# US 11,299,559 B2 · Modified conjugated diene-based polymer and rubber composition including the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,559 B2 - Document ID: US11299559B2 - Status: Granted - Kind: B2 - Application number: 16/754,600 - Filed: 2018-11-30 - Published: 2020-11-12 - Granted: 2022-04-12 - Earliest claimed: 2017-12-05 - Assignees: LG Chem, Ltd. - Applicants: LG Chem, Ltd. - Inventors: Ho Young Lee; Jae Hoon Choe; Kyung Chang Seo; No Ma Kim - Web page: https://patentgrep.com/patent/US11299559B2 ## CPC - C08C 19/28: Reaction with compounds containing carbon-to-carbon unsaturated bonds (graft polymers C08F279/00) - C07C 211/27: having amino groups linked to the six-membered aromatic ring by saturated carbon chains - C07D 295/03: with the ring nitrogen atoms directly attached to acyclic carbon atoms - C07D 295/033: with the ring nitrogen atoms directly attached to carbocyclic rings - C08F 236/04: conjugated - C08F 236/10: with vinyl-aromatic monomers - C08K 3/36: Silica - C08L 9/00: Compositions of homopolymers or copolymers of conjugated diene hydrocarbons - B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition - Y02T 10/86: Optimisation of rolling resistance, e.g. weight reduction - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract A modified conjugated diene-based polymer and a rubber composition including a modified conjugated diene-based polymer are disclosed herein. In some embodiments, a modified conjugated diene-based polymer includes a functional group derived from a modification initiator at one terminal and a functional group derived from a modifier represented by the Formula 2 or Formula 3 at the other terminal, wherein the modified conjugated diene-based polymer having a unimodal molecular weight distribution, and a polydispersity index of 1.0 to less than 1.7. The modified conjugated diene-based polymer prepared by continuous polymerization and having remarkable processability, narrow molecular weight distribution and excellent physical properties. ## Claims ### Claim 1 A modified conjugated diene-based polymer, comprising: a functional group derived from a modification initiator at one terminal; and a functional group derived from a modifier represented by the following Formula 2 or Formula 3 at the other terminal, wherein the modification initiator is a reaction product of a compound represented by the following Formula 1 and an organometal compound: in Formula 1, R1 to R3 are each independently hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R4 is a single bond; a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms with a substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms with a substituent; or a substituted or unsubstituted arylene group of 5 to 20 carbon atoms with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R5 is an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, and n is an integer of 1 to 5, and at least one of R5 groups is a functional group represented by the following Formula 1a or Formula 1b, in case where n is an integer of 2 to 5, a plurality of R5 groups may be the same or different, in Formula 1a, R6 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms with a substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms with a substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R7 and R8 are each independently a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms with an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R9 is hydrogen; an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and X is an N, O or S atom, in case where X is O or S, R9 is not present, in Formula 1b, Rio is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms with a substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms with a substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and R11 and R12 are each independently an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, in Formula 2, R20 is a single bond, or an alkylene group of 1 to 10 carbon atoms, R21 and R22 are each independently an alkyl group of 1 to 10 carbon atoms, R23 is a single bond or an alkylene group of 1 to 10 carbon atoms, R24 is hydrogen, an alkyl group of 1 to 10 carbon atoms or a substituted divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1 to 10 carbon atoms, a is an integer of 2 or 3, c is an integer of 1 to 3, and b is an integer of 0 to 2, where b+c=3, in Formula 3, A1 and A2 are each independently an alkylene group of 1 to 20 carbon atoms, R25 to R28 are each independently an alkyl group of 1 to 20 carbon atoms, and L1 to L4 are each independently a substituted divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1 to 10 carbon atoms, or an alkyl group of 1 to 20 carbon atoms, wherein the modified conjugated diene-based polymer having a unimodal molecular weight distribution, and a polydispersity index of 1.0 to less than 1.7. ### Claim 2 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein in Formula 1, R1 to R3 are each independently hydrogen; an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or an alkynyl group of 2 to 10 carbon atoms, R4 is a single bond; an unsubstituted alkylene group of 1 to 10 carbon atoms, and R5 is an alkyl group of 1 to 10 carbon atoms; an alkenyl group of 2 to 10 carbon atoms; an alkynyl group of 2 to 10 carbon atoms; or a functional group represented by Formula 1a or Formula 1b, in Formula 1a, R6 is an unsubstituted alkylene group of 1 to 10 carbon atoms, R7 and R8 are each independently an unsubstituted alkylene group of 1 to 10 carbon atoms, and R9 is an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms, and in Formula 1b, R10 is an unsubstituted alkylene group of 1 to 10 carbon atoms, and R11 and R12 are each independently an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms. ### Claim 3 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein in Formula 2, R20 is a single bond, or an alkylene group of 1 to 5 carbon atoms, R21 and R22 are each independently an alkyl group of 1 to 5 carbon atoms, R23 is a single bond or an alkylene group of 1 to 5 carbon atoms, and R24 is hydrogen, an alkyl group of 1 to 5 carbon atoms or a substituted tetravalent alkylsilyl group with an alkyl group of 1 to 5 carbon atoms. ### Claim 4 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein in Formula 3, A1 and A2 are each independently an alkylene group of 1 to 10 carbon atoms, R25 to R28 are each independently an alkyl group of 1 to 10 carbon atoms, and L1 to L4 are each independently a substituted tetravalent alkylsilyl group with an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 10 carbon atoms. ### Claim 5 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, and a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol. ### Claim 6 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a Si content of 50 ppm or more and a N content of 50 ppm or more, respectively, based on the total weight of the modified conjugated diene-based polymer. ### Claim 7 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a mooney stress relaxation ratio of 0.7 to 3.0 when measured at 100° C. ### Claim 8 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a shrinking factor of 1.0 to 3.0, the shrinking factor being an average value of a ratio ([η]/[η]0) of intrinsic viscosity ([η]) of the polymer at an absolute molecular weight to the intrinsic viscosity ([η]0) of a linear polymer at the absolute molecular weight. ### Claim 9 (depends on 1) The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a coupling number (C.N.) of 1