University of Akron

Turgut Nugay

Joseph P Kennedy

Nihan Nugay

Mukerrem Cakmak

Kalman Csaba Toth

Tejal J Deodhar

Susan Dollinger

A star block copolymer and a thermoplastic elastomer including plurality of the star block copolymers and a method of making both is taught. The star block copolymers of the present invention include a core component having a styrene oligomer wherein arms emanate from the core component and the arms are poly(isobutylene-block-styrene) diblock copolymers.

Star isobutylene-based thermoplastic elastomers

A polyisobutylene-based polymer network comprising the thiol-ene reaction product of at least two thiol-terminated polyisobutylene precursor polymers and at least one multi-functional allyl-containing precursor moiety or polymer in the presence of light or heat. The at least two thiol-terminated polyisobutylene precursor polymers have at least two thiol end groups. When each polyisobutylene precursor polymer has only two thiol end groups then the allyl-containing precursor moiety or polymer has at least three functional groups, and wherein when the allyl-containing precursor moiety or polymer has two functional groups then each polyisobutylene precursor polymer has at least three thiol end groups.

High molecular weight polyisobutylenes and polyisobutylene networks from liquid polyisobutylenes by thiol-ene clicking

The present invention generally relates to polyurethanes and polyurethane nanocomposites having improved mechanical, rheological, and thermal properties over ordinarily produced polyurethanes and polyurethane nanocomposites. Such polyurethanes and polyurethane nanocomposites include very small amounts of a small chain diol, such as glycerol, and more specifically, between 0.01 and 4 weight percent of the small chain diol, based on the total polymer composition.

Glycerol containing polyurethanes and polyurethane nanocomposites

A thermoplastic elastomeric network is taught. The thermoplastic elastomer network includes hyperbranched styrenic block copolymers and styrenic block copolymers physically crosslinked though aggregation. Additionally, the hyperbranched styrenic block copolymers of the thermoplastic elastomeric network are a plurality of styrenic block copolymers chemically crosslinked.

Styrenic block copolymer-hyperbranched styrenic block copolymer networks

In various embodiments, the present invention is directed to new low cost initiator compositions for use with the production of well-defined telechelic PIBs (by LCP of isobutylene). In various other embodiments, the present invention is directed to methods for using these novel compositions as initiators for isobutylene (IB) and other cationically polymerizable monomers, such as styrene and its derivatives. In still other embodiments, the present invention is directed to structurally new, allyl (and chlorine) telechelic PIBs formed from these new initiator compositions and their derivatives (in particular, hydroxyl telechelic PIB and amine telechelic PIB). In yet other embodiments, the present invention is directed to structurally new polyurethanes, polyureas, and polyurethane ureas made using telechelic PIBs formed from these new initiator compositions.

Initiators for living carbocationic polymerization

A star block copolymer and a thermoplastic elastomer including plurality of the star block copolymers and a method of making both is taught. The star block copolymers of the present invention include a core component having either a styrene oligomer or &#x3b1;-methyl styrene oligomer, wherein arms emanate from the core component and the arms are poly(isobutylene-block-styrene) diblock copolymers.

Synthesis of star isobutylene-based thermoplastic elastomers

In various embodiments, the present invention is directed to a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group having the formula wherein each R is selected from the group consisting of a polymer or a copolymer, such as a polyisobutylene polymer or a poly(isobutylene-b-styrene) copolymer.

Centrally functionalizable living cationic polymer or copolymer and methods of synthesizing the same

A polystyrene-g-(polyisobutylene-b-polystyrene) is taught. The polystyrene-g-(polyisobutylene-b-polystyrene) is synthesized by first providing a polystyrene backbone. Once the polystyrene backbone is provided, the polystyrene backbone is acetylated to provide acetyl groups on the polystyrene backbone. Next, the acetyl groups are converted to &#x2014;C(CH)OH groups. Finally, the living polymerization of isobutylene is initiated, which is then followed by the living block polymerization of styrene. A polymer network of polystyrene-g-(polyisobutylene-b-polystyrene)s is also provided.

High-strength low-creep thermoplastic elastomer

A star block copolymer and a thermoplastic elastomer including plurality of the star block copolymers and a method of making both is taught. The star block copolymers of the present invention include a core component having an &#x3b1;-methylstyrene oligomer wherein arms emanate from the core component and the arms are poly(isobutylene-block-styrene) diblock copolymers.

Sulfur containing, hydroxyl-telechelic PIBs, hydrolytically and oxidatively resistant, biocompatible and biostable polyurethanes (PUs) made therefrom, and methods for making both are disclosed. Well-defined hydroxyl telechelic PIBs are synthesized by a thiol-ene click photochemical reaction between PIBs carrying unsaturated end groups and 2-mercaptoethanol (HS&#x2014;CHCH&#x2014;OH). This regioselective process affords HO&#x2014;CHCH&#x2014;S-PIB-S&#x2014;CHCH&#x2014;OH (abbreviated herein as HO&#x2014;S-PIB-S&#x2014;OH) in high yield. In some embodiments, these HO&#x2014;S-PIB-S&#x2014;OH polymers may be reacted with diisocyanates and a chain extender to form sulfur containing PIB-based PUs. These sulfur containing PIB-based PUs have been found to have properties and chemical stability that are very similar to that of PUs made from di-hydroxyl terminated PIBs (OH-PIB-OHs) without sulfur, but have surprisingly increased creep resistance and are easier and less expensive to make.

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The present invention is directed to a new class of thermoplastic elastomers (TPEs) and processes for making them. In some embodiments of the present invention, the end groups of the multi-arm PIB copolymer is a conjugated diene, whereas the other component is a multi-functional dienophile. The components of the TPE of the present invention are chemically connected via the well-known Diels-Alder reaction which is thermally reversible (by the retro-Diels-Alder reaction) at moderately elevated temperatures. The reversibility of the Diels-Alder retro-Diels-Alder reactions allows the recovery of the original components of the TPE and thus its recyclability and also gives the TPE the ability to be reshaped or reformed.

Polyisobutylene-based thermoplastic elastomers

A PIB-based polymer network includes at least one sulfur containing segment and at least two PIB polymer segments. The at least two PIB polymer segments each include a core and at least two polyisobutylene polymer chains extending therefrom. The at least one sulfur containing segment includes at least one sulfur atom that is located between any two polyisobutylene polymer chains from two different PIB polymer segments, so that the sulfur containing segment connects those two different PIB polymer segments together. The PIB-based polymer network is produced by the thiol-ene reaction in the presence of light or heat. The reaction products include at least two polyisobutylene polymer precursor moieties, each polyisobutylene polymer precursor moiety having at least two end group selected from the end groups &#x2014;CH&#x2014;CH(CH)&#x2550;CH, &#x2014;CH&#x2550;C(CH), and &#x2014;CH&#x2014;CH&#x2550;CH; and at least one multi-functional thiol.

Preparation of polyisobutylene-based polymer networks by thiol-ene chemistry

The present invention relates to novel hydroxyl-terminated polyisobutylenes and methods of making and using them. The hydroxyl-terminated polyisobutylenes contain a sulfur unit, &#x2014;S&#x2014;, within each terminal end group. The well-defined, sulfur containing, primary hydroxyl-terminated polyisobutylenes of the present invention can be simply, rapidly, and essentially quantitatively obtained by subjecting the unsaturated telechelic PIBs and mercapto alcohols to UV light-activated thiol-ene reactions. The resultant sulfur containing, primary hydroxyl-terminated polyisobutylenes can then be used in the production of polyurethanes and like materials.

Photochemical preparation of hydroxyl-terminated polyisobutylenes and related methods and uses

A method of preparing an amiphiphilic co-network comprising preparing a molecularly-bimodal crosslinkable amphiphilic graft by polymerizing a dihydrocarbylacrylamide monomer in the presence of a first asymmetric-telechelic polydihydrocarbylsiloxane monomer mixture and a second asymmetric-telechelic polydihydrocarbylsiloxane monomer mixture where the molar mass ratio between average molar mass of the first asymmetric-telechelic monomer mixture polydihydrocarbylsiloxane and average molar mass of the second asymmetric-telechelic monomer mixture polydihydrocarbylsiloxane is between 1:2 and 1:20; and crosslinking the molecularly-bimodal crosslinkable amphiphilic graft with a siloxane compound that includes at least two Si&#x2014;H bonds.

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Istanbul, Turkey

Turgut Nugay