POLY(ACRYLATED POLYOL) AND METHOD FOR MAKING AND USING THEREOF AS ASPHALT RUBBER MODIFIERS, ADHESIVE, FRACKING ADDITIVES, OR FRACKING FLUIDS

• US 20150337078A1
• Filed: 05/20/2015
• Published: 11/26/2015
• Est. Priority Date: 05/21/2014
• Status: Active Grant

• Current Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Original Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Inventors: Cochran, Eric W., Williams, R. Christopher, Hernandez, Nacu, Ferreira Peralta, Elvira Joana, Forrester, Michael John
• Granted Patent: US 10,066,051 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 122/1006 of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
• CPC Class Codes: C08F 222/1006 of polyhydric alcohols or polyhydric phenols
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08L 21/00 Compositions of unspecified rubbers
• CPC Class Codes: C08L 2205/03 containing three or more polymers in a blend
• CPC Class Codes: C08L 2207/04 Thermoplastic elastomer
• CPC Class Codes: C08L 2555/34 Recycled or waste materials, e.g. reclaimed bitumen, asphalt, roads or pathways, recycled roof coverings or shingles, recycled aggregate, recycled tires, crumb rubber, glass or cullet, fly or fuel ash, or slag
• CPC Class Codes: C08L 2555/80 Macromolecular constituents
• CPC Class Codes: C08L 35/02 Homopolymers or copolymers of esters C08L35/06, C08L35/08 take precedence
• CPC Class Codes: C08L 95/00 Compositions of bituminous materials, e.g. asphalt, tar, pitch
• CPC Class Codes: C09J 167/00 Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09J177/12; based on polyester-imides C09J179/08; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09K 8/68 containing organic compounds

Abstract

The present invention relates to a thermoplastic copolymer, block copolymer, and statistical copolymer comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol. The present invention also relates to a method of making the thermoplastic copolymer, block copolymer, and statistical copolymer, and using them in various applications, such as asphalt rubber modifiers, adhesives, or an additive in a fracking fluid for oil fracking.

Claims

1. A thermoplastic copolymer comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol.

2. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer has a linear or branched-chain structure.

3. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer has a molecular weight of at least 1 KDa.

4. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 10 MDa.

5. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer has a transition temperature (T_g) below 0°

C.

6. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer has a T_g ranging from −

60°

C. to −

15°

C.

7. The thermoplastic copolymer of claim 1, wherein the polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol, talose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldotriose, aldose, allose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose, lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose, tetrose, triose, xylose, amylopectin, and stereoisomers thereof.

8. The thermoplastic copolymer of claim 1, wherein the polyol is glycerol.

9. The thermoplastic copolymer of claim 8, wherein the average degree of acrylation ranges from 1.001 to 2.9.

10. The thermoplastic copolymer of claim 8, wherein the average degree of acrylation ranges from 1.001 to 1.25.

11. The thermoplastic copolymer of claim 1, wherein the polyol is sorbitol.

12. The thermoplastic copolymer of claim 11, wherein the average degree of acrylation ranges from 1.001 to 3.

13. The thermoplastic copolymer of claim 1, wherein the polyol is dextrose.

14. The thermoplastic copolymer of claim 13, wherein the average degree of acrylation ranges from 1.001 to 3.

15. The thermoplastic copolymer of claim 1, wherein one or more acrylated polyol monomeric units contain one or more alkoxy groups derived from esterification of the un-acrylated hydroxy groups.

16. The thermoplastic copolymer of claim 15, wherein one or more acrylated polyol monomeric units contain one or more methoxy or ethoxy groups.

40. An asphalt binder composition comprising:

the thermoplastic copolymer of claim 1; and

a crumb rubber.

41. An adhesive or sealant composition comprising:

the thermoplastic copolymer of claim 1; and

a tackifier, and/or a plasticizer, and/or a solvent.

42. A tire composition comprising:

the thermoplastic copolymer of claim 1; and

a rubber compound.

43. A fracking fluid composition comprising:

water;

sand;

the thermoplastic copolymer of claim 1 as a chemical additive; and

optionally a thermoplastic polymer block added to confer a desired fluid property to the thermoplastic copolymer, thermoplastic statistical copolymer, or thermoplastic block copolymer.

87. An asphalt composition comprising:

i) an asphalt component;

ii) a crumb rubber having a weight percentage in the range of 1% to 15%; and

iii) the thermoplastic copolymer of claim 1, as an asphalt additive, modifier, and/or filler having a weight percentage in the range of 0.01% to 1.05%.

89. The asphalt composition of claim 87, wherein the ground tire rubber comprises particles capable of passing a 30 mesh screen.

90. The asphalt composition of claim 87, wherein the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber has a range of 2.5% to 6.5%.

91. The asphalt composition of claim 87, wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to 1.25, the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber is 4.5%.

92. The asphalt composition of claim 91, wherein said asphalt composition has one or more of the following properties:

a high temperature grade higher than 78°

C., a low temperature grade no higher than −

29°

C., a grade range higher than 107°

C., a minimum mixing temperature lower than 171°

C., and a minimum compaction temperature lower than 161°

C.

93. The asphalt composition of claim 87, wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to 1.25, the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber is 6.5%.

94. The asphalt composition of claim 93, wherein said asphalt composition has one or more of the following properties:

a high temperature grade higher than 82°

C., a low temperature grade no higher than −

28.5°

C., a grade range higher than 110°

C., a minimum mixing temperature lower than 179°

C., and a minimum compaction temperature lower than 168°

C.

95. The asphalt composition of claim 87, wherein said asphalt composition is stable and homogenous for at least 3 days under a temperature of 130°

C. to 180°

C.

96. A method for preparing a homogeneous asphalt composition, comprising:

mixing the thermoplastic copolymer of claim 1 as an asphalt additive, modifier, and/or filler, with a weight percentage in the range of 0.01% to 1.05%, into an asphalt composition comprising i) an asphalt component, and ii) a crumb rubber having a weight percentage in the range of 1% to 15%, to form a homogeneous asphalt composition.

97. The method of claim 96, wherein the crumb rubber is a ground tire rubber.

98. The method of claim 96, wherein the ground tire rubber comprises particles capable of passing a 30 mesh screen.

99. The method of claim 96, wherein the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber ranges from 2.5% to 6.5%.

100. The method of claim 96, wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to about 1.25, the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber is 4.5%.

101. The method of claim 96, wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to about 1.25, the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the weight concentration of the thermoplastic copolymer relative to the weight of the crumb rubber is 6.5%.

102. The method of claim 96, wherein said mixing is carried out at a temperature of 130°

C. to 180°

C.

103. The method of claim 96, wherein said mixing occurs at a location remote from the location at which the homogeneous asphalt composition is used, and wherein the asphalt composition is stable and homogenous for at least 3 days at a temperature of 130°

C. to 180°

C.

104. A method for preparing a fracking liquid, comprising:

mixing the thermoplastic copolymer of claim 1 as a chemical additive, with water, and sand.

105. A method for preparing an adhesive or sealant composition, comprising:

mixing the thermoplastic copolymer of claim 1 with a tackifier, and/or a plasticizer, and/or a solvent.

17. A thermoplastic block copolymer comprising at least one PA block and at least one PB block, wherein PA represents a polymer block comprising one or more units of monomer A and PB represents a polymer block comprising one or more units of monomer B, with monomer A being an acrylated polyol monomeric unit having different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol, and monomer B being a radically polymerizable monomer.

18. The thermoplastic block copolymer of claim 17, wherein the PA block and PB block each have a linear or branched-chain structure.

19. The thermoplastic block copolymer of claim 17, wherein the polyol of the monomer A is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol, talose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldotriose, aldose, allose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose, lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose, tetrose, triose, xylose, amylopectin, and stereoisomers thereof.

20. The thermoplastic block copolymer of claim 17, wherein the polyol of the monomer A is glycerol.

21. The thermoplastic block copolymer of claim 17, wherein the polyol of the monomer A is sorbitol.

22. The thermoplastic block copolymer of claim 17, wherein the polyol of the monomer A is dextrose.

23. The thermoplastic block copolymer of claim 17, wherein one or more acrylated polyol monomeric units of the PA block contain one or more alkoxy groups derived from esterification of the un-acrylated hydroxy groups.

24. The thermoplastic block copolymer of claim 17, wherein the monomer B is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer.

25. The thermoplastic block copolymer of claim 17, wherein the monomer B is selected from the group consisting of styrene, α

-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, radically polymerizable plant oils, and mixtures thereof.

26. The thermoplastic block copolymer of claim 25, wherein the monomer B is radically polymerizable plant oil selected from the group consisting of soybean oil, linseed oil, corn oil, flax seed oil, and rapeseed oil.

27. The thermoplastic block copolymer of claim 26 further comprising at least one PC block, wherein PC represents a polymer block comprising one or more units of monomer C, with monomer C being a radically polymerizable monomer.

28. The thermoplastic block copolymer of claim 17, wherein the block copolymer has a molecular weight ranging from 5 to 10 MDa.

29. The thermoplastic block copolymer of claim 17, wherein the PA block has a glass transition temperature (Tg) below 0°

C.

30. A thermoplastic statistical copolymer having a general formula of:

[A_i-B_j-C_k]_q,

wherein;

A represents monomer A, which is an acrylated polyol monomeric unit having different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol;

B represents monomer B, which is a radically polymerizable monomer;

C represents monomer C, which is a radically polymerizable monomer;

provided that the monomer B is different than the monomer A, and the monomer C is different than the monomer A or monomer B;

i,j, and k are average number of repeating units of monomer A, monomer B, and monomer C, respectively, such that i and j are each greater than 0 and less than 1, k is 0 to less than 1, provided that i+j+k=1; and

q represents the number average degree of polymerization and ranges from 10 to 100,000.

31. The thermoplastic statistical copolymer of claim 30, wherein the acrylated polyol monomeric unit contains one or more conjugated sites.

32. The thermoplastic statistical copolymer of claim 30, wherein the polyol of the monomer A is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol, talose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldotriose, aldose, allose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose, lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose, tetrose, triose, xylose, amylopectin, and stereoisomers thereof.

33. The thermoplastic statistical copolymer of claim 30, wherein the polyol of the monomer A is glycerol.

34. The thermoplastic statistical copolymer of claim 30, wherein the polyol of the monomer A is sorbitol.

35. The thermoplastic statistical copolymer of claim 30, wherein the polyol of the monomer A is dextrose.

36. The thermoplastic statistical copolymer of claim 30, wherein one or more acrylated polyol monomeric units of the monomer A contain one or more alkoxy groups derived from esterification of the un-acrylated hydroxy groups.

37. The thermoplastic statistical copolymer of claim 30, wherein the monomer B and the monomer C, if present, are each independently vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomers, a monomer with reactive functionality, or a crosslinking monomer.

38. The thermoplastic statistical copolymer of claim 30, wherein the monomer B and the monomer C, if present, are each independently styrene, α

-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, radically polymerizable plant oils, or mixtures thereof.

39. The thermoplastic statistical copolymer of claim 30, wherein the radically polymerizable plant oil is selected from the group consisting of soybean oil, linseed oil, corn oil, flax seed oil, and rapeseed oil.

44. A method of making a thermoplastic copolymer or block copolymer, comprising:

providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups,

wherein the acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol; and

polymerizing the acrylated polyol composition through controlled radical polymerization, to form the thermoplastic copolymer or block copolymer.

45. The method of claim 44, wherein said providing an acrylated polyol composition comprises:

reacting a polyol with an acrylic reagent in a stoichiometric ratio of the acrylic reagent to the polyol ranging from 1 to 3.

46. The method of claim 45, wherein said reacting is carried out at a temperature of 30 to 130°

C.

47. The method of claim 45, wherein said acrylic reagent is an unsaturated carboxylic acid or acidic halide selected from the group consisting of acrylic acid, acryloyl chloride, methacrylic acid, and other acid or acidic halide terminated with a vinyl.

48. The method of claim 44, wherein said polymerizing is carried out to produce the thermoplastic copolymer or block copolymer having a linear or branched-chain structure.

49. The method of claim 44, wherein said polymerizing is carried out under conditions effective to produce the thermoplastic copolymer or block copolymer with a molecular weight of at least 1 KDa without gelation.

50. The method of claim 44, wherein said polymerizing is carried out under conditions effective to produce the thermoplastic copolymer with a molecular weight of 50 KDa to 10 MDa without gelation.

51. The method of claim 44, wherein said polymerizing is carried out by atom transfer radical polymerization (ATRP), in the presence of a solvent, a catalyst, a counter catalyst, an initiator, and a ligand.

52. The method of claim 44, wherein said polymerizing is carried out by reversible addition-fragmentation chain-transfer polymerization (RAFT), in the presence of a free radical initiator, a solvent, and a chain transfer agent.

53. The method of claim 52, wherein said polymerizing is carried out at a temperature of 50 to 120°

C.

54. The method of claim 52, wherein said solvent is selected from the group consisting of toluene, THF, chloroform, cyclohexane, dioxane, dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentnaol, chlorobenzene, dichloromethane, diethylether, tert-butanol, 1,2,-dichloroethylene, diisopropylether, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropylalcohol, isoamylalcohol, methanol, pentane, n-propylacohol, pentachloroethane, 1,1,2,2,-tetrachloroethane, 1,1,1,-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, glycerol, and a mixture thereof.

55. The method of claim 54, wherein said solvent is methanol,

glycerol, or a mixture thereof.

56. The method of claim 52, wherein said polymerizing is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 1% to 90%.

57. The method of claim 52, wherein the free radical initiator is selected from the group consisting of benzoyl peroxide and azobisisobutyronitrile.

58. The method of claim 52, wherein the chain transfer agent is a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or a xantate compound capable of reversible association with polymerizable free radicals.

59. The method of claim 52, wherein the chain transfer agent is 1-phenylethyl benzodithioate, 1-phenylethyl 2-phenylpropanedithioate, or dibenzyl carbonotrithioate.

60. The method of claim 44, wherein the polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxytriol, talose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldotriose, aldose, allose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, gulose, hexose, idose, ketohexose, ketose, lactose, lyxose, maltose, mannose, pentose, ribose, saccharose, sucrose, talose, tetrose, triose, xylose, amylopectin, and stereoisomers thereof.

61. The method of claim 60, wherein the polyol is glycerol.

62. The method of claim 61, wherein the average degree of acrylation ranges from 1.001 to 2.9.

63. The method of claim 61, wherein the average degree of acrylation ranges from 1.001 to 1.25.

64. The method of claim 60, wherein the polyol is sorbitol.

65. The method of claim 64, wherein the average degree of acrylation ranges from 1.001 to 3.

66. The method of claim 60, wherein the polyol is dextrose.

67. The method of claim 66, wherein the average degree of acrylation ranges from 1.001 to 3.

68. The method of claim 44 further comprising reacting the thermoplastic copolymer or block copolymer with an organic acid to esterify the un-acrylated hydroxy groups in one or more acrylated polyol monomeric units.

69. The method of claim 68, wherein the organic acid is formic acid, acetic acid, hexanoic acid, ethanoic acid, or propanoic acid.

70. The method of claim 44, wherein said polymerizing is carried out in the presence of a solvent, a catalyst, a counter catalyst, a macromolecular initiator, and a ligand to form the thermoplastic block copolymer.

71. The method of claim 70 further comprising

providing a radically polymerizable monomer different than the acrylated polyol monomeric unit;

and

polymerizing the radically polymerizable monomer through atom transfer radical polymerization (ATRP) with the formed thermoplastic block copolymer as a macromolecular free radical initiator to add an additional block to the thermoplastic block copolymer.

72. The method of claim 44, wherein said polymerizing is carried out in the presence of a free radical initiator, a solvent, and a macromolecular chain transfer agent to form the thermoplastic block copolymer.

73. The method of claim 72 further comprising

providing a radically polymerizable monomer different than the acrylated polyol monomeric unit;

and

polymerizing the radically polymerizable monomer through reversible addition-fragmentation chain-transfer polymerization (RAFT) with the formed thermoplastic block copolymer as a macromolecular chain transfer agent to add an additional block to the thermoplastic block copolymer.

74. The method of claim 44 further comprising

chemically modifying the thermoplastic copolymer or block copolymer with a crosslinking agent, allowing the thermoplastic copolymer or block copolymer to undergo a crosslinking reaction at an elevated temperature.

75. The method of claim 44 further comprising

chemically modifying the thermoplastic copolymer or block copolymer with a reagent to confer an acidic or basic functionality to the thermoplastic copolymer or block copolymer, making the thermoplastic copolymer or block copolymer a pH adjusting agent.

76. The method of claim 44 further comprising

chemically modifying the thermoplastic copolymer or block copolymer with a reagent to confer a biocidic functionality to the thermoplastic copolymer or block copolymer, making the thermoplastic copolymer or block copolymer a biocide agent.

77. A method of preparing a thermoplastic statistical copolymer, said method comprising:

providing monomer A, which is an acrylated polyol monomeric unit having different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of the hydroxyl groups of the polyol;

providing a radically polymerizable monomer, represented by B; and

polymerizing monomer A and monomer B simultaneously, via reversible addition-fragmentation chain-transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer.

78. The method of claim 77 further comprising, prior to said polymerizing:

providing a radically polymerizable monomer, represented by C, wherein monomer C is different than monomer A or monomer B, wherein said polymerizing comprises polymerizing monomer A, monomer B, and monomer C simultaneously, via RAFT, in the presence of the free radical initiator and the chain transfer agent to form the thermoplastic statistical copolymer.

79. The method of claim 77, wherein the polyol of the monomer A is glycerol.

80. The method of claim 77, wherein the polyol of the monomer A is sorbitol.

81. The method of claim 77, wherein the polyol of the monomer A is dextrose.

82. The method of claim 77, wherein the monomer B is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer.

83. The method of claim 77, wherein the monomer B is selected from the group consisting of styrene, α

-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof.

84. The method of claim 77, wherein the monomer C is radically polymerizable plant oil selected from the group consisting of soybean oil, linseed oil, corn oil, flax seed oil, and rapeseed oil.

85. The method of claim 77 further comprising reacting the thermoplastic statistical copolymer with an organic acid to esterify the un-acrylated hydroxy groups in one or more acrylated polyol monomeric units.

86. The method of claim 85, wherein the organic acid is formic acid, acetic acid, hexanoic acid, ethanoic acid, or propanoic acid.

88. The asphalt composition of claim 86, wherein the crumb rubber is a ground tire rubber.