Contains Compound Of Nitrogen Patents (Class 526/180)
  • Patent number: 5620939
    Abstract: This invention reveals an initiator system which is comprised of (a) a lithium initiator, (b) a sodium alkoxide, and (c) a polar modifier; wherein the molar ratio of the sodium alkoxide to the polar modifier is within the range of about 0.1:1 to about 10:1; and wherein the molar ratio of the sodium alkoxide to the lithium initiator is within the range of about 0.01:1 to about 20:1.
    Type: Grant
    Filed: April 1, 1996
    Date of Patent: April 15, 1997
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Adel F. Halasa, Wen-Liang Hsu, David J. Zanzig, Paul H. Sandstrom, Steven K. Henning, Danielle Lucas
  • Patent number: 5616704
    Abstract: The present invention is directed toward anionic polymerization initiators which are soluble in acyclic alkane solvents. The initiators include a solubilized lithio amine having the general formula (A)Li(SOL).sub.y. SOL is a solubilizing component and A is an alkyl, dialkyl or cycloalkyl amine radical or a cyclic amine and y is from about 1 to 4. The cyclic amine has an alkylene, oxy- or amino-alkylene group having from about 3 to about 16 methylene groups. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.
    Type: Grant
    Filed: April 29, 1996
    Date of Patent: April 1, 1997
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Mark L. Stayer, Jr., David Saffles, H. James Harwood
  • Patent number: 5610237
    Abstract: A functionalized polymer according to the invention includes a polymer molecule having the general formula AYLi where A is a cyclic amine-containing radical having the general formula ##STR1## wherein R.sub.1 is a divalent alkylene, an oxy- or amino-alkylene, or substituted alkylene having from 6 to about 20 carbon atoms; R.sub.2 is a linear-, branched-, or cyclo-alkylene having from about 2 to about 20 carbon atoms; and Y is a divalent polymer radical and Li is a lithium atom bonded to a carbon atom of Y.
    Type: Grant
    Filed: June 4, 1996
    Date of Patent: March 11, 1997
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, James E. Hall, Mark L. Stayer, Jr., John R. Schreffler
  • Patent number: 5610228
    Abstract: An anionic polymerization initiator includes a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A method of preparing an anionic polymerization initiator includes reacting an excess of a cyclic secondary amine with a conjugated diene to form an adduct; and, reacting the adduct with an organolithium compound. A method of preparing a polymer includes forming a solution of one or more anionically polymerizable monomers in a hydrocarbon solvent; and, polymerizing the monomer with an anionic polymerization initiator comprising a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A functionalized polymer includes the termination product of a living polymer having the general formula AYLi, wherein A is a functional group derived from an anionic polymerization initiator; and, Y is a divalent polymer radical; wherein the anionic polymerization initiator is a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: March 11, 1997
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, James E. Hall, Mark L. Stayer, Jr.
  • Patent number: 5610227
    Abstract: The present invention provides anionic polymerization initiators, comprising lithium amino magnesiate complexes, resulting in diene polymer and copolymer elastomers. The invention initiators have stable living ends at high polymerization temperatures and produce polymers containing a high level of tertiary amine functionality. Such polymers exhibit an increased efficiency in coupling termination reactions, and elastomers and products prepared from such polymers exhibit reduced hysteresis properties. Methods are also provided for preparing the initiators, the polymers and the elastomers.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: March 11, 1997
    Assignee: Bridgestone/Firestone, Inc.
    Inventors: Thomas A. Antkowiak, James E. Hall
  • Patent number: 5605872
    Abstract: A process for the preparation of hydrocarbon solutions of monofunctional amine initiators of the following general structures: ##STR1## wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons; Z is a hydrocarbon tether group which contains 3-25 carbon atoms; A is an element selected from Group IVa of the periodic table and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, aryl or substituted aryl groups, m is an integer from 0 to 7, and n is an integer from 1 to 5, monofunctional amine initiators produced by the process, use of the initiators in a polymerization process and polymers produced by the polymerization process.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: February 25, 1997
    Assignee: FMC Corporation
    Inventors: John F. Engel, Conrad W. Kamienski, James A. Schwindeman, Randy W. Hall, Robert C. Morrison, B. Troy Dover
  • Patent number: 5605991
    Abstract: A multifunctional initiator is prepared by contacting an organo-alkali metal compound with a silane represented by the formula: ##STR1## wherein the R' are generally lower alkyl groups such as methyl and the R" is generally an .paren open-st.CH.sub.2 .paren close-st..sub.n group with n=2. Superior results are obtained presumably because of the separation of the vinyl groups and the greater solubility of the compound because of the R' groups. The resulting catalyst initiates polymerization of monomers such as conjugated dienes and monovinyl substituted aromatic compounds to give relatively monodispersed polymers with little or no crosslinking.
    Type: Grant
    Filed: March 21, 1996
    Date of Patent: February 25, 1997
    Assignee: Shell Oil Company
    Inventors: Linda R. Chamberlain, Ronald J. Hoxmeier, Philip A. DeFriend
  • Patent number: 5595951
    Abstract: The subject invention discloses a process for preparing an initiator which contains a plurality of lithium atoms and which is particularly useful for initiating the polymerization of diolefin monomers into rubbery polymers; said process being comprised of reacting an alkyl lithium compound with an unsaturated hydrocarbon containing allylic, benzylic or aryl hydrogen atoms, wherein said process is conducted in the presence of a member selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, and chelating tertiary alkyl 1,2-ethylene diamines. After the initiators of this invention have been prepared they can be employed to initiate the polymerization of diolefin monomers into rubbery polymers. They can, of course, also be employed to initiate the copolymerization of diolefin monomers and vinyl aromatic monomers into rubbery polymers. These rubbery polymers can then be used in making tire tread compounds for automobiles and trucks.
    Type: Grant
    Filed: March 16, 1995
    Date of Patent: January 21, 1997
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Adel F. Halasa, George Jalics
  • Patent number: 5578542
    Abstract: An acyclic alkane soluble anionic polymerization initiator includes a mixture of from about 90 to about 10 parts by weight of a lithio amine having the general formula A.sub.1 Li and from about 10 to about 90 parts by weight of at least one other lithio amine having the general formula A.sub.2 Li. A.sub.1 and A.sub.2 are selected from the dialkyl, alkyl, cycloalkyl and dicycloalkyl amine radicals and cyclic amine radicals. There is also provided a method of forming a mixture of anionic polymerization initiators, a functionalized polymer and a method of forming a functionalized polymer.
    Type: Grant
    Filed: March 30, 1994
    Date of Patent: November 26, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, James E. Hall, Yoichi Ozawa
  • Patent number: 5563275
    Abstract: Disclosed herein is a process for anionic polymerization of selected methacrylate monomers at elevated (as high as about 100.degree. C.) temperatures, while maintaining good "living" characteristics, by carrying out the polymerization in the presence of a silicon compound and a large cation. Also disclosed is an improved process for the polymerization of vinyl monomers, including methacrylates, which process comprises the use of an anionic intiator which is a combination of an alkali metal hydride and an alkoxysilane or a combination of an alkali metal alkoxide and a silicon hydride.
    Type: Grant
    Filed: March 7, 1995
    Date of Patent: October 8, 1996
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Frederick P. Gentry, Jr., Owen W. Webster
  • Patent number: 5554696
    Abstract: Process for the preparation of an efficient industrial .alpha., .omega.-dilithio poly(conjugated diene) diinitiator having a peak molecular weight in the range of from 1000 to 3000, comprising the reaction of mono-organolithium initiator with diisopropenyl benzene in an apolar hydrocarbon solvent, optionally in the presence of a tertiary amine, followed by addition to the reaction mixture of a small amount of conjugated diene monomer and at least 15 vol % of an aromatic ether activator at a temperature in the range of from 0.degree. to 30.degree. C.; the use of said .alpha., .omega.-dithio initiator for the manufacture of symmetrical block copolymers by anionic polymerization, from monovinylaromatic, conjugated diene and/or polar vinyl compound monomers; and block copolymers so obtained having a combination of a narrow molecular weight distribution (Mw/Mn.ltoreq.1.20) and relatively low vinyl content (.ltoreq.18%).
    Type: Grant
    Filed: May 9, 1995
    Date of Patent: September 10, 1996
    Assignee: Shell Oil Company
    Inventors: Roger M. A. Fayt, Frederik H. van der Steen, Phillippe J. Teyssie, Judith J. B. Walhof, Yi-Song Yu
  • Patent number: 5552473
    Abstract: The present invention is directed toward anionic polymerization initiators which are soluble in acyclic alkane solvents. The initiators include a solubilized lithio amine having the general formula (A)Li(SOL).sub.y. SOL is a solubilizing component and A is an alkyl, dialkyl or cycloalkyl amine radical or a cyclic amine and y is from about 1 to 4. The cyclic amine has an alkylene, oxy- or amino-alkylene group having from about 3 to about 16 methylene groups. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer wtih a multifunctionality.
    Type: Grant
    Filed: June 5, 1995
    Date of Patent: September 3, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Mark L. Stayer, Jr., David Saffles
  • Patent number: 5552499
    Abstract: The present invention is directed toward anionic polymerization employing lithio amines mixed with an organic alkali metal compound and optionally, a chelating reagent. The lithio amines have the general formula (A)Li(SOL).sub.y, where SOL is a solubilizing component, A is an alkyl, dialkyl, cycloalkyl or dicycloalkyl amine radical or a cyclic amine, and y is 0 or is from about 0.5 to about 3. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: September 3, 1996
    Assignee: Bridgestone Corporation
    Inventors: Takashi Kitamura, David F. Lawson, Koichi Morita, Yoichi Ozawa
  • Patent number: 5550203
    Abstract: A process for the preparation of hydrocarbon solutions of monofunctional amine initiators of the following general structures:M--Q.sub.n --Z--N(A(R.sup.1 R.sup.2 R.sup.3)).sub.2or ##STR1## wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons; Z is a hydrocarbon tether group which contains 3-25 carbon atoms; A is an element selected from Group IVa of the periodic table and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, substituted alkyl, cycloalkyl, aryl or substituted aryl groups, m is an integer from 0 to 7, and n is an integer from 1 to 5, monofunctional amine initiators produced by the process, use of the initiators in a polymerization process and polymers produced by the polymerization process.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: August 27, 1996
    Assignee: FMC Corporation
    Inventors: John F. Engel, Conrad W. Kamienski, James A. Schwindeman, Randy W. Hall, Robert C. Morrison, B. Troy Dover
  • Patent number: 5536801
    Abstract: An anionic polymerization initiator includes the C-lithio reaction product of an organolithium compound and a tertiary-amino allyllithium or a tertiary-amino xylyllithium. When used in an anionic polymerization, a functional group from the initiator is incorporated onto the head of the growing polymer and a lithium atom is incorporated at the "living" end of the polymer chain prior to quenching. The initiator may be used to polymerize a monomer(s) including diolefin monomers, monovinyl aromatic monomers and trienes, and the living ends of the polymers are effectively maintained even at temperatures of up to 300.degree. F. and higher. Such polymers exhibit an increased efficiency in coupling termination reactions, and products prepared from such polymers exhibit improved hysteresis characteristics. Products such as tires and the like can be prepared from such polymers and from vulcanizable elastomer compositions employing the polymers.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: July 16, 1996
    Assignee: Bridgestone Corporation
    Inventors: Thomas A. Antkowiak, James E. Hall, David F. Lawson, John R. Schreffler, Mark L. Stayer, Jr.
  • Patent number: 5532327
    Abstract: A solution polymerization process for producing an organic polymer from styrene and at least one other polymerizable monomer comprising providing a liquid reaction medium suitable for conducting said polymerization, wherein the reaction medium contains styrene and a polymerizable monomer other than styrene; and, anionically polymerizing styrene and monomer, thereby forming random copolymer chains, wherein the total quantity of said styrene used in said polymerization is at least 50% by weight based on the total weight of styrene and other polymerizable monomers used in the polymerization. A second embodiment comprises a copolymer made by the above-described method.
    Type: Grant
    Filed: February 27, 1995
    Date of Patent: July 2, 1996
    Assignee: Xerox Corporation
    Inventors: Robert D. Bayley, Thomas R. Hoffend, Timothy J. Fuller, Suresh K. Ahuja
  • Patent number: 5527753
    Abstract: A process for the preparation of hydrocarbon solutions of monofunctional amine initiators of the following general structures: ##STR1## wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons; Z is a hydrocarbon tether group which contains 3-25 carbon atoms; A is an element selected from Group IVa of the periodic table and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, aryl or substituted aryl groups, m is an integer from 0 to 7, and n is an integer from 1 to 5, monofunctional amine initiators produced by the process, use of the initiators in a polymerization process and polymers produced by the polymerization process.
    Type: Grant
    Filed: December 13, 1994
    Date of Patent: June 18, 1996
    Assignee: FMC Corporation
    Inventors: John F. Engel, Conrad W. Kamienski, James A. Schwindeman, Randy W. Hall, Robert C. Morrison, B. Troy Dover
  • Patent number: 5527860
    Abstract: A process for producing a diolefin polymer or copolymer, comprising the steps of polymerizing 55-100 wt % of a conjugated diolefin with 0-45 wt % of an aromatic vinyl compound as monomers in a hydrocarbon as a solvent, by using initiators: a reaction product [a1] between at least one secondary amine compound (A) and an organic lithium compound and/or a lithium amide compound [a2] of the at least one secondary amine compound (A) as well as a reaction product [b1] between at least one alcohol (B) and an organic lithium compound and/or a lithium alkoxide compound of the at least one alcohol (B). A rubber composition containing not less than 30 wt % of such a diolefin polymer or copolymer with respect to an entire rubber component is also disclosed. This rubber composition exhibits excellent abrasion resistance, high tensile strength, steering stability and low rolling resistance, and is suitable for tires, particularly, as treads of low fuel consumption tires.
    Type: Grant
    Filed: January 21, 1994
    Date of Patent: June 18, 1996
    Assignees: Japan Synthetic Rubber Co., Ltd., Bridgestone Corporation
    Inventors: Yoshitaka Yamakawa, Kyouyuu Yasuda, Iwakazu Hattori, Hideaki Yokoyama, Tatsuro Hamada
  • Patent number: 5523371
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from an anionic polymerization initiator. The anionic polymerization initiator comprises the general formula ##STR1## where R.sup.1 -R.sup.5 are the same or different and are selected from the group consisting of hydrogen; alkyls having from alkyls having from 1 to about 12 carbon atoms; aralkyls having from 7 to about 20 carbon atoms; dialkylaminos having from 2 to about 20 carbon atoms; and, dialkylaminoalkyls having from 3 to about 20 carbon atoms. At least one of R.sup.1 -R.sup.5 is selected from the group consisting of the dialkylaminos and the dialkylaminoalkyls. Methods of the present invention include preparing functionalized polymers and reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: April 7, 1995
    Date of Patent: June 4, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, Mark L. Stayer, Jr., John R. Schreffler, Hideki Komatsu
  • Patent number: 5523364
    Abstract: A process for the preparation of hydrocarbon solutions of monofunctional amine initiators of the following general structures: ##STR1## wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons; Z is a hydrocarbon tether group which contains 3-25 carbon atoms; A is an element selected from Group IVa of the periodic table and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, aryl or substituted aryl groups, m is an integer from 0 to 7, and n is an integer from 1 to 5, monofunctional amine initiators produced by the process, use of the initiators in a polymerization process and polymers produced by the polymerization process.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: June 4, 1996
    Assignee: FMC Corporation
    Inventors: John F. Engel, Conrad W. Kamienski, James A. Schwindeman, Randy W. Hall, Robert C. Morrison, B. Troy Dover
  • Patent number: 5521309
    Abstract: An anionic polymerization initiator includes the C-lithio reaction product of an organolithium compound and a tertiary-amino allyllithium or a tertiary-amino xylyllithium. When used in an anionic polymerization, a functional group from the initiator is incorporated onto the head of the growing polymer and a lithium atom is incorporated at the "living" end of the polymer chain prior to quenching. The initiator may be used to polymerize a monomer(s) including diolefin monomers, monovinyl aromatic monomers and trienes, and the living ends of the polymers are effectively maintained even at temperatures of up to 300.degree. F. and higher. Such polymers exhibit an increased efficiency in coupling termination reactions, and products prepared from such polymers exhibit improved hysteresis characteristics. Products such as tires and the like can be prepared from such polymers and from vulcanizable elastomer compositions employing the polymers.
    Type: Grant
    Filed: December 23, 1994
    Date of Patent: May 28, 1996
    Assignee: Bridgestone Corporation
    Inventors: Thomas A. Antkowiak, James E. Hall, David F. Lawson, John R. Schreffler, Mark L. Stayer, Jr.
  • Patent number: 5521255
    Abstract: A method for preparing a telechelic polydiene having at least 70% 1,4-microstructure and at least 70% of its end groups capped by reactive silyl functionality is disclosed, said method comprising:(I) reacting, in a non-polar solvent solution,(A) at least one diene monomer,(B) a dianionic initiator which is soluble in said non-polar solvent and, optionally,(C) a polymerization adjuvant to form a dianionically active polydiene; and(II) capping both ends of said dianionically active polydiene from step (I) with(D) a silane, said capping being carried out in the presence of(E) a promoter selected from the group consisting of a tertiary amine and a crown ether based on 12-crown-4.
    Type: Grant
    Filed: May 30, 1995
    Date of Patent: May 28, 1996
    Assignee: Dow Corning Corporation
    Inventor: Aroop K. Roy
  • Patent number: 5519086
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from an anionic polymerization initiator. The anionic polymerization initiator comprises the general formula ##STR1## where R.sup.1 -R.sup.5 are the same or different and are selected from the group consisting of hydrogen; alkyls having from alkyls having from 1 to about 12 carbon atoms; aralkyls having from 7 to about 20 carbon atoms; dialkylaminos having from 2 to about 20 carbon atoms; and, dialkylaminoalkyls having from 3 to about 20 carbon atoms. At least one of R.sup.1 -R.sup.5 is selected from the group consisting of the dialkylaminos and the dialkylaminoalkyls. Methods of the present invention include preparing functionalized polymers and reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: April 7, 1995
    Date of Patent: May 21, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, Mark L. Stayer, Jr., John R. Schreffler, Hideki Komatsu
  • Patent number: 5502130
    Abstract: An anionic polymerization initiator includes a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A method of preparing an anionic polymerization initiator includes reacting an excess of a cyclic secondary amine with a conjugated diene to form an adduct; and, reacting the adduct with an organolithium compound. A method of preparing a polymer includes forming a solution of one or more anionically polymerizable monomers in a hydrocarbon solvent; and, polymerizing the monomer with an anionic polymerization initiator comprising a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A functionalized polymer includes the termination product of a living polymer having the general formula AYLi, Wherein A is a functional group derived from an anionic polymerization initiator; and, Y is a divalent polymer radical; wherein the anionic polymerization initiator is a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: March 26, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, James E. Hall, Mark L. Stayer, Jr.
  • Patent number: 5502131
    Abstract: An anionic polymerization initiator includes the C-lithio reaction product of an organolithium compound and a tertiary-amino allyllithium or a tertiary-amino xylyllithium. When used in an anionic polymerization, a functional group from the initiator is incorporated onto the head of the growing polymer and a lithium atom is incorporated at the "living" end of the polymer chain prior to quenching. The initiator may be used to polymerize a monomer(s) including diolefin monomers, monovinyl aromatic monomers and trienes, and the living ends of the polymers are effectively maintained even at temperatures of up to 300.degree. F. and higher. Such polymers exhibit an increased efficiency in coupling termination reactions, and products prepared from such polymers exhibit improved hysteresis characteristics. Products such as tires and the like can be prepared from such polymers and from vulcanizable elastomer compositions employing the polymers.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: March 26, 1996
    Assignee: Bridgestone Corporation
    Inventors: Thomas A. Antkowiak, James E. Hall, David F. Lawson, John R. Schreffler, Mark L. Stayer, Jr.
  • Patent number: 5500447
    Abstract: An anionic polymerization initiator includes a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A method of preparing an anionic polymerization initiator includes reacting an excess of a cyclic secondary amine with a conjugated diene to form an adduct; and, reacting the adduct with an organolithium compound. A method of preparing a polymer includes forming a solution of one or more anionically polymerizable monomers in a hydrocarbon solvent; and, polymerizing the monomer with an anionic polymerization initiator comprising a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene. A functionalized polymer includes the termination product of a living polymer having the general formula AYLi, wherein A is a functional group derived from an anionic polymerization initiator; and, Y is a divalent polymer radical; wherein the anionic polymerization initiator is a carbon-lithio salt of the adduct of a cyclic secondary amine with a conjugated diene.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: March 19, 1996
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, James E. Hall, Mark L. Stayer, Jr.
  • Patent number: 5464914
    Abstract: A liquid hydrocarbon soluble difunctional organolithium initiator (DFI) is reacted with an anionically polymerizable monomer, such as isoprene or 1,3-butadiene, in the presence of a diamine or a triamine to form a polymer having low polydispersity and high tensile strength. The DFI is prepared by reacting a dialkenylarylene compound with an alkyllithium in a nonpolar solvent and in the presence of sufficient quantities of a trisubstituted amine to prevent precipitation of the DFI in the solvent.
    Type: Grant
    Filed: June 29, 1994
    Date of Patent: November 7, 1995
    Assignee: The Dow Chemical Company
    Inventors: Grace Y. Lo, Arnold L. Gatzke
  • Patent number: 5463004
    Abstract: A method for preparing a polymer having low hysteresis loss value, good breaking properties and good processability with good productivity is provided by adding a tin compound during the propagation step of polymerization of a conjugated diene and/or an aromatic vinyl hydrocarbon. Polymers produced in accordance with this method have high molecular weight and star-shaped structures with branches having the same or different molecular weight.
    Type: Grant
    Filed: March 25, 1994
    Date of Patent: October 31, 1995
    Assignee: Bridgestone Corporation
    Inventor: Yasuo Horikawa
  • Patent number: 5463003
    Abstract: A method for preparing a polymer having low hysteresis loss value and good breaking properties using a novel lithium initiator compound for polymerization of a conjugated diene and/or an aromatic vinyl hydrocarbon. Polymers produced in accordance with this method contain tin in an amount more than usual, and can be manufactured with good productivity.
    Type: Grant
    Filed: December 28, 1993
    Date of Patent: October 31, 1995
    Assignee: Bridgestone Corporation
    Inventors: Yasuo Horikawa, Toshiki Takizawa, Taro Akazawa
  • Patent number: 5436290
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from an anionic polymerization initiator. The anionic polymerization initiator comprises the general formula ##STR1## where R.sup.1 -R.sup.5 are the same or different and are selected from the group consisting of hydrogen; alkyls having from alkyls having from 1 to about 12 carbon atoms; aralkyls having from 7 to about 20 carbon atoms; dialkylaminos having from 2 to about 20 carbon atoms; and, dialkylaminoalkyls having from 3 to about 20 carbon atoms. At least one of R.sup.1 -R.sup.5 is selected from the group consisting of the dialkylaminos and the dialkylaminoalkyls. Methods of the present invention include preparing functionalized polymers and reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: August 10, 1993
    Date of Patent: July 25, 1995
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, Mark L. Stayer, Jr., John R. Schreffler, Hideki Komatsu
  • Patent number: 5420219
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from an anionic polymerization initiator. The anionic polymerization initiator comprises the general formula ##STR1## where R.sup.1 -R.sup.5 are the same or different and are selected from the group consisting of hydrogen; alkyls having from alkyls having from 1 to about 12 carbon atoms; aralkyls having from 7 to about 20 carbon atoms; dialkylaminos having from 2 to about 20 carbon atoms; and, dialkylaminoalkyls having from 3 to about 20 carbon atoms. At least one of R.sup.1 -R.sup.5 is selected from the group consisting of the dialkylaminos and the dialkylaminoalkyls. Methods of the present invention include preparing functionalized polymers and reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: August 10, 1993
    Date of Patent: May 30, 1995
    Assignee: Bridgestone Corportion
    Inventors: David F. Lawson, Thomas A. Antkowiak, Mark L. Stayer, Jr., John R. Schreffler, Hideki Komatsu
  • Patent number: 5393721
    Abstract: The present invention is directed toward artionic polymerization employing lithio amines mixed with an organic alkali metal compound and optionally, a chelating reagent. The lithio amines have the general formula (A)Li(SOL)y, where SOL is a solubilizing component, A is an alkyl, dialkyl, cycloalkyl or dicycloalkyl amine radical or a cyclic amine, and y is 0 or is from about 0.5 to about 3. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.
    Type: Grant
    Filed: October 16, 1992
    Date of Patent: February 28, 1995
    Assignee: Bridgestone Corporation
    Inventors: Takashi Kitamura, David F. Lawson, Koichi Morita, Yoichi Ozawa
  • Patent number: 5358976
    Abstract: Curable norbornene-thiol compositions are stabilized by addition of a non-acidic Nitroso compound.
    Type: Grant
    Filed: December 23, 1992
    Date of Patent: October 25, 1994
    Assignee: Loctite (Ireland) Limited
    Inventors: Joseph P. Dowling, Sarah C. Richardson, Killian Quigley
  • Patent number: 5354822
    Abstract: An anionic polymerization initiator comprising the reaction product of a functionalizing agent selected from the group consisting of substituted aldimines, ketimines and secondary amines and, an organolithium compound. Elastomeric polymers prepared with these initiators have functional sites incorporated at the initiator end of the polymer chain and provide vulcanizable rubber compounds exhibiting reduced hysteresis. Articles such as tires, produced with low hysteresis elastomeric polymers have lower rolling resistance. Methods are also provided for preparing the initiators, functionalized polymers and vulcanizable elastomeric compounds having reduced hysteresis.
    Type: Grant
    Filed: September 8, 1992
    Date of Patent: October 11, 1994
    Assignee: Bridgestone/Firestone, Inc.
    Inventors: Thomas A. Antkowiak, David F. Lawson, Russell W. Koch, Mark L. Stayer, Jr.
  • Patent number: 5332810
    Abstract: The present invention is directed toward anionic polymerization initiators which are soluble in acyclic alkane solvents. The initiators include a solubilized lithio amine having the general formula (A)Li(SOL).sub.y. SOL is a solubilizing component and A is an alkyl, dialkyl or cycloalkyl amine radical or a cyclic amine and y is from about 1 to 4. The invention is also directed toward polymers and other products made using the initiator, and methods therefore. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.
    Type: Grant
    Filed: October 2, 1992
    Date of Patent: July 26, 1994
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Mark L. Stayer, Jr., H. James Harwood
  • Patent number: 5329005
    Abstract: The present invention is directed toward anionic polymerization initiators which are soluble in hydrocarbon solvents. The initiators include a lithio amine having the general formula ALi. The component A is a dialkyl or dicycloalkyl amine radical or a cyclic amine. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.
    Type: Grant
    Filed: October 2, 1992
    Date of Patent: July 12, 1994
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Koichi Morita, Yoichi Ozawa, Mark L. Stayer, Jr., Ryota Fujio
  • Patent number: 5312871
    Abstract: This invention concerns a "living" free radical polymerization process for preparing polymers having a narrow distribution of molecular weights.
    Type: Grant
    Filed: July 27, 1993
    Date of Patent: May 17, 1994
    Assignee: Carnegie Mellon University
    Inventors: Daniela Mardare, Krzysztof A. Matyjaszewski
  • Patent number: 5284927
    Abstract: The subject invention relates to a technique for synthesizing rubbery terpolymers of styrene, isoprene and butadiene. These rubbery terpolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. By utilizing such terpolymers in tire treads, tires having improved wet skid resistance can be built without sacrificing rolling resistance or tread wear characteristics. The subject invention specifically discloses a process for preparing a rubbery terpolymer of styrene, isoprene, and butadiene having multiple glass transition temperatures and having an excellent combination of properties for use in making tire treads which comprises: terpolymerizing styrene, isoprene and 1,3-butadiene in an organic solvent at a temperature of no more than about 40.degree. C. in the presence of (a) tripiperidino phosphine oxide, (b) an alkali metal alkoxide and (c) an organolithium compound.
    Type: Grant
    Filed: July 31, 1992
    Date of Patent: February 8, 1994
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Wen-Liang Hsu, Adel F. Halasa
  • Patent number: 5274106
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from an anionic polymerization initiator. The anionic polymerization initiator comprises the general formula ##STR1## where R.sup.1 -R.sup.5 are the same or different and are selected from the group consisting of hydrogen; alkyls having from alkyls having from 1 to about 12 carbon atoms; aralkyls having from 7 to about 20 carbon atoms; dialkylaminos having from 2 to about 20 carbon atoms; and, dialkylaminoalkyls having from 3 to about 20 carbon atoms. At least one of R.sup.1 -R.sup.5 is selected from the group consisting of the dialkylaminos and the dialkylaminoalkyls. Methods of the present invention include preparing functionalized polymers and reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: December 30, 1991
    Date of Patent: December 28, 1993
    Assignee: Bridgestone Corporation
    Inventors: David F. Lawson, Thomas A. Antkowiak, Mark L. Stayer, Jr., John R. Schreffler, Hideki Komatsu
  • Patent number: 5272220
    Abstract: The subject invention discloses a styrene-isoprene-butadiene rubber which is particularly valuable for use in making truck tire treads, said rubber being comprised of repeat units which are derived from about 5 weight percent to about 20 weight percent styrene, from about 7 weight percent to about 35 weight percent isoprene, and from about 55 weight percent to about 88 weight percent 1,3-butadiene, wherein the repeat units derived from styrene, isoprene and 1,3-butadiene are in essentially random order, wherein from about 25% to about 40% of the repeat units derived from the 1,3-butadiene are of the cis-microstructure, wherein from about 40% to about 60% of the repeat units derived from the 1,3-butadiene are of the trans-microstructure, wherein from about 5% to about 25% of the repeat units derived from the 1,3-butadiene are of the vinyl-microstructure, wherein from about 75% to about 90% of the repeat units derived from the isoprene are of the 1,4-microstructure, wherein from about 10% to about 25% of the re
    Type: Grant
    Filed: September 14, 1992
    Date of Patent: December 21, 1993
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Michael B. Rodgers, Stanley M. Mezynski, Adel F. Halasa, Wen-Liang Hsu, Barry A. Matrana, Joel L. Cox
  • Patent number: 5238893
    Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from the polymerization initiator. The polymerization initiator is selected from the group consisting of ##STR1## where R.sup.1 and R.sup.2 are the same or different and are selected from the group consisting of alkyls having from 1 to about 12 carbon atoms, cycloalkyls having from 3 to about 14 carbon atoms, and aryls having from 6 to about 20 carbon atoms. Methods of the present invention include preparing the initiator, preparing functionalized polymers and, reducing the hysteresis of vulcanizable elastomeric compounds.
    Type: Grant
    Filed: December 30, 1991
    Date of Patent: August 24, 1993
    Assignee: Bridgestone Corporation
    Inventors: William L. Hergenrother, John M. Doshak
  • Patent number: 5231153
    Abstract: It has been unexpectedly discovered that various compounds, such as alkyl tetrahydrofurfuryl ethers, can be used to modify anionic polymerizations of conjugated diene monomers. These modifiers can be used to polymerize isoprene monomer into high 3,4-polyisoprene at excellent polymerization rates. This is in contrast to the modifiers such as tetramethylethylene diamine which are typically used to modify such polymerizations. This invention more specifically discloses a process for the synthesis of 3,4-polyisoprene which comprises polymerizing isoprene monomer in an organic solvent in the presence of a catalyst system which is comprised of (a) a lithium initiator and (b) ethyltetrahydrofurfuryl ether.
    Type: Grant
    Filed: April 6, 1992
    Date of Patent: July 27, 1993
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Wen-Liang Hsu, Adel F. Halasa, Barry A. Matrana
  • Patent number: 5173550
    Abstract: The subject invention relates to a process for synthesizing random styrene-isoprene copolymers having a medium vinyl microstructure. These random styrene-isoprene rubbers have physical properties which make them highly desirable for utilization in tire tread rubber compounds. The utilization of such random styrene-isoprene rubbers in tire tread rubber results in improved tread wear, rolling resistance and traction characteristics. This invention more specifically relates to a process for preparing a random styrene-isoprene rubber having a medium vinyl microstructure which comprises copolymerizing isoprene and styrene in the presence of (a) at least one organolithium compound and (b) at least one modifier slected from the group consisting of 1,2-dipiperidinoethane, dipiperidinomethane, and tripiperidinophosphine oxide.
    Type: Grant
    Filed: April 5, 1991
    Date of Patent: December 22, 1992
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Wen-Liang Hsu, Adel F. Halasa
  • Patent number: 5171810
    Abstract: Random or block copolymers with (1-hydro-1-R-1-sila-cis-pent-3-ene), poly(1-hydro-1-R-3,4 benzo-1-sila pent-3-ene), and disubstituted 1-silapent-3-ene repeating units of the general formula ##STR1## where R is hydrogen, an alkyl radical containing from one to four carbon atoms or phenyl, R.sup.1 is hydrogen, an alkyl radical containing from one to four carbon atoms, phenyl or a halogen and R.sup.2 is hydrogen, or R.sup.1 and R.sup.2 are combined to form a phenyl ring, are prepared by the anionic ring opening polymerization of silacyclopent-3-enes or 2-silaindans with an organometallic base and cation coordinating ligand catalyst system or a metathesis ring opening catalyst system.
    Type: Grant
    Filed: September 12, 1991
    Date of Patent: December 15, 1992
    Assignee: University of Southern California
    Inventors: William P. Weber, Stephen Q. Zhou
  • Patent number: 5171800
    Abstract: An organic compound of an alkali metal, of the formula I ##STR1## which is obtained by reaction of an appropriate diarylethylene of the formula II with an alkali metal (M), especially lithium, ##STR2## where Ar.sup.1 and Ar.sup.2 are identical or different aryl or hetaryl radicals which have one or more rings which are either separate or fused, and where R is at least one substituent different from hydrogen and which is chemically inert to the alkali metal or its alkyl, with the proviso that the total of the carbon atoms in all the R is at least 3, and m and n are each an integer up to 4, is used for the preparation of polymers whose monomers are amenable to anionic polymerization.
    Type: Grant
    Filed: June 13, 1990
    Date of Patent: December 15, 1992
    Assignee: BASF Aktiengesellschaft
    Inventor: Klaus Bronstert
  • Patent number: 5169916
    Abstract: Poly(1-hydro-1-R-1-sila-cis-pent-3-ene) and poly(1-hydro-1-R-3,4 benzo-1-sila pent-3-ene) polymers having repeating units of the general formula ##STR1## where R is hydrogen, an alkyl radical containing from one to four carbon atoms or phenyl, R.sup.1 is hydrogen, an alkyl radical containing from one to four carbon atoms, phenyl or a halogen and R.sup.2 is hydrogen, or R.sup.1 and R.sup.2 are combined to form a phenyl ring, are prepared by the anionic ring opening polymerization of silacyclopent-3-enes or 2-silaindans with an organometallic base and cation coordinating ligand catalyst system.
    Type: Grant
    Filed: December 31, 1990
    Date of Patent: December 8, 1992
    Assignee: University of South California
    Inventors: William P. Weber, Stephen Q. Zhou
  • Patent number: 5153159
    Abstract: An anionic polymerization initiator comprising the reaction product of a functionalizing agent selected from the group consisting of substituted aldimines, ketimines and secondary amines and, an organolithium compound. Elastomeric polymers prepared with these initiators have functional sites incorporated at the initiator end of the polymer chain and provide vulcanizable rubber compounds exhibiting reduced hysteresis. Articles such as tires, produced with low hysteresis elastomeric polymers have lower rolling resistance. Methods are also provided for preparing the initiators, fuctionalized polymers and vulcanizable elastomeric compounds having reduced hysteresis.
    Type: Grant
    Filed: April 9, 1990
    Date of Patent: October 6, 1992
    Assignee: Bridgestone/Firestone, Inc.
    Inventors: Thomas A. Antkowiak, David F. Lawson, Russell W. Koch, Mark L. Stayer, Jr.
  • Patent number: 5130390
    Abstract: Crosslinkable saturated and unsaturated carbosilane polymers are prepared by polymerizing vinyl substituted 1-silacyclo-pent-3-ene or vinyl substituted 1-silacyclobutane monomers in the presence of an anionic ring opening catalyst.
    Type: Grant
    Filed: September 10, 1991
    Date of Patent: July 14, 1992
    Assignee: University of Southern California
    Inventors: William P. Weber, Xiugao Liao
  • Patent number: 5112929
    Abstract: A method for preparing a diene polymer or copolymer having increased amounts of 1,2-microstructure is provided. The method involves polymerizing a diene monomer or mixture of a diene monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent in the presence of a catalytically effective amount of a catalyst composition comprising: (a) an organolithium initiator and (b) an oxolanyl cyclic acetal having the structural formula: ##STR1## wherein R is selected from the group consisting of hydrogen and alkyl groups containing from 1 to 4 carbon atoms and X is 0 or 1.
    Type: Grant
    Filed: April 5, 1991
    Date of Patent: May 12, 1992
    Assignee: Bridgestone Corporation
    Inventor: James E. Hall
  • Patent number: 4965327
    Abstract: Synthetic elastomers are typically made commercially by employing emulsion polymerization or solution polymerization techniques. In such solution polymerization techniques, it is desirable to operate at the highest solids content which is practical. As a general rule, it is not practical to prepare such rubbers by solution polymerization at solids contents of higher than about 20 percent. However, the subject invention reveals a technique for preparing such rubbers by high solids solution polymerization at extremely high solids contents. This technique offers substantial advantages associated with eliminating large quantities of organic solvents.
    Type: Grant
    Filed: October 23, 1989
    Date of Patent: October 23, 1990
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Robert W. Stachowiak, Anthony J. Puccio, Thomas J. Eberhart