Microstructure of isotactic polypropylene obtained using Ziegler–Natta catalyst at high polymerization temperature

Homogeneous Ziegler-Natta catalyst are formed when transition metal halide and a metal alkyl interact to produce a soluble catalyst. Usually the transition halide is itself soluble in the solvent used. However, the polymer is very often precipitated as it is formed. The polypropylene synthesized using a rac-ethylenebisindenyl zirconium dichloride (rac-Et(Ind)2ArCl2) and methylaluminoxane (MAO) catalyst system under a variety of operating conditions are characterized. The observed maximum activity was 22,196 gPP/mmoleZr.hr at the polymerization temperature 50℃. The activation energy was 13.25 kcal/mole and the conversion was 44.73-69.04%. The results from characterization showed that this catalyst system synthesized isotactic polypropylene with high molecular weight (32,00 t/mole) and narrow molecular weight distribution (polydispersity index or Mw/Mn about 2-3). The results of isotacticity from Fourier Transform Infrared Spectroscopy (FT-IR), melting point from Differential Scanning Calorimetry (DSC), and molecular weight and molecular weight distribution from Gel Permeation Chromatography (GPC) varied with polymerization temperature. Zirconium and aluminium cpmcemtratopm and AI:Zr ratio had no significant effect on the properties of polymer. Monomer concentration and zirconium and aluminium concentration had slight effect on molecular weight.

Ethylisobutylaluminoxane (EBAO) and its analogues were synthesized by a reaction between an triethylaluminum (Et3Al)/triisobutylaluminum (i‐Bu3Al) mixture and 4‐fluorobenzeneboronic acid, phenylboronic acid, or n‐butaneboronic acid and subsequent hydrolysis with water. They were used as cocatalysts in ethylene polymerization catalyzed by an iron complex {[(ArNC(Me))2C5H3N]FeCl2, where Ar is 2,6‐diisopropylphenyl}. Polyethylene with a high molecular weight and a narrow molecular weight distribution was prepared with modified EBAOs, and the performance of the iron complex at high polymerization temperatures was greatly improved. The activators for the iron complex also affected the polymerization activity and the molecular weight of the resultant polyethylene. It was suggested that the stereo and electronic effects of the substitute groups of aluminoxane contributed to the improved performance of the new activators. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1093–1099, 2004

Owing to the importance of poly(vinyl chloride) (PVC) as the second‐largest plastic in volume after the polyolefins and above styrene polymers, the control of the free‐radical polymerization of vinyl chloride (VC) is of high industrial and academic interest. But still the term “controlled” polymerization is not yet clearly defined. Often it is used for quasi‐living polymerizations with equilibrium reactions in the initiation and/or termination step or for the control of the molecular weight distribution (MWD), but it can also be applied to several structural aspects such as stereochemistry, branching, or special technical properties. In the present article, the control of chain growth and chain transfer is discussed. It has been well known for many years that the propagation step in the VC polymerization is terminated to a large degree by the rather frequent and temperature‐dependent chain transfer of the growing macromolecules to the monomer. Therefore, the degree of polymerization is strongly governed by the polymerization temperature. However, this transfer step does not result in a controlled or a narrow MWD. By means of free‐radical nitroxide‐mediated polymerization of VC in suspension, PVC with a narrower MWD can be obtained also at higher polymerization temperatures. The resulting PVC with nitroxide end groups can act as a macro‐initiator for various monomers, resulting in two‐block copolymers, which are, e.g., interesting compatibilizers in blends with PVC. J. VINYL ADDIT. TECHNOL., 11:86–90, 2005. © 2005 Society of Plastics Engineers

Two commercial biaxially oriented polypropylene (BOPP) resins, resin A and resin B , having different processing properties, were fractionated by preparative temperature-rising elution fractionation (TREF). The TREF fractions were further characterized by gel permeation chromatography (GPC), gel permeation chromatography coupled with light scattering (GPC-LS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). GPC-LS did not find visible long-chain branching in either resin A or B . The results from TREF and DSC indicate that the fractional melting parameter f ( T ) may be used to predict the profile of the TREF cumulative weight distribution curve. GPC results show that the molecular weights of the fractions tend to increase with elution temperature. WAXD and DSC data show that the crystallinity of fractions does not increase monotonically with increase of elution temperature. There appears to be a maximum in the plot of crystallinity versus elution temperature. The high-speed BOPP resin A has a lower isotacticity but a homogeneous isotacticity distribution and a higher molecular weight but a broader molecular weight distribution than resin B .

Two catalysts, denoted as catalyst 1 [silica/MAO/(nBuCp) 2ZrCl2] and catalyst 2 [silica/nBuSnCl 3/MAO/(nBuCp)2ZrCl2] were synthesized and subsequently used to prepare, without separate feeding of methylaluminoxane (MAO), ethylene homopolymer 1 and homopolymer 2, respectively, and ethylene-1-hexene copolymer 1 and copolymer 2, respectively. Gel permeation chromatography (GPC), Crystaf, differential scanning calorimetry (DSC) [conventional and successive self-nucleation and annealing (SSA)], and 13C nuclear magnetic resonance (NMR) polymer characterization results were used, as appropriate, to model the catalyst active-center distribution, ethylene sequence (equilibrium crystal) distribution, and lamellar thickness distribution (both continuous and discrete). Five different types of active centers were predicted in each catalyst, as corroborated by the SSA experiments and complemented by an extended X-ray absorption fine structure (EXAFS) report published in the literature. 13C NMR spectroscopy also supported this active-center multiplicity. Models combined with experiments effectively illustrated how and why the active-center distribution and the variance in the design of the supported MAO anion, having different electronic and steric effects and coordination environments, influence the concerned copolymerization mechanism and polymer properties, including inter- and intrachain compositional heterogeneity and thermal behaviors. Copolymerization occurred according to the first-order Markovian terminal model, producing fairly random copolymers with minor skewedness toward blocky character. For each copolymer, the theoretical most probable ethylene sequences, nE MPDSC-GT and n E MPNMR-Flory, as well as the weight-average lamellar thicknesses, Lwav DSC-GT and Lwav SSA DSC, were found to be comparable. To the best of our knowledge, such a match has not previously been reported. The percentage crystallinities of the homo- and copolymers increased linearly as a function of LMPDSC-GT. This indicates that the homo- and copolymer chains folded excluding the butyl branch. The results of the present study will contribute to developing future supported metallocene catalysts that will be useful in the synthesis of new grades of ethylene-α-olefin linear low-density polyethylenes (LLDPEs). © 2013 American Chemical Society.

A comparative study of ULDPE utilizing DSC and TREF

Characterization of the molecular structure of two highly isotactic polypropylenes

Fundamental studies on the separation of coal derivatives by means of gel permeation chromatography (GPC) are reported on (1) the chromatographic conditions for preparative GPC separation for structural analyses of coal and (2) basic experiments to odtain the molecular weight distributtion from analytical GPC elution curves using the chloroform soluble qart (γ-part) of pyridine extract from Akabira coal. On the basis of this informaton, the distributions of molecularweight of oil and asphaltene obtained from hydrogenolysis of Akabira coal are investigated by GPC analyses and their variation with reaction temperature is discussed.The petroleum soluble portion (γ1-part) and the insoluble portion (γ2-4-part) from the γ-part were selected as the sample for the discussion of the optimum conditions for GPC separation, such as pore size of gel and elution solvent. From the experimental results, it is obvious that separation by preparative GPC is achieved, odtaining fractions of considerably narrow molecular weight distribution. This contributed remarkably to the resolution of thechemical structure of coal. The relationship detween the elution volume (Ve) of the analytical GPC and average molecular weight (M) estimated by vapor pressure osmometry is fairly good for the fractionation products from preparative GPC (Fig. 9, 10). The M-Ve correlation lines of the 1- and the 2-4-parts were straight lines of different slope. Therefore it was assumed that the difference was due to a difference in structural type on the components. Consequently, these γ relationships of log M-Ve can be applied to the estimation of the molecular weight distribution from analytical GPC chromatograms as the correlation lines of high-molecular and low-molecular weight components respectively for the coal derived liquids.Oil and asphaltene in hydrogenolysis products werealso separated into fraction on the basis of molecular weight by preparative GPC and each fraction was correlated by elution counts of analytical GPC and average molecular weight. The results of these relationships were in fairly good agreement with correlation lines of log M-Ve odtained from the γ1 and the γ2-4 componets respectively (Fig. 13, 14). From the elution curves of analytical GPC for oil and asphaltene of varying reaction temperature, it is recognized that the distribution of molecular wight for asphaltene shifts gradually in the direction of a lower molecular weight distribution as the reaction temperature increases. On the other hand, the distribution of moleclar weight of oil changes only slightly and tends to converge to the constant distribution of low molecular weight components.

ABSTRACTIn this article, comonomer effects in copolymerization of ethylene and 1‐hexene with four MgCl2‐supported Ziegler‐Natta catalysts using either ethylene or 1‐hexene as the main monomer were investigated. It was found that no matter which monomer was used as the main monomer, the polymerization activity was significantly enhanced by introducing small amount of comonomer. In copolymerization with ethylene as the main monomer, the strength of comonomer effects was much stronger in active centers producing low‐molecular‐weight polymer than those producing high‐molecular‐weight polymer. In copolymerization with 1‐hexene as the main monomer, the number of active centers ([C*]/[Ti]) was determined, and the propagation rate constants (kp) were calculated. Deconvolution of the polymer molecular weight distribution into Flory components were made to study the active center distribution. Introduction of small amount of ethylene caused marked increase in the number of active centers and decrease in average chain propagation rate constant. Introducing internal electron donor in the catalyst enhanced not only the number of active centers but also the chain propagation rate constant. In copolymerization of 1‐hexene with small amount of ethylene, the internal donor weakened the comonomer effects to some extent and changed the distribution of comonomer effects among different types of active centers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41264.

A commercial, linear, low-density polyethylene (LLDPE) synthesized by a metallocene catalyst was analyzed by temperature-rising elution fractionation, Fourier transform infrared, and 13C-nuclear magnetic resonance spectroscopy. It was found that the LLDPE sample is mainly butyl branch. The degree of branching decreased with increasing elution temperature. The results from wide-angle x-ray diffraction and size exclusion chromatography confirmed that the fractionation was based on the ability of fractions to crystallize rather than molecular weight. The LLDPE sample has a narrow molecular-weight distribution.

The distributions of molecular weight and chemical composition of two linear low-density poly-ethylene resins synthesized with Ziegler-Natta catalysts were analyzed with several microstructural characterization techniques and the results were used to investigate the nature of the active site types present on the catalyst. Deconvolution of the molecular weight distribution measured by gel permeation chromatography and of the chemical composition distribution measured by either crystallization analysis fractionation or temperature rising elution fractionation or temperature rising elution fractionation leads to consistent results that indicate the presence of multiple active site types on the catalyst. This shows that these fractionation techniques, when combined with adequate mathematical models, are powerful tools to understand the behavior of Ziegler-Natta catalysts and structural properties of the produced resins.

Novel MgCl2-supported Ziegler-Natta (Z-N) catalysts prepared using a new one-pot ball milling method can effectively control the amounts of Ti-loading in the catalysts. Complex GPC data on polypropylene synthesized by these novel catalysts were analyzed using the method of fitting the molecular weight distribution (MWD) curves with a multiple Flory-Schulz function. It was found that multiple active centers exist in these novel catalysts. Detailed study of the effects of the Ti-loadings in the catalysts on the distribution of the active centers showed that the Ti-loadings in the novel MgCl2-supported Z-N catalysts might affect the proportion of each type of active centers; and might be the main factor responsible for the effect of the Ti-loadings on the microstructure, the molecular weight and molecular weight distribution width of the resultant polymer, the catalytic activity and polymerization kinetics.

Norbornene polymerization using the commercially available and inexpensive catalyst system, cyclopentadienylzirconium trichloride (CpZrCl3) and isobutyl‐modified methylaluminoxane (MMAO), were carried out over a wide range of polymerization temperatures and monomer concentrations. For the CpZrCl3 catalyst system activated by aluminoxane with a 40 mol % methyl group and a 60 mol % isobutyl group (MMAO40/60), the polymerization temperature and monomer concentration significantly affected the molecular weight (Mn) of the obtained polymer and the catalytic activity. With an increase in the polymerization temperature from 0 to 27 °C, the catalytic activity and Mn increased, but these values dramatically decreased with the increasing polymerization temperature from 27 to 70 °C, meaning that the most suitable temperature was 27 °C. The CpZrCl3/MMAO40/60 ([Al]/[Zr] = 1000) catalyst system with the [NB] of 2.76 mol L−1 at 27 °C showed the highest activity of 145 kg molZr−1 h−1 and molecular weight of 211,000 g mol−1. The polymerization using the CpZrCl3/MMAO40/60 catalyst system proceeds through the vinyl addition mechanism to produce atactic polynorbornene, which was soluble in chloroform, toluene, and 1,2‐dichlorobenzene, but insoluble in methanol. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1185–1191, 2008

Seven titanium complexes bearing fluorine-containing phenoxy-imine chelate ligands, TiCl(2)[eta(2)-1-[C(H)=NR]-2-O-3-(t)Bu-C(6)H(3)](2) [R = 2,3,4,5,6-pentafluorophenyl (1), R = 2,4,6-trifluorophenyl (2), R = 2,6-difluorophenyl (3), R = 2-fluorophenyl (4), R = 3,4,5-trifluorophenyl (5), R = 3,5-difluorophenyl (6), R = 4-fluorophenyl (7)], were synthesized from the lithium salt of the requisite ligand and TiCl(4) in good yields (22%-76%). X-ray analysis revealed that the complexes 1 and 3 adopt a distorted octahedral structure in which the two phenoxy oxygens are situated in the trans-position while the two imine nitrogens and the two chlorine atoms are located cis to one another, the same spatial disposition as that for the corresponding nonfluorinated complex. Although the Ti-O, Ti-N, and Ti-Cl bond distances for complexes 1 and 3 are very similar to those for the nonfluorinated complex, the bond angles between the ligands (e.g., O-Ti-O, N-Ti-N, and Cl-Ti-Cl) and the Ti-N-C-C torsion angles involving the phenyl on the imine nitrogen are different from those for the nonfluorinated complex, as a result of the introduction of fluorine atoms. Complex 1/methylalumoxane (MAO) catalyst system promoted living ethylene polymerization to produce high molecular weight polyethylenes (M(n) > 400 000) with extremely narrow polydispersities (M(w)/M(n) < 1.20). Very high activities (TOF > 20 000 min(-1) atm(-1)) were observed that are comparable to those of Cp(2)ZrCl(2)/MAO at high polymerization temperatures (25, 50 degrees C). Complexes 2-4, which have a fluorine atom adjacent to the imine nitrogen, behaved as living ethylene polymerization catalysts at 50 degrees C, whereas complexes 5-7, possessing no fluorine adjacent to the imine nitrogen, produced polyethylenes having M(w)/M(n) values of ca. 2 with beta-hydrogen transfer as the main termination pathway. These results together with DFT calculations suggested that the presence of a fluorine atom adjacent to the imine nitrogen is a requirement for the high-temperature living polymerization, and the fluorine of the active species for ethylene polymerization interacts with a beta-hydrogen of a polymer chain, resulting in the prevention of beta-hydrogen transfer. This catalyst system was used for the synthesis of a number of unique block copolymers such as polyethylene-b-poly(ethylene-co-propylene) diblock copolymer and polyethylene-b-poly(ethylene-co-propylene)-b-syndiotactic polypropylene triblock copolymer from ethylene and propylene.

Hollow-fiber carbon membranes were produced by the pyrolysis of acrylonitrile-based precursors that were spun using a wet phase-inversion technique. The fibers were used in the catalytic conversion of cyclohexane. Thermogravimetric (TGA) and variance analyses were carried out on the fibers produced. The TGA analyses involved the determination of the percentage aromatization and cyclization mass-losses as functions of process variables, such as polymerization temperature, monomer concentration, stirrer speed and initiator concentration. An empirical approach was adopted that employed statistical experimental designs that were used to recognize analytical and statistical methods that translated the process responses into comprehensible terms. A low methylcrylate (MA) concentration and a high azo-bis-isobutyronitrile (AIBN) concentration yielded a polymer that resulted in a precursor with low mass loss during carbonization. Both high AIBN concentration and low stirrer speed on the one hand and a high polymerization temperature at a low stirrer speed on the other hand yielded a low mass loss. The response plot function of the percentage mass loss indicated that a low MA concentration at a low polymerization temperature would give the lowest mass loss. Chemical shrinkage, corresponding to the cyclization process, started only at temperatures ≈200°C, while the aromatization process commenced above 350°C.