16.2, and 47.9 mol % are studied by transmission electron microscopy and electron diffraction. The electron diffraction results show that the 1-butene units are included in the crystalline phase of the sPP homopolymer. A small amount of 1-butene (<4.2 mol %) has no significant influence on the antichiral chain packing of sPP. With increasing content of 1-butene units, an increasing packing disorder is observed in the PPBU copolymers. The antichiral packing model is, however, always the predominant chain packing structure of the copolymers with the analyzed composition. Bright-field electron microscopy observation shows that the PPBU single crystals exhibit always regular rectangular or lathlike shapes with preferred growth direction along their crystallographic b-axes owing to their packing features. The incorporated 1-butene units influence the crystallization behavior of sPP distinctly. With the increase of the 1-butene units, the aspect ratio of the single crystals increases. Furthermore, the typical transverse microcracks and ripples of the highly stereoregular sPP are no more so prominent for the copolymers. The microcracks are occasionally observed in the single crystals of copolymers with low 1-butene content (less than or equal to4.2 mol %), while transverse ripples are only seen in the crystals of the copolymer having a 1-butene content of 9.9 mol %. With a further increase in the content of 1-butene units, the copolymers behave like the low stereoregular sPP, where neither cracks nor ripples are observed any more.

Single crystal structure of form I syndiotactic poly(butene-1)

The structures of single crystals of syndiotactic poly(butene-1) in form I, produced by thin-film growth, are studied by transmission electron microscopy and electron diffraction. Bright-field electron microscopy observation shows that the single crystal exhibits a regular rectangular shape with the long axis along its crystallographic b-axis. Electron diffraction results indicate an isochiral C-centered packing of a-fold helical chains in an orthorhombic unit cell corresponding to the C222(1) space group, according to the model proposed in the literature. The differences with the polymorphic behavior of syndiotactic polypropylene concerning the formation and the stability of the isochiral mode of packing are outlined.

UNSTEADY DIFFUSION KINETICS OF ZIEGLER-NATTA HETEROGENEOUS CATALYST POLYMERIZATION .4. PREDICTION OF EXPERIMENTAL RESULTS OF PROPYLENE ETHYLENE 1-HEXADECENE TERPOLYMERIZATION

The prediction, based on unsteady diffusion kinetics, of the enhancement of reactivity and incorporation of 1-hexadecene in its copolymerization with propylene on adding a small amount of ethylene (increase from 5,2 mol-% to 10,8 mol-% when 2% of ethylene was added, and to 16,1 mol-% when 5% was added) was verified in the terpolymerization of propylene/1-hexadecene/ethylene on a commercial Solvay-type delta-TiCl3 catalyst. The catalyst efficiency was thus also increased. These augmentations originate from the increase in diffusion coefficient of 1-hexadecene at the catalyst surface when the PP crystallinity decreases on introduction of ethylene. Calculation based on unsteady diffusion kinetics showed that the order of diffusion coefficients ethylene > propylene > 1-hexadecene is reversed as the monomer concentration increases when the monomers are not at their equilibrium concentration. Sequence distribution as determined by means of C-13 NMR revealed a tendency of blocky structure rather than a Bernoullian one. The terpolymer compositions obtained by means of an IR method developed in this work conform rather well with the NMR results. Results in this work not only support the unsteady diffusion kinetics but also provide a new route to prepare olefinic copolymer rubbers with heterogeneous titanium catalysts.

SOME NEWER CONCEPTS OF ETHYLENE ALPHA-OLEFIN COPOLYMERIZATION ON HETEROGENEOUS ZIEGLER-NATTA CATALYSTS

Unsteady diffusion kinetic, recently advanced by this laboratory, is applied to the examination of some polymerization and molecular chain structure problems. Hitherto deemed "anomalous" phenomena, such as the faster rate of copolymerization of ethylene/alpha-olefin than the homopolymerization of ethylene and the enrichment in the incorporation of a higher alpha-olefin in its copolymerization with ethylene by a lower alpha-olefin, are reasonably explained by unsteady diffusion of monomers. Molecular chain structure of copolymers, such as compositional heterogeneity and its dependence on comonomer incorporation originates from the difference in diffusion coefficients of the monomers. A copolymer composition equation taking into consideration the unsteady diffusion was developed. In cases where simulated curves were compared with experimental curves, good agreements were found.

Performance of palladium-containing supported catalysts in the oxidation of 1-butene

Performance of palladium-containing supported catalysts in the oxidation of 1-butene was investigated in a fixed-bed flow microreactor. The Pd-Fe-HCl/Ti-Al catalyst is the best among the five Pd-Fe-HCl/X (A = SiO2, gamma-Al2O3, Al-Ti, TiO2, MCM-22) catalysts for the oxidation of I-butene to butanone. It is interesting that high propionic acid selectivity can be obtained when V and H2SO4 are added to the palladium-containing supported catalysts.

Dimerization of 1-butene via zirconium-based Ziegler-Natta catalyst

A zirconium-based Ziegler-Natta catalytic system has been tested in the dimerization of 1-butene. It was found that the concentration of Et2AlCl, Ph3P and PhONa as well as the reaction temperature had great influences on the activity and selectivity of the catalyst. Under the optimum reaction conditions, the conversion of 1-butene is 91.9%, and the selectivity of dimers is 76.7%. Basic ligands such as Ph3P and PhONa can inhibit isomerization of 1-butene to 2-butene effectively. In addition, the metal hydride mechanism was also suggested and some indirect evidence was obtained in favor of this mechanism.

Preparation of a blocked isocyanate compound and its grafting onto styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer

The epsilon-caprolactam was used to block the isocyanate group to enhance the storage stability of allyl (3-isocyanate-4-tolyl) carbamate. The spectra of FTIR and NMR showed that blocked allyl (3-isocyanate-4-tolyl) carbamate (BTAI) possesses two chemical functions, an 1-olefin double bond and a blocked isocyanate group. The FTIR spectrum showed BTAI could regenerate isocyanate group at elevated temperature. DSC and TG/DTA indicated the minimal dissociation temperature was about 135 degrees C and the maximal dissociation rate appeared at 226 degrees C. Then the styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) was functionalized by BTAI via melt free radical grafting. The effect of temperature, monomer and initiator concentrations on the grafting degree and grafting efficiency was evaluated. The highest grafting degree was obtained at 200 degrees C. The grafting degree and grafting efficiency increased with the enhanced concentration of BTAI or initiator.

Direct formation of form I poly(1-butene) single crystals from melt crystallization in ultrathin films

The morphologies and crystalline structures of melt-crystallized ultrathin isotactic poly(1-butene) films have been studied with transmission electron microscopy and electron diffraction. It is demonstrated that a bypass of form II crystallization can be achieved with an increase in its crystallization temperature. Electron microscopy observations show that melt-grown isotactic poly(1-butene) single crystals have a well-shaped hexagonal form, whereas form I crystals converted from form II display the morphologies of their tetragonal precursors. Electron diffraction results indicate that, instead of the twinned hexagonal pattern of the converted form I crystal, the directly formed form I single crystals exhibit an untwinned hexagonal pattern.

Study of the alkylation of isobutane with n-butene over WO3/ZrO2 strong solid acid. 1. Effect of the preparation method, WO3 loading, and calcination temperature

A series of strong solid acids composed of WO3/ZrO2 were prepared. Their crystal structure, surface state, and acidity were determined by the methods of X-ray diffraction, thermal gravimetric and differential thermal analysis, temperature-programmed reduction, laser Raman, and acidity measurement. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in the tetragonal phase, the addition of WO3 plays an important role in stabilizing the tetragonal phase of ZrO2, and all of the samples possessed large surface areas. WO3 in WO3/ZrO2 is mainly monolayer dispersed, and a small amount crystallized on the ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, acting as the strong solid acid center. The catalytic properties of WO3/ZrO2 strong solid;acids for alkylation of isobutane with butene at different conditions were investigated. They had a better reaction performance than other strong solid acids; a parallel relationship could be drawn between the catalytic activity and the acid amounts as well as the acidic strength of the catalysts.

Comonomer sequence distribution in metallocene-based ethylene/1-butene (S-34) and ethylene/1-hexene (S-43) copolymers

Metallocene based polyethylenes were prepared by SMOPEC's "metallocene adduct" technology in a gas phase fluidized bed model reactor. The C-13-NMR spectra of ethylene/1-butene (S-34) and ethylene/1-hexene(S-43) copolymers were studied in a manner analogous to that established by Hsieh and Cheng. The comonomer sequence distributions of copolymer samples were obtained. The results show that these metallocene based copolymers contain a small amount of butene and hexene, and the EE and EEE sequences are dominant.

Catalytic cracking of 1-butene to propene and ethene on MCM-22 zeolite

Catalytic cracking of butene to propene and ethene was investigated over HMCM-22 zeolite. The performance of HMCM-22 zeolite was markedly influenced by time-on-stream (TOS) and reaction conditions. A rapid deactivation during the first I h reaction, followed by a quasi-plateau in activity, was observed in the process along with significant changes in product distributions, which can be attributed to the fast coking process occurring in the large supercages of MCM-22.