Exxonmobil Research and Engineering Company

Exxonmobil Chemical Patents Inc.

International Business Machines Corporation

Massachusetts Institute of Technology

Nikos Hadjichristidis

David John Lohse

Andy Haishung Tsou

Pamela Jean Wright

Cesar Alberto Garcia-Franco

Scott Thomas Milner

Lewis J Fetters

Robert A Mendelson

David W Mead

Johannes Matthieu Soulages

Paul Edward Schuenzel

César Garcia-Franco

Robert Dennis Miller

Pradeep P Shirodkar

Edwin Lorimer Thomas

Victor Y Lee

Thomas T Sun

Suzzy C H Ho

Martin N Webster

Suzzy Chen Hsi Ho

Vera Minak-Bernero

Vanessa Z H Chan

Apostolos Avgeropoulos

Provided are blends of branched hydrocarbon comb polymers having tailored branching and molecular weight parameters, with substantially linear polymers. Such blends have been found to have improved extensional rheological properties, while maintaining nearly the viscosity of the substantially linear polymers. The blends of the hydrocarbon comb polymers with the substantially linear polymers thus maintain the extrusion processing characteristics of the linear polymer alone, but have improved extensional flow processability, with strain hardening ratios (SHR) greater than 1. The blends are effective in blown film processing. Also disclosed are related methods for improving extensional flow processability using the branched hydrocarbon comb polymers, as well as the branched hydrocarbon comb polymers themselves, including as a property enhancing additive for such substantially linear polymers.

Branched saturated hydrocarbon polymers as extensional rheology modifiers without impacting shear properties

Provided is a method for stabilizing a dispersion of a carbon nanomaterial in a lubricating oil basestock. The method includes providing a lubricating oil basestock; dispersing a carbon nanomaterial in the lubricating oil basestock; and adding at least one block copolymer thereto. The at least one block copolymer has two or more blocks includes at least one alkenylbenzene block and at least one linear alpha olefin block. The at least one block copolymer is present in an amount sufficient to stabilize the dispersion of the carbon nanomaterial in the lubricating oil basestock. Also provided is a lubricating engine oil having a composition including: a lubricating oil base stock; a carbon nanomaterial dispersed in the lubricating oil basestock; and at least one block copolymer.

Lubricant compositions and processes for preparing same

A process for making a substantially saturated dendritic hydrocarbon polymer. The process has the following steps: (a) polymerizing an amount of a first alkadiene monomer under anionic conditions in the presence of a first organic monolithium initiator to produce a linear polyalkadiene having a lithiated chain end; (b) reacting the linear polyalkadiene with an amount of a second organic monolithium initiator in the presence of tetramethylethylene diamine to form a multilithiated polyalkadiene; (c) reacting the multilithiated polyalkadiene with an amount of a second alkadiene monomer to form a branched polyalkadiene; (d) repeating steps (b) and (c) with the branched polyalkadiene one or more times to prepare a dendritic polyalkadiene; and (e) hydrogenating the dendritic polyalkadiene to form the substantially saturated dendritic hydrocarbon polymer.

Process for making a saturated dendritic hydrocarbon polymer

A process for making a substantially saturated dendritic hydrocarbon polymer. The process has the following steps: (a) polymerizing an amount of one or more alkadiene monomers and/or one or more alkenylaromatic polymers under anionic conditions in the presence of a di- or tri-functional organic lithium initiator to produce a polyalkadiene defining a multiplicity of lithiated chain ends; (b) reacting the polyalkadiene with an amount of a tri- or di-functional silane coupling agent to form a dendritic polyalkadiene; and (c) hydrogenating the dendritic polyalkadiene to form a substantially saturated dendritic hydrocarbon polymer. Also a process for process for making a dendritic hydrocarbon polymer, comprising: (a) polymerizing an amount of one or more alkadiene monomers and/or one or more alkenylaromatic polymers under anionic conditions in the presence of a di- or tri-functional organic lithium initiator to produce a hydrocarbon polymer defining a multiplicity of lithiated chain ends; and (b) reacting the hydrocarbon polymer with an amount of a tri- or di-functional silane coupling agent to form a dendritic hydrocarbon polymer.

Process for making dendritic hydrocarbon polymers

Provided is a process for making a saturated star hydrocarbon polymer. The process has the following steps: (A) hydrosilylating tetraethylene silicon with methyldichlorosilane in the presence of a hydrosilylating catalyst to form a chlorosilane dendrimer; (B) reacting the chlorosilane dendrimer with vinylmagnesium bromide in the presence of a lithium and/or organolithium initiator stepwise to build a higher generation chlorosilane dendrimer; (C) anionically polymerizing polybutadiene in the presence of a lithium and/or organolithium initiator to form living poly(butadienyl)lithium; (D) attaching the living poly(butadienyl)lithium to the higher generation dendrimer to form a star polybutadiene; and (E) hydrogenating the star polybutadiene to form the saturated star hydrocarbon polymer. There is also provided a saturated star hydrocarbon polymer made according to the above process and a polymer composition of a matrix ethylene polymer and the saturated star hydrocarbon polymer.

Star hydrocarbon polymer, process for making, and a polymer blend composition having same

The present invention relates to a method to produce highly branched polymers with a polyolefin backbone structure of ethylene and precise control of the nature of the branching. In particular, the distribution of branch length and number of branches can be more precisely controlled via the polymerization method of the present invention. The method comprises using anionic chemistry to make unsaturated polydienes with a well-defined, highly-branched structure, and then hydrogenating these polydienes to form highly branched or dendritic saturated hydrocarbon polymers. Highly branched or dendritic polyethylene, ethylene-propylene copolymer and atactic polypropylene are among the saturated hydrocarbon polymers that can be anionically synthesized via the proper selection of diene monomer type, coupling agent, and hydrogenation conditions.

Synthesis and use of well-defined, highly-branched saturated hydrocarbon polymers

The current invention involves periodically ordered nanostructured materials and methods of using and modifying the materials. In some embodiments, the invention provides periodically structured microphase separated polymeric articles that include periodically occurring separate domains. The polymeric species comprising one or more of the domains, for some embodiments, contains an inorganic species capable of forming an inorganic oxide ceramic. In another aspect, the invention provides methods for modifying the polymeric articles by oxidation and/or radiation to form periodically structured porous and relief articles that, in some embodiments, include a ceramic oxide in their structure. The invention also provides methods of use for the novel articles and novel structures constructed utilizing the articles.

Periodic porous and relief nanostructured articles

The present invention relates to a method to produce highly branched polymers with a polyolefin backbone structure of ethylene and precise control of the nature of the branching. In particular, the distribution of branch length and number of branches can be more precisely controlled via the polymerization method of the present invention. The method comprises using anionic chemistry to make unsaturated polydienes with a well-defined, highly-branched structure, and then hydrogenating these polydienes to form highly branched or dendritic saturated hydrocarbon polymers. Highly branched or dendritic polyethylene, ethylene-propylene copolymer and atactic polypropylene are among the saturated hydrocarbon polymers that can be anionically synthesized via the proper selection of diene monomer type, coupling agent, and hydrogenation conditions. These polymers find application in injection molding and extrusion processes as a minor additive for improving processability of linear polyolefins by delaying the onset of melt fracture, and correspondingly increasing melt throughput rates.

The invention is directed to essentially saturated hydrocarbon polymer composition comprising essentially saturated hydrocarbon polymers having A) a backbone chain; B) a plurality of essentially hydrocarbyl sidechains connected to A), said sidechains each having a number-average molecular weight of from 2500 Daltons to 125,000 Daltons and a MWD by SEC of 1.0-3.5; and having A) a Newtonian limiting viscosity (&eegr; ) at 190&deg; C. at least 50% greater than that of a linear olefinic polymer of the same chemical composition and weight average molecular weight, preferably at least twice as great as that of said linear polymer, B) a ratio of the rubbery plateau modulus at 190&deg; C. to that of a linear polymer of the same chemical composition less than 0.5, preferably <0.3, C) a ratio of the Newtonian limiting viscosity (&eegr; ) to the absolute value of the complex viscosity in oscillatory shear (&eegr;*)at 100 rad/sec at 190&deg; C. of at least 5, and D) a ratio of the extensional viscosity measured at a strain rate of 1 sec , 190&deg; C., and time&equals;3 sec (i.e., a strain of 3) to that predicted by linear viscoelasticity at the same temperature and time of 2 or greater. Ethylene-butene prepared by anionic polymerization and hydrogenation illustrate and ethylene-hexene copolymers prepared by coordination polymerization illustrate the invention. The invention polymers exhibit improved processing characteristics in that the shear thinning behavior closely approaches that of ideal polymers and exhibit improved strain thickening.

Processing olefin copolymers

The invention is directed to essentially saturated hydrocarbon polymer composition comprising essentially saturated hydrocarbon polymers having A) a backbone chain, B) a plurality of essentially hydrocarbyl sidechains connected to A), said sidechains each having a number-average molecular weight of from 2500 Daltons to 125,000 Daltons and a MWD by SEC of 1.0-3.5; and having A) a Newtonian limiting viscosity (&eegr; ) at 190&deg; C. at least 50% greater than that of a linear olefinic polymer of the same chemical composition and weight average molecular weight, preferably at least twice as great as that of said linear polymer, B) a ratio of the rubbery plateau modulus at 190&deg; C. to that of a linear polymer of the same chemical composition less than 0.5, preferably <0.3, C) a ratio of the Newtonian limiting viscosity (&eegr; ) to the absolute value of the complex viscosity in oscillatory shear (&eegr;*)at 100 rad/sec at 190&deg; C. of at least 5, and D) a ratio of the extensional viscosity measured at a strain rate of 1 sec , 190&deg; C., and time&equals;3 sec (i.e., a strain of 3) to that predicted by linear viscoelasticity at the same temperature and time of 2 or greater. Ethylene-butene prepared by anionic polymerization and hydrogenation illustrate and ethylene-hexene copolymers prepared by coordination polymerization illustrate the invention. The invention polymers exhibit improved processing characteristics in that the shear thinning behavior closely approaches that of ideal polymers and exhibit improved strain thickening.

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Athens, Greece

Nikos Hadjichristidis