Supported hybrid early and late transition metal catalysts for the synthesis of polyethylene with tailored molecular weight and chemical composition distributions

Supported hybrid catalysts using metallocenes and a nickel diimine catalyst were synthesized and used for ethylene slurry polymerization and ethylene/1-hexene copolymerization. Two types of metallocenes, together with a nickel diimine catalyst were supported onto SiO₂ through chemical bonding, and a borate compound was physisorbed for the activation of the catalysts. These supported hybrid catalysts had high catalyst activities and made free-flowing polymer particles. The chemical composition distribution, molecular weight averages and distributions of resultant polymers were controlled by catalyst structure and polymerization conditions such as reaction temperature and the use of α-olefin. According to GPC-IR, ¹³C NMR and CEF characterization results of some polymers, more 1-hexene was incorporated in the high molecular weight region, short chain branches were generated by the chain walking mechanism in low molecular weight region. The morphologies of the resulting particles were investigated by SEM.     

Vinyl polymerization of norbornene with dinuclear diimine nickel dichloride/MAO

Vinyl‐addition polymerization of norbornene was accomplished by two novel dinuclear diimine nickel dichloride complexes in combination with methylaluminoxane (MAO). The activities were moderate. The catalyst structure, Al/Ni molar ratio, solvents, and polymerization temperature all affected the catalytic activities. The obtained polynorbornenes were characterized by ¹H‐NMR, ¹³C‐NMR, FTIR, DSC, WAXD, and intrinsic viscosity measurements. The vinyl‐addition polymers were amorphous but with a short‐range order and high packing density. The polynorbornenes showed glass transition temperatures (T_g) above 240°C and decomposed above 400°C. The catalyst structure and polymerization conditions have effects on the molecular weight and the microstructure of the polymers. The nickel complex with bulkier substituents in the ligand produced polynorbornene with a higher packing density and higher regularity and, therefore, with higher T_g. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3273–3278, 2003     

HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

Radical styrene polymerization in the presence of trace levels of sulfonic acids

The bulk polymerization of styrene in the presence of the vinyl functional sulfonic acid 2‐sulfoethylmethacrylate (SEM) was found to have utility for making polystyrenes with narrow polydispersity, bimodal polydispersity, and ultrahigh molecular weight at fast polymerization rates. Narrow polydispersity polymers were made by the addition of SEM to nitroxide‐mediated polymerizations. Bimodal polydispersity polymers were made by the ultrahigh molecular weight component being made in the presence of SEM in the absence of an initiator and the low molecular weight component being made in the presence of an initiator and/or chain‐transfer agent. Ultrahigh molecular weight monomodal polystyrenes were prepared at much faster polymerization rates than possible via spontaneous polymerization in the absence of SEM. SEM was found to be more effective, by an order of magnitude, than camphor sulfonic acid on a weight basis and, because it is copolymerized into the polymer chain, should not lead to corrosion problems during fabrication of the polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 869–875, 2003     

Polymerization of butadiene in toluene with nickel (II) stearate-diethyl aluminum chloride catalyst. I. Catalytic behaviors

The polymerization of butadiene with nickel (II) stearate–Et₂AlCl catalyst has been studied in a batch reactor. The rate of polymerization is first order with respect to monomer and increases with the addition of water. In this system, no appreciable termination reaction has been found and the chain transfer to monomer dictates the molecular weight distribution of the polymer products. Molecular weight increases with conversion and water content. The cis-1,4 content was found to be a function of the extent of polymerization.     

Synthesis of low molecular weight polyethylenes and polyethylene mimics with controlled chain structures

The controlled synthesis of narrowly distributed low molecular weight polymers with functionalization possibilities is of great industrial interests. Although living polymerization allows for control over polymer architecture, the production of low molecular weight polymers with low polydispersities via living polymerization systems is challenged by the use of large amounts of catalysts and broadening in molecular weight distribution. This review addresses the synthesis of narrowly distributed, functional, low molecular weight polyethylene and polyethylene mimics. The review is structured for quick identification of relevant systems for the production of specific polymer architectures with specific cost, efficiency, and safety concerns.     

宽分子量分布聚合物的制备

分别对采用物理共混法、自由基聚合、配位聚合和离子聚合法制备宽分子量分布聚合物进行了综述。指出目前应用较为广泛的是物理共混法，配位聚合容易实现分子量和分子量分布宽度可控，近几年已成为研究热点。     

Optimizing polymer reactivities for the solid-state polycondensation of AA and BB type monomers

A new method is presented to optimize the reactivities of a prepolymer for the solid-state polymerization of AA and BB type monomers to obtain high molecular weight polymers. The proposed method consists of blending the prepolymers of different end group mole ratios to maintain optimal reaction stoichiometry, and developing a computational procedure to calculate the molecular weight of the polymer in the solid-state polymerization. A molecular species model is used to calculate the molecular weight moments of the optimized prepolymer and to calculate the molecular weight development in a solid-state polymerization. The molecular weight moments of different polymer species in the prepolymer mixture are estimated by performing the dynamic simulations of a melt prepolymerization process model in conjunction with a numerical optimizer. The model simulation results show that the proposed method offers a significantly improved process performance to obtain high molecular weight condensation polymers in a solid-state polymerization. Bisphenol A polycarbonate is selected as an example to illustrate the proposed method.     

Hydrogen effect on the molecular weight distribution of polymers obtained by polymerization of ethylene and α-olefins over supported titanium-magnesium catalysts

Comparative data on the molecular weight distribution of polymers obtained by polymerization of ethylene, propylene and 1-hexene, and copolymerization of ethylene with α-olefins over the titanium-magnesium catalysts (TMC) in the absence and presence of hydrogen are presented. In contrast to the ethylene polymerization, in the cases of propylene and 1-hexene polymerization and copolymerization of ethylene with α-olefins, the hydrogen addition is characterized by noticeable narrowing of the molecular weight distribution (MWD) due to lower contribution of the MWD component with high molecular weight. This result is an evidence of the increased reactivity of TMC active sites producing high molecular weight poly-α-olefins and copolymers of ethylene with α-olefins in the chain transfer reaction with hydrogen. It is suggested that the increased reactivity of these sites in the transfer reaction with hydrogen appears after the 2,1-addition of α-olefin to the growing polymer chain.     

单茂金属化合物催化烯烃聚合

综述了单茂金属化合物催化烯烃聚合的机理及研究进展，指出IVB族元素钛、锆、铪的单茂金属化合物催化烯烃及α－烯烃的均聚和共聚的活性很好，并通过改变配体结构及聚合条件可得到立构规整性的聚合物，桥联的单茂金属化合物催化乙烯，丙烯聚合的活性相当高，可得到高间规度的聚丙烯和支化的超低密度聚乙烯，但催化苯乙烯的活性很低，VB族元素钒，铌、钽的单茂金属化合物作为烯烃催化剂可得到分子量分布相当窄（1．05）的聚烯烃，另外，单茂铬化合物在很低的Al/Cr(45-100)下具有相当高的催化活性，单茂镍化合物由于其亲氧性小，可催化极性单体（如甲基丙烯酸甲酯等）聚合。     

聚丙烯酰胺类水溶性聚合物制备中分子量的控制

聚丙烯酰胺类水溶性聚合物在油气开采过程中有着十分广泛的应用,其分子量的大小决定着产品的性能和用途。该类聚合物的合成一般采用自由基聚合,聚合反应中通过控制单体浓度、引发剂浓度、聚合反应温度可以调节聚合物的分子量。另外,通过选择引发体系、聚合工艺、适度交联以及添加链转移剂也可以达到控制聚丙烯酰胺类水溶性聚合物分子量的目的。     

Einfluß des stofftransportes bei der polymerisation von äthylen und 1-okten mit Ziegler-Katalysatoren

The polymerization of ethylene and 1-octene with supported Ziegler-catalysts was investigated with regard to the influence of mass transport of monomers on the kinetics, molecular weight and molecular weight distribution. In the case of the polymerization of ethylene, it was found that for certain conditions of reaction the mass transport of ethylene can influence the kinetics of polymerization respectively the catalyst efficiency strongly. The molecular weight and molecular weight distribution of the polyethylene formed are practically not affected by the conversion as well as particle size of catalyst and polymer. The molecular weight distribution however is affected by the concentration of the catalyst. The polymerization process of ethylene in suspension is distinguished by chemical and physical processes. A continuous chain initiation, for example, is based on the continuous reduction of the catalyst particles to small pieces during the course of polymerization. An apparent chain termination respectively catalyst deactivation can occur when catalyst particles are encapsulated within the growing polymer particles. The polymerization of 1 -octene for similar conditions of reaction gave polymers which were solved completely in the system used. The molecular weight distribution of the polymer formed nevertheless was very broad. This indicates that the mass transport of the monomers through the solid phase of polymer cannot be the main reason for the broad molecular weight distribution of the polymers which are produced by heterogeneous Ziegler-catalysts in suspension.     

High-molecular weight diepoxide-dicarboxylic acid addition polymers

Summary The addition polymerization of 2,2-bis[4-(2,3-epoxypropoxy)phenyl] propane (DGEBA) and dicarboxylic acid results in high molecular weight addition polymers (M_n 8000–13000). Their molecular weight distribution is rather broad (M_w/M_n=11,6) due to side reactions such as transesterification and formation of ether linkages. Due to the incorporation of the aliphatic dicarboxylic acid moieties in the polymer backbone, the addition polymers show relatively low glass transition temperatures ranging from 26 to 45 °C.     

Facile preparation of a novel nickel-containing metallopolymer via RAFT polymerization

While the metallocene polymers were comprehensively studied, other metallopolymers are rarely explored. The major challenge is the lack of a synthetic platform for the preparation of metal coordinated derivatives, monomers, and polymers. Therefore, the development of a facile synthesis of new metal coordinated monomers and polymers is critically needed. A novel successfully synthesized methacrylate-containing nickel complex is reported in this communication. Controlled RAFT polymerizations are further carried out to prepare a series of side-chain nickel containing polymers with different molecular weight and narrow Polydispersity Index (PDI). This new metallopolymer performs specific electrochemical and excellent thermal properties. This study provides a novel and convenient strategy to prepare metallopolymer with controllable molecular weight, which has potential applications in assembled, catalytic and magnetic materials.     

Cationic polymerization in iodine/liquid sulfur dioxide system

Summary Poly(alpha-methylstyrene) with narrow molecular weight distribution (MWD) was obtained by cationic polymerization initiated by iodine in methylene chloride/liquid SO₂ (80/20 vol.%) or toluene/liquid SO₂ (45/55 vol.%) mixed solvent at-60°C. The average number molecular weights of the product polymers increased with monomer conversion but the dependence was not linear because of the low initiation efficiency at the beginning of the reaction. On addition of a fresh feed of monomer at the end of the polymerization, the added feed was polymerized at the same rate with an increase of molecular weight. The low dispersity was kept after the second monomer addition. The initiation efficiency increased during the polymerization.     

Some effects of emulsion polymerization conditions on molecular polydispersity and rheological properties of poly(methyl methacrylate)

Emulsion polymerization conditions of free-radical-polymerized poly(methyl methacrylate) have been examined in relation to the molecular weight and molecular polydispersity of the resulting polymers. In turn, molecular weight and molecular polydispersity have been related to the apparent viscosity and the appearance of the extrudate produced by an Instron capillary rheometer. The length of time for monomer addition to the polymerization medium was found to be a variable of primary concern in the emulsion polymerization. Continuous monomer addition (from 1 to 2 hr) resulted in a poly(methyl methacrylate) with a narrow distribution (～2.0) and medium molecular weight (～132 × 10³). Both molecular weight and polydispersity were found to significantly affect apparent viscosity and extrudate appearance. Differences in the rheological parameters were most marked at the lowest shear rate run in this study. The poly(methyl methacrylate) samples with medium molecular weight and more narrow molecular polydispersity exhibited the best combination of low apparent viscosity and smooth glossy appearance.     

Living cationic polymerization of isobutyl vinyl ether initiated by the trimethylsilyl iodide/zinc iodide system

Summary Trimethylsilyl iodide in conjunction with zinc iodide (Me₃SiI/ZnI₂) as an initiating system led to living cationic polymerization of isobutyl vinyl ether in toluene at 0 or –40°C or in methylene chloride at –40°C (ZnI₂ was dissolved in acetone). The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit trimethylsilyl iodide. At room temperature (+25°C), however, the polymerization failed to give perfectly living polymers; the polymer molecular weight was smaller than the calculated value. On addition of a fresh feed of monomer at the end of the polymerization at –40°C, the added feed was smoothly polymerized at nearly the same rate as in the first stage, and the polymer molecular weight continued to increase in direct proportion to monomer conversion. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (M_w/M_n< 1.1).Living cationic polymerization of vinyl ethers by electrophile/Lewis acid initiating systems, part 2. For part 1 see ref. 2     

Preparation of hyperbranched polymers through ATRP of in situ formed AB* monomer

The self‐condensing vinyl polymerization of an AB* monomer formed in situ by atom transfer radical addition from divinylbenzene (DVB) and (1‐bromoethyl)benzene (BEB) using atom transfer radical polymerization technique was studied. The catalyst concentration has a dramatic effect on polymerization. To study the polymerization mechanism and to achieve high molecular weight polymer, the polymerization was carried out in bulk with a catalyst to monomer ratio, 2,2′‐bipyridine to DVB, of 0.2 at 90°C. Proton nuclear magnetic resonance (¹H NMR) spectroscopy and size‐exclusion chromatography coupled with multiangle laser light scattering were used to analyze the polymerization aliquots and the obtained polymer. The intrinsic viscosities of the prepared polymers were also measured. Experimental results, from the comparison of the apparent molecular weights measured by size‐exclusion chromatography with the absolute values measured by multiangle laser light scattering as well as viscosity measurements, indicate the existence of hyperbranched structures in the prepared polymers. In sharp contrast to hyperbranched polymers from AB* monomer preprepared, hyperbranched ploy(divinylbenzene) prepared at equimolar amount of DVB and BEB has numerous residual pendant vinyl groups rather than only one double bond at its focal point. The hyperbranched polymers show relatively narrow molecular weight distribution (2.13–3.77) and exhibit excellent solubility in common organic solvents such as acetone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 850–856, 2006     

Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Study of chain sequence in the controlled radical telomerization of vinyl acetate with Co(acac)2 catalyst in bulk

A series of porphyrin-containing polymers with triazole rings as linkers have been successfully synthesized by click polymerization. The polycycloadditions of porphyrin-containing dialkyne 1 and 1,4-diazidobenzene 2 were initiated either by simple heating or by Cu(I)-catalyst, affording polymers P1-P8 with relatively high molecular weight. The polymerization process was monitored by gel permeation chromatography analysis. The polymer prepared by thermally initiated click polymerization has unimodal molecular weight distribution and moderate polydispersity index after prolonging reaction time to 170?h. Compared with the metal-free click polymerization, the rate of molecular weight growth in Cu(I)-catalyzed click polymerization declined, leading to relatively low molecular weight of the resulting polymer. The as-synthesized polymers are soluble in common organic solvents and stable at a temperature up to 350?°C. The photophysical properties of the porphyrin monomer and the polymer were investigated by UV?Cvis and fluorescence spectroscopy. This approach offers practical advantages over other synthetic methods used to prepare main-chain porphyrin-containing polymers with regard to the absence of byproducts generated during the polymerization reaction.