Patent Publication Number: US-2006014901-A1

Title: Novel wax-like polymer for use in hot melt adhesive applications

Description:
CROSS REFERENCES TO RELATED APPLICATIONS  
      This application is a continuation-in-part application of U.S. patent application Ser. No. 10/666,488, filed 19 Sep. 2003, the contents of which are hereby incorporated by reference herein, and assigned to HRD Corporation, the assignee of the present application. U.S. patent application Ser. No. 10/666,488, filed 19 Sep. 2003 claims the benefit of U.S. Provisional Patent Application Ser. No. 60/471,318, filed 19 May 2003, the contents of which are hereby incorporated by reference herein. 
    
    
     FIELD OF THE INVENTION  
      An embodiment of the present invention is a novel hot melt adhesive composition comprising a low viscosity, low molecular weight ethylene/alpha-olefin interpolymer that has wax-like properties, one or more tackifiers, and an ethylene vinyl acetate interpolymer. The wax component is a low viscosity, low number average molecular weight (M n  between 700 and &lt;1000) ethylene/α-olefin interpolymer prepared using a single metallocene catalyst system. Hot melt adhesive composition embodiments made with this interpolymer have adhesive properties that are similar to those of conventional hot melt adhesives which include a wax, a tackifier and other polymer or copolymer.  
     BACKGROUND OF THE INVENTION  
      Hot melt adhesives (“HMAs”) are ubiquitous in many areas of commerce including consumer and industrial packaging where a bond is required between a substrate and a second item. HMAs are routinely used in the manufacture of corrugated cartons, boxes, cereal boxes and the like. They are also used in diverse areas, such as bookbinding; sealing the ends of paper bags; furniture manufacturing; manufacture of particleboard, linerboard, various other paper goods, and for adhering other articles, such as glass, metals and various plastics, including attaching paper labels to plastic containers. Additional uses of hot-melt adhesives also include, for example only, carpet seam sealing tape, lamination, product assembly, non-woven construction, and potting and encapsulation compounds.  
      Because of these diverse applications, hot melt adhesives may be required to maintain a strong bond over a wide range of temperature conditions. For example, in the manufacture of corrugated cartons used for shipping refrigerated or frozen foods, or foods packed in ice, hot melt adhesives are generally selected because of their ability to maintain a strong bond under low temperature conditions. However in other applications the hot melt adhesive may have to maintain a strong bond to the substrate under extremes of stress and shock in handling, and high humidity.  
      Unlike other adhesives, which are often applied as a solution in a solvent, HMAs are generally solids, and, in commercial applications, are typically applied to substrates in their molten state at temperatures of about 350 degrees F. (177 degrees C.). As the molten adhesive cools and solidifies, a bond is formed between the substrate and the second item. Various techniques can be used to apply hot melt adhesives to a substrate including roll coaters, knife coaters and spray devices.  
      Two other important factors in hot melt adhesive performance are the so-called “set time” and “open time” of the adhesive. The “open time” of a hot melt adhesive is the time it takes to solidify to a point where it can no longer bond with the intended article. The “set time” of a hot melt adhesive is the time required for the adhesive to cool to the point where it has enough strength to form a bond. Set speed is an important parameter for applications such as high speed packaging lines, where bonding needs to occur rapidly to avoid poorly sealed or unsealed boxes.  
      Most hot melt adhesives are mixtures of three components: a wax, a tackifying agent and a polymeric resin. Although each component is generally present in roughly equal proportions in an HMA formulation, their relative ratio is often “fine tuned” for a particular application&#39;s need.  
      The polymer component provides the strength to the adhesive bond. The tackifier provides tack to the adhesive by improving wetting, which serves to secure the items to be bonded while the adhesive sets, and reduces the viscosity of the system making the adhesive easier to apply to the substrate. The wax shortens the open time and also reduces the viscosity of the system. In general, the percent wax is minimized and added in quantities sufficient to achieve the desired viscosity and set speeds.  
      A number of hot melt adhesive formulations utilize a vinyl acetate (“VA”) polymer as the polymer component and the formulations are varied according to the vinyl acetate content of the polymer. Low vinyl acetate content polymers are preferred due to their lower cost, and as they are relatively non polar, they can be formulated with other relatively non-polar tackifiers and waxes to yield compatible formulations. Higher vinyl acetate content polymer resins (with greater than about 18% vinyl acetate content) when used in hot melt adhesive formulations result in a stronger ionic bond to polar substrates such as paper, thereby creating a stronger adhesive. However, the use of higher vinyl acetate content polymers requires formulating with more polar waxes and tackifiers to maintain formulation compatibility. More polar waxes, such as Fischer-Tropsch (“FT”) waxes are generally more expensive than paraffin wax and the selection and supply of these more polar waxes is limited. They are difficult to obtain domestically and are thus potentially subject to supply interruptions caused by world events.  
      In addition to bonding requirements, HMAs require performance in other areas such as thermal and oxidative stability. Holt melt adhesives are applied in a molten state; consequently many applications involve prolonged exposure to high temperatures. Good thermal and oxidative stability means that the HMA will not darken nor produce a char or skin or gel, nor will it exhibit a substantial viscosity change over time. Such charring, skinning, gel formation and/or viscosity changes also increase the propensity of the formulation to cause plugged lines and nozzles while in use, as in industrial applications. The introduction of any wax into an HMA formulation, and especially the more polar waxes, tends to lower the formulation&#39;s thermal and oxidative stability.  
      Hot melt adhesives comprised of ethylene polymers other than those incorporating vinyl acetate have also been disclosed in the prior art. For instance, U.S. Pat. No. 5,021,257, issued on Jun. 4, 1991, to Foster et al., discloses a hot-melt adhesive composition having a viscosity of about 3,000 to about 25,000 centipoise at 135° C., and a Ring and Ball softening point of about 90° C. to about 125° C., said adhesive composition comprising a blend of at least one substantially amorphous propylene/hexene copolymer, at least one tackifier, and at least one substantially crystalline, low viscosity hydrocarbon wax.  
      U.S. Pat. No. 5,530,054, issued Jun. 25, 1996 to Tse et al., claims a hot melt adhesive composition consisting essentially of: (a) 30 percent to 70 percent by weight of a copolymer of ethylene and about 6 percent to about 30 percent by weight of a C 3  to C 20  α-olefin produced in the presence of a catalyst composition comprising a metallocene and an alumoxane and having an M w  of from about 20,000 to about 100,000; and (b) a hydrocarbon tackifier which is selected from a recited list.  
      U.S. Pat. No. 5,548,014, issued Aug. 20, 1996 to Tse et al., claims a hot melt adhesive composition comprising a blend of ethylene/alpha-olefin copolymers wherein the first copolymer has a M w  from about 20,000 to about 39,000 and the second copolymer has a M w  from about 40,000 to about 100,000. Each of the hot melt adhesives exemplified comprises a blend of copolymers, with at least one of the copolymers having a polydispersity greater than 2.5. Furthermore, the lowest density copolymer exemplified has a specific gravity of 0.894 g/cm 3 .  
      U.S. Pat. No. 6,107,430, issued on Aug. 22, 1991, to Dubois et al., discloses hot melt adhesives comprising at least one homogeneous linear or substantially linear interpolymer of ethylene with at least one C 2 -C 20  α-olefin interpolymer having a density from 0.850 to 0.895 g/cm 3 , optionally at least one tackifying resin; and optionally at least one wax, wherein the hot melt adhesive has a viscosity of less than about 5000 cP at 150° C.  
      Also, EP 0 886 656 B1, published on Sep. 19, 2001, to Simmons et al., discloses hot melt adhesives comprising from 5 to 95 weight percent at least one homogeneous linear or substantially linear interpolymer of ethylene with at least one α-olefin interpolymer having a polydispersity index, Mw/Mn, of from 1.5 to 2.5, and a density from 0.850 to 0.885 g/cm 3 , from 5 to 95 weight percent of at least one tackifying resin; and optionally at least one wax.  
      Tse, in Application of Adhesion Model for Developing Hot Melt Adhesives Bonded to Polyolefin Surfaces, Journal of Adhesion, Vol. 48, Issue 1-4, pp. 149-167, 1995, notes that compared with hot melt adhesives based on ethylene-vinyl acetate copolymer, hot melt adhesives based on homogeneous linear ethylene/.alpha.-olefin interpolymers show higher viscosity and inferior tensile strength, but better bond strength to polyolefin surfaces, higher strain at break and lower yield stress.  
      Hot melt adhesives comprising these polymers can be made which match the strength performance of the vinyl-acetate containing HMA formulations, but their ability to be formulated with non polar tackifiers render the resulting hot melt formulation more thermally stable than vinyl acetate containing hot melt adhesives.  
      However, neither the prior art involving vinyl acetate-based adhesives nor the prior art involving non-vinyl acetate containing polymer-based adhesives anticipates the present invention whereby a low viscosity, low molecular weight synthetic polymer can be created that can substitute for the wax component of a hot melt adhesive formulation.  
      Such a hot melt adhesive formulation, comprising a wax, a tackifier and a polymer or copolymer) would be highly advantageous. It would also be highly advantageous to have an HMA formulation, which can be prepared with a minimum of mixing steps, thus minimizing the cost and variability of the formulation. It would also be highly advantageous to have an HMA formulation which is able to match the adhesion performance of HMA&#39;s comprising high VA containing ethylene-vinyl acetate (“EVA”) polymers but without the requirement of incorporating expensive petroleum waxes that are primarily imported and/or derived from imported oil based feedstocks. It would also be highly advantageous if such hot melt adhesive formulations were able to exhibit the strength and adhesion characteristics of the EVA-containing formulations and would also have good thermal and oxidative stability.  
      A wax for use in hot melt adhesives should have a relatively sharp melt point to yield an adhesive with a short ‘set speed’ and controllable open time. The wax should be compatible with the other components of the HMA formulation. The melt point is another property in addition to compatibility. The wax must also allow for a reduction of overall adhesive viscosity to allow for the proper application or coating of the hot melt adhesive on the intended substrate. Generally, hot melt adhesive formulations are heated to 300-350 degrees F. (149-177 degrees C.) prior to application in order to reduce viscosity. The wax should be stable at these temperatures to allow for extended periods as a molten product prior to application. Antioxidants and free radical scavenger compounds can be added to the adhesive compound to further enhance thermal stability.  
      Synthetic ethylene vinyl acetate waxes have been developed and are commercially available for use with high vinyl acetate content polymer in adhesive formulations. Low molecular weight ethylene vinyl acetate waxes such as AC 400 (available from Honeywell); EVA1 (BASF); and MC400, available through Marcus Oil and Chemical, are examples of such commercially available materials. These waxes, however, are not widely used because of their relatively high cost to manufacture and resulting high selling price. These waxes also have relatively poor set speed characteristics when incorporated into adhesive formulations due to their low crystallinity and a lack of a sharp melting point.  
      Various attempts to utilize alternatives to imported and/or petroleum derived waxes have been reported (U.S. Pat. No. 4,749,739, U.S. Pat. No. 4,396,673 and U.S. Pat. No. 4,388,138; these patents are incorporated by reference herein).  
      For example, Foster et al. (U.S. Pat. No. 4,749,739) discloses incorporation of a synthetic polyethylene wax, hydrocarbon tackifier and amorphous propylene polymer to create a low viscosity hot melt adhesive.  
      Ball et al. (U.S. Pat. Nos. 4,396,673 and 4,388,138) mention use of vegetable wax in combination with an isocyanate binder as a release agent in the manufacture of particleboard.  
      Mehaffy et al. (U.S. Pat. No. 6,117,945) highlight the need for low application temperature (between 200 to 300 degrees F.) hot melt adhesives and suggests a styrene, alpha-methylstyrene and/or vinyltoluene polymer combined with ethylene vinyl acetate polymer and paraffin wax.  
      These references illustrate the use of petroleum-derived waxes and synthetic waxes for formulating hot melt adhesive compounds. Borsinger et al. (U.S. Pat. Appl. Pub. No. 2003/0229168 A1, also assigned to HRD Corp., the assignee of the present specification) disclose use of vegetable-derived highly hydrogenated triglyceride waxes for use in hot melt adhesive formulations, as a naturally derived product obtainable from a renewable source (plant extracts), instead of petroleum derived or synthetic waxes.  
      The hot melt adhesives of the present invention comprise a synthetic, low viscosity, low number average molecular weight (M n  between 700 and &lt;1000) interpolymer, which has wax-like properties, as the wax component. Depending upon the ultimate application, additional components such as one or more tackifiers, and a polymer or copolymer, such as an ethylene vinyl acetate copolymer, can be added to form the HMA. Thus the HMA compositions of the present invention require a minimum of mixing steps, each of which introduce both additional cost and variability to the final HMA formulation. Some HMA compositions described herein can function without the requirement of an expensive polar wax in the formulation.  
      The HMA compositions of the present invention also exhibit adhesion and strength properties that are comparable to those of conventional EVA-containing hot melt adhesives.  
     BRIEF SUMMARY OF THE INVENTION  
      The present invention comprises hot melt adhesive compositions having a low viscosity, low number average molecular weight, ethylene/α-olefin interpolymer that has wax-like properties, one or more tackifiers and a thermoplastic copolymer consisting essentially of ethylene, or ethylene and vinyl acetate, and copolymers and terpolymers thereof. The ethylene/α-olefin polymer was synthesized using a single metallocene catalyst polymerization process.  
      An embodiment of the present invention is a hot melt adhesive composition comprising: 
          A) from about 10 to 50 percent by weight (based on the final weight of the hot melt adhesive composition) of a thermoplastic copolymer consisting essentially of ethylene, or ethylene and vinyl acetate, and copolymers and terpolymers thereof;     B) from 10 to about 90 percent by weight (based on the final weight of the hot melt adhesive composition) of one or more tackifiers; and     C) from 1 to about 40 percent by weight (based on the final weight of the hot melt adhesive composition) of a wax, the wax being a homogeneous ethylene/α-olefin interpolymer.        

      A second embodiment of the present invention is a hot melt adhesive composition wherein; 
          A) the wax is present in an amount of from about 10 to about 30 percent by weight (based on the final weight of the hot melt adhesive composition) and the wax is characterized by having: 
            i) a Brookfield Viscosity (measured at 300° F./149° C.) of from about 10 to about 100 cP and     ii) a number average molecular weight (Mn) of from about 700 to about 1000; and     iii) a density of from about 0.880 to about 0.950 g/cm 3 ;    
            B) the one or more tackifiers is present in an amount of from about 35 to about 65 percent by weight (based on the final weight of the hot melt adhesive composition); and wherein     C) the hot melt adhesive composition is characterized by having: 
            i) a Peel Adhesion Failure Temperature (“PAFT”) of greater than or equal to 60° C.; and     ii) a Shear Adhesion Failure Temperature (“SAFT”) of greater than or equal to 70° C.    
               

      Another embodiment is a cellulosic article formed using a hot melt adhesive composition, the adhesive composition comprising: 
          A) from about 10 to 50 percent by weight (based on the final weight of the hot melt adhesive composition) of a thermoplastic, copolymer consisting essentially of ethylene, or ethylene and vinyl acetate, and copolymers and terpolymers thereof;     B) from 10 to about 90 percent by weight (based on the final weight of the hot melt adhesive composition) of one or more tackifiers; and     C) from 1 to about 40 percent by weight (based on the final weight of the hot melt adhesive composition) of a wax, the wax being a homogeneous ethylene/α-olefin interpolymer.        

      Another embodiment is a method of producing a polymer composition comprising admixing: 
          an amount of from about 10 to 50 percent by weight (based on the final weight of the hot melt adhesive composition) of a thermoplastic copolymer consisting essentially of ethylene, or ethylene and vinyl acetate, and copolymers and terpolymers thereof;     an amount of from 10 to about 90 percent by weight (based on the final weight of the hot melt adhesive composition) of one or more tackifiers; and     an amount of from 1 to about 40 percent by weight (based on the final weight of the hot melt adhesive composition) of a wax, the wax being a homogeneous ethylene/α-olefin interpolymer.        

      The adhesive characteristics of the inventive hot melt adhesive compositions (“HMAs”) were tested and their properties were comparable to conventional hot-melt adhesive formulations which comprise a polymer, a wax and a tackifier.  
    
    
     DETAILED DESCRIPTION OF THE INVENTION  
      Unless indicated otherwise, the following testing procedures and definitions are to be employed: 
          Melt index (I 2 ), is measured in accordance with ASTM D-1238, condition 190° C./2.16 kg (formally known as “Condition (E)”).     Molecular weight is determined using gel permeation chromatography (GPC). The chromatographic system consisted of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 unit. The column and carousel compartments were operated at 140° C. The columns used were 3 Polymer Laboratories 10-micron Mixed-B columns. The solvent is 1,2,4-trichlorobenzene. The samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The solvent used to prepare the samples contained 200 pp, of butylated hydroxytoluene (“BHT”). Samples were prepared by agitating lightly for 2 hours at 160° C. The injection volume used was 100 microliters and the flow rate was 1.0 milliliter/min.        

      Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 degrees Celsius with gentle agitation for 30 minutes. The narrow standards mixtures were run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation: 
 
 M   polyethylene   =a* ( M   polystyrene ) b.  
 
      Where M is the molecular weight, a has a value of 0.431 and b=1.0. Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0.  
      Melt viscosity is determined in accordance with the following procedure using a Brookfield Laboratories DVII+ Viscometer in disposable aluminum sample chambers. The spindle used is a SC-31 hot-melt spindle, suitable for measuring viscosities in the range of from 10 to 100,000 centipoise. A cutting blade is employed to cut samples into pieces small enough to fit into the 1 inch wide, 5 inches long (25.4 mm wide, 127 mm long) sample chamber. The sample is placed in the chamber, which is in turn inserted into a Brookfield Thermosel and locked into place with bent needle-nose pliers. The sample chamber has a notch on the bottom that fits the bottom of the Brookfield Thermosel to ensure that the chamber is not allowed to turn when the spindle is inserted and spinning. The sample is heated to the desired temperature, such as 300° F. (149° C.) or 350° F. (177° C.), with additional sample being added until the melted sample is about 1 inch (25.4 mm) below the top of the sample chamber. The viscometer apparatus is lowered and the spindle submerged into the sample chamber. Lowering is continued until brackets on the viscometer align on the Thermosel. The viscometer is turned on, and set to a shear rate which leads to a torque reading in the range of 30 to 60 percent. Readings are taken every minute for about 15 minutes, or until the values stabilize, which final reading is recorded.  
      Percent crystallinity is determined by differential scanning calorimetry using a TA-Q 1000. The percent crystallinity may be calculated with the equation: 
 
percent  C =( A/ 292  J/g )×100, 
 
 wherein percent C represents the percent crystallinity and A represents the heat of fusion of the ethylene polymer in Joules per gram (J/g). 
 
      Density is measured in accordance with ASTM D-792. The samples are annealed at ambient conditions for 24 hours before the measurement is taken.  
      Hardness was determined by the needle penetration test according to ASTM D-1321.  
      Comonomer and monomer incorporation was determined using nuclear magnetic resonance (NMR) spectroscopy.  13 C NMR analysis was used to determine ethylene content and comonomer content using the following procedures:.  
       13 C NMR Analysis  
      The samples were prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromium acetylacetonate (relaxation agent) to 0.4 g sample of polymer in a 10 mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150° C. The data was collected using a Varian Unity Plus 400 MHz spectrometer, corresponding to a  13 C resonance frequency of 100.4 MHz. Acquisition parameters were selected to ensure quantitative  13 C data acquisition in the presence of the relaxation agent. The data was acquired using gated  1 H decoupling, 4000 transients per data file, a 6 sec pulse repetition delay, spectral width of 24,200 Hz and a file size of 32K data points, with the probe head heated to 130° C.  
      The term “interpolymer” is used herein to indicate a copolymer, or a terpolymer, or the like. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer.  
      The term “narrow composition distribution” used herein describes the comonomer distribution for homogeneous interpolymers. The narrow composition distribution homogeneous interpolymers can also be characterized by their SCBDI (short chain branch distribution index) or CDBI (composition distribution branch index). The SCBDI or CBDI is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer content.  
      The CDBI of a polymer is readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbreviated herein as “TREF”) as described, for example, in Wild et al,  Journal Of Polymer Science, Poly. Phys. Ed ., Vol. 20, p. 441 (1982), or in U.S. Pat. No. 5,548,014, the disclosures of which are incorporated herein by reference. Thus, the following procedure for calculating CDBI can be used: 
          (1) Generate a normalized, cumulative distribution plot of copolymer concentration versus elution temperature, obtained from the TREF.     (2) Determine the elution temperature at which 50 weight percent of the dissolved copolymer has eluted.     (3) Determine the molar comonomer content within the copolymer fraction eluting at that median elution temperature.     (4) Calculate limiting mole fraction values of 0.5 times and 1.5 times the molar comonomer content within the copolymer fraction eluting at that median temperature.     (5) Determine limiting elution temperature values associated with those limiting mole fraction values.     (6) Partially integrate that portion of the cumulative elution temperature distribution between those limiting elution temperature values.     (7) Express the result of that partial integration, CDBI, as a percentage of the original, normalized, cumulative distribution plot. 
 
 a) Homogeneous Ethylene/α-Olefin Interpolymer Component 
       

      By the term “homogeneous interpolymer” is used herein to indicate a linear or substantially linear ethylene interpolymer prepared using a constrained geometry or single site metallocene catalyst. By the term homogeneous, it is meant that any comonomer is randomly distributed within a given interpolymer molecule and substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. The melting peak of homogeneous linear and substantially linear ethylene polymers, as determined by differential scanning calorimetry (DSC), will broaden as the density decreases and/or as the number average molecular weight decreases.  
      The homogeneous linear or substantially linear ethylene polymers can be characterized as having a narrow molecular weight distribution (Mw/Mn). For the linear and substantially linear ethylene polymers, the Mw/Mn is preferably from 1.5 to 2.5, preferably from 1.8 to 2.2. However, certain interpolymers described herein may have much larger values of Mw/Mn, and still exhibit excellent adhesive properties.  
      Note that the ethylene polymers described herein differ from low density polyethylene prepared in a high pressure process. In one regard, whereas low density polyethylene is an ethylene homopolymer having a density of from 0.900 to 0.935 g/cm 3 , the ethylene polymers described herein require the presence of a comonomer to reduce the density to less than 0.935 g/cm 3 .  
      Substantially linear ethylene polymers are homogeneous polymers having long chain branching. The long chain branches have the same comonomer distribution as the polymer backbone and can be as long as about the same length as the length of the polymer backbone. When a substantially linear ethylene polymer is employed as described herein, such polymer may be characterized as having a polymer backbone substituted with from 0.01 to 3 long chain branches per 1000 carbons.  
      For quantitative methods for determination, see, for instance, U.S. Pat. Nos. 5,272,236 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2 &amp;3), p. 285-297), which discusses the measurement of long chain branching using  13 C nuclear magnetic resonance spectroscopy, Zimm, G. H. and Stockmayer, W. H., J. Chem. Phys., 17, 1301 (1949); and Rudin, A., Modern Methods of Polymer Characterization, John Wiley &amp; Sons, New York (1991) pp. 103-112, which discuss the use of gel permeation chromatography coupled with a low angle laser light scattering detector (“GPC-LALLS”) and gel permeation chromatography coupled with a differential viscometer detector (“GPC-DV”).  
      The homogeneous linear or substantially linear ethylene polymer will be an interpolymer of ethylene with at least one alpha-olefin. When ethylene propylene diene terpolymers (“EPDM&#39;s”) are prepared, the dienes are typically non-conjugated dienes having from 6 to 15 carbon atoms. Representative examples of suitable non-conjugated dienes that may be used to prepare the terpolymers include: 
      (a) Straight chain acyclic dienes such as 1,4-hexadiene; 1,5-heptadiene; and 1,6-octadiene;     (b) Branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene;     (c) Single ring alicyclic dienes such as 4-vinylcyclohexene; 1-allyl-4-isopropylidene cyclohexane; 3-allylcyclopentene; 4-allylcyclohexene; and 1-isopropenyl-4-butenylcyclohexene;     (d) Multi-ring alicyclic fused and bridged ring dienes such as dicyclopentadiene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene; 5-methylene-6-methyl-2-norbornene; 5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclopentenyl)-2-norbornene; 5-ethylidene-2-norbornene; 5-cyclohexylidene-2-norbornene; etc.    

      The preferred dienes are selected from the group consisting of 1,4-hexadiene; dicyclopentadiene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 7-methyl-1,6 octadiene; 4-vinylcyclohexene; etc. One preferred conjugated diene which may be employed is piperylene.  
      Most preferred are interpolymers of ethylene with at least one C 3 -C 30  α-olefins (for instance, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentine, and 1-octene), with interpolymers of ethylene with at least one C 3 -C 20  α-olefin being most preferred.  
      The homogeneous interpolymer described herein is a homogeneous polymer of ethylene with at least one ethylenically unsaturated monomer, conjugated or nonconjugated diene, polyene, etc.  
      Homogeneously branched linear ethylene/α-olefin interpolymers may be prepared using polymerization processes (such as is described by Elston in U.S. Pat. No. 3,645,992) which provide a homogeneous short chain branching distribution. In his polymerization process, Elston uses soluble vanadium catalyst systems to make such polymers. However, others such as Mitsui Petrochemical Company and Exxon Chemical Company have used so-called single site metallocene catalyst systems to make polymers having a homogeneous linear structure. Homogeneous linear ethylene/α-olefin interpolymers are currently available from Mitsui Petrochemical Company under the tradename “TAFMER” and from Exxon Chemical Company under the tradename “EXACT™”.  
      Substantially linear ethylene/α-olefin interpolymers are available from The Dow Chemical Company as AFFINITY® polyolefin plastomers. Substantially linear ethylene/.alpha-olefin interpolymers may be prepared in accordance with the techniques described in U.S. Pat. No. 5,272,236 and in U.S. Pat. No. 5,278,272, the entire contents of both of which are herein incorporated by reference.  
      An embodiment of the present invention is a polymer composition, derived from ethylene and alpha olefin, which has a low viscosity, low molecular weight and wax-like properties such that this polymer can be used to formulate a hot melt adhesive that is subsequently used to bond articles, yet which HMA composition has adhesive properties similar to conventional hot melt adhesives containing wax, tackifier and polymer.  
      The present inventors have discovered that a specific type of homogeneous interpolymer can unexpectedly be used by itself or in combination with a tackifier to produce commercially acceptable hot melt adhesives. In another embodiment, the subject of the present specification, we describe several hot melt adhesive compositions comprising a specific synthetic, low viscosity, low molecular weight interpolymer that, when combined with a suitable tackifier and polymer or copolymer, can be used as an alternative hot melt adhesive formulation, and whose adhesive properties are comparable to conventional hot melt adhesive formulations that utilize a wax, polymer and tackifier mixture.  
      The homogeneous interpolymer described herein may be prepared using the constrained geometry catalysts disclosed in U.S. Pat. No. 5,064,802, No. 5,132,380, No. 5,703,187, No. 6,034,021, EP 0 468 651, EP 0 514 828, WO 93/19104, and WO 95/00526, all of which are incorporated by references herein in their entirety. Another suitable class of catalysts is the metallocene catalysts disclosed in U.S. Pat. No. 5,044,438; No. 5,057,475; No. 5,096,867; and No. 5,324,800, all of which are incorporated by reference herein in their entirety. It is noted that constrained geometry catalysts may be considered as metallocene catalysts, and both are sometimes referred to in the art as single-site catalysts.  
      For example, catalysts may be selected from the metal coordination complexes corresponding to the formula:  
                 
 
 wherein: M is a metal of group 3, 4-10, or the lanthanide series of the periodic table of the elements; Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an η 5  bonding mode to M; Z is a moiety comprising boron, or a member of group 14 of the periodic table of the elements, and optionally sulfur or oxygen, the moiety having up to 40 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system; X independently each occurrence is an anionic ligand group, said X having up to 30 non-hydrogen atoms; n is 2 less than the valence of M when Y is anionic, or 1 less than the valence of M when Y is neutral; L independently each occurrence is a neutral Lewis base ligand group, said L having up to 30 non-hydrogen atoms; m is 0, 1, 2, 3, or 4; and Y is an anionic or neutral ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 40 non-hydrogen atoms, optionally Y and Z together form a fused ring system. 
 
      Suitable catalysts may also be selected from the metal coordination complex which corresponds to the formula:  
                 
 
 wherein R′ each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms; X each occurrence independently is selected from the group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms; L independently each occurrence is a neural Lewis base ligand having up to 30 non-hydrogen atoms; Y is —O—, —S—, —NR*—, —PR*—, or a neutral two electron donor ligand selected from the group consisting of OR*, SR*, NR* 2 , PR* 2 ; M, n, and m are as previously defined; and Z is SIR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , GeR* 2 , BR*, BR* 2 ; wherein: R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Y, Z, or both Y and Z form a fused ring system. 
 
      It should be noted that whereas formula I and the following formulas indicate a monomeric structure for the catalysts, the complex may exist as a dimer or higher oligomer.  
      Further preferably, at least one of R′, Z, or R* is an electron donating moiety. Thus, highly preferably Y is a nitrogen or phosphorus containing group corresponding to the formula —N(R″″)— or —P(R″″)—, wherein R″″ is C 1-10 alkyl or aryl, i.e., an amido or phosphido group.  
      Additional catalysts may be selected from the amidosilane- or amidoalkanediyl-compounds corresponding to the formula:  
                 
 
 wherein: M is titanium, zirconium or hafnium, bound in an η 5  bonding mode to the cyclopentadienyl group; R′ each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms; E is silicon or carbon; X independently each occurrence is hydride, halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons; m is 1 or 2; and n is 1 or 2 depending on the valence of M. 
 
      Examples of the above metal coordination compounds include, but are not limited to, compounds in which the R′ on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, etc.; the cyclopentadienyl group is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc.; R′ on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, etc.; and X is chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, etc.  
      Specific compounds include, but are not limited to, (tertbutylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediylzirconium dimethyl, (tert-butylamido) (tetramethyl-η 5 -cyclo penta dienyl)-1,2-ethanediyltitanium dimethyl, (methylamido) (tetramethyl-η 5 -cyclopenta dienyl)-1,2-ethanediylzirconium dichloride, (methylamido)(tetramethyl-η 5 -eyelopenta dienyl)-1,2-ethane diyltitanium dichloride, (ethylamido)(tetramethyl-η 5 -cyclopentadienyl)-methylenetitanium dichloro, (tertbutylamido)diphenyl(tetramethyl-η 5 -cyclopentadienyl)-silane zirconium dibenzyl, (benzylamido)dimethyl-(tetramethyl-η 5 -cyclopentadienyl) ilanetitaniumdichloride, phenylphosphido)dimethyl(tetramethyl-η 5 -cyclopentadienyl) silane zirconium dibenzyl, and the like.  
      Another suitable class of catalysts is substituted indenyl containing metal complexes as disclosed in U.S. Pat. No. 5,965,756 and No. 6,015,868, which are incorporated by reference herein in their entirety. Other catalysts are disclosed in U.S. Pat. Nos. 6,268,444, 6,515,155, and 6,613,921 and copending application WO 01/042315 A1. The disclosures of all of the preceding patents and patent applications are incorporated by reference herein in their entirety. These catalysts tend to have a higher molecular weight capability.  
      One class of the above catalysts is the indenyl containing metal wherein:  
                 
 
      M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidation state; 
          A′ is a substituted indenyl group substituted in at least the 2 or 3 position with a group selected from hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germyl and mixtures thereof, the group containing up to 40 non-hydrogen atoms, and the A′ further being covalently bonded to M by means of a divalent Z group; Z is a divalent moiety bound to both A′ and M via σ-bonds, the Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen; X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, π-bound ligand groups; X′ independently each occurrence is a neutral Lewis base, having up to 20 atoms; p is 0, 1 or 2, and is two less than the formal oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1; and q is 0, 1 or 2.        

      The above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a neutral Lewis base, especially a trihydrocarbylamine, trihydrocarbylphosphine, or halogenated derivative thereof.  
      Preferred catalysts are complexes corresponding to the formula:  
                 
          wherein R 1  and R 2  independently are groups selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germyl and mixtures thereof, the group containing up to 20 non-hydrogen atoms, with the proviso that at least one of R 1  or R 2  is riot hydrogen; R 3 , R 4 , R 5 , and R 6  independently are groups selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germyl and mixtures thereof, the group containing up to 20 non-hydrogen atoms; M is titanium, zirconium or hafnium; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, the moiety having up to 60 non-hydrogen atoms; p is 0, 1 or 2; q is zero or one; with the proviso that: when p is 2, q is zero, M is in the +4 formal oxidation state, and X is an anionic ligand selected from the group consisting of halide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido, di(hydrocarbyl)phosphido, hydrocarbyl sulfido, and silyl groups, as well as halo-, di(hydrocarbyl)amino-, hydrocarbyloxy- and di(hydrocarbyl)phosphino-substituted derivatives thereof, the X group having up to 20 non-hydrogen atoms, when p is 1, q is zero, M is in the +3 formal oxidation state, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)-aminobenzyl, or M is in the +4 formal oxidation state, and X is a divalent derivative of a conjugated diene, M and X together forming a metallocyclopentene group, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X′ is a neutral, conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbyl groups, the X′ having up to 40 carbon atoms and forming a π-complex with M.        

      More preferred catalysts are complexes corresponding to the formula:  
                 
 
 wherein: R 1  and R 2  are hydrogen or C 1-6  alkyl, with the proviso that at least one of R 1  or R 2  is not hydrogen; R 3 , R 4 , R 5 , and R 6  independently are hydrogen or C 1-6  alkyl; M is titanium; Y is, —O—, —S—, —NR*—, —PR*—; Z* is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , or GeR* 2 ; R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, the R* having up to 20 non-hydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system; p is 0, 1 or 2; q is zero or one; with the proviso that: when p is 2, q is zero, M is in the +4 formal oxidation state, and X is independently each occurrence methyl or benzyl, when p is 1, q is zero, M is in the +3 formal oxidation state, and X is 2-(N,N-dimethyl)aminobenzyl; or M is in the +4 formal oxidation state and X is 1,4-butadienyl, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene. The latter diene is illustrative of unsymmetrical diene groups that result in production of metal complexes that are actually mixtures of the respective geometrical isomers. 
 
      Other catalysts, cocatalysts, catalyst systems, and activating techniques which may be used in the practice of the invention disclosed herein may include those disclosed in; U.S. Pat. No. 5,616,664, WO 96/23010, published on Aug. 1, 1996, WO 99/14250, published Mar. 25, 1999, WO 98/41529, published Sep. 24, 1998, WO 97/42241, published Nov. 13, 1997, WO 97/42241, published Nov. 13, 1997, those disclosed by Scollard, et al., in J. Am. Chem. Soc 1996, 118, 10008-10009, EP 0 468 537 B1, published Nov. 13, 1996, WO 97/22635, published Jun. 26, 1997, EP 0 949 278 A2, published Oct. 13, 1999; EP 0 949 279 A2, published Oct. 13, 1999; EP 1 063 244 A2, published Dec. 27, 2000; U.S. Pat. No. 5,408,017; U.S. Pat. No. 5,767,208; U.S. Pat. No. 5,907,021; WO 88/05792, published Aug. 11, 1988; WO88/05793, published Aug. 11, 1988; WO 93/25590, published Dec. 23, 1993;U.S. Pat. No. 5,599,761; U.S. Pat. No. 5,218,071; WO 90/07526, published Jul. 12, 1990; U.S. Pat. No. 5,972,822; U.S. Pat. No. 6,074,977; U.S. Pat. No. 6,013,819; U.S. Pat. No. 5,296,433; U.S. Pat. No. 4,874,880; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,621,127; U.S. Pat. No. 5,703,257; U.S. Pat. No. 5,728,855; U.S. Pat. No. 5,731,253; U.S. Pat. No. 5,710,224; U.S. Pat. No. 5,883,204; U.S. Pat. No. 5,504,049; U.S. Pat. No. 5,962,714; U.S. Pat. No. 5,965,677; U.S. Pat. No. 5,427,991; WO 93/21238, published Oct. 28, 1993; WO 94/03506, published Feb. 17, 1994; WO 93/21242, published Oct. 28, 1993; WO 94/00500, published Jan. 6, 1994, WO 96/00244, published Jan. 4, 1996, WO 98/50392, published Nov. 12, 1998; Wang, et al., Organometallics 1998, 17, 3149-3151; Younkin, et al., Science 2000, 287, 460-462, Chen and Marks, Chem. Rev. 2000, 100, 1391-1434, Alt and Koppl, Chem. Rev. 2000, 100, 1205-1221; Resconi, et al., Chem. Rev. 2000, 100, 1253-1345; Ittel, et al., ChemRev. 2000, 100, 1169-1203; Coates, Chem. Rev., 2000, 100, 1223-1251; WO 96/13530, published May 9, 1996; all of which patents and publications are herein incorporated by reference in their entirety. Also useful are those catalysts, cocatalysts, and catalyst systems disclosed in U.S. Pat. No. 6,268,444; U.S. Pat. No. 5,965,756; U.S. Pat. No. 6,150,297; and U.S. Pat. No. 6,515,155; all of which patents and publications are herein incorporated by reference in their entirety. In addition, methods for preparing the aforementioned catalysts are described, for example, in U.S. Pat. No. 6,015,868, the entire contents of which are herein incorporated by reference.  
      Cocatalysts:  
      The above-described catalysts may be rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique. Suitable activating cocatalysts for use herein include, but are not limited to, polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as C 1-30  hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 30 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron and perfluorinated tri(aryl)aluminum compounds, mixtures of fluoro-substituted(aryl)boron compounds with alkyl-containing aluminum compounds, especially mixtures of tris(pentafluorophenyl)borane with trialkylaluminum or mixtures of tris(pentafluorophenyl)borane with alkylalumoxanes, more especially mixtures of tris(pentafluorophenyl)borane with methylalumoxane and mixtures of tris(pentafluorophenyl)borane with methylalumoxane modified with a percentage of higher alkyl groups (MMAO), and most especially tris(pentafluorophenyl)borane and tris(pentafluorophenyl)aluminum; non-polymeric, compatible, non-coordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, non-coordinating anions, or ferrocenium salts of compatible, non-coordinating anions; bulk electrolysis and combinations of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, EP-A-468,651 (equivalent to U.S. Ser. No. 07/547,718), EP-A-520,732 (equivalent to U.S. Ser. No. 07/876,268, now U.S. Pat. No. 5,271,185), and EP-A-520,732 (equivalent to U.S. Ser. No. 07/884,966 filed May 1, 1992, now U.S. Pat. No. 5,350,723). The disclosures of all of the preceding patents or patent applications are incorporated by reference herein in their entirety.  
      Combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts. It has been observed that the most efficient catalyst activation using such a combination of tris(pentafluoro-phenyl)borane/alumoxane mixture occurs at reduced levels of alumoxane. Preferred molar ratios of Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane are from 1:1:1 to 1:5:10, more preferably from 1:1:1 to 1:3:5. Such efficient use of lower levels of alumoxane allows for the production of olefin polymers with high catalytic efficiencies using less of the expensive alumoxane cocatalyst. Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained.  
      Suitable ion forming compounds useful as cocatalysts in some embodiments of the invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, non-coordinating anion, A − . As used herein, the term “non-coordinating” means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A non-coordinating anion specifically refers to an anion which, when functioning as a charge balancing anion in a cationic metal complex, does not transfer an anionic substituent or fragment thereof to the cation thereby forming neutral complexes during the time which would substantially interfere with the intended use of the cationic metal complex as a catalyst. “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are non-interfering with desired subsequent polymerization or other uses of the complex.  
      Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, the anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitrites. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, known in the art and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.  
      Preferably such cocatalysts may be represented by the following general formula: 
 
( L*−H ) d   + ( A ) d−   Formula VII 
 
 wherein L* is a neutral Lewis base; (L*−H)+is a Bronsted acid; A d−  is an anion having a charge of d−, and d is an integer from 1 to 3. More preferably A d−  corresponds to the formula: [M′Q 4 ] − , wherein M′ is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), the Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,433. 
 
      In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A − . Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: 
 
( L*−H ) + ( M′Q   4 ) − ;  Formula VIII 
 
 wherein L* is as previously defined; M′ is boron or aluminum in a formal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 non-hydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl. Most preferably, Q in each occurrence is a fluorinated aryl group, especially a pentafluorophenyl group. Preferred (L*−H)+cations are N,N-dimethylanilinium, N,N-di(octadecyl)anilinium, di(octadecyl)methylammonium, methylbis(hydrogenated tallowyl)ammonium, and tributylammonium. 
 
      Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst are tri-substituted ammonium salts such as: trimethylammonium tetrakis(pentafluorophenyl) borate; triethylammonium tetrakis(pentafluorophenyl) borate; tripropylammonium tetrakis (pentafluorophenyl) borate; tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate; tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate; N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate; N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate; N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate; N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate; N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate; N,N-dimethylanilinium pentafluoro phenoxytris(pentafluorophenyl) borate; N,N-diethylanilinium tetrakis(pentafluorophenyl) borate; N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate; trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate; triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate; tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate; tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetra fluorophenyl) borate; N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate; N,N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; and N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; di-substituted oxonium salts such as: diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis (pentafluorophenyl) borate, and di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts such as: diphenylsulfonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and bis(2,6-dimethylphenyl) sulfonium tetrakis(pentafluorophenyl) borate.  
      Preferred silylium salt activating cocatalysts include, but are not limited to, trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluoro-phenylborate and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem. Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is disclosed in U.S. Pat. No. 5,625,087, which is incorporated by reference herein in its entirety. Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used in embodiments of the invention. Such cocatalysts are disclosed in U.S. Pat. No. 5,296,433, which is also incorporated by reference herein in its entirety.  
      The catalyst system may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent in which polymerization will be carried out by solution polymerization procedures. The catalyst system may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material. When prepared in heterogeneous or supported form, it is preferred to use silica as the support material.  
      At all times, the individual ingredients, as well as the catalyst components, should be protected from oxygen and moisture. Therefore, the catalyst components and catalysts should be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen or argon.  
      The molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1:1000 to 2:1, more preferably from 1:5 to 1.5:1, most preferably from 1:2 to 1:1. In the preferred case in which a metal complex is activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane, the titanium:boron:aluminum molar ratio is typically from 1:10:50 to 1:0.5:0.1, most typically from about 1:3:5.  
      In general, the polymerization may be accomplished at conditions for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, reactor pressures ranging from atmospheric to 3500 atmospheres (34.5 kPa). The reactor temperature should be greater than 80° C., typically from 100° C. to 250° C., and preferably from 100° C. to 150° C., with higher reactor temperatures, that is, reactor temperatures greater than 100° C. generally favoring the formation of lower molecular weight polymers.  
      Generally the polymerization process is carried out with a differential pressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa), most preferably from 40 to 60 psi (300 to 400 kPa). The polymerization is generally conducted at a temperature of from 80 to 250° C., preferably from 90 to 170° C., and most preferably from greater than 95 to 160° C.  
      In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10 −12 :1 to 10 −1 :1, more preferably from 10 −9 :1 to 10 −5 :1.  
      Solution polymerization conditions utilize a solvent for the respective components of the reaction. Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and ISOPAR® E, available from Exxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.  
      The solvent will be present in an amount sufficient to prevent phase separation in the reactor. As the solvent functions to absorb heat, less solvent leads to a less adiabatic reactor. The solvent:ethylene ratio (weight basis) will typically be from 2.5:1 to 12: 1, beyond which point catalyst efficiency suffers. The most typical solvent:ethylene ratio (weight basis) is in the range of from 5:1 to 10:1.  
      The polymerization may be carried out as a batchwise or a continuous polymerization process, with continuous polymerization processes being required for the preparation of substantially linear polymers. In a continuous process, ethylene, comonomer, and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom.  
      b) Tackifier Component  
      Addition of tackifier is desirable to allow for bonding prior to solidifying or setting of the adhesive. An example of this is in high-speed cereal box sealing operations where the overlapping flaps of the box need to adhere to one another while the hot melt adhesive solidifies.  
      Tackifying resins useful in the present invention include aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons and hydrogenated versions; terpenes and modified terpenes and hydrogenated versions; and rosins and rosin derivatives and hydrogenated versions; and mixtures thereof. These tackifying resins have a ring and ball softening point from 70° C. to 150° C., and will typically have a viscosity at 350° F. (177° C.), as measured using a Brookfield viscometer, of no more than 2000 centipoise. They are also available with differing levels of hydrogenation, or saturation, which is another commonly used term. Useful examples include Eastotac™ H-100, H-115 and H-130 from Eastman Chemical Co. in Kingsport, Term., which are partially hydrogenated cycloaliphatic petroleum hydrocarbon resins with softening points of 100° C., 115° C. and 130° C., respectively. These are available in the E grade, the R grade, the L grade and the W grade, indicating differing levels of hydrogenation with E being the least hydrogenated and W being the most hydrogenated. The E grade has a bromine number of 15, the R grade a bromine number of 5, the L grade a bromine number of 3 and the W grade has a bromine number of 1. Eastotac™H-142R from Eastman Chemical Co. has a softening point of about 140° C. Other useful tackifying resins include Escorez™5300, 5400 and 5637, partially hydrogenated cycloaliphatic petroleum hydrocarbon resins, and Escorez™5600, a partially hydrogenated aromatic modified petroleum hydrocarbon resin all available from Exxon Chemical Co. in Houston, Tex.; WINGTACK® Extra, which is an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical Co. in Akron, Ohio; WINGTACK® 95, an aliphatic C-5 petroleum hydrocarbon resin (Goodyear Chemical); Hercolite™ 2100, a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules, Inc. in Wilmington, Del.  
      There are numerous types of rosins and modified rosins available with differing levels of hydrogenation including gum rosins, wood rosins, tall-oil rosins, distilled rosins, dimerized rosins and polymerized rosins. Some specific modified rosins include glycerol and pentaerythritol esters of wood rosins and tall-oil rosins. Commercially available grades include, but are not limited to, Sylvatac™ 1103, a pentaerythritol rosin ester available from Arizona Chemical Co., Unitac™ R-100 Lite, a pentaerythritol rosin ester from Union Camp in Wayne, N.J., Permalyn™ 305, an erythritol modified wood rosin available from Hercules and Foral 105 which is a highly hydrogenated pentaerythritol rosin ester also available from Hercules. Sylvatac™R-85 and 295 are 85° C. and 95° C. melt point rosin acids available from Arizona Chemical Co. and Foral AX is a 70° C. melt point hydrogenated rosin acid available from Hercules, Inc. Nirez V-2040 is a phenolic modified terpene resin available from Arizona Chemical Co.  
      Another exemplary tackifier, Piccotac 115, has a viscosity at 350° F. (177° C.) of about 1600 centipoise. Other typical tackifiers have viscosities at 350° F. (177° C.) of much less than 1600 centipoise, for instance, from 50 to 300 centipoise.  
      Exemplary aliphatic resins include those available under the trade designations Escorez™, Piccotac™, Mercures™, Wingtack®, Hi-Rez™, Quintone™, Tackirol™, etc. Exemplary polyterpene resins include those available under the trade designations Nirez™, Piccolyte™, Wingtack®, Zonarez™, etc. Exemplary hydrogenated resins include those available under the trade designations Escorez™, Arkon™, Clearon™, etc. Exemplary mixed aliphatic-aromatic resins include those available under the trade designations Escorez™, Regalite™, Hercures™, AR™, Imprez™, Norsolene™ M, Marukarez™, Arkon™ M, Quintone™, etc. These tackifiers may be employed with the polymers described herein, providing they are used at compatible levels. Other tackifiers may be employed, provided they are compatible with the homogeneous linear or substantially linear ethylene/alpha.-olefin interpolymer.  
      In certain applications it is anticipated the hot melt adhesive embodiments will be prepared without the use of a tackifier or with a minimal quantity of tackifier. As tackifiers are malodorous, tend to cause corrosion of mechanical equipment, and cannot be easily separated from recycled paper pulp, hot melt adhesives which minimize the use of tackifiers are advantageous. Moreover, as tackifiers generally undergo degradation at elevated temperatures, hot melt adhesives which minimize the use of tackifiers will exhibit improved thermal stability.  
      Tackifiers added to hot-melt adhesives can be characterized by parameters such as their softening points, specific gravities, or by acid number. A tackifier can be selected from among the variety of tackifiers, as described above but not limited thereto, and from tackifiers characterized by a range of acid numbers, such as acid numbers between 0 and 100, and in one embodiment of a hot melt adhesive, preferably between 0 and 25.8.  
      c) Waxes  
      The choice of wax used in an adhesive formulation affects many of the properties of the adhesive composition, from the viscosity and melting temperature of the adhesive, the amount of time required for the adhesive to become tacky upon application to a substrate, to dry after application, or the strength of the adhesive bond that is formed. The wax employed should also be compatible with the other components of the adhesive composition.  
      A wax for use in hot melt adhesives should have a relatively sharp melt point to yield an adhesive with a short ‘set speed’ and controllable open time. The wax should also allow for a reduction of overall adhesive viscosity to allow for the proper application or coating of the hot melt adhesive on the intended substrate.  
      Naturally occurring and synthetic waxes are extensively used in a wide cross-section of industries including the food preparation, pharmaceutical, cosmetic, and personal hygiene industries. The term wax is used to denote a broad class of organic ester and waxy compounds, which span a variety of chemical structures and display a broad range of melting temperatures. Among these compounds are triglycerides and olefins, such that a compound can have wax-like properties, as are characteristic of embodiments of the present invention. Often the same compound may be referred to as either a “wax,” “fat” or an “oil” depending on the ambient temperature. By whatever name it is called, the choice of a wax for a particular application is often determined by whether it is a liquid or solid at the temperature of the product with which it is to be used. Frequently it is necessary to extensively purify and chemically modify a wax to make it useful for a given purpose. Despite such efforts at modification, many of the physical characteristics of waxes still prevent them from being used successfully or demand that extensive, and oftentimes, expensive, additional treatments be undertaken to render them commercially useable.  
      Hot-melt adhesive compositions previously described generally utilize waxes derived from petroleum products, and include the paraffins and microcrystalline waxes. Oxidized polyethylene waxes, also derived from petroleum products, may be used. Additionally, Fischer-Tropsch waxes can be utilized, but they are not preferred because of their having to be imported and their generally higher cost compared to the petroleum-derived waxes.  
      d) Other Additives  
      Adhesives, including embodiments of the present invention may also contain a number of additional components, such as a stabilizer, plasticizer, filler or antioxidant. Among the applicable stabilizers or antioxidants which can be included in embodiments of adhesive compositions of the present invention are high molecular weight hindered phenols and multifunctional phenols, such as sulfur-containing and phosphorous-containing phenols. Hindered phenols, known to those skilled in the art, may be described as phenolic compounds, which also contain sterically bulky radicals in close proximity to the phenolic hydroxyl group. Specifically, tertiary butyl groups generally are substituted onto the benzene ring in at least one of the ortho positions relative to the phenolic hydroxyl group. The presence of these sterically bulky substituted radicals in the vicinity of the hydroxyl group serves to retard its stretching frequency, and correspondingly, its reactivity. It is this hindrance that provides the stabilizing properties of these phenolic compounds.  
      Representative hindered phenols include; but are not limited to: 2,4,6-trialkylated monohydroxy phenols; 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene; pentaerythritol tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, commercially available under the trademark IRGANOX® 1010; n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; 4,4′-methylenebis (4-methyl-6-tert-butyl-phenol); 4,4′-thiobis (6-tert-butyl-o-cresol); 2,6-di-tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5 triazine; 2-(n-octylthio)ethyl 3,5-di-tert-butyl-4-hydroxy-benzoate; di-n-octadecyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate; and sorbitol hexa(3,3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate.  
      Antioxidants include, but are not limited to, butylated hydroxy anisole (“BHA”) or butylated hydroxy toluene (“BHT”) which may also be utilized to render the formulation more thermally stable. These stabilizers and antioxidants are added in amounts ranging approximately 0.01% to approximately 5% by weight of the formulation.  
      Utilizing known synergists in conjunction with the antioxidants may further enhance the performance of these antioxidants. Some of these known synergists are, for example, thiodipropionate esters and phosphates. Chelating agents and metal deactivators, may also be used. Examples of these compounds include ethylenediaminetetraacetic acid (“EDTA”), and more preferably, its salts, and disalicylalpropylenediamine. Distearylthiodipropionate is particularly useful. When added to embodiments of the adhesive composition, these stabilizers, if used, are generally present in amounts of about 0.1 to about 1.5 weight percent, and more preferably in the range of about 0.25 to about 1.0 weight percent.  
      The present invention includes addition of a polymer or copolymer to the adhesive. The polymeric additive can be selected from the group consisting of ethylene methyl acrylate polymers containing 10 to 28 weight percent by weight methyl acrylate; ethylene acrylic acid copolymers having an acid number of 25 to 150; polyethylene; polypropylene; poly(butene-1-co-ethylene) polymers and low molecular weight and/or low melt index ethylene n-butyl acrylate copolymers. When such a polymeric additive is added, it is present in amounts up to about 15 weight percent by weight of composition.  
      Depending on the contemplated end uses of the adhesive composition, other additives such as plasticizers, pigments and dyestuffs that are conventionally added to hot-melt adhesives may be included. In addition, small amounts of additional (secondary) tackifiers and/or waxes such as microcrystalline waxes, hydrogenated castor oil, styrene-ethylene butyl styrene (SEBS) resins and vinyl acetate modified synthetic waxes may also be incorporated in minor amounts, i.e., up to about 10 weight percent by weight, into the formulations of the present invention. A plasticizer may be used in lieu of, or in combination with, the secondary tackifier to modify viscosity and improve the tack properties of the adhesive composition.  
      A dispersant can also be added to these compositions. The dispersant can be a chemical, which may, by itself, cause the composition to be dispersed from the surface to which it has been applied, for example, under aqueous conditions. The dispersant may also be an agent which when chemically modified, causes the composition to be dispersed from the surface to which it has been applied. As known to those skilled in the art, examples of these dispersants include surfactants, emulsifying agents, and various cationic, anionic or nonionic dispersants. Compounds such as amines, amides and their derivatives are examples of cationic dispersants. Soaps, acids, esters and alcohols are among the known anionic dispersants. The addition of a dispersant may affect the recyclability of products to which a hot-melt adhesive may have been applied.  
      The surfactants can be chosen from a variety of known surface-active agents. These can include nonionic compounds such as ethoxylates available from commercial suppliers. Examples include alcohol ethoxylates, alkylamine ethoxylates, alkylphenol ethyoxylates, octylphenol ethoxylates and the like. Other surfactants, such as a number of fatty acid esters may be employed; for example, but not limited to, glycerol esters, polyethyleneglycol esters and sorbitan esters.  
      Although embodiments of the present invention have been described with a certain degree of particularity, it is to be understood that the examples below are merely for purposes of illustrating embodiments of the present invention, the scope of the present invention intended to be defined by the claims.  
      Composition and Properties of A Hot Melt Adhesive  
      An embodiment of a hot melt adhesive of the present invention comprises from about 10 to about 50 weight percent, (based on the final weight of the hot melt adhesive) of a thermoplastic copolymer consisting essentially of ethylene, or ethylene and vinyl acetate, and copolymers and terpolymers thereof; of from 10 to about 90 weight percent, preferably from about 35 to about 65 weight percent, more preferably from about 45 to about 55 weight percent (based on the final weight of the hot melt adhesive) of one or more tackifiers; and of from 1 to about 40 weight percent, preferably from about 10 to about 30 weight percent, more preferably from about 15 to about 25 weight percent (based on the final weight of the hot melt adhesive) of a wax.  
      The wax component of the hot melt adhesive is an ethylene alpha-olefin interpolymer having a density of from about 0.880 to about 0.950 g/cm 3 , preferably from about 0.910 to about 0.940 g/cm 3 , and more preferably from about 0.903 to about 0.940 g/cm 3 .  
      The wax component of the hot melt adhesive has a number average molecular weight (Mn as measured by GPC) of from about 700 to about 1,000, preferably from about 720 to about 950, more preferably from about 740 to about 910.  
      The wax component of the hot melt adhesive has a Brookfield Viscosity (measured at 300° F./149° C.) of from about 10 to about 100 cP, preferably from about 20 to about 75 cP, more preferably from about 20 to about 40 cP.  
      The hot melt adhesives of the present invention have a Peel Adhesion Failure Temperature (PAFT) of greater than or equal to 60° C., preferably greater than or equal to 65° C., more preferably between 70° C. and 90° C.  
      The hot melt adhesives of the present invention have a Shear Adhesion Failure Temperature (SAFT) of greater than or equal to 70° C., greater than or equal to 75° C., more preferably between 80° C. and 110° C.  
     PREPARATION OF EXAMPLES  
      Unless otherwise stated, the following examples&#39; reference to viscosity was determined in accordance with the following procedure using a Brookfield Laboratories DVII+ Viscometer in disposable aluminum sample chambers. The spindle used is a SC-31 hot-melt spindle, suitable for measuring viscosities in the range of from 10 to 100,000 centipoise. A cutting blade is employed to cut samples into pieces small enough to fit into the 1 inch wide, 5 inches long (25.4 mm wide, 127 mm long) sample chamber. The sample is placed in the chamber, which is in turn inserted into a Brookfield Thermosel and locked into place with bent needle-nose pliers. The sample chamber has a notch on the bottom that fits the bottom of the Brookfield Thermosel to ensure that the chamber is not allowed to turn when the spindle is inserted and spinning. The sample is heated to the desired temperature, such as 300° F. (149° C.) or 350° F. (177° C.), with additional sample being added until the melted sample is about 1 inch (25.4 mm) below the top of the sample chamber. The viscometer apparatus is lowered and the spindle submerged into the sample chamber. Lowering is continued until brackets on the viscometer align on the Thermosel. The viscometer is turned on, and set to a shear rate which leads to a torque reading in the range of 30 to 60 percent. Readings are taken every minute for about 15 minutes, or until the values stabilize, which final reading is recorded.  
      Unless otherwise stated, the Shear Adhesion Failure Temperature (“SAFT”) test, (a test commonly used to evaluate adhesive performance, and well known to those versed in the industry) was conducted using a standard SAFT test method (ASTM D-4498). SAFT tests were run using a ChemInstruments HT-8 Oven Shear Tester using a 500 gm weight. The tests were started at room temperature (25° C./77° F.) and the temperature increased at the rate of 0.5 degrees C./min. The results were converted and reported in degrees F. The SAFT test measures the temperature at which an adhesive fails.  
      Unless otherwise stated, Peel Adhesion Failure Temperature (“PAFT”) was conducted according to ASTM D- D4498 (modified for peel mode) using 100 gram weights. PAFT gives a measure of the adherence, when peeled at 180° angle, to a standard steel panel or to other surface of interest for a single-coated tape.  
      Unless otherwise stated % fiber tear on corrugated paper was conducted according to standard industry test methods where a drop of adhesive heated to 350 degrees F. (177 degrees C.) is applied on the paper. After 1.5 seconds another paper of a given size (11 inches×3 inches/279.4 mm×76.2 mm) is placed on the adhesive drop and laminated to the base paper. The two sheets are manually pulled apart rapidly and the % fiber tear (FT) estimated.  
      Unless otherwise stated, melting points of the adhesive formulations of the present invention used Differential Scanning Calorimetry (“DSC”). A few milligrams of sample are placed into the instrument and the temperature was increased from room temperature to 180° C. at 10° C. per minute. The sample was then held isothermally at 180° C. for 3 minutes, and then the temperature was ramped down at 10° C. per minute to minus 40° C. The sample was held isothermally at −40° C. for 3 minutes. The temperature was then ramped up at 110° C. per minute to 150° C. Crystallinity and melting point data were reported from the second heat curve.  
      Density of the samples was determined in accordance with ASTM D 792.  
      Hardness of the samples was determined using the needle penetration test of ASTM D-1321.  
      The drop point of the samples was determined in accordance with ASTM 3954 (Mettler Drop Point).  
      Unless otherwise stated the evaluation of the adhesive properties of the inventive formulations was conducted by coating onto 45# basis weight kraft paper typically used in the manufacture of cardboard boxes, and purchased from National Papers, Minneapolis, Minn.  
               TABLE 1                          Commercially Available Materials Used in Evaluations                     Ingredient   Supplier               Escorez 5400   ExxonMobil Chemical Company Houston, TX - Cyclical           hydrogenated hydrocarbon tackifier resin with softening point of           103° C.       Escorez 5637   ExxonMobil Chemical Company Houston, TX - aromatic modified           cycloaliphatic hydrocarbon tackifier resin with softening point of           127-133° C.       Eastotack H   Eastman Chemical Company Kingsport, TN. ring and ball softening       1300W   point of 130° C. and a Gardner color (molten state) of &lt;1, Eastotac           hydrocarbon resins are hydrogenated C 5  aliphatic hydrocarbon           tackifying resins.       Wingtack ® 95   Goodyear Chemical, Akron, OH - Aliphatic C-5 petroleum           hydrocarbon resin, softening point of 98° C., CAS #26813-14-9.       Advantra ® HL-   H.B. Fuller Company St. Paul, MN - formulated adhesive for carton       9250   and uncoated corrugated stocks with a viscosity at 325° F. (163° C.) of           1,255 cps and specific gravity of 0.929 g/cm 3 .       Advantra ® HL-   H.B. Fuller Company St. Paul, MN - formulated adhesive for       9255   wrapper and coated carton stocks with a viscosity at 325° F. (163° F.)           of 1,140 cps and specific gravity of 0.943 g/cm 3 .       BAM Futura 1   IDC - A Division of Ambersil, England - hot melt adhesive for           books, magazines, catalogues and directories.       HL-7268   H.B. Fuller Company St. Paul, MN.       HL-2835   H.B. Fuller Company St. Paul, MN - formulated adhesive with           moderate speed of set, good flexibility, for bonding a variety of           substrates, with a viscosity at 300° F. (149° C.) of 2,200 cP.       Henkel 80-8488   Henkel Consumer Adhesives Inc. Avon, OH - formulated adhesive           for bonding a variety of substrates, with a viscosity at 350° F. (177° C.)           of 1,080 cP.       Henkel 80-8368   Henkel Consumer Adhesives Inc. Avon, OH - formulated adhesive           for bonding a variety of substrates, with a viscosity at 350° F. (177° C.)           of 970 cP.       ULTRATHENE ®   EVA resin with 18% VA content, made by Equistar Chemical, LP.       612-04       FORAL ® 85   Rosin Ester tackifier, made by Hercules.       EVA-1   A formulation of 33 wt % ULTRATHENE ® 612-04 (18% vinyl           acetate co-monomer); 33% FORAL ® 85 33% Wax, 1251/7.       ELVAX ® 240   DuPont Industrial Polymers, Wilmington, DE. Ethylene-vinyl           acetate copolymer resin with 28% VA content.       Wax, 1251/7   Microcrystalline Control supplied by Frank B. Ross Co.       PARAFLINT ®   Fischer Tropsch wax supplied by SASOL, South Africa.       H1                  
 
     Example 1  
     Ethylene/alpha-Olefin Polymer Preparation Using Single Metallocene Catalyst System  
      A series of ethylene/α-olefin interpolymers was prepared in a 1 gallon (3.8 liter), oil jacketed, Autoclave continuously stirred tank reactor (“CSTR”). A magnetically coupled agitator with Lightning A-320 impellers provided the mixing. The reactor ran liquid full at 475 psig (3,275 kPa). Process flow was in at the bottom and out of the top. A heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction. At the exit of the reactor was a Micro-Motion™ flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.  
      ISOPAR-E solvent and comonomer were supplied to the reactor at 30 psig (206.8 kPa) pressure. The solvent feed to the reactors was measured by a Micro- Motion™ mass flow meter. A variable speed diaphragm pump controlled the solvent flow rate and increased the solvent pressure to reactor pressure. The comonomer was metered by a Micro-Motion™ mass flow meter and flow controlled by a Research control valve. The comonomer stream was mixed with the solvent stream at the suction of the solvent pump and was pumped to the reactor with the solvent. The remaining solvent was combined with ethylene and (optionally) hydrogen and delivered to the reactor. The ethylene stream was measured by a Micro-Motion™ mass flow meter just prior to the Research valve controlling flow. Three Brooks flow meter/controllers (1-200 sccm and 2-100 sccm) were used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.  
      The ethylene or ethylene/hydrogen mixture combined with the solvent/comonomer stream at ambient temperature. The temperature of the solvent/monomer as it enters the reactor was controlled with two heat exchangers. This stream enters the bottom of the 1 gallon (3.8 liter) CSTR. The three component catalyst system and its solvent flush also enter the reactor at the bottom but through a different port than the monomer stream.  
      Polymerization was stopped with the addition of catalyst kill into the reactor product line after the meter measuring the solution density. Other polymer additives could be added with the catalyst kill. The reactor effluent stream then entered a post reactor heater that provides additional energy for the solvent removal flash. This flash occurs as the effluent exits the post reactor heater and the pressure is dropped from 475 psig (3275 kPa) down to 10 (68.94 kPa) at the reactor pressure control valve.  
      This flashed polymer entered a hot oil jacketed devolatilizer. Approximately 90% of the volatiles were removed from the polymer in the devolatilizer. The volatiles exit the top of the devolatilizer. The remaining stream is condensed with a chilled water jacketed exchanger and then enters a glycol jacket solvent/ethylene separation vessel. Solvent is removed from the bottom of the vessel and ethylene vents from the top. The ethylene stream is measured with a Micro-Motion™ mass flow meter. This measurement of unreacted ethylene was used to calculate the ethylene conversion. The polymer separated in the devolatilizer and was pumped out with a gear pump. The product is collected in lined pans and dried in a vacuum oven at 140° C. for 24 hr. Table 2 summarizes the polymerization conditions and Table 3 the properties of the resulting polymers.  
               TABLE 2                          Ethylene/α-Olefin Interpolymer Preparation Conditions*                                                         Reactor   Solvent   Ethylene   Octene   Propylene   Hydrogen   C2   B/Ti               Temp   Flow   Flow   Flow   Flow   Flow   Conversion   Molar   MMAO/Ti       Polymer   ° C.   lb/hr   lb/hr   lb/hr   lb/hr   sccm   (%)   Ratio   Molar Rati                                                             1   150   25.4   2.65   1.37   —   143.8   90.10   1.16   4.99       2   150   25.2   2.65   1.20   —   139.9   90.00   1.23   5.03       3   150   25.6   2.65   1.15   —   149.9   90.40   1.21   4.93       4   151   25.0   2.65   1.90   —   167.3   90.22   1.24   5.00       5   150   25.2   2.65   1.72   —   197.0   89.75   1.21   4.93       6   151   25.1   2.65   1.85   —   144.2   90.47   1.25   4.97       7   150   25.2   2.65   1.67   —   175.4   90.36   1.20   4.95       8   148   25.5   2.65   1.00   —   126.6   89.95   1.15   4.99       9   151   25.2   2.65   1.30   —   111.5   90.09   1.14   4.97       10   150   25.1   2.65   1.24   —   108.2   90.42   1.20   9.92       11   148   25.1   2.65   1.35   —   107.9   90.05   1.21   4.99       12   148   25.3   2.65   1.15   —   113.9   90.00   1.19   5.01       13   147   25.1   2.65   1.31   —   106.9   90.09   1.24   5.04       14   147   25.5   2.65   1.00   —   114.9   90.02   1.15   4.98       15   151   25.2   2.65   1.30   —   83.7   89.88   1.13   4.93       16   150.5   25.2   2.65   —   0.60   159.9   90.2   1.22   5.01       17   150.1   25.2   2.65   —   0.75   164.8   89.9   1.20   4.94       18   150.2   25.2   2.65   —   0.45   165.5   90.0   1.18   4.91       19   150.1   25.2   2.65   —   0.90   166.0   89.8   1.20   5.02       20   150.4   25.2   2.65   —   0.70   124.9   90.3   1.26   5.04       21   150.4   25.2   2.65   —   0.52   126.9   89.9   1.21   5.05       22   149.9   25.2   2.62   —   0.70   94.9   90.0   1.22   4.72       23   150.7   25.2   2.65   —   0.52   96.2   90.5   1.20   5.02                 *The catalyst for all polymerizations was (C 5 Me 4 SiMe 2 N t Bu)Ti(η 4 -1,3-pentadiene) prepared according to Example 17 of U.S. Pat. No. 5,556,928, the entire disclosure of which patent is incorporated herein by reference. The primary cocatalyst for all polymerisations was Armeenium Borate [methylbis(hydrogenatedtallowalkyl) ammonium tetrakis (pentafluoro phenyl) borate prepared as in U.S. Patent # 5,919,983, Ex. 2, the entire          # disclosure of which patent is incorporated herein by reference. The secondary cocatalyst for all polymerizations was a modified methylaluminoxane (MMAO) available from Akzo Nobel as MMAO-3A (CAS# 146905-79-10).           
 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                   
               
               
                 Properties of Ethylene/α-Olefin Interpolymers 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                   
                   
                 Drop 
                   
                   
                 Heat of 
                   
                   
                   
               
               
                 Polymer 
                 Viscosity @ 
                 Density 
                   
                   
                   
                 Wt % 
                 Mol % 
                 Point 
                 T m  1 
                 T m  2 
                 Fusion 
                   
                 T c  1 
                 T c  2 
               
               
                 # 
                 300° F. (cP) 
                 (g/cm 3 ) 
                 M w   
                 M n   
                 M w /M n   
                 Com. 
                 Com. 
                 (° C.) 
                 (° C.) 
                 (° C.) 
                 (J/g) 
                 % Cryst 
                 (° C.) 
                 (° C.) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 1,375 
                 0.9073 
                 8,890 
                 3,420 
                 2.60 
                 19.2 
                 5.6 
                 105.6 
                 99.1 
                 103.3 
                 122.6 
                 42 
                 90.0 
                 50.5 
               
               
                 2 
                 1,442 
                 0.9125 
                 9,000 
                 3,480 
                 2.59 
                 20 
                 5.9 
                 108.9 
                 102.1 
                 107.0 
                 142.4 
                 49 
                 92.4 
                 54.1 
               
               
                 3 
                 1,490 
                 0.9153 
                 8,940 
                 3,380 
                 2.64 
                 15.7 
                 4.4 
                 109.5 
                 104.0 
                 107.6 
                 140.2 
                 48 
                 94.6 
                 55.9 
               
               
                 4 
                 1,638 
                 0.8953 
                 9,310 
                 3,650 
                 2.55 
                 28.3 
                 9.0 
                 99.3 
                 93.3 
                 83.2 
                 99.1 
                 34 
                 82.5 
               
               
                 5 
                 1,716 
                 0.8991 
                 9,280 
                 3,640 
                 2.55 
                 22.2 
                 6.7 
                 102.4 
                 95.8 
                   
                 113.6 
                 39 
                 85.8 
               
               
                 6 
                 2,229 
                 0.8958 
                 10,100 
                 4,080 
                 2.48 
                 27.8 
                 8.8 
                 100.0 
                 93.3 
                 83.3 
                 99.7 
                 34 
                 82.8 
               
               
                 7 
                 2,253 
                 0.9014 
                 9,970 
                 4,070 
                 2.45 
                 21.9 
                 6.5 
                 103.6 
                 96.5 
                   
                 111.9 
                 38 
                 86.1 
               
               
                 8 
                 2,959 
                 0.9146 
                 10,800 
                 4,860 
                 2.22 
                 16.4 
                 4.7 
                 110.5 
                 103.3 
                 106.9 
                 134.9 
                 46 
                 93.1 
                 53.9 
               
               
                 9 
                 3,054 
                 0.9085 
                 10,700 
                 4,080 
                 2.62 
                 19.1 
                 5.6 
                 107.4 
                 101.1 
                   
                 126.4 
                 43 
                 91.4 
                 51.1 
               
               
                 10 
                 3,029 
                 0.9092 
                 10,800 
                 4,310 
                 2.51 
                 18.2 
                 5.3 
                 107.1 
                 99.7 
                   
                 122.3 
                 42 
                 89.1 
                 48.9 
               
               
                 11 
                 3,139 
                 0.9035 
                 11,000 
                 4,850 
                 2.27 
                 20.6 
                 6.1 
                 104.5 
                 97.4 
                   
                 112.1 
                 38 
                 86.9 
               
               
                 12 
                 3,545 
                 0.9088 
                 11,600 
                 5,370 
                 2.16 
                 18.7 
                 5.4 
                 107.4 
                 100.3 
                   
                 123.8 
                 42 
                 88.9 
                 47.9 
               
               
                 13 
                 3,802 
                 0.9039 
                 11,700 
                 5,150 
                 2.27 
                 20.5 
                 6.1 
                 105.1 
                 97.4 
                   
                 114.3 
                 39 
                 85.9 
               
               
                 14 
                 4,109 
                 0.9143 
                 11,800 
                 5,300 
                 2.23 
                 16.8 
                 4.8 
                 110.7 
                 103.5 
                   
                 135.3 
                 46 
                 93.3 
                 53.2 
               
               
                 15 
                 5,899 
                 0.9078 
                 12,800 
                 4,890 
                 2.62 
                 19.3 
                 5.6 
                 107.5 
                 100.4 
                   
                 123.8 
                 42 
                 90.2 
                 48.5 
               
               
                 16 
                 1,458 
                 0.9152 
                 9,070 
                 4,030 
                 2.25 
                 12.2 
                 8.5 
                 103.1 
                 85.6 
                 99.5 
                 147.2 
                 50 
                 87.7 
                 58.1 
               
               
                 17 
                 1,503 
                 0.9088 
                 9,010 
                 3,920 
                 2.30 
                 14.9 
                 10.5 
                 99.2 
                 79.7 
                 95.0 
                 128.4 
                 44 
                 82.9 
                 53.1 
               
               
                 18 
                 1,545 
                 0.9267 
                 9,100 
                 3,900 
                 2.33 
                 11.3 
                 7.8 
                 110.2 
                 106.4 
                   
                 163.9 
                 56 
                 95.5 
               
               
                 19 
                 1,557 
                 0.9003 
                 9,060 
                 3,970 
                 2.28 
                 18.9 
                 13.4 
                 94.6 
                 74.9 
                 90.2 
                 112.4 
                 38 
                 77.9 
                 68.6 
               
               
                 20 
                 2,884 
                 0.9172 
                 10,700 
                 4,550 
                 2.35 
                 11.3 
                 7.8 
                 105.5 
                 101.2 
                   
                 135.6 
                 46 
                 89.9 
                 59.1 
               
               
                 21 
                 3,005 
                 0.9187 
                 10,800 
                 4,690 
                 2.30 
                 11.1 
                 7.7 
                 106.0 
                 102.1 
                   
                 149.3 
                 51 
                 90.7 
                 60.4 
               
               
                 22 
                 5,889 
                 0.9161 
                 12,900 
                 5,460 
                 2.36 
                 11.8 
                 8.2 
                 96.7 
                   
                   
                 143.1 
                 49.0 
                 91 
                 59.2 
               
               
                 23 
                 6,019 
                 0.9162 
                 12,900 
                 5,470 
                 2.36 
                 11.9 
                 8.3 
                 106.2 
                 87.5 
                 100.5 
                 141.1 
                 48 
                 89.4 
                 58.5 
               
               
                   
               
            
           
         
       
     
     Example 2A  
     Preparation of Adhesive Formulations with Tackifier  
      Ingredients were blended in a metal container to a total weight of 100 g. Tackifier resin was added into the container and allowed to heat for 10 minutes with a heating mantle for temperature control. The inventive polymer was slowly added over 3-5 minutes. Once melted, the ingredients were mixed by hand using a metal spatula at a moderate rate of speed. After complete addition of the polymer, the adhesive was allowed to mix an additional 15 minutes to assure uniformity. The final adhesive temperature in all cases was 350-360° F. (177-182° C.). A single tackifier was used in some formulations, while other formulations used a combination of tackifiers.  
     Example 2B  
     Preparation of Multi-Component Adhesive Formulations  
      Ingredients were blended in a metal container to a total weight of 100 g. Tackifier resin was added into the container and allowed to heat for 10 minutes with a heating mantle for temperature control. A resin, such as an ethylene vinyl acetate containing resin such as ELVAX® 240 or the like, was slowly added to the tackifier while mixing. The inventive polymer was then slowly added over 3-5 minutes. Once melted, the ingredients were mixed by hand using a metal spatula at a moderate rate of speed. After complete addition of the polymer, the adhesive was allowed to mix an additional 15 minutes to assure uniformity. The final adhesive temperature in all cases was 350-360° F. A single tackifier was used in some formulations, while other formulations used a combination of tackifiers.  
     Example 3  
     Evaluation of Adhesive Formulations  
      The adhesive formulations prepared according to Example 2 were evaluated for their adhesive properties using the testing methods previously described. The properties of these adhesive formulations are summarized in Tables 4-6, and are compared with the properties of several commercially available adhesives (Table 7).  
      Most of the ethylene/alpha-olefin polymers synthesized using ethylene and 1-octene showed good performance when fiber tear was evaluated over the higher range of temperatures (between 77 degrees F. and 140 degrees F.). Several of these formulations also were effective at 35 degrees F.  
               TABLE 4                          Properties of Hot Melt Adhesives: Ethylene/1-Octene Interpolymers.                                             Polymer   Polymer   Escorez   FiberTear (%)       Viscosity @                                                             Ex #   Sample #   (wt %)   5637 (wt %)   0° F.   35° F.   77° F.   120° F.   140° F.   PAFT (° F.)   SAFT (° F.)   350° F. (cP)                                                                     1   1   85.0   15.0   100   100   100   0   0   86   202   680       2   1   72.5   27.5   0   0   100   100   100   118   198   510       3   1   60.0   40.0   0   0   0   100   100   136   191   430       4   3   85.0   15.0   0   0   0   0   0   108   212   620       5   3   72.5   27.5   0   0   0   100   100   122   207   525       6   3   60.0   40.0   0   0   0   100   100   142   203   465       7   4   85.0   15.0   100   100   100   0   0   93   183   680       8   4   72.5   27.5   0   100   100   100   100   100   178   540       9   4   60.0   40.0   0   0   100   100   100   126   174   440       10   6   85.0   15.0   100   100   100   0   0   86   186   910       11   6   72.5   27.5   50   100   100   0   0   115   181   790       12   6   60.0   40.0   0   0   100   100   100   128   176   585       13   7   60.0   40.0   0   0   0   100   100   135   185   750       14   8   78.0   22.0   0   0   100   100   100   116       1,120       15   8   73.0   27.0   0   0   100   100   50   127       1,000       16   8   68.0   32.0   0   0   100   100   0   140       930       17   9   72.5   27.5   0   100   100   100   100   122   201   1,020       18   10   78.0   22.0   0   0   100   100   100   110   205   1,115       19   10   73.0   27.0   0   0   100   100   100   119   203   1,050       20   10   68.0   32.0   0   0   100   100   100   128   201   950       21   11   78.0   22.0   0   100   100   100   100   106       1,240       22   11   73.0   27.0   0   100   100   100   100   124       1,090       23   11   68.0   32.0   0   0   100   100   100   127       985       24   12   78.0   22.0   0   50   100   100   100   112       1,290       25   12   73.0   27.0   0   0   100   100   100   125       1,190       26   12   68.0   32.0   0   0   100   100   100   130       1,150       27   13   78.0   22.0   0   100   100   50   100   111       1,320       28   13   73.0   27.0   0   100   100   100   100   119       1,310       29   13   68.0   32.0   0   0   100   100   100   131       1,260       30   14   78.0   22.0   0   0   100   100   50   123       1,380       31   14   73.0   27.0   0   0   100   50   50   129       1,340       32   14   68.0   32.0   0   0   100   50   50   136       1,230       33   15   85.0   15.0   100   100   100   100   100   112   206   2,250       34   15   72.5   27.5   0   100   100   100   100   126   203   1,820       35   15   60.0   40.0   0   0   0   100   100   142   199   1,435                  
 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                   
               
               
                 Properties of Hot Melt Adhesives: Ethylene/Propylene Interpolymers. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Polymer 
                 Tackifier* 
                 FiberTear (%) 
                   
                 Viscosity @ 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Ex # 
                 Sample # (wt %) 
                 (wt %) 
                 0° F. 
                 35° F. 
                 77° F. 
                 120° F. 
                 140° F. 
                 PAFT (° F.) 
                 SAFT (° F.) 
                 350° F. (cP) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 36 
                 16 
                 15.0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 92 
                 201 
                 745 
               
               
                 37 
                 16 
                 27.5 
                 0 
                 0 
                 0 
                 100 
                 100 
                 106 
                 199 
                 590 
               
               
                 38 
                 18 
                 15.0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 108 
                 215 
                 800 
               
               
                 39 
                 18 
                 40.0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 138 
                 207 
                 490 
               
               
                 40 
                 19 
                 15.0 
                 0 
                 100 
                 100 
                 0 
                 0 
                 93 
                 176 
                 695 
               
               
                 41 
                 19 
                 27.5 
                 0 
                 0 
                 100 
                 0 
                 0 
                 92 
                 171 
                 630 
               
               
                 42 
                 19 
                 40.0 
                 0 
                 0 
                 0 
                 100 
                 100 
                 123 
                 168 
                 485 
               
               
                 43 
                 21 
                 15.0 
                 0 
                 100 
                 0 
                 0 
                 0 
                 111 
                 206 
                 1370 
               
               
                 44 
                 21 
                 40.0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 139 
                 197 
                 822 
               
               
                 45 
                 22 
                 15.0 
                 0 
                 100 
                 0 
                 0 
                 0 
                 108 
                 206 
                 2490 
               
               
                 46 
                 22 
                 27.5 
                 0 
                 0 
                 0 
                 0 
                 100 
                 128 
                 203 
                 1975 
               
               
                 47 
                 22 
                 40.0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 143 
                 198 
                 1490 
               
               
                   
               
               
                   *In all examples the tackifier used was Escorez 5637    
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                   
               
               
                 Properties of Hot Melt Adhesives Prepared With Mixed Tackifiers) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Polymer 
                 Tackifier 
                   
                   
                 Viscosity 
               
               
                   
                 Sample # 
                 (wt %) 
                 FiberTear (%) 
                   
                 (cP) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Ex # 
                 (wt %) 
                 E-5400 1   
                 E-5637 2   
                 0° F. 
                 35° F. 
                 77° F. 
                 120° F. 
                 140° F. 
                 PAFT (° F.) 
                 SAFT (° F.) 
                 300° F. 
                 350° F. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 48 
                 4(70.0) 
                 22.5 
                 7.5 
                 10 
                 100 
                 — 
                 20 
                 0 
                 98 
                 177 
                 1090 
                 550 
               
               
                 49 
                 4(65.0) 
                 17.5 
                 17.5 
                 0 
                 80 
                 — 
                 80 
                 80 
                 118 
                 174 
                 1200 
                 520 
               
               
                 50 
                 4(75.0) 
                 12.5 
                 12.5 
                 20 
                 100 
                 — 
                 10 
                 0 
                 100 
                 181 
                 1180 
                 610 
               
               
                 51 
                 4(75.0) 
                 0 
                 25.0 
                 50 
                 100 
                 — 
                 100 
                 50 
                 104 
                 182 
                 1250 
                 640 
               
               
                 52 
                 4(65.0) 
                 0 
                 35.0 
                 0 
                 0 
                 — 
                 100 
                 75 
                 114 
                 177 
                 1100 
                 545 
               
               
                 53 
                 4(67.5) 
                 7.5 
                 25.0 
                 0 
                 80 
                 — 
                 100 
                 100 
                 112 
                 177 
                 1210 
                 580 
               
               
                 54 
                 4(70.0) 
                 30.0 
                 0 
                 10 
                 100 
                 — 
                 60 
                 10 
                 95 
                 175 
                 1050 
                 535 
               
               
                 55 
                 4(65.0) 
                 0 
                 35.0 
                 0 
                 0 
                 — 
                 100 
                 10 
                 119 
                 176 
                 1050 
                 550 
               
               
                 56 
                 4(75.0) 
                 25.0 
                 0 
                 50 
                 100 
                 — 
                 50 
                 10 
                 94 
                 179 
                 1145 
                 595 
               
               
                 57 
                 4(65.0) 
                 35.0 
                 0 
                 0 
                 100 
                 — 
                 100 
                 50 
                 100 
                 173 
                 992 
                 500 
               
               
                 58 
                 4(65.0) 
                 35.0 
                 0 
                 10 
                 100 
                 — 
                 100 
                 50 
                 101 
                 174 
                 990 
                 490 
               
               
                 59 
                 4(75.0) 
                 0 
                 25.0 
                 0 
                 100 
                 — 
                 100 
                 50 
                 104 
                 179 
                 1260 
                 650 
               
               
                 60 
                 4(70.0) 
                 0 
                 30.0 
                 0 
                 80 
                 — 
                 100 
                 50 
                 113 
                 180 
                 1185 
                 600 
               
               
                 61 
                 6(60.0) 
                 40.0 
                 0 
                 0 
                 0 
                 — 
                 100 
                 100 
                 127 
                 177 
                 1330 
                 625 
               
               
                 62 
                 6(67.5) 
                 32.5 
                 0 
                 0 
                 0 
                 — 
                 80 
                 80 
                 119 
                 179 
                 1490 
                 720 
               
               
                 63 
                 6(75.0) 
                 25.0 
                 0 
                 0 
                 100 
                 — 
                 20 
                 10 
                 102 
                 186 
                 1640 
                 830 
               
               
                 64 
                 6(60.0) 
                 40.0 
                 0 
                 0 
                 0 
                 — 
                 100 
                 100 
                 125 
                 178 
                 1340 
                 630 
               
               
                 65 
                 6(65.0) 
                 35.0 
                 0 
                 0 
                 0 
                 — 
                 80 
                 80 
                 122 
                 178 
                 1420 
                 680 
               
               
                 66 
                 6(75.0) 
                 25.0 
                 0 
                 0 
                 100 
                 — 
                 25 
                 20 
                 100 
                 188 
                 1630 
                 825 
               
               
                 67 
                 6(70.0) 
                 30.0 
                 0 
                 0 
                 50 
                 — 
                 100 
                 100 
                 118 
                 181 
                 1510 
                 745 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                   
               
               
                 Properties of Commercial Hot Melt Adhesives of Prior Art 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Viscosity @ 
                 Viscosity @ 
                 FiberTear 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Comp Ex # 
                 Name 
                 Type 
                 300° F. (cp) 
                 350° F. (cp) 
                 0° F. 
                 35° F. 
                 77° F. 
                 120° F. 
                 140° F. 
                 PAFT (° F.) 
                 SAFT (° F.) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 ADVANTRA 
                 AFFINITY*- 
                 1680 
                 860 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 142 
                 198 
               
               
                   
                 HL-9250 
                 Based 
               
               
                 2 
                 ADVANTRA 
                 AFFINITY*- 
                 1560 
                 750 
                 0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 151 
                 192 
               
               
                   
                 HL-9256 
                 Based 
               
               
                   
                 BAM Futura 1 
                   
                 1440 
                 650 
                 0 
                 1.0 
                   
                 1.0 
                 1.0 
                 136 
                 192 
               
               
                   
                 EVA 1 
                 EVA-Based 
                 1587 
                   
                   
                   
                   
                 1.0 
                   
                   
                 150 
               
               
                 3 
                 Fuller HL-7268 
                 EVA-Based 
                   
                 960 
                   
                   
                 1.0 
                 1.0 
                 1.0 
                 144 
                 192 
               
               
                 4 
                 Fuller HL-2835 
                 EVA-Based 
                   
                 1,070 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 126 
                 153 
               
               
                 5 
                 Henkel 80-8488 
                 EVA-Based 
                   
                 1,080 
                   
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 150 
                 176 
               
               
                 6 
                 Henkel 80-8368 
                 EVA-Based 
                   
                 970 
                   
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 142 
                 190 
               
               
                   
               
               
                   *AFFINITY ® is a homogeneous polymer, which is a trademark of and available from The Dow Chemical Company.    
               
            
           
         
       
     
      The results show that combinations of these polymers and tackifier(s) can produce an adhesive with properties that can be formulated to meet the needs of a wide range of adhesive applications.  
      The results also show that these novel polymers, when formulated with a suitable tackifier, have adhesive properties that are either equivalent to or better than a conventional EVA hot melt adhesive which is formulated with wax and tackifier and EVA resin. The results also demonstrate that the novel polymers described herein, when compounded with select tackifiers, have properties comparable to a premium hot melt adhesive as demonstrated by fiber tear.  
     Example 4  
     Preparation of Low Molecular Weight Interpolymers Containing Propylene  
      Using the single metallocene catalyst system described in Example 1 and propylene as the comonomer, a series of low molecular weight interpolymers were prepared. The reaction conditions were similar to those previously described, except that the quantity of hydrogen, which is believed to act as the chain terminator, added to the reactor was increased, to produce interpolymers having molecular weights lower than those described in Examples 2-7 of the parent application, U.S. Pat. App. Pub. No. 2004/02326002 A1, published 25 Nov. 2004 and incorporated by reference.  
      Suitable polyolefin metallocene waxes include homopolymers of ethylene or copolymers of ethylene or propylene with one another or with one or more alpha-olefins. Alpha-olefins used include linear or branched olefins having 2-18 carbon atoms, preferably 2-8 carbon atoms. Examples of such compounds are propylene, 1-butene, 1-hexene, 1-octene or 1-octadecene, and styrene.  
      These low molecular weight ethylene-propylene interpolymers have properties summarized in Table 8. Because these interpolymers have wax-like properties, they are also being referred to as “metallocene waxes” or “waxes” followed by a reference number, such as Wax 02, etc. These waxes, designated as Wax 02; 04 and 06, are ethylene-propylene copolymers, and the waxes which have a greater hardness (i.e., having a higher penetration, determined using a needle penetration test) have a higher propylene content.  
               TABLE 8                          Properties of waxes produced by metallocene catalysis                                                         Needle   Viscosity           Heat of   %                       Penetration   @300 F.   DSC Melt   Density   Fusion   Crystal           @ 77 F. dmm   CPS   Point (C.)   (g/cc)   (J/g)   linity   M w     M n     M w /M n                                                               02 wax   5   35   100.9/113.9   0.9396   193.3   66.2   2150   910   2.36       04 wax   19   44   81.4/96.8   0.9035   131   44.9   2430   910   3.67       06 wax   9   22    93/108   0.9299   179   61.3   1690   740   2.28       PARAFLINT ®   3    9*   93.1,   0.95   236.4   81   860   750   1.15       H1           105.5                 *Viscosity of Paraflint H1 determined @ 275° F.             
 
     Example 5  
     Preparation of Hot Melt Adhesive Formulations and Evaluation of Adhesive Properties of Low Molecular Weight Ethylene-Propylene Interpolymers (“Metallocene Waxes”)  
      Because these low molecular weight ethylene-propylene interpolymers have wax-like properties, experiments were done to determine if these copolymers could be used in hot melt adhesive formulations instead of waxes that are conventionally used in HMAs, such as paraffin or other petroleum-derived waxes.  
      Batches of hot melt adhesives, using the 02, 04 and 06 waxes, and a control wax (PARAFLINT® H1) were prepared in a manner similar to that described in Example 2, but with the addition of wax to the mixture containing the olefin (ELVAX®) and tackifier (WINGTACK® 95). Adhesive formulations were prepared by mixing ingredients in a glass beaker and stirring while on a hot plate. Adhesive properties were determined using the PAFT and SAFT tests described previously.  
      The HMA formulations were prepared using the compositions shown in Table 9. The control sample (sample D) used the Fischer-Tropsch wax PARAFLINT® H1 (SASOL, South Africa), a wax widely used in the adhesive industry because it is considered to have a good balance of properties.  
               TABLE 9                          Composition of Hot Melt Adhesive Formulations Using Low       Molecular Weight Ethylene-Propylene Interpolymers.                                 INGREDIENT in Parts           FORMULATION   Per Formulation (Per Cent)                                     FORMULATION   C5 Resin a     EVA b     Wax                       A (02 Wax)   5 (50%)   3 (30%)   2 (20%)           B (06 Wax)   5 (50%)   3 (30%)   2 (20%)           C (04 Wax)   5 (50%)   3 (30%)   2 (20%)           D (PARAFLINT ® H1   5 (50%)   3 (30%)   2 (20%)                           a C5 resin is a hydrocarbon resin produced by Goodyear Chemical, Akron, OH, and sold under the name of WINGTACK ® 95.                  b The ethylene-vinyl acetate (EVA) preparation used is ELVAX ® 240, DuPont Chemical, Wilmington, DE.             
 
      The adhesive properties of the above formulations were determined using PAFT and SAFT tests, and the data, shown below indicates that hot melt adhesives made with waxes having low viscosities, and which waxes were made using metallocene catalysts, have superior peel and shear bonding strength compared to hot melt adhesives made with conventionally used waxes.  
               TABLE 10                          Properties Hot Melt Adhesive Formulations Containing Low Molecular       Weight Ethylene-Propylene Interpolymers.                                         Brookfield                       Viscosity   PAFT   SAFT           FORMULATION   (149° C.)   (° C.)   (° C.)                                                 A   5000 cps   90   104           B   5010 cps   84   99           C   5010 cps   81   93           D   5010 cps   70   81