Quaternary organosilane-ester/amide compounds and applications thereof. TECHNICAL FIELD

[001] The present disclosure generally relates to a class of reactive silane compounds, and more specifically to quaternary organosilane-ester/amide compounds or mixture of such compounds, which have a variety of uses including additives for warm-mix asphalt formulations.

[002] The present disclosure also provides a process for preparing the quaternary organosilane-ester/amide compounds or mixtures thereof.

BACKGROUND

[003] It is known in the art to heat aggregates to 150-170°C to remove water and mix with hot bitumen (also sometimes referred to as asphalt or asphalt binder) at 150-170°C in the mixing chambers of a drum mix plant,a pug mill batch mix plant, or a dual mixer. Additives can be added to the aggregate or bitumen to improve bonding of the bitumen to aggregate and various physical performance parameters of the final hot mix asphalt (HMA).

[004] The prepared HMA is compacted for surface paving at around 120- 135°C. For the past two decades, many technologies have evolved to prepare the asphalt/bitumen mix at lower temperatures. For instance, U.S. Patent No. 7,297,204 is directed to mixing at a lower temperature and to ensure the workability (flow) and compact ability at a reduced temperature (e.g., 15-35°C lower than customary) at the paving stage.

[005] Additional efforts have been tried to expand the bitumen by water injection of 1 - 4% on the bitumen weight (24 March 2008, Warm Mix Asphalt: Best Practices, NAP A 53rd Annual Meeting - Brian D. Prowell). Addition of water containing zeolite or fillers and water-in-oil emulsion in collar section in the mixing zone are also known in the art. However, it has been noted that the presence of water results in lower compressive strength and poor tensile strength ratio (TSR) for Marshall Mix Design or Super Pave Mix Design.

[006] Further, combinations of emulsifiers and additives have been added to improve wetting & lubrication to achieve the objective of 15-35°C lower temperature asphalt mix preparation and compaction. Typical chemical additive compositions that are known in the art include mixtures of amines, polyamines, amidoamines, Fischer Tropsch waxes, polyethylene waxes, tall oil, castor oil and other similar fatty acids and their derivatives.

[007] However, a class of fatty acid derivatives that have not been previously explored as effective lubricants for warm-mix asphalt (WMA) include estolides, oligoester compositions derived from fats and oils. An estolide structure is identified by an ester linkage of one fatty acyl molecule to the alkyl backbone of another fatty acid fragment. The generic formula (Formula I) below depicts the basic nomenclature of an estolide illustrating the ester linkage, a capping fatty acid, and the estolide number (EN). The EN indicates the extent of oligomerization of the molecule.

Formula I

[008] There are a broad range of estolides, both natural and synthetic, that have been found to serve as emulsifiers, rheology modifiers and lubricating agents in cosmetics, inks, textiles etc. US patent 4,428,850 describes the incorporation of estolides in railway diesel engine lubricating oil for improved defoaming, while US patent 6,3 1 6,649 describes biodegradable estolides for use as a lubricant base stock.

[009] While surfactant based technologies have proven to be effective, they are known to suffer from poor wet tensile strength due to increased moisture susceptibility. The increased moisture susceptibil ity is likely due to the residual moisture on the aggregate surface that does not fully evaporate at WMA preparation temperatures. Th is leads to poorer wetting and coating of bitumen on the aggregate surface, thereby resulting in a weak interface prone to moisture damage.

[0010] As such, there remains a need for suitable chemical additive compositions that not only allow for lower mixing, laying and compaction temperatures for asphalt pavements, but also offer an increased resistance to moisture damage.

SUMMARY

[0011] The present disclosure satisfies at least some of the aforementioned needs by providing, in one aspect, quaternary organosilane - ester/amide compounds (or mixtures thereof) of Formula II:

Formula II

wherein,

Y is independently selected from moieties that hydrolyze to liberate a mono or poly hydroxy compound, OH or a halogen;

Ri _; R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted C 1.C4 alkyl;

W ) , W ₂ , and W ₃ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C4 hydrocarbon;

Z is a bond (i.e., W i is directly attached to W ₂ ), O, o NR;

R is a C 1-C4 alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion;

R4 is selected from a fatty acid group or a derivative thereof of the formula R'-COOH , wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ] -C ₂₃ hydrocarbon, Formula 111 or Formula IV Formula III Formula IV wherein:

A] and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ i hydrocarbon;

R ₅ is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i -C ₂ 3 hydrocarbon;

R ₆ and R are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C1-C21 hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10); in certain preferred embodiments p comprises a value from 1 to 5.

[0012] In another aspect, the present disclosure provides a process for preparing compounds (or mixtures thereof) of Formula II.

[0013] In yet another aspect, the present disclosure provides an asphalt composition, comprising: an asphalt binder; an aggregate; and from 0.01 % to 20 % wt of at least one compound according to claim I based on the weight of the asphalt binder.

[0014] The present disclosure provides a water-based asphalt mineral composition and a foamed asphalt binder composition.

[0015] In another aspect, the present disclosure provides a process for the preparation of an asphalt composition and a foamed asphalt binder composition

[0016] These and other features, aspects, and advantages of the present subject matter will become better understood with reference to the fol lowing description and appended claims. This Summary is provided to introduce a selection of concepts in a simpl ified form. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. DETAILED DESCRIPTION

[0017] The present disclosure will be described more fully hereinafter. Indeed, the present disclosure can be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. As used in the specification, and in the appended claims, the singular forms "a", "an", "the", include plural referents unless the context clearly dictates otherwise.

[0018] In the structural formula given herein and throughout the present disclosure, the following terms have the indicated meaning, unless specifically stated otherwise.

[0019] The term "optionally substituted" as used herein means that the group in question is either unsubstituted or substituted with one or more of the substituents specified. When the group in question is substituted with more than one substituent, the substituent may be same or different.

[0020] "Halo" or "Halogen", alone or in combination with any other term means halogens such as chloro (CI), bromo (Br), fluoro (F) and iodo (I).

[0021] The term "alkyl" refers to a saturated or an unsaturated, cyclic, straight chain or branced, substituted or unsubstituted hydrocarbon chain having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 1 9, 20, 21 , 22 or 23. This term is exemplified by groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl n-hexyl, n- decyl, tetradecyl, and the l ike which optionally carries one or more substituents, preferably one to two, each independently selected from CI, Br, F, 1, OH.

[0022] M refers to counter anion.

[0023] Accordingly, the present disclosure provides quaternary organosilane- ester/amide compounds or mixture of such compounds, which are useful in a variety of applications including use as additives for warm-mix asphalt formulations. Compounds or mixtures thereof, in accordance with certain embodiments of the present disclosure, serve the dual purpose of significantly increasing the moisture resistance of asphalt pavements, while simultaneously decreasing the mixing, laying and compacting effort to enable warm-mix asphalt (WMA) preparation. Compounds or mixtures in accordance with embodiments of the present disclosure have been found to effectively improve mixing and compaction of pavements at temperatures lower than those associated with conventional hot mix asphalt (HMA), while simultaneously improving moisture resistance of the pavements.

[0024] In one aspect, the present disclosure provides a class of reactive quaternary organosilane-ester/amide compounds or mixtures thereof that can be derived from fatty acids or estolides. Compounds and mixtures thereof in accordance with certain embodiments of the present disclosure not only serve as effective chemical additives for warm-mix asphalt (WMA) preparations by significantly improving the wetting and coating during asphalt mix preparation, but also significantly improve the moisture resistance of the final pavement by forming a chemically bound organic layer on the aggregate surface.

[0025] The chemically bound organic layer makes the aggregate surface significantly more compatible with the incoming bitumen, thereby forming a stronger aggregate- bitumen interface that is less susceptible to moisture ingress.

[0026] The present disclosure provides a quaternary organosilane-ester/amide compounds (or mixtures thereof) of Formula II:

Formula I I

wherein,

Y is independently selected from moieties that hydrolyze to l iberate a mono or poly hydroxy compound, OH or a halogen;

Ri R.2 and 3 are independently selected from a straight chain or branched, substituted or unsubstituted C ]_C ₄ alkyl;

W ] , W ₂ , and W3 are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C4 hydrocarbon; Z is a bond (i.e., Wj is directly attached to W ₂ ), O, or NR.

R is a Ci.C ₄ alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂₃ hydrocarbon, Formula III or Formula IV

Formula III Formula IV wherein:

A I and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i-C ₂ i hydrocarbon;

R is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C23 hydrocarbon;

R.6 and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ i hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 1 0); in certain preferred embodiments p comprises a value from 1 to 5.

[0027] In certain embodiments in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of Formula II are provided as follows:

R. Formula II

wherein,

Y is independently selected from the group consisting of -OR, -0(CH ₂ CH ₂ 0) ₀ H, - 0(CH ₂ CHCH ₃ 0) ₀ H, (CH ₃ OCH ₂ CH ₂ 0), (CH ₃ CH ₂ OCH ₂ CH ₂ 0), and a halogen; wherein o is an integer from 1 to 10.

Ri R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted C].C ₄ alkyl, wherein Ri , R ₂ and R ₃ are optionally substituted wiuV halogen, OH;

Wi , W ₂ , and W ₃ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C ₄ hydrocarbon;

Z is a bond, O, or NR;

R is a Ci.C ₄ alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion, selected from the group consisting of chloride, bromide, fluoride, and iodide;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon, Formula I I I or Formula IV

Formula III Formula IV wherein:

A I and A ₂ are independently selected from a saturated or an unsaturated, cycl ic, straight chain or branched, substituted or unsubstituted C ] -C ₂ i hydrocarbon;

R5 is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C |-C ₂₃ hydrocarbon; R ₆ and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ i hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10); in certain preferred embodiments p comprises a value from 1 to 5.

[0028] In certain embodiments in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of Formula II are provided as follows:

wherein,

Y is independently selected from moieties that hydrolyze to liberate a mono or poly hydroxy compound, OH or a halogen

Ri R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted Ci.C ₄ alkyl wherein Ri , R ₂ and R ₃ are optionally substituted with halogen, OH;

Wi , W ₂ , and W ₃ are independently selected from -(CH ₂ ) _n - , where n is 1 , 2, 3, or 4;

Z is a bond, O, or NR;

R is a C 1 -C4 alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion, selected from the group consisting of chloride, bromide, fluoride and iodide;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C23 hydrocarbon, Formula III or Formula IV

Formula III Formula IV wherein:

A I and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i-C ₂ i hydrocarbon;

R5 is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci -C ₂₃ hydrocarbon;

R ₆ and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C] -C ₂ i hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10) in certain preferred embodiments p comprises a value from 1 to 5.

[0029] In yet another embodiment in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of formula II are provided as follows:

Formula I I

wherein,

Y is independently selected from CI or OR,

Ri R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted C | .C ₄ alkyl wherein Ri , R ₂ and R ₃ are optionally substituted with halogen, OH;

W ) , W ₂ , and W ₃ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C4 hydrocarbon;

Z is a bond, O, or NR;

R is a C 1.C4 alkyl or H;

X is selected from O or NH; a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M ^~ is a counter anion, selected from the group consisting of chloride, bromide, fluoride and iodide;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂₃ hydrocarbon, Formula III or Formula IV

Formula III Formula IV

wherein:

Ai and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C I -C ₂ I hydrocarbon;

R ₅ is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂₃ hydrocarbon;

Re and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C| -C ₂ i hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10); in certain preferred embodiments p comprises a value from 1 to 5.

[0030] In another embodiment in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of formula II are provided as follows:

Formula I I wherein,

Y is independently selected from CI or OR,

Ri _; R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted C1.C4 alkyl wherein Rj , R ₂ and R ₃ are optionally substituted with halogen, OH;

Wi , W ₂ , and W ₃ are independently selected from -(CH ₂ ) _n - , where n is 1 , 2, 3, or 4; Z is a bond (i.e., Wi is directly attached to W ₂ ), O, or NR;

R is a C i.C ₄ alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion, selected from the group consisting of chloride, bromide, fluoride and iodide;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i -C ₂₃ hydrocarbon, Formula III or Formula IV

Formula H I Formula IV

wherein:

A i and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C21 hydrocarbon;

R5 is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C | -C ₂₃ hydrocarbon, or OH;

R ₆ and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C21 hydrocarbon;

p is a value selected from 1 to 1 0 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 1 0); in certain preferred embodiments p comprises a value from 1 to 5. [0031] In one aspect of the present disclosure, the quaternary organosilane-ester/amide compounds can be formed from fatty acids (or derivatives thereof) and/or estolides with a free acid group (or derivatives thereof), wherein the fatty acid or its derivative and/ or the estolide or its derivative are treated with a functional ized amine species (preferably a tertiary amine species) to form an amine adduct. The tertiary amine functional group of the amine adduct can be subsequently quaternized using suitable organosi lanes. If the amine species are not tertiary in nature, they can be alkylated to tertiary state via common alkylating agents at any stage prior to the quaternization.

[0032] In accordance with certain embodiments of the present disclosure, a tertiary amine can be obtained from a secondary amine or a primary amine. Non-limiting examples include monoethanolamine, diethanolamine, monomethylethanolamine, 2- (2aminoethoxy)ethanol, aminoethylethanolamine. Non-limiting examplesof tertiary amines include triethanolamine,2-{[2-(Dimethylamino)ethyl]methylamino}ethan ol, dimethylethanolamine, N-methyldiethanolamine, dimethylaminopropylamine, dimethylaminobutylamine, aminopropylmorpholine, N,Ndimethyl-2(2- aminoethoxy)ethanol, alkanolamines and substituted propylamines.

[0033] Non-limiting examples of organosilane are 3-chloropropyltrimethoxysilane,3- chloropropyltriethoxysilane,(3-chloropropyl)dimethoxy(methyl )silane,(3- chloropropyl)diethoxy(methyl)silane,chIoromethyltrimethoxysi lane,chloromethyltrietho xysilane,chloromethylmethyldimethoxysilane,chloromethylmethy ldiethoxysilane and the like

[0034] The fatty acid compound or a fatty acid group, in accordance with embodiments of the present disclosure can be of the form of Formula II I, Formula IV or R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C23 hydrocarbon. Further, the term "fatty acid compound or fatty acid group" is intended to cover fatty acids per se or derivatives thereof. The term "derivative" as used herein, in accordance with embodiments of the present disclosure, is to be understood as a compound wherein the -COOH group of the fatty acid is. functional ized in such a way that it wi l l return to the -COOFI group upon treatment, for example hydrolysis. Non-limiting examples of fatty acid derivatives include acid chlorides, esters, anhydrides and amides. More specifically, the fatty acid compound or the fatty acid group, or derivatives thereof contain groups which are amenable to typical reactions such as esterification and amidation.

[0035] Non-limiting examples of fatty acids include ricinoleic acid, 12-hydroxystearic acid, meadowfoam oil, vernolic acid, lesquerella oil, epoxystearic acid, 2-hydroxy-9- cisoctadeconoic acid, l O-hydroxy-2-decenoic acid, 9, 10- dihydroxyoctadecanoic acid, phloinolic acid, lauric acid, stearic acid, and palmitic acid, and combinations thereof, or derivatives thereof.

[0036] Estolides are oligoesters derived from fats and oils. As noted above, the estolide structure is identified by an ester linkage of one fatty acyl molecule to the alkyl backbone of another fatty acid fragment. In accordance with certain embodiments of the present disclosure, the estolide is a compound according to Formula 111 or Formula IV formed by condensation of an oil, or a fatty acid or its derivative, or mixtures thereof,

Formula III Formula IV wherein:

Ai and A ₂ are independently selected from a saturated or an unsaturated, cycl ic, straight chain or branched, substituted or unsubstituted C i-C? i hydrocarbon;

R ₅ is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ] -C23 hydrocarbon;

R ₆ and R ₇ are independently selected from a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ] -C ₂ i hydrocarbon;

p is a value selected from 1 to 1 0 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 1 0)in certain preferred embodiments p comprises a value from 1 to 5. [0037] In certain embodiments in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of Formula 11 are provided as follows:

Formula II

wherein,

Y is independently selected from moieties that hydrolyze to liberate a mono or polyhydroxy compound, OH or a halogen;

Ri _; R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted Ci_C ₄ alkyl, wherein R] , R ₂ and R ₃ are optionally substituted with halogen, OH;

Wi , W ₂ , and W ₃ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C4 hydrocarbon;

Z is R;

R is a C ,_C ₄ alkyl or H;

X is selected from O or NH;

a is an integer from 1 to 3 (e.g., 1 , 2, or 3);

M is a counter anion, selected from the group consisting of chloride, bromide, fluoride and iodide;

R ₄ is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon, Formula 111 or Formula IV

Formula III Formula IV wherein:

A| and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci -C ₂ j hydrocarbon;

R ₅ is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci -C ₂₃ hydrocarbon;

R ₆ and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i -C ₂ i hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10); in certain preferred embodiments p comprises a value from 1 to 5.

[0038] In certain embodiments in accordance with the present disclosure, quaternary organosilane-ester/amide compounds (or mixtures thereof) of Formula II are provided as follows:

Formula II

wherein,

Y is independently selected from moieties that hydrolyze to liberate a mono or poly hydroxy compound, OH or a halogen;

R _{1 .} R ₂ and R ₃ are independently selected from a straight chain or branched, substituted or unsubstituted C ₁ .C4 alkyl wherein R] , R ₂ and R ₃ are optionally substituted with halogen, OH;

W i , W ₂ , and W ₃ are independently selected from a saturated or an unsaturated, cycl ic, straight chain or branched, substituted or unsubstituted C | -C ₄ hydrocarbon;

Z is O;

X is selected from O or NH;

a is an integer from I to 3 (e.g., 1 , 2, or 3); M is a counter anion, selected from the group consisting of chloride, bromide, fluoride and iodide;

R4 is selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C1 -C23 hydrocarbon, Formula III or Formula IV

Formula III Formula IV wherein:

Ai and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C1 -C21 hydrocarbon;

R5 is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C 1 -C23 hydrocarbon, or OH;

R ₆ and R ₇ are independently selected from H or a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C i -C ₂ | hydrocarbon;

p is a value selected from 1 to 10 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10); in certain preferred embodiments p comprises a value from 1 to 5.

[0039] In certain embodiments of the present disclosure, the fatty acids and/or estolides can have hydroxy, epoxy and other substitutions, or unsaturation, part of the hydrocarbon chain that does not participate in the previously described reaction scheme, but are amenable to additional functional ization nonetheless. Such additional functionaHzation of the fatty acid or estoiide can be carried out at any suitable stage during the synthesis.

[0040] Two exemplary generic structures of quaternary organosilane-ester/amide compounds in accordance with certain embodiments of the present disclosure include:

wherein R is a Ci-C ₄ alkyl or H; R ₄ is a moiety selected from a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C]-C ₂₃ hydrocarbon; Formul

Formula III Formula IV

[0041] In another aspect, the present disclosure also provides a process for preparing quaternary organosilane- estolide compounds of Formula II, or mixtures thereof. In certain embodiments of the present disclosure, preparation of quaternary organosilane- estolide compounds of Formula II, or mixtures thereof, can be accomplished by treating (i) a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cycl ic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon; or (ii) an estolide with an amine (preferably a tertiary amine) to obtain an am ine adduct. The amine adduct can then be reacted with an organosilane to obtain a quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof.

[0042] In accordance with certain processes of the present disclosure, amine species that are not tertiary in nature, can also be employed by alkylating to tertiary amine by common alkylating agents at any stage prior reacting with the organosilane to obtain the quaternary organosilane- ester/amide compound. [0043] Certain embodiments of the present disclosure provide a process for preparing a quaternary organosilane-estolide compound of Formula II, or mixtures thereof, wherein the estolide used in the process is a compound of Formula III or Formula IV:

Formula III Formula IV wherein:

A] and A ₂ are independently selected from a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ j hydrocarbon;

R.5 is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ 3 hydrocarbon;

R ₆ and R ₇ are independently selected from a saturated or unsaturated, cyclic, straight chain or branched, substituted or unsubstituted Ci-C ₂ i hydrocarbon; and

p is a value selected from 1 to 10.

[0044] In certain embodiments, the estolide is obtained by condensing an oil, or a fatty acid or its derivative, or mixtures thereof.

[0045] In yet another embodiment, the present disclosure provides a process for preparing a quaternary organosilane estolide compound of Formula I I, or mixtures thereof, comprising the steps of treating (i) a fatty acid selected from the group consisting of ricinoleic acid, 12-hydroxystearic acid, meadowfoam oil, vernolic acid, lesquerella oil, epoxystearic acid, 2-hydroxy-9-cisoctadeconoic acid, 10-hydroxy-2- decenoic acid, 9, 1 0- dihydroxyoctadecanoic acid, ph loinolic acid, lauric acid, stearic acid, and palmitic acid, derivatives thereof, and combinations thereof; or (i i) an estolide with an amine (preferably tertiary amine) to obtain an amine adduct; and reacting the amine adduct with an organosilane to obtain a quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof.

[0046] In certain embodiments of the present disclosure, a process for preparing a quaternary organosilane- estolide compound of Formula II, or mixtures thereof, is provided. The process can comprise the steps of treating (i) a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon; or (ii) an estolide with a tertiary amine obtained from a secondary amine or a primary amine selected from monoethanolamine, diethanolamine, monomethylethanolamine, 2- (2aminoethoxy)ethanol, aminoethylethanolamine, to form an amine adduct; and reacting the amine adduct with an organosilane to obtain a quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof.

[0047] In certain other embodiments of the present disclosure, a process for preparing a quaternary organosilane- estolide compound of Formula II, or mixtures thereof, is provided comprising the following steps: treating (i) a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon; or (ii) an estolide, with an amine (preferably tertiary amine) to form an amine adduct; and reacting the amine adduct with an organosilane selected from the group consisting of 3- chloropropyltrimethoxysilane, 3-chloropi pryltriethoxysilane, (3- chloropropyI)dimethoxy(methyl)si lane, (3-chloropropyl)diethoxy(methyl)silane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, chloromethylmethyldimethoxysilaneandchloromethylmethyldietho xysilane to obtain a quaternary organosilane-ester/amide compound of Formula 11, or mixtures thereof.

[0048] In another embodiment of the present disclosure, a process for preparing a quaternary organosilane- estol ide compound of formula I I, or mixtures thereof, is provided comprising the following steps: treating (i) a fatty acid group or a derivative thereof of the formula R'-COOH, wherein R' is a saturated or an unsaturated, cyclic, straight chain or branched, substituted or unsubstituted C ₁ -C23 hydrocarbon; or (i i) an estolide, with a tertiary amine selected from the group consisting of triethanolamine, dimethylethanolamine, N-methyldiethanoiamine, dimethylaminopropylamine, aminopropylmorpholine,N,Ndimethyl-2(2-aminoethoxy)ethano) and tetramethyldipropylenetriamine to form an amine adduct; and reacting the amine adduct with an organosilane to obtain a quaternary organosilane- ester compound of formula II, or mixtures thereof.

[0049] Processes in accordance with certain embodiments of the present disclosure yield not only a single type of a quaternary organosilane- ester/amide compound (e.g., a single resultant compound), but mixtures of such compounds according to Formula II. Hence it is to be understood that the present disclosure covers varying mixtures of quaternary organosilane- ester/amide compounds of formula II (and methods of synthesizing/producing such mixtures), besides a single type (compound) of quaternary organosilane- ester/amide compound formed by the processes the preparation.

[0050] In another aspect, the present disclosure provides quaternary organosilane- ester/amide compounds of Formula II (or mixtures thereof) used in asphalt formulations/compositions. Beneficially, the quaternary organosilane- ester/amide compounds of the present disclosure beneficially provide enhanced lubricity and moisture resistance when incorporated into asphalt pavement formulations. Characteristics of enhanced lubricity can be recognized via improvement in ease of mixing of asphalt binder and aggregate, as well as, via improved compaction and densification at lower than conventional hot mix temperatures, improved moisture resistance can be recognized via higher adhesion of asphalt binder (e.g., bitumen) in a standard water boil test, as well as, via improved Marshall Stability of the asphalt pavement.

[0051] Accordingly, the present disclosure provides and asphalt composition, suitable for a wide variety of asphalt paving applications, comprising: (i) an asphalt binder, (ii) an aggregate (or mixture of aggregates), and (iii) from 0.01 % to 20 % wt. of at least one quaternary organosilane- ester/amide compound of Formula I I, or mixtures thereof based on the weight of the asphalt binder. In certain embodiments, the amount of the at least one quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof can comprise from of at least about any of the following: 0.01 %, 0.05%, 1 %, and 2% wt. based on the weight of the asphalt binder; and/or at most about any of the following: 5%, 10% 15%, and 20 % wt. based on the weight of the asphalt binder. In certain embodiments, for instance, the amount of the at least one quaternary organosilane- ester/amide compound of Formula II (or mixtures thereof) can comprise from about 0.01 % to 10% wt. based on the weight of the asphalt binder.

[0052] In another aspect, the present disclosure also provides a water-based asphalt mineral compositions, suitable for a wide variety of asphalt paving applications, comprising: (i) an emulsion of an asphalt binder dispersed in water; (ii) a mineral aggregate (or mixture of aggregates); and (iii) from 0.01 % to 20 % wt. of at least one quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof based on the weight of the asphalt binder. In certain embodiments, the amount of the at least one quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof can comprise from of at least about any of the following: 0.01 %, 0.05%, 1 %, and 2% wt. based on the weight of the asphalt binder; and/or at most about any of the following: 5%, 10% 15%, and 20 % wt. based on the weight of the asphalt binder. In certain embodiments, for instance, the amount of the at least one quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof can comprise from about 0.01 % to 10% wt. based on the weight of the asphalt binder.

[0053] As used herein, the term "asphalt binder" can include bitumen, natural asphalt, oil residue of paving grade, plastic residue from coal tar distillation, petroleum pitch and coal tar. Asphalt binders are customarily used in paving constructions as a glue or binder for aggregate particles. That is, the asphalt binder is used to coat and bind aggregate particles together. These thermoplastic-like materials which soften when heated and harden upon cooling also exhibit viscoelastic properties (e.g., exhibit the mechanical characteristics of viscous flow and elastic deformation) over a certain temperature range. [0054] Asphalt binders, however, are highly complex and not well-characterized materials containing a variety of saturated and unsaturated aliphatic and aromatic compounds. These compounds can often include up to 150 carbon atoms. Particular asphalt binder compositions vary depending on the source of crude oil. Many of the compounds contain oxygen, nitrogen, sulfur, and other heteroatoms. Asphalt binders typically contains about 80% by weight of carbon; around 10% hydrogen; up to 6% sulfur; small amounts of oxygen and nitrogen; and trace amounts of metals such as iron, nickel, and vanadium. The molecular weights of the constituent compounds range from several hundred to many thousands.

[0055] A wide variety of asphalt binders may be used in accordance with certain embodiments of the present disclosure. In general, any paving grade asphaltic binder satisfactory for preparing paving compositions is contemplated as being useful. Paving grade asphaltic binders can have a wide range of penetration values ranging from as low as 30 or 40 dmm for the harder asphalts to 200 to 300 dmm at 25°C (100 g, sec.) for the softer asphalts. The most widely used paving asphalt binders according to embodiments of the present disclosure generally have a penetration at 25°C of about 60 to 100 dmm (e.g., 60-70, 70-80, or 80- 100 dmm). In preferred embodiments, however, the asphalt binder remains viscoelastic in all weather conditions.

[0056] In certain embodiments of the present disclosure, the asphalt binder comprises "Bitumen's" and/or "Modified Bitumens" which as used herein, are those which exhibit rheological properties that are appropriate for paving application under specific climatic condition such as those which conform to the Strategic Highway Research Program (SHPvP)) pavement binder specification. The bitumen component may be naturally occurring bitumens (such as Trinidad Lake Asphalt and the l ike), naturally occurring bituminous materials such as gilsonite and gi lsonite derivatives, or it can be produced by crude oil or petroleum pitches (such as asphalt) produced during cracking process and coal tar or blends of bituminous materials. The bitumen may also conform to specification of viscosity graded and/or penetration graded bitumens. [0057] Additives which are traditionally added to bitumen to produce a modified bitumen meeting performance-grade standards (such as SHRP) are suitable for use in certain embodiments according to the present disclosure. Such additives include, but are not limited to, natural rubbers, synthetic rubbers, plastomers, thermoplastic resins, thermosetting resins, elastomers, and combinations thereof. Examples of these additives include styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), poly-isoprene, polybutylenes, butadiene-styrene rubbers, vinyl polymers, ethylene vinyl acetate, ethylene vinyl acetate derivatives, and the like. Bitumens used in processes according to embodiments of the present disclosure can also contain recycled crumb rubber from recycled tires. In certain embodiments, the modified bitumen can contain at least one member selected from the group consisting of sulfur, sulfur-containing crosslinkers, acid modifiers such as tall oil acids, tall oil pitches, and phosphoric acid derivatives and combinations thereof. It is well within the ability of a skilled artisan to produce modified bitumen containing the noted additives.

[0058] Where desired, additional additives traditionally employed in the production of bitumen include styrene-butadiene-rubber latex, polyisoprene latex, salts, and the like can be included in certain embodiments according to the present disclosure. Such additives also include but are not limited to acid modifiers such as poly-phosphoric acid, crude and distil led tall oi l acids and tall oil pitches, and derivatives thereof, and wax modifiers such as ontan wax, beeswax, and Fisher-Tropsch waxes, etc.

[0059] In certain embodiments, anti-stripping additives like Lime or Hydrated Lime can be used either as powder mixed with aggregates or hydrated lime mixed with water and further mixed with aggregate to marinate at room temperature (e.g., for 10 to 30 hours, particularly 24 firs).

[0060] According to certain embodiments of the present disclosure, anti-stripping additives which are bitumen sol uble/dispersible such as organic amine or quaternary compounds, and silanes having a boiling point above 100°C can be used as anti- stripping additives in conjunction with quaternary organosilanes according to embodiments of the present disclosure and added to the asphalt binder (e.g., bitumen) or quaternary organosilane aqueous-based composition added to the asphalt binder for the formation of a stable foam that is exceptional for coating aggregates. The following examples are given for illustrative purposes only as useful compounds according to certain embodiments of the present disclosure. The following compounds, however, are not an exhaustive list of all useful compounds. That is, the following list of compounds is not limiting and similar compounds within a generic category meeting the 100°C boiling point criteria can be suitable if desired. For exemplary purposes, compounds such as an organic amine like di-methyl octadecyl amine, poly alkylene poly amines, fatty amido amines derived from Cj ₂ -C ₂₄ fatty acids, ethoxylated Ci ₂ -C ₂ 4 monoalkyl amines, etc, quaternary compounds like tri-methyl octa decyl ammonium chloride, dimethyl ethoxy poly 12 hydroxy stearate ammonium di-methyl sulfate salt, etc, silanes such as tri-methoxy propyl silyl octa decyl ammonium chloride, di-methoxy, hydroxy ethoxy propyl silyl octa decyl ammonium chloride, etc. The choice and use of these additives or others does not limit the spirit and scope of this disclosure.

[0061] Aggregates or mineral aggregates are coarse particulate materials used in construction, including sand, gravel, crushed stone, soil, slag, recycled concrete, or mixtures thereof. Mineral fillers are also aggregates which typically include dolomite, granites, river-bed crushed gravel, sandstone, limestone, basalt and other inorganic stones which can be added to the system.

[0062] The particular aggregates, sand, soils etc. used to form the asphalt formulations/compositions/asphalt -mineral compositions of the present disclosure are not critical as long as they have functional groups or reactive sites (e.g., silanol groups) on the surface that will bond with the silanols created by hydrolysis of the silane alkoxy groups of the compounds according to the present disclosure.

[0063] Aggregate used in paving materials and road construction, road rehabilitation, road repair, and road maintenance are derived from natural and synthetic sources. As in any construction process, aggregates are selected for asphalt paving appl ication based on a number of criteria, including physical properties, compatibi lity with the bitumen to be used in the construction process, availabi l ity, and abil ity to provide a finished pavement that meets the performance specifications of the pavement layer for the traffic projected over the design life of the project. Among the aggregate properties that are key to successful road construction is gradation, which refers to the percent of aggregate particles of a given size. For most load-bearing asphalt pavements, three gradations are common: dense-graded, gap-graded and open-graded. Dense-graded aggregate exhibit the greatest mineral surface area (per unit of aggregate). Open-graded aggregate largely consist of a single, large-sized (e.g., around 0.375 to 1.0 inch) stone with very low levels (typically less than about two percent of the total aggregate) of fines (material less than 0.25 inch) or filler (mineral material less than 0.075 mm). Gap-graded aggregate fall between dense-graded and open-graded classes. Reclaimed asphalt pavement (RAP) material generally reflects the gradation of the pavement from which the reclaimed material was obtained. If the original pavement was a dense-graded mix, the RAP generally will also be dense graded, although the filler content is generally observed to be lower than the design limits of the original aggregate specifications. Any such aggregates, alone or in combination, are suitable for certain embodiments of the present disclosure.

[0064] Any aggregate which is traditionally employed in the production of bituminous/asphalt paving compositions can be used in certain embodiments according to the present disclosure, including dense-graded aggregate, gap-graded aggregate, open-graded aggregate, stone-matrix asphalt, recycled asphalt paving, and mixtures thereof. In certain embodiments, aggregate which is not fully dried can be employed. In such embodiments, for instance, pre-treatment of the aggregate with an anti-stripping agent can optionally be performed. In certain embodiments, pre-treatment of the aggregate with solution (preferably in water) including at least one quaternary organosilane- ester/amide compound of Formula II (or mixtures thereof) provides excellent anti-stripping performance. Alternatively, however, the at least one quaternary organosilane- ester/amide compound of Formula II, or mixtures thereof can be mixed with or added to the asphalt binder. [0065] In yet another aspect, the present disclosure provides a composition (e.g., an organosilane composition) comprising one or more quaternary organosilane-ester/amide compounds, in accordance with certain embodiments of the present disclosure (i.e., quaternary organosilane-ester/amide compounds disclosed herein), suspended or dissolved in a solvent. In certain embodiments, the solvent can consist of water (i.e., water alone). Alternatively, the solvent can comprise one or more organic co-solvents (in addition to water). In certain embodiments, for instance, the organic co-solvents can include at least one alcohol. However, suitable organic co-solvents should preferably not negatively impact the stability of the quaternary organosilane-ester/amide compounds. Suitable co-solvents can generally include, but are not necessarily limited to, alcohols (preferably glycols), ketones, ester based solvents and polar acetate solvents.

[0066] Examples of alcohols include methanol, ethanol, benzyl alcohol, isopropanol and gylcols; examples of glycols that can be used according to certain embodiments of the present disclosure include, but are not limited to, ethylene glycol, propylene glycol, ether alcohols such as ethylene glycol, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; dialkyl ethers of ethylene, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monohexyl ether acetate, propylene glycol monoethyl ether, and propylene glycol dibutyl ether; the mono- and dialkylethers of diethylene glycol such as diethylene glycol monoethyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether acetate.

[0067] Examples of ketones that can be used according to certain embodiments of the present disclosure include, but are not limited to, acetone, acetophenone, butanone, cyclohexanone, ethyl isopropyl ketone, diacetone, isophorone, methyl isobutyl ketone, methyl isopropyl ketone, methylethyl ketone, methylamyl ketone, and 3-pentanone.

[0068] Examples of ester based solvents and acetate solvents that can be used according to certain embodiments of the present disclosure include, but are not limited to, benzyl benzoate, butyl acetate, methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, isoamyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, sec- butyl acetate, tert-butyl acetate, ethyl acetate, ethyl acetoacetate, methyl acetate propyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0069] In certain embodiments the composition can comprises from about 10 - 99 % by wt. (e.g., 10-95%, 20-90%, 40-80%, 45-75% by wt., etc.) of one or more quaternary organosilane-ester/amide compounds based on the total weight of the composition.

[0070] In certain embodiments, compositions including comprising one or more quaternary organosilane-ester/amide compounds, in accordance with certain embodiments of the present disclosure (i.e., quaternary organosilane-ester/amide compounds disclosed herein), can be provided in the form of a gel.

[0071] In certain alternative embodiments, however, the present disclosure provides a composition in the form of a powder. Such powder compositions can include one or more quaternary organosilane-ester/amide compounds in accordance with certain embodiments of the present disclosure (i.e., quaternary organosilane-ester/amide compounds disclosed herein). In certain such embodiments, powder-based composition can comprise from about 10-100% (e.g., 25-100%, 45- 100%, 75- 100%, 95-100% by wt., etc.) by weight of one or more quaternary organosilane-ester/amide compounds based on the total weight of the composition.

[0072] In another aspect, the present disclosure provides a foamed asphalt binder composition comprising: an asphalt binder, water, and one or more quaternary organosilane-ester/amide compounds in accordance with certain embodiments of the present disclosure (i.e., quaternary organosilane-ester/amide compounds disclosed herein). In certain embodiments, the foamed asphalt binder compositions are in the form of an expanded foam (e.g., liquid foam). In another embodiment, the asphalt binder comprises bitumen.

[0073] In yet another aspect, the present disclosure provides a process for preparation of a foamed asphalt binder composition comprising steps of heating an asphalt binder to a temperature sufficient to obtain a flowable asphalt binder, adding an organosilane composition comprising one or more quaternary organosi lane-ester/amide compounds in an aqueous-based solvent to the flowable asphalt binder, and mixing the flowable asphalt binder and the organosilane composition at a temperature sufficient to provide a foamed asphalt binder composition.

[0074] In certain embodiments, the aqueous-based solvent comprises a mixture of water and at least one alcohol as described previously. However, the aqueous-based solvent can also consist of water (i.e., water alone).

[0075] In certain embodiments, the step of adding the organosilane composition to the flowable asphalt binder comprises injecting the organosilane composition into the flowable asphalt binder. Preferably, the injecting step is performed via a nozzle, orifice, or valve.

[0076] In yet another aspect, the present disclosure provides a process for preparation of an asphalt composition comprising steps of heating an asphalt binder to a temperature sufficient to obtain a flowable asphalt binder, adding an organosilane composition comprising one or more quaternary organosi lane-ester/amide compounds (preferably in an aqueous-based solvent system) to the flowable asphalt binder, mixing the flowable asphalt binder and the organosilane composition at a temperature sufficient to provide a foamed asphalt binder composition, and mixing the foamed asphalt binder composition and aggregate to form the asphalt composition.

EXAMPLES

[0077] The present disclosure is further illustrated by the following examples, which in no way should be construed as being further limiting. One skilled in the art will readily appreciate that the specific methods and results described are merely illustrative, not limiting.

Example 1

[0078] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 800 grams of 12-hydroxystearic acid. To this solution, 1 .2 grams of p-toluenesulfonic acid was added as catalyst, and the temperature was gradually increased to 1 80°C over 1 0 minutes. Water of esterification was slowly removed from the system, till the acid value was noted to be 73. 200 grams of dimethylethanolamine was added and maintained at 210-230°C for 5 hours to obtain the amine adduct. Excess dimethylethanolamine and water of esterifi cation mixture was removed from the system, till the acid value was noted to be 4. 700 grams of the amine adduct was mixed with 351 grams of 3-chloropropyltriethoxysilane (diluted in 30 weight percent ethanol) and an additional 300 grams of ethanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a reaction conversion of 94.6 % with major products being a mixture of the compound(s) shown below with p = l and 2.

Example 2

[0079] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 800 grams of ricinoleic acid. To this solution, 1 .2 grams of p-toluenesulfonic acid was added as catalyst, and the temperature was gradually increased to I 80°C over 10 minutes. Water of esterification was slowly removed from the system, till the acid value was noted to be 76. 200 grams of dimethylethanolamine was added and maintained at 2 10-230°C for 5 hours to obtain the amine adduct. Excess dimethylethanolamine and water of esterification mixture was removed from the system, till the acid value was noted to be 5. 700 grams of the amine adduct was mixed with 345 grams of 3-chloropropyltriethoxysilane (diluted in 30 weight percent ethanol) and an additional 300 grams of ethanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a conversion of 94.2 % with major products being a mixture of the compound(s) shown below with p = 1 and 2.

Example 3

[0080] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 800 grams of ricinoleic acid. To this solution, 1 .2 grams of p-toluenesulfonic acid was added as catalyst, and the temperature was gradually increased to 180°C over 10 minutes. Water of esterification was slowly removed from the system over the course of one hour, till the acid value was noted to be 76. 200 grams of dimethylethanolamine was added and maintained at 2 I 0-230°C for 5 hours to obtain the amine adduct. Excess dimethylethanolamine and water of esterification mixture was removed from the system, till the acid value was noted to be 5. 700 grams of the amine adduct was mixed with 287.5 grams of 3- chloropropyltrimethoxysilane (diluted in 30 weight percent methanol) and an additional 300 grams of methanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a conversion of 93.4% with major products being a mixture of the compound(s) shown below with p = 1 and 2.

Example 4

[0081] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 800 grams of 12-hydroxystearic acid. To this solution, 1.2 grams of p-toluenesulfonic acid was added as catalyst, and the temperature was gradually increased to 180°C over 10 minutes. Water of esterification was slowly removed from the system, till the acid value was noted to be 70. 100 grams of dimethylaminopropylamine was added and maintained at 210-230°C for 5 hours to obtain the amine adduct. Excess water of esterification mixture was removed from the system, till the acid value was noted to be 1 3. 400 grams of the amine adduct was mixed with 243 grams of 3-chloropropyltriethoxysilane (diluted in 30 weight percent ethanol) and an additional 165 grams of ethanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a reaction conversion of 90.6 %, with major products being a mixture of the compound(s) shown below with p = 1 and 2.

Example 5

[0082] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 523 grams of distilled palm kernel fatty acid and 395grams of dimethylethanolamine. To this solution, 4.5 grams of p- toluenesulfonic acid was added as catalyst, and the temperature was gradually increased to 230°C. Water of esterification was slowly removed from the system till acid value was noted to be 12.2. Excess dimethylethanolamine was removed from the system under vacuum. 400 grams of the adduct was mixed with 300 grams of 3- chloropropyltrimethoxysilane (diluted in 30 weight percent methanol) and an additional 300 grams of methanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a conversion of 98.8 %.

Example 6

[0083] A two-liter, three-necked flask equipped with a condenser, stirrer, thermometer and a distillation head, was charged with 400 grams of ricinoleic acid and 400 grams of 12- hydroxystearic acid. To this solution, 1 .2 grams of p-toluenesulfonic acid were added as catalyst, and the temperature was gradually increased to 180°C over 10 minutes. Water of esterification was slowly removed from the, till the acid value was noted to be 73. 200 grams of dimethylethanolamine was added and maintained at 210- 230°C for 5 hours. Excess dimethylethanolamine and water of esterification mixture was removed from the system, till the acid value was noted to be 6.3. 680 grams of the adduct were mixed with 323 grams of 3- chloropropyltriethoxysilane (diluted in 30 weight percent ethanol) and an additional 290 grams of ethanol. The mixture was heated and maintained at 120°C and 70 psi for approximately 48 hours under constant stirring. A reaction conversion based on base titration for amine indicated a conversion of 95.5 %, with major products being a mixture of the compound(s)

Example 7

[0084] Basalt aggregates with gradation suitable for binder course was chosen. Standard aggregate and stone powder mix for these experiments with fol lowing composition - 20 mm passing 40%, 10 mm passing 30%, 6 mm passing 30% were used for preparation.

[0085] The mixes were mixed by hand. The aggregate and mixing vessels were preheated in an oven at approximately 10°C higher than desired/recorded temperature to account for cooling during mixing at room temperature. The bitumen was also heated to desired mixing temperature. Product of Example 1 was added to the hot PG 64-22 bitumen, which was used at 4.6 % by weight of aggregate. Parameters of ease of mixing and time for complete coating were recorded and are shown in Table 1. The "Ease of Mixing" was based on a scale ranging from 1 to 5, with 1 meaning easiest to freely mix by hand and a rating of 5 representative of extreme difficulty to freely mix by hand.

Example 8

[0087] Compacted moulds were prepared using 75 marshall blows on both sides. The aggregate mix design was as prepared as in example 7. Product of Example 1 was added to the hot PG 64-22 bitumen, which was used at 4.6% by weight of aggregate. Two compaction temperatures were tested, and the aggregate mix with binder was prepared at 20°C above the compaction temperature. Mixes that incorporate the quaternary organosilane ester/amide compound, or mixtures of the present disclosure, showed a marked improvement in compaction results as i llustrated by the data summarized in Table 2. [0088] Table 2: Ease of Compaction Using Marshall Hammer

Example 9

[0089] PG 64-22 asphalt samples were prepared to contain 0.0 % (Control mixture), 0.5 %, and 1 .0 % by weight of product of Example 1 . The prepared asphalt was added at 4.6 % on weight of the basalt aggregates and mixed at 120°C. The aggregate mix design was as in previous examples. The mixtures were cured for 120 minutes at 135°C as standard conditioning time and then allowed to cool to room temperature, after which water boiling tests according to ASTM D3625 (2005) - Standard Practice for Effect of Water on Bituminous-Coated Aggregate Using Boiling Water were conducted. The results are shown in Table 3.

[0090] Table 3: Water Boil Test to Demonstrate Enhanced Moisture Resistance

[0091] These results clearly il lustrate that the inclusion of quaternary organosi lane ester/amide compounds of Formula 11, or mixtures thereof results in a signi ficant increase in the amount of bitumen retained on the aggregate surface. Example 10

[0092] PG 64-22 asphalt samples with and without 0.1 % of Example 1 were prepared. The prepared asphalt was added at 4.6 % on weight of the basalt aggregates and mixed at 120°C. The aggregate mix design was as in previous examples. Marshall Stability of wet and dry compacted mixtures as well as stability ratios were determined according to ASTM D 1075/AASHTO T165 - Standard Test Method for Effect of Water on Compressive Strength of Compacted Bituminous Mixtures. The results are summarized in Table 4.

[0093] Table 4: Test for Effect of Water on Compressive Strength of Compacted Bituminous Mixtures

[0094] These results clearly illustrate that quaternary organosilane ester/amide compounds of Formula I I, or mixtures thereof provide better stability ratio than a composition without using the same, and are more resistant to moisture damage and ingress.

Example 11

[0095] 500 grams mix basalt aggregates having a particle size distribution as follows: 50% passed through a 20mm screen but retained on a 10mm screen, 50% retained through a 10 mm screen but retained on a 6mm screen. The 500 g of mix basalt aggregates was used for making cold mix asphalt. The control sample was prepared by mixing aggregates with 58.3 g rapid setting grade asphalt emulsion (containing 60% solids) by manual mixing. [0096] The rapid setting asphalt emulsion was mixed with 0.6 wt % of Example 5. The cold mix asphalt composition was prepared as described above. Both samples were dried for 48 hours in open air (atmospheric condition, temperatures range 25 to 40°C).

[0097] Table 5: Test for Effect of Moisture Damage in Asphalt Emulsion

[0098] These results illustrate that the samples containing Example 1 & 5 showed improved bonding of the asphalt to the aggregate.

[0099] Although the subject matter has been described in considerable detail with reference to certain preferred embodiments thereof, other embodiments are possible. As such, the scope of the appended claims should not be limited to the description of the preferred embodiment contained therein. That is, many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which this disclosure pertains having the benefit of the teachings presented in the foregoing description. Therefore, it is to be understood that the disclosure is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.