Abstract: Supported onium salts used as initiators for the synthesis of polycarbonates by copolymerization of carbon dioxide with epoxides are described. Embodiments of the present disclosure describe initiators comprising an insoluble portion including an onium cation attached to an insoluble support; and an anion, wherein the anion is a counter-ion to the onium cation. Embodiments further describe methods of making polycarbonates using the initiator, methods of making initiators, and the like.

Abstract: Embodiments include degradable polyethers comprising ester units from a cyclic ester or carbonate units from carbon dioxide incorporated into a poly(ethylene oxide) backbone or a multifunctional core of a degradable polyether star. Embodiments include methods of forming a degradable polyether comprising contacting an ethylene oxide monomer with a lactide monomer or carbon dioxide in the presence of an alkyl borane and an initiator. Embodiments include methods of forming degradable polyether stars comprising contacting a diepoxide monomer with carbon dioxide and/or a cyclic ester in the presence of an initiator and a first amount of an alkyl borane to form a multifunctional core comprising degradable carbonate linkages and/or degradable ester linkages, and contacting the multifunctional core with an ethylene oxide monomer in the presence of a second amount of an alkyl borane to form arms of a polyether attached to the degradable multifunctional core.

Abstract: Embodiments of the present disclosure describe polymerization systems for the synthesis of polycarbonate polyols, methods of synthesizing polycarbonate polyols using the polymerization systems, methods of recovering initiators and/or activators for use or re-use in the synthesis of polycarbonate polyol, and the like. The polymerization systems can comprise an initiator including a mono- or multi-functional carboxylate or carbonate salt having an organic cation as a counter-ion; an optional co-initiator including a mono- or multi-functional protic compound selected from acids, alcohols, water, and combinations thereof; and an activator including a borane compound selected from alkyl boranes and aryl boranes; wherein the activator and one or more of the initiator and co-initiator associate to form an ate complex.

Abstract: Embodiments of the present disclosure describe a method of removing an end group from a polymer comprising contacting a polymer having a thiocarbonylthio end group, or a solution containing such a polymer, with an excess of a borane compound in the presence of oxygen. Embodiments of the present disclosure further describe a method of polymerization comprising contacting one or more monomers with an initiator and a chain transfer agent to form a polymer having a thiocarbonylthio end group in a reaction solution and contacting the polymer with a borane compound in the presence of oxygen to remove the thiocarbonylthio end group from the polymer.

Abstract: Degradable ethylene oxide-based copolymers, including random, tapering, and block copolymers are described. For example, the present disclosure describes materials and methods for synthesizing degradable hydrophilic ethylene oxide-based copolymers, degradable amphiphilic ethylene oxide-based block copolymers, degradable hydrophobic polyethers and degradable functionalized polyethers via boron-activated copolymerization of ethylene oxide monomers with carbon dioxide.

Abstract: Supported onium salts used as initiators for the synthesis of polycarbonates by copolymerization of carbon dioxide with epoxides are described. Embodiments of the present disclosure describe initiators comprising an insoluble portion including an onium cation attached to an insoluble support; and an anion, wherein the anion is a counter-ion to the onium cation. Embodiments further describe methods of making polycarbonates using the initiator, methods of making initiators, and the like.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.