Inventors: Anatoly I. Kramer, Elizabeth A. Turner, Helge Jaensch

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 62/831,441, filed April 9, 2019, and European Patent Application No. 19183407.6, filed June 28, 2019, the disclosures of which are incorporated by reference.

FIELD

[0002] The present disclosure relates to wax compositions and methods for their production and use.

BACKGROUND

[0003] Wax compositions are hydrophobic organic substances that occur in petroleum or other oleaginous materials or are biosynthesized by plants and animals. They are usually malleable solids at room temperature. Wax compositions may comprise one or more higher alkanes, lipids and/or oils. Traditional wax compositions in common use include, for example, paraffin wax (e.g., slack wax), beeswax, and hydrogenated vegetable oils (e.g., soy wax). Petroleum-derived paraffinic waxes are particularly prevalent. Wax blends may also be used in certain applications.

[0004] The global wax market is projected to experience significant growth over the coming years. Waxes are in demand for making items such as, for example, candles, coatings, lubricants (e.g. , PVC extrusion lubricants), separating agents, food additives, pharmaceutical agents, and many other purposes. There is considerable variability among different wax sources. Consequently, certain wax compositions are better suited for some applications compared to others. Factors that may dictate the suitability of a wax composition for an intended application include, for example, viscosity, density, melting point, congealing point, burning properties as well as secondary performance factors influenced by these parameters.

[0005] Significant quantities of wax are used in the candle industry. Waxes having relatively high melting points, e.g. >50°C, may be desirable for free standing pillar candle making in order to maintain the candle’s form at ambient temperatures and to extend burn times. Container candles may utilize waxes with lower melting points, such as >45 °C. High- quality waxes are usually needed for both types of candles, as well as to maintain a uniform distribution of colorant and fragrance within the candle body. Conventional wax blends, including petroleum slack waxes, tend to be low quality and unsuitable for use in candle making because of their high oil content, poor burning characteristics (e.g., soot generation), unpleasant odor, low melting points and poor fragrance and colorant retention properties.

SUMMARY

[0006] In any embodiment, the present disclosure provides wax compositions. The wax compositions comprise (or consist of, or consist essentially of) a linear alpha olefin (LAO) dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, and a blending wax. The LAO dimer is formed by dimerization of one or more C14, or C16 to C20, or C24 LAOs. The wax compositions have melting points of 40°C or greater.

[0007] In any embodiment, the present disclosure provides candles. The candles comprise (or consist of, or consist essentially of) a wick, a blending wax, and an LAO dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, wherein the LAO dimer, the methyl paraffin, or any combination thereof and the blending wax are combined to form a wax composition. The wax composition defines a body of the candle, from which the wick extends. The LAO dimer is formed by dimerization of one or more C14, or C16 to C20, or C24 LAOs.

[0008] In still any embodiment, the present disclosure provides methods for forming a wax composition. The methods comprise (or consist of, or consist essentially of) providing an LAO dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, and combining the LAO dimer, the methyl paraffin, or any combination thereof with a blending wax in an amount sufficient to form a wax composition having a melting point of 40°C or above. The LAO dimer is formed by dimerization of one or more C14, or C16 to C20, or C24 LAOs.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following figures are included to illustrate certain aspects of the present disclosure, and should not be viewed as exclusive embodiments.

[0010] FIG. 1A is a low-temperature microscopy image showing the microstructure of an illustrative LAO wax of the present disclosure.

[0011] FIG. IB is a low-temperature microscopy image showing the microstructure of an illustrative low-melt paraffinic slack wax.

[0012] FIG. 1C is a low-temperature microscopy image showing the microstructure of an illustrative C28 methyl paraffin of the present disclosure. [0013] FIG. 2A is a differential scanning calorimetry plot of an illustrative C28 methyl paraffin of the present disclosure.

[0014] FIG. 2B is a differential scanning calorimetry plot of an illustrative low-melt paraffinic slack wax.

DETAILED DESCRIPTION

[0015] The present disclosure relates to wax compositions and, more specifically, to high- quality wax blends containing a blending wax in combination with LAO dimers containing a vinylidene group or a hydrogenated reaction product thereof and methods for production and use thereof.

[0016] As discussed above, there is a growing demand for waxes, especially high-quality waxes, such as those suitable for making candles. As a result of this high demand, wax shortages, especially high-quality wax shortages, are anticipated over the coming years. To compensate, interest in wax blends is increasing, particularly those including low-quality or less expensive waxes. However, many wax blends are not broadly suited for certain types of applications. For instance, wax blends formed from low-quality waxes (e.g., slack wax) tend to remain low quality, which may lead to weeping of oils, fragrances, colorants, or other components. Odor of conventional slack wax blends may also be problematic. As such, low- quality wax blends tend to have poor retention of uniform color and fragrance over an extended period of time, thereby making them unsuitable for candle making. Low melting points may also be problematic in some instances, particularly for forming candles with a mechanically stable structure.

[0017] The present disclosure demonstrates that certain abundant products of the chemical and petroleum industries may be suitable precursors for forming high-quality wax compositions (blends). More specifically, the present disclosure utilizes linear alpha olefins (LAOs) as a precursor for forming LAO dimers comprising a vinylidene group, which may be further hydrogenated to form the corresponding methyl paraffins as a reaction product. Trisubstituted olefin dimers may also be formed in the olefin dimerization process, and the trisubstituted olefin dimers and/or their corresponding hydrogenated reaction products (also a methyl paraffin) may be incorporated in the wax blends described herein. Both types of LAO dimers, the corresponding methyl paraffins of both types of LAO dimers, or any combination thereof may be blended with various waxes to form high-quality wax compositions, even when formulated with an otherwise low-quality wax. Surprisingly, such LAO dimers or methyl paraffins formed as a hydrogenated reaction product of such LAO dimers may allow the foregoing advantages to be realized. [0018] Specifically, LAO dimers containing a vinylidene group, or hydrogenated reaction products formed therefrom may provide wax compositions having melting points above 40°C when combined with a blending wax. Trisubstituted olefin dimers or their corresponding methyl paraffin reaction products may afford similar melting points when combined with a blending wax, either alone or in combination with LAO dimers comprising a vinylidene group and/or their hydrogenated reaction products. Surprisingly, such melting points may be obtained even when such LAO dimers or the methyl paraffins formed therefrom are blended with an otherwise low-quality wax. Melting points of the wax compositions may allow for the preparation of decorative candles that otherwise may require significant quantities of high- quality wax. That is, the LAO dimers or methyl paraffins described herein may allow otherwise low-quality waxes, such as petroleum slack wax, to be transformed (upgraded) into high- quality wax compositions. The melting points of the wax compositions described herein may be adjusted depending upon the ratio at which the blending wax and the LAO dimers and/or the methyl paraffins are combined with one another, thereby allowing tailoring to be realized for particular applications. Hydrogenation of the LAO dimers to produce the corresponding methyl paraffins only increases the melting point by 3-7°C, so it is particularly surprising that both LAO dimers containing a vinylidene group and/or a trisubstituted olefin group or a hydrogenated reaction product thereof are suitable to form wax compositions having a sufficiently high melting point, preferably 40°C or more. Moreover, at least some of the wax compositions described herein may provide good colorant and fragrance retention properties, which may be desirable for producing candles therefrom. Additionally, any embodiment of the present disclosure provide wax compositions that are stable, suitable for forming candles, and do not substantially elute (weep) oil. Further, wax compositions of the present disclosure may result in a clean-buming candle with characteristics of a high-quality candle, namely low soot and smoke production.

[0019] Unless otherwise indicated, ambient temperature (room temperature) is 25°C.

[0020] As used in the present disclosure and claims, the singular forms“a,”“an,” and“the” include plural forms unless the context clearly dictates otherwise.

[0021] The term“and/or” as used in a phrase such as“A and/or B” herein is intended to include“A and B,”“A or B,”“A,” and“B.”

[0022] For the purposes of the present disclosure, the new numbering scheme for groups of the Periodic Table is used. In said numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides). [0023] The term“hydrocarbon” refers to a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term“C _n ” refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer. Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic. When referenced with respect to an LAO, the term“C _n ” refers to a hydrocarbyl group bearing at least one double bond. Optional heteroatom substitution may be present in a hydrocarbyl group.

[0024] The terms“hydrocarbyl” and“hydrocarbyl group” are used interchangeably herein. The term“hydrocarbyl group” refers to any Ci-Cioo hydrocarbon group bearing at least one unfilled valence position when removed from a parent compound.

[0025] The term“alkyl” refers to a hydrocarbyl group having no unsaturated carbon-carbon bonds.

[0026] The term“alkenyl” refers to a hydrocarbyl group having a carbon-carbon double bond. The terms“alkene” and“olefin” are used synonymously herein. Similarly, the terms “alkenic” and“olefinic” are used synonymously herein. Unless otherwise noted, all possible geometric isomers are encompassed by these terms.

[0027] The terms“linear” and“linear hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side chain branching.

[0028] The term“linear alpha olefin (LAO)” refers to an alkenic hydrocarbon bearing a carbon-carbon double bond at a terminal (end) carbon atom of the main carbon chain.

[0029] The terms “branch,” “branched” and “branched hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a linear main carbon chain in which a hydrocarbyl side chain extends from the linear main carbon chain. The term“unbranched” refers to a straight-chain hydrocarbon or hydrocarbyl group.

[0030] The term“vinylidene” refers to an olefin moiety bearing two hydrogen atoms upon C-l and two hydrocarbyl groups upon C-2 of the olefin moiety.

[0031] The term“trisubstituted” refers to an olefin moiety bearing two hydrocarbyl groups upon a first carbon atom of the olefin moiety and one hydrocarbyl group and one hydrogen atom upon a second carbon atom of the olefin moiety, wherein the olefin moiety is non terminal. [0032] LAOs, which also may be referred to as terminal olefins or terminal alkenes, may be isolated from a petroleum refinery stream. Alternatively, they may be synthesized by several processes starting from low molecular weight feedstock materials, such as via oligomerization of ethylene or through byproduct isolation from the Fischer-Tropsch synthesis. LAOs are composed of a linear hydrocarbon chain, and have a chemical formula of C _x FL _x (x is an integer greater than or equal to 3, particularly an even integer greater than or equal to 4) with a double bond between C-l and C-2.

[0033] Wax compositions of the present disclosure may comprise an LAO dimer comprising a vinylidene group and/or a methyl paraffin formed from such LAO dimers in combination with a blending wax. In any embodiment, wax compositions of the present disclosure may comprise a blending wax and an LAO dimer comprising a vinylidene group and/or a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer. Such LAO dimers may be formed by dimerization of one or more C14, or C16 to C20, or C24 LAOs. The LAO dimers may be formed from LAOs of the same or differing lengths. In any embodiment, the resulting wax compositions may have a melting point of 40°C or greater. In some or any embodiment, the melting point may be 45 °C or greater.

[0034] In any embodiment, LAO dimers comprising a vinylidene group may comprise the sole olefin dimer product obtained from dimerization of one or more LAOs. In any embodiment, trisubstituted LAO dimers may be formed as well during dimerization of one or more LAOs. As such, trisubstituted LAO dimers may also be formed through dimerization of one or more C14 to C24 LAOs, wherein the trisubstituted LAO dimers may be formed from LAOs of the same or differing lengths. The amounts of trisubstituted LAO dimers that are formed during dimerization may be less than, greater than, or substantially equal to the quantities of LAO dimers comprising a vinylidene group that are formed. More typically, the trisubstituted LAO dimers are formed as a minor dimerization product in the embodiments described herein. After undergoing hydrogenation, the trisubstituted LAO dimers also form methyl paraffins suitable for use in the disclosure herein. When present, trisubstituted LAO dimers and/or methyl paraffin hydrogenated reaction products formed therefrom may allow wax compositions having melting points of 40°C or above or 45°C or above to be obtained.

[0035] Accordingly, in any embodiment, the wax compositions disclosed herein may further comprise a trisubstituted LAO dimer and/or a methyl paraffin formed from such trisubstituted LAO dimers in combination with the blending wax. That is, certain wax compositions of the present disclosure may comprise a mixture of an LAO dimer comprising a vinylidene group and trisubstituted LAO dimer and/or methyl paraffin hydrogenated reaction products formed therefrom. Such trisubstituted LAO dimers are described in further detail below.

[0036] In alternative embodiments of the present disclosure, wax compositions described herein may comprise a trisubstituted LAO dimer and/or a methyl paraffin comprising a hydrogenated reaction product of such trisubstituted LAO dimers in combination with the blending wax. Such trisubstitutetd LAO dimers may be formed by dimerization of one or more C14 to C24 LAOs. The trisubstituted LAO dimers may be formed from LAOs of the same or differing lengths. In any embodiment, the resulting wax compositions may have a melting point of 40°C or greater. In some or any embodiment, the melting point may be 45 °C or greater [0037] LAO dimers comprising a vinylidene group suitable for use in the disclosure herein may be synthesized by selective oligomerization of LAOs, particularly Cu to C24 linear alpha olefins. Particular catalyst systems may be chosen such that the LAO dimers are vinylidene olefins, which may undergo subsequent hydrogenation to form methyl paraffins. Minor to significant amounts of trisubstituted LAO dimers may be formed in some instances, with the amount formed being dependent upon the catalyst choice. The LAOs used for forming the LAO dimers of either type may be of the same or different chain lengths. In any embodiment, the LAOs may be predominately of the same chain length. In any embodiment, the LAOs may comprise a blend of two or more C14 to C24 LAOs, particularly LAOs having an even number of carbon atoms within this range. Such LAO dimers may be suitable for forming the wax compositions disclosed herein. In some or any embodiment, such LAO dimers of either type may undergo subsequent hydrogenation to form methyl paraffins that may also be suitable for use in the disclosure herein. Saturated methyl paraffins may be less reactive and have a higher melting point that the corresponding LAO dimer, typically by 3-7°C.

[0038] The reaction to form LAO dimers comprising a vinylidene group or a mixture of such LAO dimers in combination with a trisubstituted LAO dimer may be promoted by various metallocene catalyst systems, most preferably bis-cyclopentadienyl (or ligands isolobal to cyclopentadienyl) titanium, zirconium or hafnium metallocenes. In any embodiment, the cyclopentadienyl group is selected from the group consisting of indenyl, fluorenyl, cyclopental /; |naphthalenyl, cyclopenta[a]naphthalenyl, cyclopenta[/]phenanthrenyl, cyclopental b |anthracenyl, c y c 1 o pen La | a | a n th race n y 1 , indeno| 1 ,2-/;|anthracenyl, dibenzol /;,/; | fluorenyl, benzo|/;|lluorenyl, hydrogenated versions thereof, substituted versions thereof (e.g., having groups such as alkyls, aryls, halogens or hydroxy groups pendant and bound to the cyclopentadienyl), and heterocyclic versions thereof (meaning ring structures incorporating non-carbon atoms such as oxygen, nitrogen, sulfur, etc.). [0039] According to any embodiment of the present disclosure, catalyst systems suitable for oligomerizing LAOs into LAO dimers, particularly vinylidene or trisubstituted LAO dimers, may comprise a metallocene catalyst system, such as bis(cyclopentadienyl)zirconium(IV) dichloride (Cp ₂ ZrCl ₂ ) (Structure 1 below) in combination with a suitable activator.

Structure 1

Catalyst systems comprising the foregoing metallocene catalyst may selectively or predominantly produce LAO dimers having a vinylidene group extending from the main carbon chain. Greater than 99% vinylidene olefin dimers maybe produced in certain instances, with the remaining product constituting trisubstituted LAO dimers. The vinylidene moiety (group) in such LAO dimers may be hydrogenated to produce the corresponding methyl paraffin. Similarly, trisubstituted LAO dimers may be hydrogenated to afford similar methyl paraffins as well.

[0040] Alumoxanes, such as methyl alumoxane (MAO), may be suitable activators for the catalyst of Structure 1 and other metallocene catalysts discussed herein. Catalyst systems comprising a metallocene catalyst may contain a ratio of metallocene: alumoxane (or other activator) ranging from 1:10,000 to 10,000:1, or 1: 1,000 to 1,000: 1, or 1 :500 to 500: 1, or 1:250 to 250: 1, or 1 : 100 to 100: 1. The foregoing ratios represent M: .41 ratios, wherein A1 is the molar amount of aluminum in the alumoxane and M is the molar amount of metal in the metallocene catalyst. More preferably, the ratio may be an Al:Zr molar ratio ranging from 1 to 6 or 3 to 12.

[0041] Other suitable activators for the catalyst of Structure 1 and other metallocene catalysts discussed herein may include compounds containing a non-coordinating anion (NCA), especially borane and borate compounds. Particularly useful borane and borate compounds containing a non-coordinating anion or similar entity include, for example, B(C ₆ F ₅ ) ₃ , [PhNMe ₂ H] ⁺ [B(C ₆ F ₅ ) ₄ ]-, [Ph ₃ C] ⁺ [B(C ₆ F ₅ ) ₄ ]-, and [PhNMe ₂ H] ⁺ [B(CioF ₇ ) ]-.

[0042] A non-coordinating anion (NCA) is defined to mean an anion either that does not coordinate to a transition metal center or that does coordinate to a transition metal center, but only weakly. The term NCA is defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate, that contain an acidic cationic group and the non- coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. Typically, NCAs coordinate weakly enough that a neutral Lewis base, such as an olefin can displace it from the metal center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term non-coordinating anion includes neutral activators, ionic activators, and Lewis acid activators.

[0043] Particularly suitable NCAs may include, for example, N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, or any combination thereof.

[0044] Other metallocene catalysts that may be suitably used for forming the LAO dimers disclosed herein include, for example, bis-(n-propylcyclopentadienyl) zirconium(IV) dichloride (Structure 2), bis(l -butyl-3 -methylcyclopentadienyl) zirconium dichloride (Structure 3), Schwartz’s reagent (zirconocene chloride hydride, Structure 4), or rac- dimethylsilyl-bis-(tetrahydroindenyl) zirconium dimethyl (Structure 5). Other hydrocarbyl- substituted metallocenes may also be suitably used herein.

Structure 2 Structure 3

Structure 4 Structure 5

[0045] Still other suitable metallocene catalysts that may be used for synthesizing LAO dimers comprising a vinylidene group and/or trisubstituted LAO dimers may be found in commonly owned U.S. Patent Application Publication 2018/0282359, which is incorporated herein by reference in its entirety.

[0046] Additionally, other catalysts that may be suitably used for reacting LAOs to form the LAO dimers disclosed herein include molecular sieves, particularly medium-pore size zeolites (approximately 4 A to 7 A) such as ZSM-23, ZSM-35, ZSM-12, ZSM-48 and similar zeolite catalysts familiar to one having ordinary skill in the art. Particularly suitable ZSM-48 may have exhibit a S1O2: AI2O3 molar ratio ranging from 20 to 400, with higher activities being realized at lower molar ratios.

[0047] Reaction 1 below illustrates the general structure for a pair of LAOs and their subsequent dimerization to form an LAO dimer comprising a vinylidene group. Subsequent and optional hydrogenation to form the corresponding methyl paraffin is also shown in Reaction 1. Accordingly, for Reaction 1, R is an alkyl group having from 14 to 24 carbon atoms. The R groups in each LAO may be of the same length, or they may be of differing lengths.

Reaction 1

The formation of the corresponding trisubstituted olefin dimers and associated methyl paraffins is shown in Reaction 2 below, wherein indeterminate olefin geometry is indicated by a wavy bond. The R groups are defined in the same manner as Reaction 1.

Reaction 2

[0048] The LAO dimer resulting from Reaction 1 (LAO dimer comprising a vinylidene group) may be alternately characterized below as Structure 6, where R ¹ is an alkyl group having from 14 to 24 carbon atoms and R ² is an alkyl group having from 12 to 22 carbon atoms. The differing carbon count range for R ¹ and R ² results from the terminal C LCH unit derived from one of the LAOs. The corresponding methyl paraffins are shown in Structure 7, wherein R ¹ and R ² are defined as above.

Structure 6

Structure 7

[0049] Similarly, the LAO dimer resulting from Reaction 2 (trisubstituted LAO dimer) may be alternately characterized below as Structure 8, where R ³ and R ⁴ are independently alkyl groups having from 14 to 22 carbon atoms. Due to the manner in which the trisubstituted LAO dimers are presented in Structure 8, R ³ and R ⁴ are defined with the same carbon count range in this case. The corresponding methyl paraffins are shown in Structure 9, wherein R ³ and R ⁴ are defined as above.

Structure 8

Structure 9

[0050] Hydrogenation of both types of LAO dimers may be carried out in a slurry or fixed bed reactor system using a variety of Ni, Pt or Pd hydrogenation catalysts. Suitable hydrogenation conditions, hydrogenation catalysts, reactors and the like will be familiar to one having ordinary skill in the art.

[0051] Blending waxes suitable for forming the wax compositions disclosed herein may include, for example, petroleum slack wax, refined wax, semi-refined wax, scale wax, stearic acid wax, microcrystalline wax, beeswax, vegetable -based waxes such as soy and palm wax, synthetic waxes such as C20 ₊ LAO waxes and Fischer-Tropsch waxes, and various combinations thereof. Other types of blending wax may be suitable as well.

[0052] Petroleum slack wax (slack wax) is a generic term for a byproduct of a petroleum refining process that contains oil and wax. Slack wax is a complex combination of hydrocarbons obtained from a petroleum fraction by solvent crystallization {i.e. , dewaxing) or as a distillation fraction from a waxy crude. Slack wax is substantially comprised of saturated straight and branched chain hydrocarbons that predominantly have carbon numbers of C20 or greater. Slack wax is often in abundance where petroleum is processed, so it can be obtained cheaply.

[0053] In any embodiment, the blending wax in the wax compositions disclosed herein may comprise a slack wax with a free oil content of at least 2 wt. %, or at least 3 wt. % or at least 5 wt. %. The free oil content of the slack wax may be 35 wt. % or less or 20 wt. % or less. Suitable ranges of free oil in slack wax may include 2 wt. % to 20 wt. %, 10 wt. % to 20 wt. %, or 3 wt. % to 20 wt. %. Suitable slack wax may have a melting point in a range of 43°C to 66°C, for example from 50°C to 53°C. Slack waxes generally can have a color ranging from white to brown.

[0054] In any embodiment, the wax compositions of the present disclosure may comprise, for example, 5% to 50% by weight LAO dimers and/or methyl paraffins, wherein the remainder by weight is a blending wax, or 2% to 40% by weight LAO dimers and/or methyl paraffins. In any embodiment, the wax compositions may comprise 30 percent by weight LAO dimers and/or methyl paraffins. In still any embodiment, the wax compositions may comprise, for example, from 35 wt. % to 40 wt. %, or from 30 wt. % to 35 wt. %, or from 25 wt. % to 30 wt. %, or from 20 wt. % to 25 wt. %, or from 15 wt. % to 20 wt. %, or from 10 wt. % to 15 wt. %, or from 5 wt. % to 10 wt. %, or any other amount within any of the above ranges. Certain wax compositions may comprise only the LAO dimers, while other wax compositions may comprise only the methyl paraffins, and still other wax compositions may comprise a combination of the two in any ratio. Particular wax compositions may comprise the foregoing amounts of LAO dimers comprising a vinylidene group or a methyl paraffin formed therefrom.

[0055] In any embodiment, the viscosity index of the LAO dimers and/or the methyl paraffins may range from 160 to 250. In any embodiment, the viscosity index of the LAO dimers and/or the methyl paraffins may be 175. Other physical properties that may be used to characterize the wax compositions disclosed herein include, for example, needle penetration depth and viscosity.

[0056] The wax compositions of the present disclosure may be suitably used in various applications, such as in candles. Candles formed from a wax composition of the present disclosure may comprise a wick, a blending wax and a LAO dimer comprising a vinylidene group, a hydrogenated reaction product of the LAO dimers, or any combination thereof. The LAO dimers may be formed by dimerization of one or more C14 to C24 LAOs. The LAO dimers and/or methyl paraffins and the blending wax are mixed, blended or otherwise combined to form a wax composition, which may be used to define a body of the candle. The wick of the candle extends from the wax composition defining the body of the candle.

[0057] Optionally, candles formed according to the present disclosure may comprise a wax composition that further comprises a trisubstituted LAO dimer and/or a methyl paraffin formed from such trisubstituted LAO dimers in combination with the blending wax. Suitable trisubstituted LAO dimers and conditions for producing the corresponding methyl paraffins are provided hereinabove.

[0058] The relatively high melting points achieved by a blend of LAO dimers and/or the corresponding methyl parafffins and a blending wax according to the present disclosure may result in a high-quality candle. In any embodiment, the blending wax of the candle may be slack wax, which may be blended with LAO dimers and/or methyl paraffins synthesized from LAOs, as discussed above, to form a candle with a high melting point and a stable composition.

[0059] In any embodiment, the candle includes a fragrance or scent. Scents included may be an artificial fragrance or a scent derived from natural sources, or a combination of both. In any embodiment, the scent may be an essential oil, such as an oil derived from oranges, eucalyptus, peppermint, lavender, or cedarwood, or any combination thereof.

[0060] In any embodiment, the scent or fragrance may be present in a weight ratio of 1 : 18 to 1: 10 of the total weight of the LAO dimers and/or the corresponding methyl paraffins and blending wax. In any embodiment, the scent may be present in a weight ratio of 1 :75, 1:50, 1:25 or 1 :16. In addition to the ratios listed above, ratios or approximately the same as any of the listed ratios may also be found in any embodiment. In embodiments including a scent, the weight percentages of the LAO dimers and/or the methyl paraffins and blending wax described above may be adjusted to account for the addition of scent. For example, such candles may include 63% to 70% by weight blending wax, 27% to 30% by weight LAO dimers and/or methyl paraffins, and a non-zero amount of scent up to 10% by weight scent. Alternatively, the candle may include 72% to 80% by weight blending wax, 18% to 20% by weight LAO dimers and/or methyl paraffins, and a non-zero amount up to 10% by weight scent. The candle may also include 60% to 80% by weight blending wax and a non-zero amount up to 10% by weight scent, wherein the balance of the weight is LAO dimers and/or methyl paraffins. The percentage of the scent in any of the above embodiments may be <0.5%, <1%, <2%, <3%, <4%, <5%, <6%, <7%, <8%, <9%, or <10%. In addition to the percentages listed above, percentages or approximately the same as any of the listed percentages also may be found in any embodiment. The percentages may be further adjusted if UV stabilizers or other candle additives are included, as will be understood by one skilled in the art.

[0061] The candles described herein may be formed into a variety of shapes, including, but not limited to, pillar candles and those situated within a container. Container candles are candles formed within a vessel or similar container by pouring a wax composition into the container, inserting one or more wicks, and then allowing the candle to set, with the one or more wicks protruding from the wax composition. Pillar candles are freestanding and, in any embodiment, may be formed using wax compositions formed from higher LAO dimers, such as dimers formed from C20 ₊ LAOs. Taper candles may also be suitably formed by the disclosure herein.

[0062] The one or more wicks used may be one or more of hemp-core cotton, zinc-core cotton, coreless cotton, cotton with paper filaments, flat-braided wick, wooden wick, or a wick having a paper core, or any other suitable wick known to one having ordinary skill in the art. In any embodiment, the wick may be a high-melting point wick, such as a square braid wick, an ECO wick, a hemp-core wick or a coreless cotton wick. In any embodiment, the wick may be a square braid wick.

[0063] In any embodiment, the candle is comprised of a mix of blending wax and LAO dimers and/or the corresponding methyl paraffins in weight ratios or at weight percentages as described above. The candle may be formed by heating the mixture thoroughly until it becomes liquid ( e.g . , at a temperature of 82 to 88°C or 68 to 73°C), suspending a wick in a container or mold, pouring the liquefied mixture into the container or mold, and cooling the mixture. Alternatively, the candle may be formed by mixing blending wax and LAO dimers and/or methyl paraffins in weight ratios or at weight percentages as described above, heating the mixture thoroughly until it becomes liquid ( e.g ., 82 to 88°C or 68 to 73°C), and repeatedly dipping a wick into the liquefied mixture until a taper candle having a desired width is obtained. Between successive dips the taper candle may be below the melting point of the wax composition.

[0064] Other suitable techniques for forming candles using the wax compositions disclosed herein include, for example, extrusion, compression and slurry processing. Suitable extrusion processes may include, for example, screw, hydraulic ram and rotary drum extrusion, in which the wax compositions are squeezed through a suitably sized orifice and then cut to length. In compression processes, the wax compositions may be poured into a mould, and the finished candle may be ejected from the mould following solidification. Slurry processes comprise slurrying air or another gas with the wax compositions and forming a candle, thereby utilizing less of the wax compositions than in other types of processes.

[0065] Dyes or other colorants may be included in the candles in a suitable amount to afford an aesthetically pleasing candle. Suitable amounts of dyes or other colorants will be familiar to one having ordinary skill in the art. Other additives that may be suitably included in the candles disclosed herein include, for example, UV stabilizers, antioxidants, polyethylene waxes, microwaxes, mineral oil, stearic acid or other fatty acids, and any combination thereof.

[0066] In some or any embodiment, candles of the present disclosure may be formed by mixing a blending wax and LAO dimers and/or methyl paraffins in a weight ratio of 3:2 to 4:1, heating the mixture thoroughly until it becomes liquid {e.g., 82 to 88°C), suspending a wick in a container or mold, pouring the liquefied mixture into the container or mold, and cooling the mixture. Alternatively, candles of the present disclosure may be formed by mixing a blending wax and LAO dimers and/or methyl paraffins in a weight ratio of 3:2 to 4:1, heating the mixture thoroughly until it becomes liquid {e.g. , 82 to 88°C, and) dipping a wick into the mixture. LAO dimers comprising a vinylidene group, trisubstituted LAO dimers, a methyl paraffin formed therefrom, or any combination thereof may be used.

[0067] Methods for forming wax compositions of the present disclosure are also described herein. In various embodiments, the methods may comprise combining LAO dimers, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimers, or any combination thereof with a blending wax in an amount sufficient to form a wax composition having a melting point of 40 °C or above. In any embodiment, such LAO dimers may be formed by dimerization of one or more C 14 to C24 LAOs. The blending wax may be slack wax or another wax suitable for wax compositions as discussed above.

[0068] To facilitate a better understanding of the embodiments described herein, the following examples of various representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the present disclosure.

[0069] Embodiments disclosed herein include:

[0070] Wax compositions. The wax compositions comprise: a linear alpha olefin (LAO) dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, the LAO dimer being formed by dimerization of one or more C14 to C24 LAOs; and a blending wax; wherein the wax composition has a melting point of 40°C or greater.

[0071] B. Candles comprising a wax composition. The candles comprise: a wick; a linear alpha olefin (LAO) dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, the LAO dimer being formed by dimerization of one or more C14 to C24 LAOs; and a blending wax; wherein the LAO dimer, the methyl paraffin, or any combination thereof and the blending wax are combined to form a wax composition, the wax composition defining a body of the candle and the wick extending therefrom.

[0072] C. Methods for forming a wax composition. The methods comprise: providing a linear alpha olefin (LAO) dimer comprising a vinylidene group, a methyl paraffin comprising a hydrogenated reaction product of the LAO dimer, or any combination thereof, the LAO dimer being formed by dimerization of one or more C14 to C24 LAOs; and combining the LAO dimer, the methyl paraffin, or any combination thereof with a blending wax in an amount sufficient to form a wax composition having a melting point of 40°C or above.

[0073] Embodiments A-C may have one or more of the following additional elements in any combination:

[0074] Element 1 : wherein the wax composition has a melting point of 45°C or greater.

[0075] Element 2: wherein the blending wax comprises petroleum slack wax.

[0076] Element 3: wherein the LAO dimer, the methyl paraffin, or any combination thereof comprises 30 wt. % or greater of the wax composition.

[0077] Element 4: wherein the methyl paraffin has a structure of and the LAO dimer has a structure of

wherein R ¹ is an alkyl group having from 14 to 24 carbon atoms, and R ² is an alkyl group having from 12 to 22 carbon atoms.

[0078] Element 5: wherein R ¹ and R ² are both unbranched alkyl groups.

[0079] Element 6: wherein the LAO dimer is formed by dimerization of a C14 LAO.

[0080] Element 7 : wherein the wax composition further comprises a trisubstituted LAO dimer, a methyl paraffin comprising a hydrogenated reaction product of the trisubstituted LAO dimer, or any combination thereof, the trisubstituted LAO dimer being formed by dimerization of the one or more C14 to C24 LAOs.

[0081] Element 8: wherein the methyl paraffin or the LAO dimer has a viscosity index of 165 to 230.

[0082] Element 9: wherein the candle further comprises: a dye, a fragrance, or any combination thereof.

[0083] Element 10: wherein the method further comprises dimerizing the one or more LAOs in the presence of a metallocene catalyst to form the LAO dimer.

[0084] Element 11 : wherein the metallocene catalyst comprises bis(cyclopentadienyl)zirconium(IV) dichloride.

[0085] Element 12: wherein the method further comprises: combining a trisubstituted LAO dimer, a methyl paraffin comprising a hydrogenated reaction product of the trisubstituted LAO dimer, or any combination thereof with the blending wax, the trisubstituted LAO dimer being formed by dimerization of the one or more C14 to C24 LAOs.

[0086] By way of non-limiting example, exemplary combinations applicable to A include

1 and 2; 1 and 3; 1 and 4; 1, 4 and 5; 1 and 6; 1 and 7; 1 and 8; 2 and 3; 2 and 4; 2, 4 and 5; 2 and 6; 2 and 7; 2 and 8; 3 and 4; 3-5; 3 and 6; 3 and 7; 3 and 8; 4 and 6; 4 and 5; 4-6; 4 and 6; 4 and 7; 4, 5 and 7; 4 and 8; 4, 5 and 8; 6 and 7; 6 and 8; and 7 and 8. Exemplary combinations applicable to B include 1 and 2; 1 and 3; 1 and 4; 1, 4 and 5; 1 and 6; 1 and 7; 1 and 8; 2 and 3; 2 and 4; 2, 4 and 5; 2 and 6; 2 and 7; 2 and 8; 3 and 4; 3-5; 3 and 6; 3 and 7; 3 and 8; 4 and 6; 4 and 5; 4-6; 4 and 6; 4 and 7; 4, 5 and 7; 4 and 8; 4, 5 and 8; 6 and 7; 6 and 8; and 7 and 8, any of which may be in further combination with 9. Further exemplary combinations applicable to B include 1 and 9; 2 and 9; 3 and 9; 4 and 9; 4, 5 and 9; 6 and 9; 7 and 9; and 8 and 9. Exemplary combinations applicable to C include 1 and 2; 1 and 3; 1 and 4; 1, 4 and 5; 1 and 6; 1 and 7; 1 and 8; 2 and 3; 2 and 4; 2, 4 and 5; 2 and 6; 2 and 7; 2 and 8; 3 and 4; 3-5; 3 and 6; 3 and 7; 3 and 8; 4 and 6; 4 and 5; 4-6; 4 and 6; 4 and 7; 4, 5 and 7; 4 and 8; 4, 5 and 8; 6 and 7 ; 6 and 8; and 7 and 8, any of which may be in further combination with 10, 11 and/or 12. Further exemplary combinations applicable to C include 1 and 10; 2 and 10; 3 and 10; 4 and 10; 4, 5 and 10; 6 and 10; 7 and 10; 8 and 10; 10 and 12; 1, 10 and 11; 2, 10 and 11 ; 3, 10 and 11; 4, 10 and 11; 4, 5, 10 and 11; 6, 10 and 11 ; 7, 10 and 11 ; 8, 10 and 11 ; 1 and 12; 2 and 12; 3 and 12; 4 and 12; 4, 5 and 12; 6 and 12; 7 and 12; and 8 and 12.

EXAMPLES

[0087] Example 1: Methyl Paraffin Formation. C14 linear alpha olefins were oligomerized in the presence of bis(cyclopentadienyl)zirconium(IV) dichloride catalyst (BisCpZrCh) and methylalumoxane (MAO) as a catalytic activator. Vinylidene olefin dimers were obtained as the principal reaction product, along with some trisubstituted olefins. Hydrogenation of the olefin dimers provided a C28 methyl paraffin, which had an appearance of solid waxy crystals.

[0088] Ci4 LAOs were oligomerized using a continuous polymerization unit with a continuous stirred-tank reactor (CSTR), which was provided with a commercial feed comprising approximately 90 wt. % C14 LAOs. The feed was passed through a bed of molecular sieves and activated alumina prior to contacting the catalyst system to remove moisture, oxygenates, and other impurities. The resulting product was further subjected to vacuum in a degassing vessel to remove dissolved N2.

[0089] The catalyst system was prepared by mixing powdered CpiZrCF with purified, dewatered toluene. MAO, supplied in a toluene solution, was further diluted and kept in a separate container. Both components of the catalyst system were fed from separate vessels into the reactor subsurface via a dip tube and were subsequently mixed with the LAOs therein.

[0090] Oligomerization process conditions included a pressure of 25 psig, a temperature of 70°C, and approximately 6 hours of residence time. The molar ratio of aluminum to zirconium was approximately 5. The molar ratio of LAO to zirconium plus aluminum was approximately 3000. Other experimental ratios and ranges utilized were a pressure of 15 to 100 psig, a temperature of 45°C to 120°C, and a residence time of 0.5 hours to 30 hours, more typically 1 hour to 12 hours. The molar ratio of aluminum to zirconium was from 1 to 100, or 1 to 60, or 2 to 50, from 3 to 32. The LAO to zirconium plus aluminum molar ratio was from 50000 to 1000, or 15000 to 2000, or 20000 to 100, or 6000 to 500.

[0091] The reactor effluent was quenched with water and distilled. The oligomerization reaction resulted in approximately 78% LAO conversion, with 98% dimer selectivity. The distilled product contained -99% of vinylidene LAO dimers and -1% trisubstituted LAO dimers. The product was further hydrogenated using slurry hydrogenation in the presence of D-49 Ni / Ni monoxide powder catalyst supported on silicon dioxide. The hydrogenation reaction was carried out at approximately 230°C and approximately 650 Psi for 2 hours. The catalyst charge was approximately 0.5 wt. %. The resulting product exceeded 99% C28 methyl paraffins.

[0092] The methyl paraffins produced by the reaction had a dimer content that exceeded 99 percent by weight. The viscosity index was 175, as determined according to ASTM D2270, using the calculated viscosity index from kinematic viscosities measured at 40°C and 100°C. The kinematic viscosity at 100°C was 3.57 centistokes (cSt), and 12.8 cSt at 40°C, as measured using ASTM D445. The resulting paraffin was analyzed by low temperature microscopy and was found to have crystal morphology (microstructure) that was quite distinct from the crystal morphology of both LAO wax, shown in FIG. 1A, and petroleum base slack wax, shown in FIG. IB. The resulting methyl paraffin had a“starhurst-like” microstructure, as shown in FIG. 1C. This may be contrasted with the needlelike crystal network of the LAO wax crystal (FIG.

1A), and the irregularly arranged long needlelike crystals observed with petroleum slack wax (FIG. IB).

[0093] The resulting methyl paraffins were formulated into a wax composition containing 30 percent by weight of C28 methyl paraffins and 70 percent by weight petroleum slack wax. The melting point of the wax blend was observed to be 44.4°C as determined by ASTM D87.

[0094] Differential scanning calorimetry (DSC) was used to determine the crystallization temperature upon cooling and the melting temperature upon heating of the resulting methyl paraffin. The sample solidified at 12°C and melted at 19°C. An unexpected result was that the hydrogenated C28 LAO dimers underwent hysteresis with respect to the phase transition temperature, as shown in FIG. 2A. The hysteresis is not typical of paraffinic wax. A typical DSC profile of paraffinic wax, in this instance low melt paraffin slack wax, is shown in FIG. 2B.

[0095] Example 2: Candle Formation. A container candle was prepared by blending 30 percent by weight of C28 methyl paraffins (Example 1) and 70 percent petroleum slack wax (PROW AX 401). A flat braided wick was positioned in the wax composition prior to solidification. The melting point of the wax blend was observed to be 44.4°C as determined by ASTM D87. The blend resulted in a smooth candle aesthetic, which may be contrasted with the mottled/blotched appearance of petroleum slack wax alone. [0096] The wax blend was found to have no oil bleed and no side shrinkage, with such features being sustained over several months of observation. Despite the low melting point of C28 methyl paraffins, no liquid migrated to the candle surface to form an oil pool. This shows that the paraffinic wax was adequately stabilized by the C28 methyl paraffins. Additionally, the color of candles dyed with pigment was sustained over 6 months in the absence of UV stabilizing additives. This was unexpected, as paraffinic slack wax alone requires the addition of UV stabilizing additives to retain color, especially when blended with dyes and fragrances. Indeed, a control candle formed from petroleum slack wax alone formed an oil pool after 4 weeks and had a mottled appearance and non-uniform color throughout. The candle formed from the methyl paraffins, in contrast, did not exhibit these properties and exhibited better burning capabilities, as no excessive soot or unpleasant odor was noticed.

[0097] Two burn cycles were used to test bum performance. Sooting was minimal or negligible for the container candle including the dimer in the wax composition, in contrast to the performance of the petroleum slack wax alone. The burn performance was also good for the wax composition, particularly during the second burn cycle. A melt pool was established and the candle did not entirely liquefy during each burn cycle. The bum performance could be improved further by using either a cotton core wick or a thicker flat braided wick.

[0098] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. For example, the compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.

[0099] The term“comprising” is considered synonymous with the term“including.” Whenever a method, composition, element or group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.