Precise control of polyolefin stereochemistry using single-site metal catalysts.

Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architectures of bottlebrushes provide a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers. Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: (i) bottlebrush self-assembly in melts and bulk thin films, (ii) bottlebrushes for photonics and lithography, (iii) bottlebrushes for small molecule encapsulation and delivery in solution, and (iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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Structure, function, self-assembly, and applications of bottlebrush copolymers

Unique copolymers comprising propylene, ethylene and/or one or more unsaturated comonomers are characterized as having: at least one, preferably more than one, of the following properties: (i) 13C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) a B-value greater than about 1.4 when the comonomer content of the copolymer is at least about 3 wt%, (iii) a skewness index, S?ix?, greater than about -1.20, (iv) a DSC curve with a Tme that remains essentially the same and a Tmax that decreases as the amount of comonomer in the copolymer is increased, and (v) an X-ray diffraction pattern that reports more gamma-form crystals than a comparable copolymer prepared with a Ziegler-Natta catalyst. These polypropylene polymers are made using a nonmetallocene, metal-centered, heteroaryl ligand catalyst. These polymers can be blended with other polymers, and are useful in the manufacture of films, sheets, foams, fibers and molded articles.

Isotactic propylene copolymers, their preparation and use

Embodiments of the present invention relate to article comprising 1) a functionalized component, 2) tackifier, and 3) an olefin polymer comprising one or more C3 to C40 olefins, optionally one or more diolefins, and less than 5 mole % of ethylene having a Dot T-Peel of 1 Newton or more, a branching index (g′) of 0.95 or less measured at the Mz of the polymer; and an Mw of 100,000 or less; where the functional component is selected from the group consisting of functionalized polymers, functionalized oligomers and beta nucleating agents; and where the Gardner color of the adhesive does not change by more than 7 Gardner units when the adhesive has been heat aged at 180° C. for 48 hours as compared to the Gardner color of the unaged composition.

Polyolefin adhesive compositions and articles made therefrom

Constrained geometry complexes—Synthesis and applications

The invention is directed to olefin polymerization processes using bridged hafnocene catalyst complexes comprising highly substituted noncoordinating anions that are surprisingly stable under high temperature olefin polymerization processes such that olefin copolymers having significant amount of incorporated comonomer can be prepared with high molecular weights. More specifically, the invention is a polymerization process for ethylene copolymers having a melt index of about 0.87 to about 0.930 comprising contacting, under homogeneous polymerization conditions at a reaction temperature at or above 140° C. to 225° C., ethylene and one or more comonomers capable of insertion polymerization with a bridged hafnocene catalyst complex derived from A) a biscyclopentadienyl hafnium organometallic compound having i) at least one unsubstituted cyclopentadienyl ligand or aromatic fused-ring substituted cyclopentadienyl ligand, ii) one aromatic fused-ring substituted cyclopentadienyl ligand, iii) and a covalent bridge connecting the two cyclopentadienyl ligands, said bridge comprising a single carbon or silicon atom; and B) an activating cocatalyst, precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion wherein each aryl substituent contains at least two cyclic aromatic rings.

High temperature olefin polymerization process

The present invention relates to a mixed catalyst system of at least one bridged, bulky ligand metallocene-type compound, and at least one bridged, asymmetrically substituted, bulky ligand metallocene-type compound, a method of making the mixed catalyst system and to their use in a polymerization process to produce polymers having an unexpected improvement in processability.

Mixed catalysts and their use in a polymerization process

The present invention relates to a process for polymerizing olefin(s) utilizing a cyclic bridged metallocene-type catalyst system to produce enhanced processability polymers.

A polymerization process for producing easier processing polymers

This invention relates to a co-oligomer having an Mn of 300 to 30,000 g/mol comprising 10 to 90 mol % propylene and 10 to 90 mol % of ethylene, wherein the oligomer has at least X % allyl chain ends, where: 1) X=(−0.94 (mole % ethylene incorporated)+100), when 10 to 60 mole % ethylene is present in the co-oligomer, and 2) X=45, when greater than 60 and less than 70 mole % ethylene is present in the co-oligomer, and 3) X=(1.83*(mole % ethylene incorporated)−83), when 70 to 90 mole % ethylene is present in the co-oligomer. This invention also relates to a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 100 ppm aluminum. This invention also relates to a process of making homo-oligomer, comprising propylene, wherein the productivity is greater than 4500 g/mmol Hf (or Zr)/hour.

High vinyl terminated propylene based oligomers

Cyclic olefins copolymerize efficiently with ethylene using metallocene catalysts to make rigid engineering polyolefins with high chemical homogeneity. Materials with a high chemical homogeneity have value because they show reduced light scattering resulting in excellent clarity. The ultimate chemical homogeneity in a two component copolymer occurs when an alternating sequence distribution is achieved. Low symmetry bis-metallocenes have been shown to make alternating, stereoregular cyclic olefin copolymers under the right process conditions. These copolymers are semicrystalline and have high melt temperatures. Herein we report two group 4 monocyclopentadienyl catalyst systems that yield semicrystalline ethylene/norbornene copolymers over a range of reactor conditions. The clear copolymers have glass transition temperatures over 110°C and melt temperatures over 240°C. Further characterization data is presented and a short discussion of a plausible polymerization mechanism is given.

Donna J. Crowther

Papers

High temperature olefin polymerization process

Mixed catalysts and their use in a polymerization process

A polymerization process for producing easier processing polymers

High vinyl terminated propylene based oligomers

Stereoregular, alternating ethylene-norbornene copolymers from monocyclopentadienyl catalysts activated with non-coordinating discrete anions