Patent Description:
It is desirable for fertilizer compositions to include slow-release nitrogen compounds to provide plants with an extended release of nutrients, minimize leaching of nutrients into the ground, and minimize the number of fertilizer applications required for optimal plant growth. However, conventional production of slow-release nitrogen compounds suffer from a number of undesirable attributes. For example, conventional production of slow-release nitrogen compounds, such as by aqueous processes or by coating processes, can have complicated production processes with multiple time consuming steps, be energy intensive, and form a blend of nitrogen compounds having undesirable ratios of desirable slow-release nitrogen compounds to other nitrogen compounds such as cold-water insoluble nitrogen compounds. <CIT> discloses a granular slow-release nitrogenous fertilizer prepared by granulating a mixture of a urea-aldehyde condensate and an oxidized wax.

The invention relates to a method of forming a fertilizer composition according to claim <NUM> and a fertilizer composition according to claim <NUM> and to a method of treating plants by applying the fertilizer composition according to claim <NUM>.

According to an embodiment of the fertilizer composition of claim <NUM>, a fertilizer composition includes slow-release nitrogen compounds. The slow-release nitrogen compounds consist essentially of methylenediurea ("MDU"), dimethylenetriurea ("DMTU"), and cold-water insoluble nitrogen. The MDU and DMTU include about <NUM>% or more of the total nitrogen in the fertilizer composition. The cold-water insoluble nitrogen includes about <NUM>% to about <NUM>% of the total nitrogen in the fertilizer composition. The fertilizer composition exhibits at least one of (a) a complex viscosity of about <NUM> PaS to about <NUM> PaS when measured at a temperature of about <NUM>; (b) a dynamic (absolute) viscosity of about <NUM> Pas to about <NUM> Pas when measured at a temperature of about <NUM>; and (c) a viscous modulus of about <NUM> Pa to about <NUM> Pa when measured at a temperature of about <NUM>.

In one embodiment of the method of the invention, the method comprises increasing the temperature of the molten methylene urea mixture to the reaction temperature to initiate a reaction of the urea and the formaldehyde to form a fertilizer composition at the reaction temperature,.

The present disclosure generally describes methods of forming fertilizer compositions having slow-release nitrogen compounds using a molten process. As used herein, slow-release nitrogen compounds mean nitrogen compounds which provide a slower and/or longer duration release of nitrogen to plants after the compounds are applied to plants. Generally, fertilizers including slow-release nitrogen compounds can make nitrogen available to plants over a period of weeks to months. The slow-release nitrogen compounds formed from the methods generally described in the present disclosure include desirable short-chain methylene urea products such as methylenediurea ("MDU") and dimethylenetriurea ("DMTU") as well as longer-chain cold-water insoluble nitrogen compounds.

As can be appreciated, slow-release nitrogen compounds such as MDU and DMTU can be formed from chain building of urea and formaldehyde under molten conditions. Under such conditions, urea and formaldehyde can undergo a series of reactions which produce methylene urea products having varying chain lengths. For example, a urea molecule can react with a formaldehyde molecule to produce a monomethylol urea molecule. The monomethylol urea molecule can then react with another urea molecule to form methylenediurea or MDU. As can be appreciated, continued reaction of the urea molecules, formaldehyde molecules, and monomethylol urea molecules can produce methylene urea products having longer chain lengths including dimethylenetriurea, trimethylene tetraurea, etc. These reactions can occur at a reaction temperature of molten urea and molten formaldehyde. According to certain embodiments, the reaction temperature can occur at a temperature of about <NUM>. As used herein, a molten state means a partially molten state, a substantially molten state, or an entirely molten state. Temperatures are measured at standard pressure (e.g., at about <NUM> atm) unless otherwise noted.

As can be appreciated however, methylene urea products having chain lengths longer than MDU and DMTU can be considered to be cold-water insoluble nitrogen compounds because such compounds have limited water solubility when used as a fertilizer. Generally, cold-water insoluble nitrogen compounds are undesirable because such compounds do not readily make nitrogen available to plants and fail to provide a meaningful fertilizing benefit. Conversely, MDU and DMTU are considered desirable because they provide a balanced measure of water solubility and advantageously make nitrogen available to plants over a period of weeks to months.

The methods described herein can form desirable slow-release nitrogen compounds, such as MDU and DMTU, in advantageous ratios with other nitrogen-containing compounds such as cold-water insoluble nitrogen compounds. Generally, the molten process can produce such desirable ratios of slow-release nitrogen compounds through the inclusion of a resin modifier, which is a crystalline polyethylene wax, to a molten mixture of urea and formaldehyde.

Specifically, it has been discovered that the inclusion of a suitable resin modifier to a molten mixture of urea and formaldehyde can hinder the reactivity of molten urea and formaldehyde to form methylene urea reaction products. Advantageously, the lowered reaction kinetics caused by the resin modifier can favor the formation of desirable short-chain methylene urea reaction products including MDU and DMTU and disfavor the formation of longer chain, cold-water insoluble nitrogen compounds.

For example, the molten process described herein can form a mixture of reaction products having about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU in certain embodiments, about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU in certain embodiments, about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU in certain embodiments, about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU in certain embodiments, and about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU in certain embodiments. In any such embodiment, about <NUM>% or less of the total nitrogen in the mixture of reaction products can be cold-water insoluble nitrogen. For example, in certain embodiments, about <NUM>%, or less, of the total nitrogen in the mixture of reaction products can be cold-water insoluble nitrogen and, in certain embodiments, about <NUM>%, or less, of the total nitrogen in the mixture of reaction products can be cold-water insoluble nitrogen. In certain embodiments, about <NUM>% to about <NUM>% of the total nitrogen in the mixture of reaction products can be cold-water insoluble nitrogen. As illustration, about <NUM>% of the total nitrogen in a mixture of reaction products can be at least one of MDU or DMTU and about <NUM>%, or less, of the total nitrogen can be cold-water insoluble nitrogen.

Generally, the distribution of reaction products can be influenced through selection of the molar ratio between urea and formaldehyde. For example, increasing the relative amount of urea to a given amount of formaldehyde can decrease the polymer chain length of the methylene urea products. By varying the molar ratio of urea and formaldehyde, specific nitrogen distribution can be obtained. Suitable ratios of urea to formaldehyde to form desirable slow-release nitrogen compound distributions vary from <NUM>:<NUM> to <NUM>:<NUM>. <FIG> show alternative ratios of urea to formaldehyde that can result in suitable slow-release nitrogen compound distributions. As can be appreciated, further alternative ratios may also be suitable by modifying the reaction conditions, reaction time, or the properties of the resin modifier.

As can be appreciated, such ratios can facilitate the formation of fertilizer compositions having desirable distributions of slow-release nitrogen compounds. In certain embodiments, the mixture of reaction products of the molten process described herein can directly be used as a fertilizer composition. Such fertilizer compositions can include desirable quantities of fast-release nitrogen compounds and desirable slow-release nitrogen compounds, such as MDU and DMTU, while including low amounts of cold-water insoluble nitrogen. As can be appreciated, unreacted urea feedstock and formaldehyde can act as a suitable source of fast-release nitrogen compounds in such embodiments.

Conversely, in other embodiments, additional processing and/or additional compounds can be added with the mixture of reaction products formed from the described molten processes to form fertilizers having slow-release nitrogen compounds.

Additional advantageous slow-release nitrogen compounds can be included in a fertilizer composition in certain embodiments. The inclusion of other types of advantageous slow-release nitrogen compounds such as triazones, urea-triazones (such as tetrahydro-s-triazone or <NUM>-methyleneuriedo-<NUM>-oxohexahydro-s-triazine), and isobutylidene-diurea ("IBDU") can allow for tailoring of the nitrogen release profile over time. The addition of such compounds can also allow the fertilizer compositions to include any suitable amount of nitrogen. For example, in certain embodiments, the fertilizer composition containing slow-release nitrogen compounds can include from about <NUM>% to about <NUM>%, by weight, nitrogen. In certain embodiments, the fertilizer compositions containing slow-release nitrogen compounds can include from about <NUM>% to about <NUM>%, by weight, nitrogen including, for example, from about <NUM>% to about <NUM>%, by weight, nitrogen. In various embodiments, the amount, by weight, nitrogen in a fertilizer composition containing slow-release nitrogen compounds can be about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, about <NUM>%, or about <NUM>%.

Additionally, or alternatively, various types of fast-release nitrogen compounds can be added including one or more of additional urea, urea ammonium nitrate ("UAN"), ammonium, and nitrate.

In certain embodiments, the fertilizer compositions can further include one or more non-nitrogen-based components. For example, a fertilizer composition can further include one or more of phosphorus, potassium, calcium, magnesium, manganese, molybdenum, sulfur, and zinc.

The inclusion of a resin modifier in the molten processes described herein can provide further benefits. For example, the continued presence of the resin modifier in the mixture of reaction products can reduce crystallization of the reaction products. Reduced crystallization rates can cause the mixture of reaction products to have desirable rheological properties including reduced viscosity and modulus. As can be appreciated, such rheological properties can provide numerous benefits to fertilizer compositions formed from the mixture of reaction products. For example, the rheological properties can facilitate processing, can improve stability, and can improve sprayability of fertilizers including the mixture of reaction products. Additionally, the improved rheological properties can facilitate granulation of the reaction products.

A mixture of reaction products formed from the molten process described herein and having about <NUM>%, or more, of the total nitrogen be at least one of MDU and DMTU and <NUM>%, or less, of the total nitrogen be cold-water insoluble nitrogen compounds, can have a complex viscosity of about <NUM> Pas to about <NUM> Pas when measured at about <NUM>, and a dynamic (absolute) viscosity of about <NUM> Pas to about <NUM> Pas when measured at a temperature of about <NUM>. Similarly, such a mixture of reaction products can also have a resin viscous modulus (G") of about <NUM> Pa to about <NUM> Pa when measured at about <NUM>.

In certain embodiments, the inclusion of a resin modifier can also influence the rheological phase angle. For example, a mixture of reaction products formed from the molten processes described herein can have a rheological phase angle of about <NUM> degrees, or greater, and can have a tan delta greater than about <NUM>. Such properties can indicate that the reaction products behave more like a viscous liquid than an elastic solid. As can be appreciated, conventionally produced methylene urea products can have a tan delta of about <NUM> indicating that such methylene urea products behave more like an elastic solid.

As can be appreciated, the resin modifier remains in the fertilizer composition after cooling of the molten reaction process. It has been advantageously discovered that the resin modifier can slow the release of nitrogen from the fertilizer compositions by occluding, or partially encapsulating, the methylene urea reaction products as illustrated in <FIG>. Specifically, <FIG> depicts a fertilizer composition <NUM> including methylene urea reaction products <NUM> and resin modifier <NUM>. The resin modifier <NUM> occludes, or partially encapsulates, the methylene urea reaction products <NUM> and can slow the release of nitrogen over time. In certain embodiments, the fertilizer compositions described herein can release nitrogen over about <NUM> days or greater, over about <NUM> days or greater, over about <NUM> days or greater, over about <NUM> days or greater, or over about <NUM> days or greater. Such desirable nitrogen release durations can be accomplished without inclusion of significant quantities of cold-water insoluble nitrogen or separate microencapsulation of the fertilizer compositions.

As can be appreciated, certain benefits imparted by the inclusion of a resin modifier can also be demonstrated by comparing the mixture of reaction products formed by processes including a resin modifier to the reaction products formed by a similar molten process free of any resin modifier.

For example, when producing similar amounts of cold-water insoluble nitrogen, the molten processes described herein can produce greater quantities of MDU and DMTU than a similar process free of a resin modifier. Specifically, in certain embodiments producing identical amounts of cold-water insoluble nitrogen, the molten processes described herein can form a mixture of reaction products having <NUM>% of the total nitrogen be MDU and DMTU while a comparative process free of a resin modifier can form a mixture wherein only <NUM>% of the total nitrogen is MDU and DMTU.

The respective mixtures also exhibit similar trends in rheological properties. For example, the reduced crystallization caused by the resin modifier can allow a mixture of resin products formed with a molten process and a resin modifier and having <NUM>% of the total nitrogen be MDU and DMTU exhibit the same complex viscosity and resin modulus as a mixture, formed without a resin modifier, having <NUM>% of the total nitrogen be MDU and DMTU.

Generally, suitable resin modifiers for the molten processes described herein include crystalline polyethylene waxes which exhibit suitable physical properties in both solid and molten forms. For example, crystalline polyethylene waxes having a number average molecular weight of about <NUM> to about <NUM>,<NUM>, a polydispersity index of about <NUM> to about <NUM>, and about <NUM>% to about <NUM>% crystallinity can be suitable because such crystalline polyethylene waxes exhibit desirable hardness in solid forms and desirable viscosity ranges while in a molten form. Crystalline polyethylene waxes having molecular weight distributions and polydispersity indexes outside of such ranges can be, for example, too soft in a solid form and too viscous in the molten state. Selection of the crystalline polyethylene wax can also influence the yield and conversion rates of the molten reactions described herein.

As used herein, the polydispersity index is used to indicate the relative width, or range, of molecular weight distributions of a polymer or blend of polymers according to Formula I:<MAT>wherein Mw is the weight average molecular weight and Mn is the number average molecular weight. As can be appreciated, these values can be obtained using any known technique such as, for example, size exclusion chromatography. Materials having a greater polydispersity index can be composed of many different chain lengths. A monodisperse polymer, where all the chain lengths are equal would have a polydispersity index of <NUM>.

As used herein, the degree of crystallinity is used to refer to the percentage of a polymer in the crystalline form. The degree of crystallinity can be measured by various techniques including x-ray diffraction, differential scanning calorimetry ("DSC"), and nuclear magnetic resonance ("NMR") among other techniques. In one alternative within claim <NUM>, suitable crystalline polyethylene waxes have a degree of crystallinity, determined via DSC, of about <NUM>% to about <NUM>%. As can be appreciated, the degree of crystallinity can be determined by DSC using the equation: % Crystallinity = [ΔHm - ΔHc] / ΔHm° * <NUM>%, where ΔHm is the heat of melting, ΔHc is the heat of cold crystallization, and ΔHm° is the heat of melting of a <NUM>% crystalline sample (e.g., <NUM> J/g for polyethylene). In certain embodiments, the crystalline polyethylene wax can have a degree of crystallinity about <NUM>% to about <NUM>%, in certain embodiments, about <NUM>% to about <NUM>%, and in certain embodiments, about <NUM>%.

In one alternative within claim <NUM>, suitable crystalline polyethylene waxes have a number average molecular weight average of about <NUM> to about <NUM>,<NUM> and a polydispersity index of about <NUM> to about <NUM>. As can be appreciated, more than one crystalline polyethylene wax can also, or alternatively, be used to reach the desired properties. For example, a first crystalline polyethylene wax having a molecular weight of about <NUM> and a second crystalline polyethylene wax having a molecular weight of about <NUM>,<NUM> can be used in certain embodiments.

Such crystalline polyethylene waxes can be suitable to both reduce the molten reaction kinetics of urea and formaldehyde and to reduce crystallization rates of the methylene urea reaction products. In certain embodiments, suitable crystalline polyethylene waxes can also exhibit a needle penetration hardness of about <NUM> to about <NUM> when measured at <NUM>. The dynamic viscosity of a suitable crystalline polyethylene wax can be about <NUM> cps to about <NUM> cps when measured at a temperature of <NUM>.

Generally, the crystalline polyethylene wax can be melted and combined in solution with the molten urea and formaldehyde to form an emulsion of two immiscible fluids which require agitation for uniformity. The emulsion hinders reactivity and can prevent excess methylene urea chain building. In certain embodiments, the crystalline polyethylene wax can be melted before addition to the molten urea and formaldehyde. In alternative embodiments, the crystalline polyethylene wax can be melted simultaneously with either of, or both of, urea and formaldehyde.

Generally, a resin modifier can be included at about <NUM>% to about <NUM>%, by weight, of the molten mixture. For example, in certain embodiments, about <NUM>% to about <NUM>%, by weight of the molten mixture can be the resin modifier. In certain embodiments, about <NUM>%, by weight of the molten mixture can be the resin modifier.

As can be appreciated, urea and formaldehyde for the molten process can be provided in any suitable manner. For example, it can be useful in certain embodiments to provide formaldehyde in the form of a urea-formaldehyde concentrate. The use of a urea-formaldehyde concentrate can simplify processing and is widely available.

In certain embodiments, a heat treatment step can be performed after formation of the reaction products to reduce crystallization of the mixture. In such embodiments, the molten mixture of reaction products can be heated to a higher temperature before being allowed to cool. As can be appreciated, once the reaction products form a solution, it can be more difficult for the reaction products to subsequently crystallize and fall out of solution even when cooled. Additionally, during a heat treatment step, the resin modifier can also block nucleation sites which seed crystallization of the reaction products. In certain embodiments, a heat treatment step can occur at a temperature ranging from about <NUM> to about <NUM> and can have a duration of about <NUM> minutes. In certain embodiments, the heat treatment step can occur at a temperature ranging from about <NUM> to about <NUM> for a duration of about <NUM> minutes. In certain embodiments, the heat treatment step can occur at a temperature of about <NUM>.

The fertilizer compositions described herein can be applied to a seed, seedling, plant, or lawn. In certain embodiments, the fertilizer compositions can be sprayed onto a soil, seed, seedling, plant, or lawn using sprayers known to one of ordinary skill in the art, such as trigger sprayers (e.g., hand-held trigger sprayers), wand sprayers, bottle sprayers, compression sprayers, tank sprayers, pump sprayers, hose-end sprayers, and backpack sprayers. The fertilizer compositions described herein can also be granulated into a solid fertilizer and applied to soil using a rotary spreader.

In certain embodiments, a fertilizer composition described herein can be applied in amounts of from about <NUM>/m<NUM> (<NUM> lb. of nitrogen per <NUM> ft<NUM>) to about <NUM>/m<NUM> ( <NUM> lbs. of nitrogen per <NUM> ft<NUM>). In certain embodiments, the fertilizer compositions can be formulated as a ready-to-use or ready-to-spray formulation.

In embodiments in which the fertilizer composition is granular, the granular compositions can be applied to a soil, seed, seedling, plant or lawn by sprinkling, or spreading, the composition onto the soil, seed, seedling, plant or lawn.

As can be appreciated, the slow-release nitrogen compounds described herein can be produced by any process that includes the addition of a resin modifier to a molten mixture of urea and formaldehyde.

In certain embodiments, the process used to form the slow-release nitrogen compounds can include the step of weighing the urea and formaldehyde, or urea-formaldehyde concentrate and melting the resin modifier. The resin modifier is a crystalline polyethylene wax, and the resin modifier can be melted at a temperature of <NUM>. Next, the urea and urea-formaldehyde concentrate can be melted at, for example, a temperature of <NUM>. In certain embodiments, it can be useful to agitate the molten mixture. In certain embodiments, the crystalline polyethylene wax can added to the urea and urea-formaldehyde concentrate as soon as the mixture melts. In such embodiments, the mixture can be held at a temperature of <NUM>, with agitation, for <NUM> to <NUM> minutes. In certain embodiments, the molten mixture of urea, urea-formaldehyde concentrate, and the resin modifier can be held at a temperature of <NUM> for <NUM> minutes. During the <NUM> minute duration, the urea and formaldehyde in the molten mixture can form methylene urea products including MDU and DMTU. In certain embodiments, substantially all of the slow-release nitrogen compounds formed are MDU and DMTU.

As an alternative to embodiments which melt each of the components at a first temperature below the reaction temperature, each of the components (e.g., the urea, formaldehyde and resin modifier) can alternatively be melted, and mixed, at the reaction temperature and then maintained at the reaction temperature until methylene urea products are formed. Remaining steps, such as a heat treatment step, can be performed substantially unmodified.

After the reaction process is completed, a heat treatment step can be performed. In certain embodiments, a heat treatment step can include heating of the molten mixture to a temperature of <NUM> for a duration of time such as a period of about <NUM> minutes. The heat treatment step can reduce crystallization of the reaction products and can improve the rheological properties of the mixture.

The following examples are included to illustrate certain aspects and embodiments of the present disclosure, and are not intended to limit the disclosure to the disclosed embodiments.

Several example fertilizer compositions having slow-release nitrogen fertilizer compounds were formed. In each example, a molten mixture with a total weight of <NUM> grams was melted at <NUM>. Each molten mixture included <NUM>%, by weight, of a crystalline polyethylene wax having a molecular weight between <NUM> and <NUM>,<NUM>, a polydispersity between <NUM> and <NUM>, and <NUM>% crystallinity. The molten mixture for each example further included varying quantities of urea and urea formaldehyde concentrate.

<FIG> depict contour plots illustrating, respectively, the ratios of urea to formaldehyde in various examples, a contour plot indicating the amount of MDU and DMTU formed as a percent of the total nitrogen, a contour plot indicating the amount of cold-water insoluble nitrogen (CWIN) formed, and a mixture contour plot indicating the rheological properties of the previous two graphs. In <FIG>, the italicized numbers indicate molar ratios of urea to formaldehyde. In <FIG>, the viscosity units are PaS.

As indicated by the graphs, molten mixtures including a ratio of urea to formaldehyde in a ratio of about <NUM>:<NUM> to about <NUM>: <NUM> formed desirable quantities of MDU and DMTU while also demonstrating low viscosity.

The fertilizing effect of Example <NUM> (a fertilizer composition prepared according to the present disclosure) was compared to Example <NUM> (Nutralene® <NUM>-<NUM>-<NUM> manufactured by the Koch Agronomic Services, LLC (Wichita, KS)). Nutralene® <NUM>-<NUM>-<NUM> is a commercial fertilizer including <NUM>% total nitrogen (<NUM>% urea, <NUM>% water soluble nitrogen, and <NUM>% water insoluble nitrogen). The nitrogen distributions of Examples <NUM> and <NUM> are depicted in Table <NUM>.

Examples <NUM> and <NUM> were evaluated using a greenhouse trial. In the greenhouse trial, Examples <NUM> and <NUM> were dried and milled to <NUM> microns and applied to 'Celebration' bermudagrass at a rate of <NUM> lbs/1000ft<NUM>. The greenhouse was set to an <NUM> °F/<NUM> °F day/night temperature cycle and held at <NUM>% humidity. <NUM>" of irrigation was delivered per week. The fertilizer response of Examples <NUM> and <NUM> was measured by determining clipping chlorophyll mass in accordance to the methods described in<NPL>. The relative chlorophyll percentage of Examples <NUM> and <NUM> was then determined from their respective clipping chlorophyll masses and is depicted in Table <NUM>.

As illustrated by Table <NUM>, Example <NUM> maintains a relative chlorophyll percentage of greater than <NUM>% <NUM> days after application to `Celebration' bermudagrass despite having only small amounts of cold water insoluble nitrogen. As such, Example <NUM> exhibits a meaningful greening effect. Prior to the present disclosure, it was believed that significant quantities of cold water insoluble nitrogen, or alternative methods to slow nitrogen release such as microencapsulation, were required for a fertilizer to exhibit continued greening over such an extended duration of time (i.e., <NUM> days). For example, traditional fertilizers including only <NUM>% cold water insoluble nitrogen, as present in Example <NUM>, would be expected to exhibit substantially no greening effect at <NUM> days.

<FIG> depicts a scanning electron microscopy image of a shaved cross section of an example composition at <NUM> times magnification. As depicted in <FIG>, the methylene urea reaction products are partially occluded by the polyethylene wax with dark areas showing areas of concentrated polyethylene wax, lighter areas with relatively little polyethylene wax, and mid-toned areas showing a mix of both polyethylene wax and methylene urea reaction products.

As used herein, all percentages (%) are percent by weight of the total composition, also expressed as weight/weight %, % (w/w), w/w, w/w % or simply %, unless otherwise indicated.

Claim 1:
A method of forming a fertilizer composition having slow-release nitrogen compounds, the method comprising:
mixing urea, formaldehyde, and crystalline polyethylene wax at a first temperature to form a molten methylene urea mixture, wherein the mole ratio of urea to formaldehyde is about <NUM>:<NUM> to about <NUM>:<NUM>;
initiating a reaction of the urea and the formaldehyde to form a fertilizer composition at a reaction temperature; and
heat treating the fertilizer composition at a second temperature above the reaction temperature; and
wherein the crystalline polyethylene wax has one or more of:
a molecular weight of about <NUM> to about <NUM>,<NUM>;
a polydispersity of about <NUM> to about <NUM>; and
a degree of crystallinity of about <NUM>% to about <NUM>%; and
wherein the first temperature is in a range from about <NUM> to about <NUM>;
the reaction temperature is in a range from about <NUM> to about <NUM>; and
the second temperature is in a range from about <NUM> to about <NUM>.