living cationic polymerization

This technology is available from Temarex Corporation.

LIVING CATIONIC POLYMERIZATION

Description:Truly living polymerization (i.e. truly terminationless and chain transferless polymerizations) are a most desirable objective of the synthetic polymer chemist.

Title:LIVING CARBOCATIONIC POLYMERIZATION OF POLY(ISOBUTYLENE-b-METHYL VINYL ETHER)

Inventor(s):J. Kennedy, T. Pernecker, B. Ivan

Disclosure 176 U.S. Patent 5,225,492

The synthesis of poly(isobutylene-b-methyl vinyl ether) (PIB-b-PMeVE) by living carbocationic polymerization (LCQPzn) employing the sequential monomer addition (SMA) technique is described.The process starts by producing the living PIBQ block employing the 2-chloro-2,4,4-trimethylpentane (TMPC11/TiCl4) initiating system in the presence of the common ion salt tetra-n-butylammonium chloride (n-Bu4NCl) in CH3Cl/n-C6H14 or CH2Cl2/n-C6H14 mixed solvents at -80o C and continues by the addition of methyl vinyl ether (MeVE).The second living block forms only in the presence of excess TiCl4, suggesting that the species that starts the second block and subsequently sustains its growth is a MeVE:TiCl4 complex.The stoichiometry of this complex (1:1 or 1:2) is uncertain.The TiCl4 remains attached to the MeVE units after their incorporation into the diblock, however, it can be readily removed by water.PMeVE obtained in the presence of excess TiCl4 degrades by dealcoholation, however, degradation is prevented by the use of n-Bu4NCl.Various length composition) diblocks have been prepared and characterized.The novel PIB-b-PMeVE's exhibit strongly amphiphilic character.

A most desirable feature of this invention is the one-spot synthesis of amphiphilic diblocks (i.e. A-B blocks in which a hydrophobic block [e.g. PIB] is bonded to a hydrophilic block [e.g. PMeVE]).

These amphiphilic blocks are potentially useful as emulsifying or blending agents, detergents, viscosifiers.Applications include such diverse areas as textiles, foods, paints, and adhesives.

Title:THERMOPLASTIC ELASTOMERS OF ISOBUTYLENE AND PROCESS OF PREPARATION

Inventor(s):J. Kennedy, J. Puskas, G. Kaszas, W. Hager

Disclosure 109 U.S. Patent 4,946,899 Disclosure 109-CIP-CON U.S. Patent Reissue 34,640

Block copolymers composed of polyisobutylene rubber soft segment of Mn of about 5,000 to above 500,000 and glassy hard segments of Mn of about 5,000 or higher and usually about 10,000 to 35,000 or more, are made by preparing a living polymer block of the polyisobutylene and polymerizing on said living polyisobutylene block the glassy hard segments by adding thereto an electron donor having a donor number of 15 to 50 and then adding and polymerizing the monomers for the glassy hard segments.The monomers for the glassy hard segments are styrene and its derivatives, indene and its derivatives and mixtures thereof.

The copolymers behave like vulcanized rubbers at room temperature and like thermoplastic polymers at higher temperatures.Thus the materials can be melt extruded like plastics, while retaining their beneficial rubbery features upon cooling.This ability is not only of advantage during processing of the polymers, but allows the materials to be reprocessed.Such materials are fundamentally elastomeric but they exhibit physical behavior similar to elastomers which have been reinforced with reinforcing agents.

This technology overcomes the product deficiencies of polymers having dual natures.The advantages of this technology are properties of the ultimate product can be tailor made providing a high Tg, good processability, oxidative stability and reprocessability in the absence of stabilizers.

The materials are useful as molding compositions alone or with other polymers or modifiers of other polymers analogous to the uses of the "Kraton" [trade name of Shell Oil Company] block copolymer.Applications include adhesives, coatings, elastic threads and others.

This technology is available for license only in specific fields of use due to existing license agreements. Initial in-vitro studies indicate that the polymers are much more oxidative and acid stable than silicone rubber and may provide a new generation of improved polymers for implant use in the body.

Title:LIVING POLYMERIZATION OF OLEFINS TO END-FUNCTIONALIZED POLYMERS

Inventor(s):J. Kennedy, M. Mishra

Disclosure 90-DIV U.S. Patent 4,929,683 Disclosure 90-DIV-DIV U.S. Patent 5,066,730

This invention concerns a new family of initiating systems, a new process for making polymers and a series of new products having specific end groups thereon.

A novel catalyst is composed of a complex of an organic ether and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of 100,000 preferably 500 or 1000 to 10,000 and higher.The complex is active, viz., living, until the complex dies, viz., is decomposed or destroyed.The complex is used to make halogen terminated polymers which are liquid or easily liquefiable from about 300 to about 10,000 and preferably from about 500 or 1000 to 10,000.

High molecular weight halogen terminated polymer with lower solubility or ease of liquification can also be prepared. Polymers in the liquid or easily liquefiable range of 300 to about 10,000 and preferably 500 or 1000 to 10,000 and higher can be made or those more difficult to be liquefied or unliquefiable, viz., those of over 10,000 up to 100,000 and having useful end groups such as the halogens and specifically chloride.

Advantages of this technology are that chain transfer to monomer will not occur in this system, and molecular weight control can be accomplished by adjusting the relative concentrations of monomer and initiating system.In addition, not only homopolymers but copolymers and block polymers can be made above the decomposition temperature of the complex.

Title:LIVING CATALYSTS, COMPLEXES AND POLYMERS THEREFROM

Inventor(s):J. Kennedy, R. Faust

Disclosure 73-CIP U.S. Patent 4,910,321 Disclosure 73-CIP-DIV U.S. Patent 5,122,572

This invention concerns a new family of initiating systems, a new process for making polymers and a series of new products having specific end groups thereon.

A novel catalyst is composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The complex is active viz., living, until the complex dies, viz., is decomposed or destroyed. The complex is used to make polymers in the liquid or easily liquefiable range of 300 to about 10,000.The complex is also used to make those more difficult to liquify or unliquefiable polymers, viz., those of over 10,000 up to 100,000 or in some cases 500,000 and polymers in the range of the elastomers, or moldable or extrudable plastics having very high molecular weights, generally in excess of 100,000 up to in excess of 500,0000. All of these polymers are formed with useful end groups such as the halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate to name some of the more useful ones.