# US 10,767,033 B2 · Asphalt compositions and methods of making same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,767,033 B2 - Document ID: US10767033B2 - Status: Granted - Kind: B2 - Application number: 15/984,127 - Filed: 2018-05-18 - Published: 2018-11-22 - Granted: 2020-09-08 - Earliest claimed: 2017-05-18 - Assignees: Kraton Polymers LLC - Applicants: Kraton Polymers LLC - Inventors: Robert Q Kluttz; Erica Jellema; Donn A. Dubois; Sebastian Puchalski; Carl L. Willis; Christopher M. Lubbers - Web page: https://patentgrep.com/patent/US10767033B2 ## CPC - C08L 9/06: Copolymers with styrene - C04B 24/2676: {Polystyrenes} - C04B 24/36: Bituminous materials, e.g. tar, pitch {(C04B24/243 takes precedence)} - C04B 26/26: Bituminous materials, e.g. tar, pitch {(C08L95/00 takes precedence)} - C08F 297/023: {using a coupling agent} - C08L 53/02: of vinyl-aromatic monomers and conjugated dienes - C08L 95/00: Compositions of bituminous materials, e.g. asphalt, tar, pitch - C08L 95/005: {Aqueous compositions, e.g. emulsions} - C09D 109/06: Copolymers with styrene - C09J 109/06: Copolymers with styrene - C04B 2103/0061: {Block (co-)polymers} - C04B 2103/0075: {Anti-dusting agents} - C04B 2111/00586: {Roofing materials} - C04B 2201/10: for the viscosity - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L 2205/03: containing three or more polymers in a blend - C08L 2555/84: Polymers comprising styrene, e.g. , polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) ## Abstract A coupled block copolymer composition with a combination of high viscosity at manufacturing, finishing and handling conditions, low viscosity at asphalt blending conditions and suitable viscosity stability is provided for use in asphalt compositions. The composition comprises: (i) a diblock copolymer, (ii) at least a linear triblock copolymer having a peak molecular weight that is 1.5 to 3.0 times the peak molecular weight of the diblock copolymer, and (iii) at least a multiarm coupled block copolymer having a peak molecular weight that is 1.5 to 9.0 times the peak molecular weight of the diblock copolymer, and mixtures thereof. The block copolymer composition is characterized as having a melt viscosity at 110° C. or less of greater than 2.0E7 Poise and a coupling efficiency after 24 hours at 180° C. is less than 25%. ## Claims ### Claim 1 A coupled block copolymer composition comprising: (i) a diblock copolymer comprising one block of a monovinylaromatic hydrocarbon and one block of a conjugated diene, and having a peak molecular weight from 30,000 to 78,000, and a vinyl content from 8 to 80 mol percent based on the number of repeat monomer units in the conjugated diene block, (ii) a linear triblock copolymer having a peak molecular weight that is 1.5 to 3.0 times the peak molecular weight of the diblock copolymer, and (iii) a multiarm coupled block copolymer having a peak molecular weight that is 1.5 to 9.0 times the peak molecular weight of the diblock copolymer, wherein the ratio of (i) to (ii) in the block copolymer composition is less than 1; wherein the coupled block copolymer composition has a sufficient coupling efficiency to have a melt viscosity at less than 110° C. of greater than 2.0E7 Poise; wherein the composition is prepared in a reaction mixture consisting of a diblock copolymer, a coupling agent, a microstructure control reagent, and a solvent, wherein the diblock copolymer is coupled with the coupling agent, and wherein the coupling agent is represented by Formula I: wherein Y is R, OR, SR′, or X (where X═F, Cl, Br and/or I); Z is O, S, or NR″ where R, R′, and R″ are independently an alkyl group or an aryl group; and Ar is an aromatic group comprises one or more rings; and wherein the coupled block copolymer composition, heated at 180° C. for 24 hours, decouples to a coupling efficiency of less than 20%. ### Claim 2 (depends on 1) The coupled block copolymer composition of claim 1, wherein the multiarm coupled block copolymer is present in an amount of less than 5 wt. % of total mass of the coupled block copolymer composition. ### Claim 3 (depends on 1) The coupled block copolymer composition of claim 1, wherein the composition is a distributed vinyl coupled block copolymer comprising uncoupled copolymers and coupled copolymers, having mixtures of copolymers having formulae S-B1-B2 and (S-B1-B2)nX, or mixtures of copolymers having formulae S-B1-B2, (S-B1-B2)nX, and any of S-B1-B1′-B2 and (S-B1-B1′-B2)nX, wherein X is residue of the coupling agent, n is an integer from 2 to 6, each of B1, B2, B1′ and B2 is a conjugated diene block, and S is a monoalkenyl arene block. ### Claim 4 (depends on 1) The coupled block copolymer composition of claim 1, wherein the ratio of the diblock copolymer to the multi-arm coupled block copolymer is from 4:5 to 1:10. ### Claim 5 (depends on 1) The coupled block copolymer composition of claim 1, wherein both the diblock copolymer and the multi-arm coupled block copolymer have a vinyl content from 8 mol % to 60 mol % and a polystyrene content from 20 mol % to 35 mol %. ### Claim 6 (depends on 1) The coupled block copolymer composition of claim 1, wherein the composition has a coupling efficiency ranging from greater than 50 to 90%. ### Claim 7 (depends on 1) The coupled block copolymer composition of claim 1, wherein the composition has a coupling efficiency ranging from greater than 50 to 75%. ### Claim 8 (depends on 1) The coupled block copolymer of claim 1, wherein the coupling agent is represented by the formula: wherein Y is R, OR, SR′, or X; X═F, Cl, Br and/or I; Z is O, S, or NR″; R, R′, and R″ each independently comprises an alkyl group or aryl group. ### Claim 9 (depends on 8) The coupled block copolymer composition of claim 8, wherein the coupling agent is methyl benzoate (MBZ). ### Claim 10 (depends on 1) An asphalt composition comprising: a) the coupled block copolymer composition of claim 1; b) an asphalt binder; and c) optionally a chemical crosslinking agent. ### Claim 11 (depends on 1) A self-adhesive roofing composition comprising the coupled block copolymer composition of claim 1. ### Claim 12 (depends on 10) A bituminous emulsion comprising the asphalt composition of claim 10. ### Claim 13 (depends on 12) The bituminous emulsion of claim 12, for use in any of fog seal, rejuvenator seal, scrub seal, prime coat, tack coat, chip seal, slurry seal, micro surfacing, an in-place recycling applications. ### Claim 14 (depends on 13) The bituminous emulsion of claim 13, for use as a pavement surface treatment for sealing and repairing roads, drive ways, parking lots and black topped surfaces. ### Claim 15 (depends on 12) The bituminous emulsion of claim 12, wherein the coupled block copolymer is present in an amount ranging from 1 to 9 wt. % based on the amount of asphalt in the emulsion composition. ### Claim 16 (depends on 1) A waterproofing composition comprising the coupled block copolymer composition of claim 1. ### Claim 17 A method for preparing a coupled block copolymer composition for use in adhesive and/or asphalt applications, the method comprising: providing a diblock copolymer, forming a reaction mixture consisting of the diblock copolymer, a coupling agent, a microstructure control reagent, and a solvent, and coupling the diblock copolymer with the coupling agent; in the presence of the microstructure control reagent, to obtain a coupled block copolymer comprising: (i) a diblock copolymer comprising one block of a monovinylaromatic hydrocarbon and one block of a conjugated diene having a peak molecular weight from 30,000 to 78,000, each block copolymer has a vinyl content from 8 to 80 mol percent based on the number of repeat monomer units in the conjugated diene block (ii) a linear triblock copolymer having a peak molecular weight that is 1.5 to 3.0 times the peak molecular weight of the diblock copolymer, and (iii) a multiarm coupled block copolymer having a peak molecular weight that is 1.5 to 9.0 times the peak molecular weight of the diblock copolymer, wherein the coupling agent is represented by Formula I: wherein Y is R, OR, SR′, or X (where X═F, Cl, Br and/or I); Z is O, S, or NR″ where R, R′, and R″ are independently an alkyl group or an aryl group; and Ar is an aromatic group comprises one or more rings; wherein the ratio of (i) to (ii) in the block copolymer composition is less than 1; wherein the coupled block copolymer composition has a sufficient coupling efficiency to have a melt viscosity at less than 110° C. of greater than 2.0E7 Poise; and wherein the coupled block copolymer composition decouples at a temperature at or above 180° C. and after 24 hours for a coupling efficiency of less than 20%. ### Claim 18 (depends on 17) The method of claim 17, wherein the coupled block copolymer composition has a coupling efficiency ranging from greater than 50% to 90%. ### Claim 19 (depends on 17) The method of claim 17, wherein the coupled block copolymer composition has a coupling efficiency ranging from greater than 50% to 75%.