A process for the production of a specialty wax polymer

Abstract

A process for producing a polymer wax includes co-polymerizing a primary monomer and a comonomer in the presence of a metallocene catalyst in a reactor to form the polymer wax. The polymer wax has a melting point below 120 oC and a viscosity of less than 7000 cP at 150 oC.

Description

3511-00101 A PROCESS FOR THE PRODUCTION OF A SPECIALTY WAX POLYMER CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 628,122 filed June 22, 2023 entitled “PROCESS FOR THE PRODUCTION OF A SPECIALTY WAX POLYMER,” which is incorporated herein by reference in its entirety for all purposes. TECHNICAL FIELD

[0002] The present disclosure relates generally to polymer chemistry. More particularly, the present disclosure relates to the production of specialty wax polymers. BACKGROUND

[0003] On-purpose waxes are produced via direct polymerization of ethylene, propylene and other alpha olefins. This creates tailored waxes with narrow molecular weight distribution, high uniformity at the molecular level using ethylene as a feedstock. On-purpose polyethylene (PE) waxes have low molecular weight and high melting points when compared to petroleum wax, which is a highly linear structure characterized by chemical resistance, lubrication, and anti-blocking properties. On purpose waxes are additives in applications that either require lubrication or physical modification in their formulation. More specifically, on purpose waxes including PE Waxes are used as additives in areas such as plastic processing, masterbatches, hot-melt adhesives, coatings, paints, inks, packaging, and tire / rubber production.

[0004] Polyethylene-hexene-1 copolymers are one of the most commercially relevant materials produced today, with new grades being continually improved and marketed. Catalyst systems used in the production of these waxes typically consist of heterogeneous titanium chloride supported on magnesium or silica. Homogeneous single site and supported single site catalysts continue to be developed as well, with new applications and inroads into several commercial applications.

[0005] Two of the biggest challenges for making on purpose waxes with any catalyst have been reducing the molecular weight and lowering the melting point. Polyethylene resin 0  3511-00101 typically melts in the 130 °C to 137 °C range. The ability of liquid wax to flow easily at lower temperatures is an important property in coating, adhesive and plastic processing applications. By nature, Ziegler-Natta heterogeneous catalysts are multi-site and make broad molecular weight distribution polymers which can also be adjusted with internal and external electron donors. Alternatively, metallocene single site catalysts of various types have been used to produce polymers into the wax range. BRIEF DESCRIPTION OF THE FIGURES

[0006] The following figures form part of the present specification and is included to further demonstrate certain aspects of the present disclosure. The subject matter of the present disclosure may be better understood by reference to the figure in combination with the detailed description of specific aspects presented herein.

[0007] Figure 1 illustrates a schematic configuration of a reactor according to an embodiment.

[0008] Figure 2 is a plot of heat flow as a function of temperature for the indicated samples prepared at varying hydrogen concentrations.

[0009] Figure 3 is a plot of heat flow as a function of temperature for the indicated samples prepared at the indicated comonomer (hexene-1) concentration.

[0010] Figure 4 is a plot of heat flow as a function of temperature for the indicated samples prepared using the indicated polymerization processes.

[0011] Figure 5 is an illustration of the shear adhesion failure temperature (SAFT) test and peel adhesion failure temperature (PAFT) test.

[0012] Figure 6 is a photograph of a test setup according to the examples.

[0013] Figure 7 is a photograph of the peeled and testing samples according to the examples. SUMMARY

[0014] In some embodiments, a process for producing a polymer wax comprises co- polymerizing a primary monomer and a comonomer in the presence of a metallocene catalyst in a reactor to form the polymer wax. The polymer wax has a melting point below 120oC and a viscosity of less than 7000 cP at 150oC. 1  3511-00101

[0015] In some embodiments, a process for producing a polymer wax comprises introducing a solvent into the reactor, dehydrating a solvent within a reactor, introducing a comonomer into the reactor after dehydrating the solvent, introducing a metallocene catalyst into the reactor after the comonomer, introducing a primary monomer to the reactor after the comonomer, and co-polymerizing the primary monomer and the comonomer in the presence of the metallocene catalyst in the reactor to form the polymer wax.

[0016] In some embodiments, a polymer wax comprises a copolymer formed between a primary monomer and a comonomer in the presence of a metallocene catalyst. The polymer wax has a melting point below 120oC and a viscosity of less than 7000 cP at 150oC.

[0017] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims. DETAILED DESCRIPTION

[0018] In general, lowering molecular weight by chain termination through added hydrogen has been used to reduce molecular weight, but hydrogen alone may not substantially reduce the polymer melting point. A series of permethylindenyl metallocene catalysts for PE wax production can be used, in the presence of hydrogen, to increase activity and reduce molecular weight, but may only have a marginal decrease in melting point. A metallocene catalyzed co-polymerizations using hexene-1 as the comonomer can be used to decrease the melt flow index (as related to molecular weight). With increasing amounts of hexene-1 added to the polymerization, however, there may be little reduction in polymer melting point. A clear process for controlling melting point in the wax range has not yet been achieved.

[0019] Disclosed herein are compositions and processes for the production of an on purpose wax having a desired melting point range, herein designated a low melting on purpose wax (lm-OPW). In one or more aspects, a lm-OPW comprises a metallocene-catalyzed polyethylene polymer, or alternatively a metallocene-catalyzed polyethylene copolymer. In one or more aspects, a lm-OPW is prepared by polymerization of an olefin monomer, and an optional olefin comonomer in the presence of a metallocene catalyst combined with an activator, to produce the desired polyolefin.

[0020] More specifically, processes are disclosed that encompass solvent purification, wax production using a catalyst such as a metallocene catalyst, ethylene as a monomer, hexene-1 as 2  3511-00101 co-monomer and hydrogen as a chain termination agent. In some embodiments, a unique specialty ultra-low density to low density wax material is produced, which can melt between 90oC to 115oC with viscosities ranging from 380 to 6300 cP at 150°C. This product also shows varying degrees of crystallinity (24-55%) depending on process conditions. The average molecular weight of polymer was 4000-7000 g / mol. and polydispersity index were (2.5-3.7).

[0021] The present invention describes a process for manufacturing a polymer having a melting point in the wax range. This can be achieved by ethylene co-polymerization with hexene-1 in the presence of hydrogen using any suitable metallocene catalyst include commercially available metallocene catalyst. Different solvents for the catalyst can be used and solvent solvency properties can affect catalyst and monomer interaction and hence the polymerization reaction. A specialty polymer in the wax range melting point was achieved by varying different process parameters such as hydrogen and hexene-1 concentration. Hexene-1 co-monomer dosing was compared in a batch process versus continuous addition of hexene-1.

[0022] Still further, a process for production of a specialty polymer wax through the co- polymerization of ethylene and hexene-1. The process includes solvent purification and the production of polymer using metallocene catalysts and different co-catalysts. The effect of hydrogen and hexene-1 concentration on polymer properties is described. As described herein, the crystallinity of polymer is affected by the hexene-1 concentration with hydrogen acting as a chain transfer agent for lowering the molecular weight and melting point. The hexene-1 and hydrogen ratios can be used for tailoring the polymer properties in the wax melting point range. The increase in hexene-1 concentration lowers the crystallinity of polymer and makes a more amorphous polymer.

[0023] In an aspect, a catalyst composition for the production of a lm-OPW comprises a metallocene compound. Herein a “metallocene” compound refers to a transition metal- containing compound having from one to three cyclopentadienyl ligands, substituted or unsubstituted, bound to the transition metal. In one or more aspects, the metallocene compound comprises an organometallic compound containing at least one π-bound cyclopentadienyl moiety. Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted indenyl, fluroenyl, indacenyl, benzindenyl, and the like. In one or more aspects, the metallocene compound comprises titanium, zirconium, hafnium, or combinations thereof. In an aspect, the metallocene catalyst comprises dichloro [rac- ethylenebis(indenyl)]zirconium(IV)] metallocene catalyst [EBI(ZrCl2)]. 3  3511-00101

[0024] In one or more aspects, a catalyst composition for the production of a lm-OPW further comprises an activator. The term “activator,” as used herein, refers generally to a substance that is capable of converting a metallocene compound into a catalyst that can polymerize olefins. This term is used herein regardless of the actual activating mechanism.

[0025] In one or more aspects, the activator comprises a metal alkyl compound such as an organoaluminum compound. For example, the organoaluminum compound utilized in the catalyst systems disclosed herein can be any organoaluminum compound which can catalyze the formation of a polymer product. In an aspect, the organoaluminum compound comprises trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n- butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n- octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or combinations thereof. In an aspect, the metal alkyl compound comprises TIBA (also known as TIBAl).

[0026] In one or more aspects, the activator comprises a metal alkyl compound such as an aluminoxane. The aluminoxane can be methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propyl-aluminoxane, n- butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1- pentyl-aluminoxane, 2-pentylaluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane, neopentylaluminoxane, or combinations thereof.

[0027] In one or more other aspects, the metal alkyl compound comprises an organoboron compound or an organoborate compound. Hereinafter, for simplicity, organoboron compounds and organoborate compounds are referred to collectively as an organic boron-containing compound. Nonlimiting examples of organic boron-containing compounds include neutral boron compounds, borate salts, and the like, or combinations thereof. In some aspects, the organic boron-containing compound comprises dimethylanilinium tetrakis (pentafluorophenyl)borate (BArF5). In some aspects, the metal alkyl compound comprises an organoaluminum compound, an aluminoxne, an organic boron-containing compound or combinations thereof.

[0028] In one or more aspects, the catalyst system can have a mole ratio of the total amount of metal alkyl compound (e.g., TIBA or TIBA and BArF5) to transition metal of the metallocene compound that is stoichiometric or approximately stoichiometric. In one or more aspects, the mole ratio of metal in the metal alkyl compound (e.g., aluminum in TIBA) to 4  3511-00101 transition metal of the metallocene ranges from about 0.1:1 to about 3:1, alternatively from about 0.2:1 to 2:1, alternatively from about 0.3:1 to about 1.5:1, alternatively from about 0.4:1 to about 1.1:1, alternatively from about 0.5:1 to about 1:1, alternatively from about 0.6:1 to about 1:1, alternatively from about 0.7:1 to about 1:1, alternatively from about 0.8:1 to about 1:1, alternatively from about 0.9:1 to about 1:1 or alternatively less than about 5:1, alternatively less than about 4:1, alternatively less than about 3:1, or alternatively less than about 2:1.

[0029] In some aspects, the catalyst system can have a mole ratio of the amount of metal in the metal alkyl compound (e.g., TIBA or TIBA and BArF5 ) to the amount of the transition metal in the transition metal of the metallocene compound that is in a range for aluminium and zirconium of between about 100 to about 600, between about 15- to about 550 or between about 180 to about 540, in some aspects, between about 182-540. For boron and zirconium, the catalyst system can have a mole ratio of the amount of metal in the metal alkyl compound to the amount of the transition metal in the transition metal of the metallocene compound that is in a range of between about 1 to about 3, or about 2. In some aspects, a higher Al / Zr ratio can favor polymers with wax properties.

[0030] In an aspect, a catalyst composition comprising a metallocene compound and activator is contacted with at least one olefin under conditions suitable for the formation of a polymer product such as a homopolymer product. In one or more aspects, the olefin comprises ethylene which can be present during the reaction at a minimum ethylene partial pressure of about 5 psi (34.5 kPa), alternatively about 50 psi (345 kPa), alternatively about 100 psi (689 kPa), alternatively about 150 psi (1.03 MPa), alternatively about 250 psi (1.72 MPa), or alternatively about 500 psi (3.5 MPa); or alternatively, about 1000 psi (6.89 MPa).

[0031] In one or more aspects, the catalyst composition comprising a metallocene compound and activator is contacted with at least two olefins under conditions suitable for formation of a copolymer product. Herein the first monomer may be the primary monomer (e.g., ethylene) such that it comprises the majority of the final polymer, specifically a copolymer product. Nonlimiting examples of comonomers suitable for use in the present disclosure include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- octadecene, or a combination thereof. In an aspect, the comonomer comprises 1-hexene. In such aspects, the amount of comonomer present constitutes less than about 10 wt.% of the total amount of solvent present. For example, the comonomer may comprise at least about 0.25 weight percent (wt.%) of the total amount of solvent present, alternatively at least about 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 5  3511-00101 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.%, 8.0 wt.%, 8.5 wt.%, 9.0 wt.% or 9.5 wt.% and up to about 15 wt.%, 14 wt.%, 13 wt.%, 12 wt.%, 11 wt.% or 10 wt.% by total weight of the solvent.

[0032] In or more aspects, conditions suitable for the formation of a polymer product include the presence of hydrogen. In such aspects, the polymerization processes disclosed herein may be carried out at a minimum hydrogen partial pressure of 1 psi (6.9 kPa), 2 psi (14 kPa), 5 psi (34 kPa), 10 psi (69 kPa), or 15 psi (103 kPa); alternatively or additionally, at a maximum hydrogen partial pressure of 200 psi (1.4 MPa) ), 150 psi (1.03 MPa), 100 psi (689 kPa), 75 psi (517 kPa), or 50 psi (345 kPa). In some aspects, the amount of hydrogen present can be less than about 10% of the total amount of olefins present. For example, hydrogen may be present in an amount of at least about 0.01 weight percent (wt.%) of the total amount of reaction mixture, alternatively at least about 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.%, 8.0 wt.%, 8.5 wt.%, 9.0 wt.% or 9.5 wt.% and up to about 15 wt.%, 14 wt.%, 13 wt.%, 12 wt.%, 11 wt.% or 10 wt.% of the total reaction mixture.

[0033] In an aspect, the polymerization processes disclosed herein may be carried out at a minimum temperature of 0 °C, 25 °C, 40 °C, or 50 °C, 90 °C, 100 °C, 150 °C, 200 °C. In an aspect, the polymerization processes disclosed herein may be carried out (or the reaction zone can operate) at a temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein. In some non-limiting aspects, the polymerization processes disclosed herein may be carried out (or the reaction zone can operate) at a temperature from 0 °C to 200 °C, from 30 °C to 150 °C, from 60 °C to 130 °C, or from 80 °C to 120 °C. Other temperature ranges that can be utilized are readily apparent to those skilled in the art with the aid of this disclosure.

[0034] The reaction time (or residence time) of the polymerization processes disclosed herein can comprise any time that can produce the desired quantity of polymer product. In some aspects, the time can range from 1 minute to 5 hours; alternatively, ranges from 10 minutes to 2.5 hours; alternatively, ranges from 30 minutes to 2 hours; or alternatively, ranges from 1 hour to 1.5 hours.

[0035] In one or more aspects, the polymerization processes disclosed herein may be carried out in a suitable solvent. The methods described herein can utilize one or more solvents. Solvents which can be utilized in aspects of the present disclosure include without limitation 6  3511-00101 water, hydrocarbons (e.g., alkanes including pentane, hexane, heptane, octane, etc. and / or aromatics such as benzene, toluene, xylene, etc.), halogenated hydrocarbons, ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles and combinations thereof. In some aspects, an aspect of the present disclosure can call for a polar solvent. Polar solvents which can be utilized include without limitation water, ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles, and mixtures thereof. Aprotic polar solvents which can be utilized include without limitation ethers, esters, ketones, aldehydes, nitriles, and mixtures thereof.

[0036] In one or more aspects, a solvent suitable for the polymerization processes disclosed herein is dehydrated to reduce the amount of water present in the solvent. Dehydration of the solvent may be carried out using any suitable methodology. Exemplary dehydration processes can include mole sieve or alumina beds configured in a swing bed configuration to remove water from the solvent. A solvent suitable for use in the present disclosure may have a water content of less than about 1 weight percent (wt.%) of the solvent composition, alternatively less than about 0.1 wt.%, 0.05wt.%, 0.04 wt.%, 0.03 wt.%, 0.02 wt.%, 0.015 wt.%, or 0.01 wt.%. Additional water scavengers can be used in the reactor to further decrease the amount of water present.

[0037] An lm-OPW of the present disclosure can be formed using any suitable olefin polymerization method which may be carried out using various types of polymerization reactors. As used herein, “polymerization reactor” includes any polymerization reactor capable of polymerizing olefin monomers to produce homopolymers or copolymers.

[0038] The various types of reactors include those that may be referred to as batch, slurry, or gas-phase. Gas phase reactors may comprise fluidized bed reactors or staged horizontal reactors. Slurry reactors may comprise vertical or horizontal loops. Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. Processes may also include partial or full direct recycle of un-reacted monomer, un-reacted co-monomer, and / or diluent.

[0039] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type. Production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor into the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. 7  3511-00101 Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, or a combination of loop and gas reactors. The multiple reactors may be operated in series or in parallel.

[0040] According to one aspect of the disclosure, the polymerization reactor system may comprise at least one loop slurry reactor comprising vertical and / or horizontal loops. Monomer, diluent, catalyst and optionally any co-monomer may be continuously fed to a loop reactor where polymerization occurs. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent. Reactor effluent may be flashed to remove the solid polymer from the liquids that comprise the diluent, monomer and / or co-monomer. Various technologies may be used for this separation step including but not limited to, flashing that may include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; or separation by centrifugation.

[0041] According to yet another aspect of this disclosure, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream may be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product may be withdrawn from the reactor and new or fresh monomer may be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for multi-step gas- phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone.

[0042] According to yet another aspect of the disclosure, the polymerization reactor may comprise a solution polymerization reactor wherein the monomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer may be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation may be employed 8  3511-00101 to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Adequate means are utilized for dissipating the exothermic heat of polymerization.

[0043] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems for the present disclosure may further comprise systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loadout, laboratory analysis, and process control.

[0044] Disclosed herein is a process for forming a lm-OPW. In some aspects, the process can begin by dehydrating the solvent as described herein. The dried solvent can be transferred to the reactor (e.g., any of the reactor systems disclosed herein). At least a portion of the comonomer can then be added to the solvent in the reactor. After adding the solvent and the comonomer, the mixture can be combined and the reactor temperature can be increased up to or near the desired reaction temperature. In some aspects, the comonomer can be added to the solvent at a percentage of less than about 10 wt.%-15 wt.% of the total solvent present (including at any of the amounts described herein). When the desired temperature is reached a scavenging agent (e.g., TiBAl, etc.) can be added to the reactor to remove any trace moisture and oxygen.

[0045] The catalyst system can then be added to the reactor. The catalyst can be prepared by adding the catalyst to a dried solvent followed by the addition of the activator. The activator can alkylate the catalyst to form the catalyst system.

[0046] The primary monomer can then be added to the reactor with or without hydrogen. The primary monomer and hydrogen can be introduced at various ratios, which can affect the final properties of the lm-OPW. In some aspects, the ratio of the primary monomer to hydrogen can be in a range of 1:2 to about 200:1, or between about 10:1 to about 100:1, or between about 10:1 to about 50:1.

[0047] The reaction can be continued for a specific time while monitoring the reaction pressure and temperature. When reaction is complete, the primary monomer and hydrogen feeds can be stopped, and the reactor pressure reduced. In some embodiments the reactor pressure can be allowed to further reduce by reacting the primary monomer to extinction. The reactor can optionally be flushed with an inert gas such as nitrogen to ensure an inert 9  3511-00101 atmosphere. Finally, the catalyst can be deactivated before opening the reactor to allow collection of the polymer. In some aspects, the catalyst can be deactivated through the addition of an alcohol and / or water to the reactor. The solvent can be removed from the polymer to obtain the final product.

[0048] Disclosed herein are compositions and processes that produce a unique specialty ultra-low density to low density wax material, the lm-OPW. In one or more aspects, the lm- OPW is characterized by a melting point ranging from about 90oC to about 120oC, alternatively from about 90oC to about 115oC, alternatively from about 90oC to about 100oC, alternatively a melting point of about 80oC, 85oC , 84oC, 86oC, 88oC, 90oC, 92oC, 94oC, 96oC, 98oC, 100oC, 102oC, 104oC, 106oC, 108oC, 110oC, 112oC, 114oC, 116oC, 118oC or 120oC.

[0049] The lm-OPW may be further characterized by viscosities ranging from about 300 centipoise (cP) to about 7000 cP at a temperature of 150oC, alternatively from about 380 cP to about 6300 cP, about 400 cP to about 6000 cP, alternatively from about 500 cP to about 5000 cP, alternatively from about 600 cP to about 4000 cP, alternatively from about 1000 cP to about 3000 cP or alternatively from about 500 cP to about 2000 cP.

[0050] In one or more aspects, the lm-OPW is characterized by a crystallinity that ranges from about 20% to about 60%, alternatively from about 25% to about 60%, alternatively from about 30% to about 50%, or about 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%.

[0051] In one or more aspects, the lm-OPW is characterized by a density that ranges from about 0.8 g / cm3to about 0.94 g / cm3. In some aspects, the density can be at least about 0.80 g / cm3, at least about 0.81 g / cm3, at least about 0.82 g / cm3, at least about 0.83 g / cm3, at least about 0.84 g / cm3, at least about 0.85 g / cm3, at least about 0.86 g / cm3, at least about 0.87 g / cm3, at least about 0.878 g / cm3, or at least about 0.88 g / cm3. In some aspects, the density can be less than about 0.94 g / cm3, less than about 0.93 g / cm3, less than about 0.92 g / cm3, or less than about 0.91 g / cm3. In some aspects, the density can be between any of the lower range and any of the upper ranges as disclosed herein.

[0052] In one or more aspects, the lm-OPW is characterized by a weight average molecular weight ranging from about 4000 gram / mole (g / mole) to about 7000 g / mol, alternatively from about 4500 g / mol to about 6000 g / mol and a polydispersity index ranging from about 2.0 to about 4.0, alternatively from about 2.5 to about3.7 or alternatively from about 3.0 to about 3.5. The weight-average molecular weight (Mw) can be calculated according to Equation 1: 10  3511-00101 ^N M 2 Mw^ ii i(1) ^iNiMi

[0053] wherein Niis the molecular weight Mi. All molecular weight averages are expressed in. The polydispersity index refers to a ratio of the Mw to the number average molecular weight Mn or Mw / Mn. The Mn is the number- average molecular weight of the individual polymers and was calculated by measuring the molecular weight Mi of Ni polymer molecules, summing the weights, and dividing by the total number of polymer molecules, according to equation 2: ^NiM Mn^ iiwherein Niis the

[0054] In one or more aspects, the lm-OPW is a component of a hot melt adhesive. In such aspects, the lm-OPW is present in the HMA in an amount of from about 0.1 wt.% to about 90 wt.%, alternatively from about 5 wt.% to about 50 wt.% or alternatively from about 5 wt.% to about 25 wt.%. A hot melt adhesive comprising a lm-OPW may have a fiber tear temperature ranging from about -50 ^C to about 50 ^C, alternatively from about -10 ^C to about 40 ^C or alternatively form about 0 ^C to about 25 ^C.

[0055] Within the described systems and processes, the relative amount of hydrogen used in the reaction system can result in an increase in the melting point of the resulting lm-OPW. Further, the amount of the comonomer can also affect the final properties of the lm-OPW. For example, excessive co-monomer can react when introduced in the reaction system in the presence of the catalyst system to produce a gel type amorphous poly alpha olefin (APAO) material. This APAO can be useful for adhesive applications in providing a good flexible adhesive property, however it can phase separately during processing of the finished products in lubricant applications. The comonomer concentration can be controlled (e.g., decreased) while increasing the amount of hydrogen to control the final properties. In general, decreasing the comonomer concentration can cause a drop in the melting point and viscosity of the lm- OPW. The crystallinity of the lm-OPW can increase with decreasing co-monomer concentration. The hydrogen concentration variation demonstrates that the properties of the lm-OPW can be adjusted by tuning the H2 and comonomer amounts to achieve the lm-OPW having properties in the wax range melting point. 11  3511-00101

[0056] The present invention describes a process for manufacturing a polymer having a melting point in the wax range. In some aspects, this can be achieved by ethylene co- polymerization with hexene-1 in the presence of hydrogen using a commercially available metallocene catalyst. Different solvents were studied and found that solvent solvency properties can affect for catalyst and monomer interaction and hence the polymerization reaction. A specialty polymer in the wax range melting point was achieved by varying different process parameters such as hydrogen and comonomer concentration. EXAMPLES

[0057] The following examples are given as particular aspects of the present disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner. Materials and method

[0058] Different solvents were used in this polymerization process. Specifically, heptane and toluene solvents (Purity >98%). All the solvents were treated through the mole sieve and alumina beds to remove moisture, and any oxygenates including peroxides. Commercial Bis(butylcyclopentadienyl)zirconium(IV) dichloride (nBuCp2ZrCl2), and Dichloro[rac- ethylenebis(indenyl)]zirconium(IV) is called EBI(ZrCl2) type metallocene catalysts were used. Different cocatalysts / activator such as modified methylaluminoxane (MMAO-12) 25% solution in in toluene, Tri-isobutyl aluminum 25% solution in hexane / heptane / toluene and dimethylanilinium Tetrakis (pentafluorophenyl)borate (BArF5), 98%, were used. Polymer grade hexene-1 was used. High purity research grade gases were used in polymerization reaction without any further treatment including nitrogen (Research grade, Purity-99.9997%) and hydrogen (Research grade, Purity-99.9999%).

[0059] Polymer products were characterized by differential scanning calorimetry (DSC), using TA DSC 250 modal, Drop melting point (DMP) was measured using METLER TOLEDO DP90. Dropping Point System, Viscosity was measured in Brookfield apparatus at 150°C, Modal: DV-II+Pro, Penetration point was measured at 25°C using ASTM D1321-02a method and apparatus modal was HUMBOLDT H-1240D, The density of the polymer was determined at room temperature using a modified version of ASTM D 1505-03. Approximately 100 grams of water was added to the beaker, followed by the introduction of a small quantity 12  3511-00101 of wax pastilles. Isopropanol was then incrementally added dropwise to the mixture until the wax pastilles achieved a neutral buoyancy point near the center of the liquid column. The density of the polymer sample was subsequently measured at room temperature using a 9 mL specific gravity cup.

[0060] High-temperature gel permeation chromatography (GPC) was employed to measure the molecular weight of the polymer, in accordance with ASTM D6474-20. Calibration of the GPC system was achieved using polyethylene standards procured from the American Polymer Standards Corporation. The analytical setup comprised two Agilent Technologies PLgel 5 μm Mixed-D columns installed within an Agilent 1260 Infinity II High Temperature GPC System. Example 1:

[0061] Catalytic co-polymerization of ethylene with hexene-1 was carried out in a 1.5 gallon stirred Parr autoclave (Model 4580 Parr, USA) connected to a reactor controller (model 4848). Prior to polymerization, the reactor was heated to 130°C under nitrogen flow (50-100 ml / min) for 2-3 h and cooled down to ~50°C before adding the solvent and comonomer hexene- 1. The solvent was pre-treated through the mole sieve and alumina beds. Solvent was transferred to the reactor under N2 pressure through another mole sieve bed to further reduce the moisture level. The moisture level of the solvent was less than 15 ppm, however typically less than 10 ppm. Ethylene and hydrogen flow rates were controlled through a Brooks 0254 mass flow controller with the hydrogen being tied to the ethylene flow.

[0062] Different metallocene catalysts were used in the polymerization reaction such as bis(butylcyclopentadienyl)zirconium(IV) dichloride (nBuCp2ZrCl2), and dichloro[rac- ethylenebis(indenyl)]zirconium(IV) is called EBI(ZrCl2). Modified methylaluminoxane (MMAO-12) 25% solution in hexene-1 was used as activator for (nBuCp2ZrCl2) catalyst. For EBI(ZrCl2) catalyst tri-isobutylaluminium (TiBAl) and dimethylanilinium tetrakis (pentafluorophenyl)borate (BArF5) was used as an activator. In a typical experiment, catalyst EBI (ZrCl2) / BArF5 complex (5.0-15.0 mg) and 4.0-6.0 ml (25% in hexane / toluene) Tri- isobutylaluminium (TiBAl) were carefully charged into the dry reactor at atmospheric condition. Catalyst was prepared in a glove box and transferred in a headspace vial. A calculated amount of EBI (ZrCl2) catalyst was dissolved in a dry toluene followed by the addition of a stoichiometric amount of TiBAl so as to alkylate the catalyst. In a separate flask, a stoichiometric amount of BArF5 and dry toluene were mixed. Finally, the alkylated EBI(ZrCl2) solution was transferred into BArF5 flask to make a boron complex. The catalyst 13  3511-00101 color changed from green to blue / purple. In the BArF5 process, the catalyst should be activated with a minimum amount of TiBAl.

[0063] Reactant and catalyst were added in the following order to the reactor: First solvent was transferred to the reactor using drying systems described earlier. Dried hexene-1 (less than 10 ppm water) was transferred by a cannula system under nitrogen pressure for a batch process. After adding the solvent and hexene-1, the agitator was turned on and the reactor temperature was increased to close to the desired reaction temperature of 80 ^C -90 ^C. When the desired temperature was reached a scavenging agent TiBAl was added to the reactor to remove any trace moisture and oxygen. This was followed by adding catalyst using a cannula system. Ethylene and hydrogen addition started promptly thereafter. Ethylene and hydrogen were tied at desired ratio as shown in Table 1. The reaction was continued for a specific time while monitoring the reaction pressure and temperature. When reaction time was over, ethylene and hydrogen supply was terminated, and the reactor pressure reduced. In some aspects the reactor pressure was allowed to further reduce by reacting the ethylene to extinction. The reactor was flushed with nitrogen three times to ensure an inert atmosphere. Finally, the catalyst was deactivated before opening the reactor to allow collection of the polymer. The solvent was removed from the polymer and the polymer was dried and characterized. Table 1 H2Activity P.P. Viscosity Tmity14  3511-00101 8 4 3.1 78,500 10.1 2444 106.5 99.2 0.8942 36.0

[0064] In Table 1, the polymerization conditions included a temperature of 90°C (80- 100°C); a run time of 24-30 / 30-180 minute; a reactor pressure of 0-52 / 0-150 psi during run time; “E” - extended period run for reacting unreacted ethylene in reactor at batch mode operation. The solvent was heptane; Comonomer: Hexene-1 % of solvent; Catalyst: 5.0- 10.0 / 5-20 mg; 5.8 / 4-7ml TiBAl (25 wt% in hexane); Al / Zr=182-540; B / Zr=2; Slaved C2= and H2gases (% of ethylene) through the mass flow controllers; * refers to the use of 10 mg catalyst; P.P: Penetration point; DMP: Drop melting point; Tm: Melting point was measured by DSC; Crystallinity was measured by DSC.Extended periods of polymerization reaction time, without releasing the reactor pressure, were investigated. In such aspects, ethylene was allowed to react to extinction residual reactor pressure which was mainly unreacted hydrogen was released to be recycled. After releasing the residual pressure, the same protocol as earlier was followed to open the reactor and collect the polymer.

[0065] The co-monomer hexene-1 effect in batch charged versus continuous addition of hexene-1 with the reaction time course was also investigated. A high pressure Eldex pump (Modal: 1MH) was used for hexene-1 charging in a continuous dosing system. A schematic diagram of polymerization reaction in Parr reactor of the hexene-1 pumping system and in 15  3511-00101 place mole sieve drying system is shown in Figure 1. A detailed schematic diagram of polymerization reaction in Parr reactor of the hexene-1 pumping system and in place mole sieve drying system was shown in Figure 1. Example 2:

[0066] Effects of H2 with constant hexene-1 concentration were studied in the system described in Example 1. It was observed that with decreasing H2concentration from 5% to 2%, melting point of polymer linearly increased from 91.0°C to 106°C as shown in Table 1 and Figure 2. Example 3:

[0067] Excessive co-monomer hexene-1 might react when introduced in the system and hence produce a gel type amorphous poly alpha olefin (APAO) material. This APAO is useful for adhesive applications in providing a good flexible adhesive property, however it can phase separately during processing of the finished products in hot melt adhesive (HMA) and polyvinyl chloride (PVC) lubricant applications. For this reason, a decrease was investigated in the hexene concentration from 4.6% to 3.1% whilst varying the H2 concentration from 2% to 8%. It was observed that with decreasing hexene-1 concentration, melting point, drop melting point and viscosity of polymer was changed as shown in Table 1. The crystallinity of polymer was increased with decreasing hexene-1 co-monomer. The hydrogen concentration variation trend followed the same trend as earlier. Figure 3 shows the influence of H2 concentration on polymer properties. Further decreasing hexene-1 concentration from 3.1% to 2.3% produced wax range melting point polymer (Table 1, Entries: 14 and 15). The chain termination effect of H2without co-monomer hexene-1 was also studied. It was observed that 50% hydrogen concentration under identical condition, reduced the melting point of polymer only from 137 °C to 127 °C (Table1, Entry 15) which is above the melting point of wax range and hence co-monomer is more effective in reducing polymer melting point. Example 4:

[0068] In this example the unreacted ethylene and H2 was allowed to fully react by extending the reaction time by a further 1 to 2 hours. It was observed that the polymer properties were very similar in extended reaction period versus the typical reaction time of less than 1 hour. The differential scanning calorimetry (DSC) patterns are also very similar and shown in Figure 4 (Table 1: Entries 12 and 13E). This study shows that the batch process can be operated 16  3511-00101 by reacting the reactants to extinction without much change in the polymer properties. This limits potential fugitive emissions. Example 5:

[0069] In this example, hexene-1 co-monomer was added in a continuous system to produce polymer. A high-pressure pump was used and allowed for the production of a homogeneous wax. The results of utilizing a continuous system is presented in Figure 4. Example 6:

[0070] In this example, yield of product was increased using sequential charging of feeds from 0-150 psig reactor pressure at a typical reaction temperature 80-100°C. The resulting polymers fell in the wax range and properties were very similar compared to without sequential charging process. Example 7: Application of novel PE wax:

[0071] Several waxes produced with varying properties are shown in Table 2. Several Hot Melt Adhesive (HMA) formulations were made with these waxes as shown in Table 3 The HMA formulation used different wax samples along with commercially available tackifier and polymers. The wax polymer produced exhibits excellent compatibility with polyolefin polymers and elastomers. These novel waxes can be readily formulated with a wide variety of polymers, tackifiers, and hot melt additives (HMA). The resulting compositions find utility in diverse applications encompassing packaging, hygiene products, automotive components, woodworking, and mattress manufacturing.   17  DPM[ 5.2 3.3 4.3 7.3 - -:.I]D6lPA0 0o;tMtr5 5a-0-0pel]de2 0 0 0TmC°1[0310311211111511eA 1N:Mtr5a-5-2- .0 0 0P HP - 1 - - 1 1ytis ]8N nl 98em / 8638. 888 6 08. 199. 169. 17;t 1A0 0 09. 19niMtr5-5-2- Dg[ 0 0 0 0 0.0opHaP01 - - -0101ygtinsCo°itcsi ]0lP5e3e A18 0 3mlb rereVc[@379503967 4 a72577CST.ifim1 2 3 4 5 6 D:CySk1 2 3 4ca ltopx xaax x x x xmD- W wawawawawawT,ybtnx- eax- Wax- WaxWalalaWicirclaeravorarararar 2edenoara a a ereocoecocococo lbrup orororom m Nre e e ece a sTrTrTrTrTrTT amo cecececemomoner r r rI mC T T T T C C- - 02-0102-019102-01---Bremyloplai1c0r1e00m -11m5o3C3511-00101 HMAs performance test:

[0072] The heat resistance was determined by measuring the shear adhesion failure temperature (SAFT) and peel adhesion failure temperature (PAFT). Both tests involved measuring the temperature at which the adhesive bond fails under shear and peel stress when subjected by increasing temperatures in an oven. Cheminstrument 8-Point Shear Oven was employed for determining PAFT and SAFT tests. Sample preparation and test methods are described below. Unconditioned Kraft paper samples were utilized for both PAFT and SAFT tests, following these procedures: Sample Preparation for PAFT and SAFT tests:

[0073] Kraft paper roll (50 lb basis weight, 48 in. width x 720 ft length x 48 lb) was acquired from ULINE. Melted Hot Melt Adhesive (HMA) was prepared in a 2 oz glass jar within a Binder Forced Air Oven (Serial Number: 20190000017401) at 175°C. A 12 mm x 42 mm Kraft paper strip was positioned on a Cheminstrument EZ Coater EC200. Melted HMA was placed onto the center of the Kraft paper on the EZ Coater. Another 12 mm x 42 mm Kraft paper strip was placed on top of the melted HMA. The EZ Coater was programmed with a coat speed of 0 to 10 knob and we used 1.5 test speed knob using a #60 wire rod to create a uniform coating. The resultant coated Kraft paper was sectioned into ten (10) samples, each measuring 2.5 cm wide and approximately 0.2-0.25 mm thick. PAFT and SAFT test process:

[0074] The prepared samples were subjected to temperature-controlled failure testing within a programmed oven. Weights of 100 g and 500 g were employed for PAFT and SAFT tests, respectively (refer to Figure 6 for illustration and Figure 7 for a picture of the test set up). Five replicates were prepared for both peel and shear tests. The testing protocol was pre- programmed to maintain an initial oven temperature of 25°C for 5 minutes, followed by a temperature ramp of 25°C / hour up to 150°C. The oven automatically recorded the failure temperature for each sample. The reported results represent the average of the five replicates for each test type (PAFT and SAFT).

[0075] HMA’s formulated with these waxes exhibit good thermal resistance properties compared to commercial hot melt adhesives. (Table 4) 20  3511-00101 Table 4 Comm. Comm. TEST HMA1 HMA2 HMA3 HMA4 HMA5 HMA6 HMA7 A B

[0076] These HMA s demonstrated significantly improved PAFT and SAFT compared to conventional HMAs. Notably, HMAs designated HMA3, HMA4, HMA5 and HMA6 exhibited SAFT exceeding 100°C, surpassing the performance of the commercially available HMAs such as Commercial HMA A and Commercial HMA B. In addition, the disclosed soft wax, characterized by a crystallinity of 31%, can be formulated solely with a tackifier (Table 3; HMA7), negating the need for additional polymers. Bonding Performance:

[0077] The adhesive strength of the HMAs at various temperatures were evaluated using the following method: The Adhesive failure test was conducted at 25°C (room temperature), - 25°C, and -40°C. Sanyo Scientific model SF-L6111 S / N 1111009675 was used for -25°C test and RC211 chiller from SP Industries and HT 135 grade fluid from Solvay was used for -40°C test. Unconditioned kraft paper and white corrugated sheet (SI products 24” x 36”, 32ECT, purchased from Staples) were used to make the samples. Samples were prepared in the same way of PAFT / SAFT samples except HMA glue coated between white corrugated sheet and kraft paper. Fifteen samples are prepared for each HMA formulation. Five samples of each are designated at 25°C (room temperature), -25°C, and -40°C. Samples were placed in a sealed plastic bag before putting into freezer or chiller for the test.

[0078] Conditioning parameters were as follows: Room temperature: Samples are maintained at ambient conditions for 24 hours Low temperature: Samples are stored at -25°C for 120 hours. Ultra-low temperature: Samples are stored at -40°C for 4 hours.

[0079] After the designated conditioning period, the adhesive bond strength of each sample is evaluated by manually separating the bonded joint (kraft paper and white corrugated sheet). An example of the test is shown in Figure 8. Fiber tearing was evaluated for peeled samples. The reported results represent the average of the five replicates for each test type: FFT = Full 21  3511-00101 Fiber Tearing bond (85-100% FT); PFT = Partial Fiber Tearing bond (50-84% FT); SFT = Slight Fiber Tearing bond (20-49% FT); NFT = No Fiber Tearing bond (0-19% FT) Table 5 Test temperature HMA5 HMA6 HMA8 Commercial A Commercial B

[0080] The invention relates to HMAs formulated with novel waxes, exhibiting excellent bonding performance at various temperatures. These HMAs demonstrate comparable performance to commercially available HMAs at room temperature (25°C), -25°C, and -40°C. Notably, no adhesive failure was observed during testing under these conditions. These HMAs are suitable for use in a wide range of climatic conditions, including both hot and cold regions.

[0081] In addition to the various systems, processes, and compositions disclosed herein, certain aspects can include, but are not limited to:

[0082] In a first aspect, a process for producing a polymer wax comprises: co-polymerizing a primary monomer and a comonomer in the presence of a metallocene catalyst in a reactor to form the polymer wax, wherein the polymer wax has a melting point below 120oC and a viscosity of less than 7000 cP at 150oC.

[0083] A second aspect can include the process of the first aspect, wherein the primary monomer is ethylene.

[0084] A third aspect can include the process of the first or second aspect, wherein the comonomer is hexene-1.

[0085] A fourth aspect can include the process of any one of the first to third aspects, wherein the metallocene catalyst comprises dichloro[rac-ethylenebis(indenyl)]zirconium(IV), and activators Tri-isobutylaluminium (TiBAl) and Dimethylanilinium Tetrakis (pentafluorophenyl)borate.

[0086] A fifth aspect can include the process of any one of the first to fourth aspects, wherein the co-polymerizing occurs in the presence of a solvent. 22  3511-00101

[0087] A sixth aspect can include the process of the fifth aspect, further comprising: drying the solvent prior to introducing the solvent to the reactor.

[0088] In a seventh aspect, a process for producing a polymer wax comprises: introducing a solvent into the reactor; dehydrating a solvent within a reactor; introducing a comonomer into the reactor after dehydrating the solvent; introducing a metallocene catalyst into the reactor after the comonomer; introducing a primary monomer to the reactor after the comonomer; and co-polymerizing the primary monomer and the comonomer in the presence of the metallocene catalyst in the reactor to form the polymer wax.

[0089] An eighth aspect can include the process of the seventh aspect, further comprising: introducing hydrogen into the reactor to control properties of the polymer wax.

[0090] A ninth aspect can include the process of the eighth aspect, wherein hydrogen is introduced in an amount of between 2%-8% by weight of the primary monomer.

[0091] A tenth aspect can include the process of the eighth or ninth aspect, further comprising: continuously dosing the comonomer into the reactor during the co-polymerization; and avoiding the formation of a gel type material based on the continuous dosing.

[0092] An eleventh aspect can include the process of any one of the eighth to tenth aspects, where the hydrogen is introduced at a ratio of the primary monomer to hydrogen in a range of 1:1 to about 200:1.

[0093] A twelfth aspect can include the process of any one of the seventh to eleventh aspects, wherein the polymer wax has a melting point in a range of 90oC to about 120oC.

[0094] A thirteenth aspect can include the process of any one of the seventh to twelfth aspects, wherein the polymer wax has a viscosity ranging from about 300 centipoise (cP) to about 7000 cP at a temperature of 150oC.

[0095] A fourteenth aspect can include the process of any one of the seventh to thirteenth aspects, wherein the polymer wax has a crystallinity ranging from about 20% to about 60%.

[0096] A fifteenth aspect can include the process of any one of the seventh to fourteenth aspects, wherein the polymer wax has density in a range of from about 0.8 g / cm3to about 0.94 g / cm3.

[0097] A sixteenth aspect can include the process of any one of the seventh to fifteenth aspects, wherein the polymer wax has a weight average molecular weight ranging from about 4000 gram / mole (g / mole) to about 7000 g / mol. 23  3511-00101

[0098] A seventeenth aspect can include the process of any one of the seventh to sixteenth aspects, further comprising: incorporating the polymer wax into a hot melt adhesive.

[0099] An eighteenth aspect can include the process of the seventeenth aspect, wherein the solvent has less than 15 ppm water in the reactor.

[0100] A nineteenth aspect can include the process of the eighteenth aspect, further comprising: continuous injecting the comonomer into the reactor during the co-polymerizing.

[0101] A twentieth aspect can include the process of the eighteenth or nineteenth aspect, wherein the comonomer is present in any amount of between 0.25 wt.% to about 10 wt.% of the reaction mixture.

[0102] In a twenty first aspect, a polymer wax comprises: a copolymer formed between a primary monomer and a comonomer in the presence of a metallocene catalyst, wherein the polymer wax has a melting point below 120oC and a viscosity of less than 7000 cP at 150oC.

[0103] A twenty second aspect can include the polymer wax of the twenty first aspect, wherein the primary monomer is ethylene.

[0104] A twenty third aspect can include the polymer wax of the twenty first or twenty second aspect, wherein the comonomer is hexene-1.

[0105] A twenty fourth aspect can include the polymer wax of any one of the twenty first to twenty third aspects, wherein the polymer wax has a melting point in a range of 90oC to about 120oC.

[0106] A twenty fifth aspect can include the polymer wax of any one of the twenty first to twenty fourth aspects, wherein the polymer wax has a viscosity ranging from about 300 centipoise (cP) to about 7000 cP at a temperature of 150oC.

[0107] A twenty sixth aspect can include the polymer wax of any one of the twenty first to twenty fifth aspects, wherein the polymer wax has a crystallinity ranging from about 20% to about 60%.

[0108] A twenty seventh aspect can include the polymer wax of any one of the twenty first to twenty sixth aspects, wherein the polymer wax has density in a range of from about 0.8 g / cm3to about 0.94 g / cm3. 24  3511-00101

[0109] A twenty eighth aspect can include the polymer wax of any one of the twenty first to twenty eighth aspects, wherein the polymer wax has a weight average molecular weight ranging from about 4000 gram / mole (g / mole) to about 7000 g / mol.

[0110] A twenty ninth aspect can include a process for producing a specialty polymer in wax range melting point of any of the preceding aspects, wherein said process comprising co- polymerizing ethylene and hexene-1 in the presence of a metallocene catalyst, said catalyst comprising: Dichloro[rac-ethylenebis(indenyl)]zirconium(IV), and activators Tri- isobutylaluminium (TiBAl) and Dimethylanilinium Tetrakis (pentafluorophenyl)borate.

[0111] A thirtieth aspect can include a process for purification of a solvent in used in any of the preceding aspects by using mole sieve and alumina beds in external place and in place for drying the solvent and hexene-1 for polymerization reaction in Parr reactor shown in Figure 1.

[0112] A thirty first aspect can include a process for controlling the melting point, drop melting point, viscosity, crystallinity produced in any of the preceding aspects by using a hydrogen percentage (2.0-8.0%) and hexene-1 comonomer percentage (2.3-4.6%).

[0113] A thirty second aspect can include a process for making an ultra-low density specialty polymer in wax range melting point in any of the preceding aspects by fine tuning of hydrogen and hexene-1 concentration for special applications in adhesive industry.

[0114] A thirty third aspect can include a process for controlling the viscosity (<520 cP) and avoiding gel type material in any of the preceding aspects by continuous dosing of hexene- 1 using high pressure pump in an identical condition except different way of hexene-1 dosing system.

[0115] Embodiments and aspects are discussed herein with reference to the Figures. However, those skilled in the art will readily appreciate that the detailed description given herein with respect to these figures is for explanatory purposes as the systems and methods extend beyond these limited embodiments. For example, it should be appreciated that those skilled in the art will, in light of the teachings of the present description, recognize a multiplicity of alternate and suitable approaches, depending upon the needs of the particular application, to implement the functionality of any given detail described herein, beyond the particular implementation choices in the following embodiments described and shown. That is, there are numerous modifications and variations that are too numerous to be listed but that all fit within the scope of the present description. Also, singular words should be read as plural and vice 25  3511-00101 versa and masculine as feminine and vice versa, where appropriate, and alternative embodiments do not necessarily imply that the two are mutually exclusive.

[0116] It is to be further understood that the present description is not limited to the particular methodology, compounds, materials, manufacturing techniques, uses, and applications, described herein, as these may vary. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present systems and methods. It must be noted that as used herein and in the appended claims (in this application, or any derived applications thereof), the singular forms "a," "an," and "the" include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to "an element" is a reference to one or more elements and includes equivalents thereof known to those skilled in the art. All conjunctions used are to be understood in the most inclusive sense possible. Thus, the word "or" should be understood as having the definition of a logical "or" rather than that of a logical "exclusive or" unless the context clearly necessitates otherwise. Structures described herein are to be understood also to refer to functional equivalents of such structures. Language that may be construed to express approximation should be so understood unless the context clearly dictates otherwise.

[0117] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this description belongs. Preferred methods, techniques, devices, and materials are described, although any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in the practice or testing of the present systems and methods. Structures described herein are to be understood also to refer to functional equivalents of such structures. The present systems and methods will now be described in detail with reference to embodiments thereof as illustrated in the accompanying drawings.

[0118] From reading the present disclosure, other variations and modifications will be apparent to persons skilled in the art. Such variations and modifications may involve equivalent and other features which are already known in the art, and which may be used instead of or in addition to features already described herein.

[0119] Although claims may be formulated in this application or of any further application derived therefrom, to particular combinations of features, it should be understood that the scope of the disclosure also includes any novel feature or any novel combination of features disclosed 26  herein either explicitly or implicitly or any generalization thereof, whether or not it relates to the same systems or methods as presently claimed in any claim and whether or not it mitigates any or all of the same technical problems as do the present systems and methods.

[0120] Features which are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination. The Applicant(s) hereby give notice that new claims may be formulated to such features and / or combinations of such features during the prosecution of the present Application or of any further Application derived therefrom.

Claims

3511-00101 herein either explicitly or implicitly or any generalization thereof, whether or not it relates to the same systems or methods as presently claimed in any claim and whether or not it mitigates any or all of the same technical problems as do the present systems and methods. [00120] Features which are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination. The Applicant(s) hereby give notice that new claims may be formulated to such features and / or combinations of such features during the prosecution of the present Application or of any further Application derived therefrom. 27  3511-00101 CLAIMS What is claimed:

1. A process for producing a polymer wax, the process comprising: co-polymerizing a primary monomer and a comonomer in the presence of a metallocene catalyst in a reactor to form the polymer wax, wherein the polymer wax has a melting point below 120oC and a viscosity of less than 7000 cP at 150oC.

2. The process of claim 1, wherein the primary monomer is ethylene.

3. The process of claim 1, wherein the comonomer is hexene-1.

4. The process of claim 1, wherein the metallocene catalyst comprises dichloro[rac- ethylenebis(indenyl)]zirconium(IV), and activators Tri-isobutylaluminium (TiBAl) and Dimethylanilinium Tetrakis (pentafluorophenyl)borate.

5. The process of claim 1, wherein the co-polymerizing occurs in the presence of a solvent.

6. The process of claim 5, further comprising: drying the solvent prior to introducing the solvent to the reactor.

7. A process for producing a polymer wax, the process comprising: introducing a solvent into the reactor; dehydrating a solvent within a reactor; introducing a comonomer into the reactor after dehydrating the solvent; introducing a metallocene catalyst into the reactor after the comonomer; introducing a primary monomer to the reactor after the comonomer; and co-polymerizing the primary monomer and the comonomer in the presence of the metallocene catalyst in the reactor to form the polymer wax.

8. The process of claim 7, further comprising: 28  3511-00101 introducing hydrogen into the reactor to control properties of the polymer wax.

9. The process of claim 8, wherein hydrogen is introduced in an amount of between 2%- 8% by weight of the primary monomer.

10. The process of claim 8, further comprising: continuously dosing the comonomer into the reactor during the co-polymerization; and avoiding the formation of a gel type material based on the continuous dosing.

11. The process of claim 8, where the hydrogen is introduced at a ratio of the primary monomer to hydrogen in a range of 1:1 to about 200:

1.

12. The process of claim 7, wherein the polymer wax has a melting point in a range of 90 oC to about 120oC.

13. The process of claim 7, wherein the polymer wax has a viscosity ranging from about 300 centipoise (cP) to about 7000 cP at a temperature of 150oC.

14. The process of claim 7, wherein the polymer wax has a crystallinity ranging from about 20% to about 60%.

15. The process of claim 7, wherein the polymer wax has density in a range of from about 0.8 g / cm3to about 0.94 g / cm3.

16. The process of claim 7, wherein the polymer wax has a weight average molecular weight ranging from about 4000 gram / mole (g / mole) to about 7000 g / mol.

17. The process of claim 7, further comprising: incorporating the polymer wax into a hot melt adhesive.

18. The process of claim 17, wherein the solvent has less than 15 ppm water in the reactor.

19. The process of claim 18, further comprising: continuous injecting the comonomer into the reactor during the co-polymerizing. 29

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