This technology is available from Temarex Corporation.


Description:Telechelic, or terminally functional linear polymers,are useful blocks for subsequent copolymerizations to form thermoplastics and thermoplastic elastomers.



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

Disclosure 280 U.S. Patent 5,733,998

This invention generally relates to the cationic, dispersion polymerization of isobutylene monomer.The great advantage of dispersion polymerization is its excellent reaction (reactor) control and the process insures outstanding heat exchange and reduces fouling.

A significant advantage of this invention is the replacement of the relatively costly and toxic CH3Cl diluent for isobutylene polymerization by the very inexpensive and environmentally friendly chlorine-free benign diluent of liquid CO2 at relatively high temperatures (i.e., in the -20 to -55¯C range).

Seven (7) successful experiments have been conducted, with polymerizations #1-6 carried out in a 300ml metal reactor, and #7 carried out in glass equipment.The next step is optimization research and further scale-up on a pilot plant scale.

Specific industrial problems solved by this invention are that this method and process eliminates the use of noxious solvents in cationic polymerization in general and butyl rubber manufacture in particular, improvements with initiators employed are achieved, and at the same time reduced reactor fouling is realized.

In addition, this invention provides a surfactant which will allow the dispersion polymerization of polyisobutylene in liquid CO2.

This technology is also suitable for producing allyl-terminated polyisobutylenes, copolymers (butyl rubber), as well as block copolymers and telechelic polymers.



Inventor(s):J. Kennedy, B. Zaschke

Disclosure 267 U.S. 5,663,234

This inventions relates to the synthesis and characterization of a series of novel thermoplastic elastomers, (AB)n multiblock copolymers, containing polyisobutylene (PIB) as the soft phase and polyamides (PA) as the hard phase.These novel PIB-PA multiblock TPEs consist of thermally stable rubbery PIB blocks connected to thermally stable crystalline PA blocks having mp's in the 220 - 280¯C range.This combination of soft and hard moieties yields not only outstanding physical and mechanical properties but also melt processibility.

All of the PIB-PA's exhibited satisfactorily high mp's and high decomposition temperatures (i.e. excellent thermal stability) both in N2 and air.This is contrast to PTHF-based TPEs which showed noticeably lower decomposition temperatures in air.By varying the structure of the PA, the melting point of the hard phase could be adjusted.



Inventor(s):H.J. Harwood, M.P. Greuel, L.D. Arvanitopoulos

Disclosure 241 U.S. Patent 5,468,785

This invention relates to the use of cobaloximes and related cobalt (II) complexes which have essentially planar equatorially coordinated ligands and a pair of axially coordinated ligands which have at least one-carbon-cobalt bond, as photoinitiators for free radical polymerizations.By selection of the appropriate cobaloximes and related complexes, it is possible to prepare polymers which have useful terminal functionality at both the head and tail ends of the growing polymer chain.The process also teaches the photochemical polymerization and copolymerization whereby the alkyl cobaloximes and related compounds, which are used as the photoinitiators, have alkyl groups, which may in essence, be polymers with carbon-cobalt chain ends, thereby allowing grafting reactions to occur to the polymer backbone.

The unanticipated result discovered is that the termination of the polymer by cobaloxime could be reversible, thus resulting in a chain end that could undergo reversible photolytic homolysis to regenerate the active radical center and subsequently reinitiate polymerization.The net result of the characterization of this reversible termination behavior, was the development of a new living polymerization system, which proceeds via a photoinitiated free radical mechanism.

Some advantages to this technology are (a) a process for controlling molecular weights, (b) preparation of polymers with controlled macromolecular structure including multiblock copolymers, star polymers, radial block copolymers, and polymers with terminal functionality, (c) a process wherein polymers with useful functional groups can be synthesized at the chain ends of the polymer.

While it is possible to synthesize the cobaloxime and related compounds initially, for subsequent addition to a monomer, it is also taught within this invention that the cobalt complex can be prepared "in-situ", such as by the routes which include: (1) Cobalt-hydride plus monomer addition; (2) free radical initiator plus monomer plus cobalt complex, the ratio of free radical initiator to cobalt complex being essentially 1:1; and (3) the reaction of Co(ii) with an alkyl halide.

The advantages of this technology are good control of molecular weights, preparation of vinyl polymers with narrow molecular weight distributions, easy preparation of telechelic polymers, block copolymers, graft polymers and polymers with star and radial-block architectures.



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

Disclosure 205 U.S. Patent 5,376,744

This invention relates to a process for carbocationically polymerizing monomers having one or more carbon-carbon double bonds in a medium primarily of carbon dioxide.The supercritical carbon dioxide can replace traditional solvents such as methyl chloride or methylene chloride for carbocationic polymerizations. It has been found that well defined polymers can be formed at higher temperatures in supercritical CO2.

The invention provides an environmentally friendly process for carrying out carbocationic polymerizations which provide many polymers such as polyisobutylene and copolymers (butyl rubber), block copolymers and telechelic polymers.Typically, these polymerizations are conducted in chlorinated hydrocarbon solvents at temperatures between -20 and -100oC to maximize the molecular weight of the resulting polymer.

The significant advantages of using CO2 as a medium for carbocationic polymerization is that it saves the considerable expense in cooling the monomers, solvents and other reactants to temperatures from -20 and -100oC; also saves the cost of recovering chlorinated solvents.CO2 is environmentally non-hazardous and available in pure form.In addition, CO2 can be considered one of the solvents of the future for ionic polymerizations.

This technology is ideally suitable for polymerizing isobutylene, styrene, and diene monomers as well as making rubbers, resins, adhesives, etc.




Inventor(s):J. Kennedy, B. Goodall, A. Lubnin

Disclosure 185 U.S. Patent 5,340,881 Disclosure 185-DIV U.S. Patent 5,442,015

This invention is related to aldehyde-telechelic polyisobutylenes free of other end groups such as alcohols, olefins, etc., are made by the hydroformylation of polyisobutylene having one or more olefinic end groups in the presence of a thodium catalyst in combination with an organic phosphorus ligand.

This technology differs from prior art in that this novel composition enables one skilled in the art to create aldehyde-capped polyisobutylenes.The advantages of this technology are very high reactivity of the terminal aldehyde group, purity of the intermediate allowing stoichiometric conversions, and very high conversions of olefin to aldehyde are made possible.

Depending on the number of aldehyde end groups per macromolecule, the telechelic polyisobutylene polymers can be utilized as precursors to form various types of block copolymers, e.g., AB, ABA, as well as more sophisticated star or radial block copolymers, with other polymers such as polyurethanes, polyesters, polyamines, and the like.

This novel composition is ideally suitable as an intermediate useful for making new flexible thermoplastic elastomers, adhesives, transparent coatings, blending agents, engineered plastics, new biomaterials, and the like.



Inventor(s):J. Kennedy, J. Carter

Disclosure 128-DIV U.S. Patent 5,075,389

New ý-phenyl-glycidyl-ether polyolefin macromonomers and copolymer of these macromonomers and ring opening polymerizable monomers have been prepared.The new copolymers based on these macromonomers form a unique set of copolymers having graft type blocks of a hydrophobic polyolefin dangling from a back bone composed of a ring opening polymerizable monomer.



Inventor(s):J. Kennedy

Disclosure 122 U.S. Patent 4,939,184

This invention solves shortcomings of polyurethane foams currently on the market, and provide new flexible foams which have a host of uniquely superior physical properties such as waterproofness, low impact resilience, low transition temperature, high oxidative resistance, high ozone resistance, low gas permeability, excellent tensile strength, resistance to moist heat, resistance to heat and other similar properties.

These new flexible polyurethane foams have a polyisobutylene skeleton obtained by reacting a polyol based on polyhydroxy terminated polyisobutylene with polyisocyanate in the presence of a blowing agent with two and three terminal hydroxy groups per polyisobutylene unit.

In case of expanding foams, water is used as the blowing agent and it is possible to add a catalyst, a foam stabilizer, a viscosity modifier, an organic solvent as a blowing agent, and each kind of organic or inorganic additives, such as a fire retardant and the like.

The organic solvent may be made of low boiling point hydrocarbons such as pentane, hexane, heptane, pentene, heptene, benzene and the like, or low boiling point halogenated hydrocarbons such as trichloromonofluoro methane, dichlorofluoromethane, methylene chloride (not recommended due to regulatory problems) and the like, and low boiling point hydrocarbon ether such as tetrahydrofuran, diethylether, 1,4-dioxane and the like, having a role as a blowing agent in addition to the object of lowering a viscosity.

In addition, the foam density can be regulated by the amount of water added in the prepolymer process.

The polyurethane foam is particularly useful as sealing material and the like for engineering works, construction, vehicles which require waterproofness.Such a polyurethane foam is useful as an excellent padding materials for the construction of safe automobile, railroad and space vehicle interiors where high damping and good gas barrier properties are important.Other applications include residential and commercial furniture.



Inventor(s):J. Kennedy, K. Peng

Disclosure 118 U.S. Patent 4,906,705

A method of treating a hydrocarbon containing tertiary chloroalkyl groups, to convert it to an allylic lithium by dehydrochlorinating the above, either simultaneously or sequentially, to first dehydrochlorinate the compound to form a terminal unsaturation and then convert it to an allylic lithium derivative.Alkyl lithium is used to generate the allylic lithium derivative alone or with a complexing agent. The complexing agents are ethers, such as tetrahydrofuran, diamines with diethyldiamino ethane being a preferred one, and t-buOK.The solvents used are tetrahydrofuran, the cycloalkanes such as cyclohexane and the alkanes such as hexanes, pentanes and heptanes.



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

Disclosure 117 U.S. Patent 5,149,743

Novel halostyrene telechelic polymers having from 2 to about 6 terminal halogens, halostyrene-polyether, block copolymers having ABA type structures in star type structures, depending on the number of halogen termini in the starting halostyrene block, and a process for their formation is described.The halostyrene polymers are formed by the initiator transfer agent or inifer polymerization method; while the polyether block is polymerized by silver catalysis of monomers such as tetrahydrofuran.The polymers and copolymers have good flame resistance.

These polymers are useful because of their inflammability, their optical properties, and their chemical resistance properties. This makes these polymers ideally suited for use as gaskets, in optically clear films that are thermally stable, oxidatively stable and inflammable and in other applications requiring inflammable, chemically resistant and/or optically clear films.



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

Disclosure 69 U.S. Patent 4,568,732

This invention describes an improved truly continuous inifer (initiator-transfer agent) polymerization process for the preparation of di- and three-arm star telechelic polyisobutylenes (PIB) and related polymers and specifically the synthesis of well defined three-arm star tertiary chlorine terminated PIB polymer by this continuous technique.

Novel telechelic halogenated polymers of cationically polymerized olefin monomers are formed carrying from two to about six terminal halogens by a continuous polymerization method.The continuous polymerization method is achieved by feeding, to a stirred reactor, a first stream composed of a solvent solution of at least one monomer and an inifer and another stream composed of a solvent solution of boron chloride, to effect the polymerization of said monomer to a telechelic halogenated polymer product, withdrawing the reaction product from said reactor essentially in amounts equal to that of the sum of the two streams, with the feeds to said reactor being simultaneously and continuously fed thereto while maintaining the temperature in the range of -10oC to -80oC.



Inventor(s):J. Kennedy

Disclosure 67 U.S. Patent 4,767,885 Disclosure 67-DIV U.S. Patent 4,814,405

Sterically hindered binifers are made as well as utilized to produce telechelic polyisobutylenes.The telechelic (terminally functional linear) polymers can be produced at high temperatures, for example -30oC.

The polymers produced are generally viscous liquids if the number of repeating units is up to approximately 10,000 and generally solid or rubbery if the number of repeating units is 10,000 or greater.The polymers are generally chemically stable and can be utilized as colorless adhesives.



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

Disclosure 63 U.S. Patent 4,599,384

This invention describes production of EPDM graft terpolymers wherein Zeigler-Natta type catalysts are used, said polymers are polyisobutylene (PIB), polystyrene (PS) or the like, and graft EPDM graft terpolymers are vulcanized.

Macromonomers of polymer-dicyclopentadiene and polymer-ethylidenenorbornene are prepared and then terpolymerized with ethylene and propylene.The terpolymer exhibits compatibilization of ethylene-propylene rubber and butyl rubber, and thus is useful as a sealant, roofing material, caulking agent and the like.



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

Disclosure 61 U.S. Patent 4,524,188

The synthesis of telechelic i.e., terminally functional, macromolecular monomers (macromers) and their subsequent homo- and copolymerization is disclosed.The macromers produced are asymmetric, having dissimilar head and tail groups which provide independent reaction sites.Macromers include alpha-phenyl-omega-t-chloropolyisobutylene, which can be reacted to form poly(methyl methacrylate-g-isobutylene). The graft copolymers provide novel physical properties which are the product of the respective grafts.




Inventor(s):J. Kennedy, S. Guhaniyogi

Disclosure 59 U.S. Patent 4,429,099

Novel telechelic (terminally functional) prepolymers are reacted to form curable epoxides.The incorporation of saturated elastomer chains into the prepolymers creates improved epoxides having increased moisture resistance and decreased brittleness.These prepolymers may be straight chain or three-armed star, emanating from a common phenyl ring nucleus.Molecular weights of the prepolymers range from about 700 to 50,000 (linear) and from about 1000 to about 75,000 (three-arm star).

The epoxides (epoxy cements) are useful as coatings, in adhesives, as additives, and the like.Properties include resistant to heat and ultraviolet light, moisture resistant, and a high degree of flexibility after cure.



Inventor(s):J. Kennedy

Disclosure 38 U.S. Patent 4,316,973 Disclosure 38-DIV U.S. Patent 4,342,849

Novel telechelic olefin and hydroxy polymers particularly those of polyisobutylene, are prepared.Preparation of a telechelic diolefin polyisobutylene includes refluxing a solution of telechelic dihalogen polyisobutylene, adding a solution of a strong base such as potassium t-butoxide and stirring to form the telechelic diolefin polyisobutylene.This telechelic diolefin can be converted to the telechelic dihydroxy by refluxing a solution of the former, hydroborating the diolefin to a polymeric borane and oxidizing the polymeric borane to form the telechelic dihydroxy polyisobutylene.The processes are also applicable to the conversion of trihalogenated polyisobutylenes to telechelic triolefin and trihydroxy polyisobutylene tristars.

Telechelic di- and trihydroxyl polyisobutylenes are also useful compounds which could be reacted with diisocyanates and triisocyanates to yield linear or crosslinked products, respectively and would be valuable intermediates for the preparation of polyurethanes via isocyanate chemistry.From this technology, compositions can be further utilized in the synthesis of other compositions such as polyurethanes, polyamides, polyesters and polyepoxides.

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.



Inventor(s):J. Kennedy, R. Smith, L. Ross, Jr.

Disclosure 35 U.S. Patent 4,276,394

Novel telechelic halogenated polymers of cationically polymerizable olefin monomers are formed carrying from 2 to about 6 terminal halogens.The telechelic halogenated polymers are formed by reacting the monomer with an initiator transfer agent, carrying at least two tertiary halogens, under cationic polymerization conditions.Additionally, novel thermoplastic elastomer block copolymers are formed from these telechelic halogenated polymers by reacting the latter with vinyl aromatic monomers in the presence of a coinitiator.

Properties include thermoplastic elastomer block copolymer comprising a central elastomer moiety, saturated and therefore possesses superior oxidative stability, and which contains a glassy component of high Tg thereby imparting superior thermal properties to the composition.Generally, the number of arms can range from 2 to about 6 and the polymer will be symmetric in that each arm will carry the same terminus.

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.