Modified asphalt using phosphorous acid
View Patent ↗A modified asphalt composition comprises or is produced from asphalt and phosphorous acid. The composition optionally further comprises one or more of an ethylene copolymer that comprises copolymerized units derived from ethylene and an epoxy-containing comonomer and a nonreactive polymer such as a styrene/conjugated-diene block copolymer. Further provided are processes for producing the composition in addition to products such as paving materials and roofing materials that comprise the compositions.
1. An asphalt composition comprising asphalt and about 0.1 to about 2 weight % of phosphorous acid, based on the total weight of the asphalt composition.
2. A polyepoxy-polymer-linked-asphalt composition comprising
(a) about 89 to about 99.4 weight % of asphalt;
(b) about 0.5 to about 10 weight % of an E/X/Y/Z epoxy-functionalized ethylene copolymer, wherein E represents the copolymerized repeat unit —(CH 2 CH 2 )— derived from ethylene; X represents the copolymerized repeat unit —(CH 2 CR 1 R 2 )—, where R 1 is hydrogen, methyl, or ethyl, and R 2 is carboalkoxy, acyloxy, or alkoxy of 1 to 10 carbon atoms; Y represents the copolymerized repeat unit —(CH 2 CR 3 R 4 )—, where R 3 is hydrogen or methyl and R 4 is carboglycidoxy or glycidoxy; and Z represents the copolymerized repeat unit derived from one or more additional comonomers; wherein the E/X/Y/Z epoxy-functionalized ethylene copolymer comprises 0 to 40 wt % of copolymerized repeat units of X, 0.3 to 25 wt % of copolymerized repeat units of Y, and 0 to 10 wt % of copolymerized repeat units of Z; wherein the weight percentages of the copolymerized repeat units of X, Y, and Z are based on the total weight of the E/X/Y/Z epoxy-functionalized ethylene copolymer; and wherein the sum of the weight percentages of E, X, Y, and Z in the E/X/Y/Z epoxy-functionalized ethylene copolymer is 100 wt %; and
(c) about 0.1 to about 1 weight % of phosphorous acid, and
wherein the weight percentages of the asphalt, the E/X/Y/Z epoxy-functionalized ethylene copolymer, and the phosphorous acid are based on the total weight of the polyepoxy-polymer-linked-asphalt composition.
3. The polyepoxy-polymer-linked-asphalt composition of claim 2 , wherein the E/X/Y/Z epoxy-functionalized ethylene copolymer comprises repeat units of one or more epoxy-containing comonomers Y selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, glycidyl butyl acrylate, and glycidyl vinyl ether.
4. The polyepoxy-polymer-linked-asphalt composition of claim 2 , wherein the E/X/Y/Z epoxy-functionalized ethylene copolymer is selected from the group consisting of an ethylene glycidyl methacrylate dipolymer, an ethylene vinyl acetate glycidyl methacrylate terpolymer, an ethylene n-butyl acrylate glycidyl methacrylate terpolymer, and an ethylene methyl acrylate glycidyl methacrylate terpolymer.
5. The polyepoxy-polymer-linked-asphalt composition of claim 2 , wherein the comonomer Y comprises a glycidyl moiety and wherein the amount of copolymerized repeat units of Y in the E/X/Y/Z epoxy-functionalized ethylene copolymer is from about 0.3 to about 15 weight %.
6. The polyepoxy-polymer-linked-asphalt composition of claim 2 , wherein the comonomer Y comprises a glycidyl moiety and wherein the amount of copolymerized repeat units of Y in the E/X/Y/Z epoxy-functionalized ethylene copolymer is from about 15.1 to about 25 weight %.
7. The polyepoxy-polymer-linked-asphalt composition of claim 2 , further comprising at least one nonreactive polymer selected from the group consisting of an ethylene acrylate, an ethylene methacrylate or an ethylene vinyl acetate copolymer; a styrene/conjugated-diene block copolymer, wherein the styrene/conjugated-diene block copolymer comprises a di-, tri- or poly-block copolymer having a linear or radial structure, with or without a random junction; and a polyolefin.
8. The polyepoxy-polymer-linked-asphalt composition of claim 7 , wherein the styrene/conjugated-diene block copolymer comprises about 10 to about 50 weight percent of copolymerized repeat units derived from styrene and about 50 to about 90 weight percent of copolymerized repeat units derived from a conjugated diene.
9. The polyepoxy-polymer-linked-asphalt composition of claim 2 , further comprising one or more additives selected from the group consisting of flux oils, liquid plasticizers, amine scavengers, hydrogen sulfide scavengers, and sulfur sources.
10. A method for preparing the asphalt composition according to claim 1 , said method comprising heating an asphalt, and mixing the heated asphalt with phosphorous acid.
11. A method for preparing the polyepoxy-polymer-linked-asphalt composition of claim 2 , said method comprising:
(1) providing one or more polymers selected from the group consisting of an epoxy-functionalized ethylene copolymer and a nonreactive polymer;
(2) heating and mixing the polymer(s) with asphalt to provide a polymer-asphalt blend;
(3) adding phosphorous acid to the polymer-asphalt blend; and
(4) mixing the phosphorous acid with the polymer-asphalt blend.
12. The method of claim 11 , wherein step (2) comprises:
a) heating the asphalt to 150 to 195° C. either prior to or after addition to a reactor for modifying with the polymer(s); and
b) adding the polymer(s) to the heated asphalt in the reactor with stirring for about 10 minutes to about 4 hours while maintaining the temperature at 150 to 250° C.; and
wherein step (3) comprises:
adding phosphorous acid to the heated polymer asphalt blend in the reactor with stirring for about 10 minutes to about 4 hours while maintaining the temperature at 150 to 250° C.
13. The method of claim 11 , wherein the polymer(s) are dissolved in flux oil or liquid plasticizer prior to mixing with the asphalt.
14. A road pavement or roofing material comprising the asphalt composition of claim 1 .
15. A road pavement or roofing material comprising the asphalt composition of claim 2 .
16. A method for preparing the polyepoxy-polymer-linked-asphalt composition of claim 2 , said method comprising the steps of heating an asphalt and mixing the heated asphalt with phosphorous acid.
17. The polyepoxy-polymer-linked-asphalt composition of claim 7 , wherein the conjugated-diene of the styrene/conjugated-diene block copolymer comprises butadiene, isoprene, ethylene butene, or 1,3-pentadiene; or wherein the polyolefin comprises polyethylene, polypropylene, polybutene, polyisobutene, ethylene/propylene copolymers, ethylene/propylene/diene terpolymers, polybutadiene, polyisoprene or polynorbornene.
18. The polyepoxy-polymer-linked-asphalt composition of claim 7 , wherein the styrene/conjugated-diene block copolymer comprises a diblock A-B type copolymer; linear (triblock) A-B-A type copolymer; or radial (A-B)n type copolymers; wherein A refers to a copolymerized repeat unit derived from styrene and B refers to a copolymerized repeat unit derived from a conjugated diene.
19. The polyepoxy-polymer-linked-asphalt composition of claim 9 , wherein the flux oil(s) comprise one or more of an aromatic oil, a paraffinic oil, a mineral oil, and a vegetable oil; or wherein the liquid plasticizer(s) comprise one or more of a dicarboxylic ester-based plasticizer, a tricarboxylic ester-based plasticizer, and an acetic acid ester of a monoglyceride, trimellitate, adipate, benzoate, adipic acid polyester, polyetherester, epoxy ester, or maleate.