Title of Invention

A PROCESS FOR PRODUCING COMPOSITION

Abstract Disclosed are hot melt adhesives comprising at least one first homogenous linear or substantially linear ethylene polymer having a particular density and melt viscosity at 350°F (177°C), and an optional wax and tackifier. In particular, disclosed is a hot melt adhesive characterized by: a) at least one homogeneous linear or substantially linear interpolymer of ethylene with at least one C3-C20 a-olefin interpolymer having a density from 0.850 g/cm3 to 0.895 g Icm3; and . b) optionally at least one tackifying resin; and c) optionally at least one wax wherein the hot melt adhesive has a viscosity of less than about 5000 cPs (50 grams/(cm.second)) at 150°C. .. Preferred hot melt adhesives for use in adhering cardboard or paperboard are disclosed, as well as the resultant adhered products. Also disclosed is a dual reactor process for the preparation of the inventive hot melt adhesives.
Full Text Hoi Melt Adhesives
The subject invention pertains to hot melt adhesives. In particular, the subject invention pertains to hot melt adhesives comprising at least one first ethylene polymer, and optionally at least one wax and/or tackifier. In particular, this invention relates to low viscosity hot melt adhesives comprising at least one homogeneous linear or substantially linear interpolymer of ethylene with at least one Cj-Cio oc-olefin, further characterized by each said interpolymer having a polydispersity less than 2.5. In preferred embodiments, the inventive hot melt adhesives may be applied at application temperatures of less than 150"C. These hot melt adhesives are particularly useful for case and carton scaling, and for tray forming applications in the packaging industry. Also disclosed is a dual reactor process for the preparation of such hot melt adhesives. Also disclosed are preferred hot melt adhesives for the bonding of cardboard or paperboard, as well as the resultattt packaging articles comprising cardboard or paperboard which have been adhered by such hot melt^ adhesives.
Hot melt adhesives are used widely in the packaging industry for such applications as case and carton sealing, tray forming and box forming. The substrates to be bonded include virgin and recycled kraft, high find low density kraft, chipboard and various types of treated and coated kraft and chipboard. Composite materials are also used for packaging applications such as for the packaging of alcoholic beverages. These composite materials may include chipboard laminated to an ahiminum foil which is further laminated to film materials such as polyethylene, mylar, polypropylene, polyvinylidene chloride, ethylene vinyl acetate and various other types of films. Additionally, these film materials also may be bonded directly to chipboard or kraft. The aforementioned substrates by no means represent an exhaustive list, as a tremendous variety of substrates, especially composite materials, find utility in the packaging industry.
Hot melt adhesives for packaging are generally extruded in bead form onto a substrate using piston pump or gear pump extrusion equipment. Hot melt application equipment is available from .several suppliers including Nordson, ITW and Slautterback. Wheel applicators are also commonly used for applying hot melt adhesives, but are used less frequently than extrusion equipment.
Hot melts are required to have sufficient adhesion to substrates to firmly hold the package together, and in many cases, end users of hot melt adhesives require full fiber tearing bonds, meaning substantially all the fiber is removed from the substrate along the entire length of the

adhesive application when the bond is separated by hand. Generally, in order to get fiill fiber
•aring bonds, hot melts need to be applied at temperatures of 175°C or greater. This increases the open time of the adhesive and lowers the viscosit>" for better penetration into the substrate. Open time refers to the amount of time that the adhesive can form a bond to the substrate.
In addition to bonding requirements, customers are demanding higher peifommnce in other areas, such as thermal stability. Good thermal stability means that the product will not darken in the glue pot with prolonged exposure to high temperatures, will not produce char, skin or gel, and will not exhibit a substantial viscosity change over time. High application temperatures, along with exposure to oxygen, can increase the degradation of the hot melt adhesives. Tliis problem is most commonly alleviated with the use of antioxidants such as Irganox® 565,1010 and 1076, which are hindered phenolic antioxidants produced by Ciba-Geigy, located in Hawthorne, NY.
Another way to reduce char, skin, gel formation, discoloration and viscosity changes, is to lower the application temperature of the hot melt adhesive. In addition to improving thermal stability, lowering the application temperature also reduces the risk of severe bums to hot melt equipment operators, decreases the "ynount of electricity required to heat the adhesives which can result in energy cost savings, decreases maintenance costs, and reduces the amount of odors due to volatiles coming from the adhesives. Decreasing the odor and fumes coming from the adhesive is particularly appealing to customers, and to the employees who work in plants utili2ing hot melt adhesives on a reguUir basis.
Hot melt adhesives are typically applied at temperatures of 175°C. For the aforementioned reasons, it is desirable to apply hot melt adhesives at temperatures of less than BS^C, and preferably from 135°C to 150°C. Hot melt adhesives intended for application temperatures of less tlian 155°C, based on polymers such as ethylene n-butyl acrylale, ethylene vinyl acetate, and polyethylene, are known. Such adhesives generally employ lower melting point raw materials such , as tackifying resins and waxes which t^nd to sacrifice important physical characteristics of the adhesive such as heat resistance. Lower application temperatures can also reduce the open time resulting in less penetration into the substrates and therefore poorer bondability of the hot meU adhesives.
Hot melt adhesives known in the art generally comprise tliree components; a polymer, a tackifier, and a wax. Each component may comprise a blend of two or more components, that is, the polymer component may comprise a blend of tw^o different

polymers. The polymer provides strength to the adhesive bond. The tackifier provides tacit the adhesive 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/close times and reduces the viscosity of the system. Certain liot melt adhesives known in the ail further comprise oil to reduce the viscosity of the .system.
Hot melt adhesives based on previously used polymers include ethylene vinyl acetate copolymers (EVA), atactic polypropylene (APP), low density polyethylene (LDPE), and homogeneous linear ethylene/a-olefm copolymers. Prior art hot melt adhesives typically employed large levels of tackifier to reduce the viscosity of the .system to levels which enabled its facile application to the substrate, e.g., to viscosities less than about 5000 centipoise (50 grams/(cm-sccond)). However, the use of such tackitlers poses disadvantages, as tackifiers have the tendency to corrode equipment, are malodorous, and impede recyclability of paperboard bearing them.
Industry would fmd advantage in hot melt adhesives exhibiting good adhesion to both coated and imcoated paperboard, which adhesives exhibit good low temperature adhesion and/or high shear adhesion failure temperatures (SAFT), Industiy would fmd particular advantage in hot melt adhesives which exhibh such properties, and, additionally, which minimize the use of tackifiers.
U.S. Pat, No. 5,041,482 to Omsteen et al. issued August 20,1991 discloses glue stick adhesives for use in glue guns that can be applied at application temperatures in the range of 82""C to 138*C, and preferably less than 12PC. Omsteen discloses ethylene vinyl acetate, polyethylene and polypropylene polymers having melt indices in excess of 750 g/10 minutes. Tlie exemplified glue stick adhesive compositions are high in viscosity, and thus imsuitable for piston pump or gear piunp extrusion application equipment used widely in the packaging induatiy.
U.S. Pat. No. 5,373,049 to Omstem ct al. is3ued December 13, 1994 teaches cool melt adhesives, again based on polyethylene, polypropylene and ethylene vinyl acetate.
U.S. Pat. No. 5,550,472 to Liedermooy et al. issued March 19, 1996 teaches a hot melt adhesive designed for low application temperature based on ethylene n-butyl acrylate copolymers havine a melt index of at least 600 g/10 min., a terpene phenolic tackifying resin and a low melting point synthetic Fischer-Tropsch wax. It is suggested that small amounts, up to 20 percent by weight, of other polymeric additives such as typically known ethylene vinyl acetate, ethylene

methyl aery late, ethylene acrylic acid, polyethylene, polypropylene, poly-(tautcnc-l-co-ethylene), lower melt index ethylene n-butyl aery late copolymers may be added.
Elu-opean Pat. Application EP 0,721,006A1, published July 10, 1996, teaches a hot melt • packaging adheaive based on ethylene n-butyl acrylate copolymers having a melt index ot at least 850 g/10 min. combined vidth a rosin ester tackifying resin and a microcrystalline or paraffm wax, which may also contain ethylene vinyl acetate copolymers, ethylene methyl acrylate copolymers, ethylene acrylic acid copolymers, polyethylene, polypropylene, poly-(butene- l-co-ethylene), and lower melt index ethylene n-butyl acrylate copolymers as a non-essential ingredient, The adhesive compositions exemplitled exliibit fiber tear in the range of 35*C to 40°C, are designed for freezer grflde applications and lack high heat resistance.
U.S. Patent No. 5,326,413, issued July 5,1994 to Esemplare et al., claims a hot rack adhesive comprising a polymer having amelt index of 300-500 dg/min per ASTM D123S, a specific wax, and a tackifier. This patent teaches tlie use of ethylene vinyl ester copolymers.
U. S, Pat. No. 5,397,843, issued Mardi 14,1995 to Lakshmanan et al., teaches blendqd polymer compositions comprising a mixture of a copolymer of ethylene and an a-oletln and an amorphous polypropylene and/or amorphous polyolefIn, or mixtures thereof. The examples set forth in Lakshmanan teach compositions with high concentrations, at least 42.5 percent by weight, of blended polymers.. The single copolymer of ethylene and an a-olefm exemplified is "Flexomer 9042" from Union Carbide, having a l-butene content of 15 percent by weight and a density of 0.900-g/cm^ These polyethylene type formulations tend to be stiffand to have poor cold temperature properties. In general, prior to the present invention, bonding capabilities of ethylene based hot melt adhesive compositions tended to be poor in comparison to ethylene vinyl acetate and ethylene n-butyl acrylate based hot melt adhesives. Although the use of amorphous polyolefins can improve flexibility, these polymers tend to be very cohesively weak due to inhomogeneo;.is branch distribution, which also tends to cause unpredictable aging characteristics. Also, amorphous polyolefms tend to soften significantly at high temperatures, resulting in a loss of heat resistance and the possibility of bond failure during shipping and storage.
U.S. Patent No. 5,530,054, issued June 25,1996 to Ise 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, to C^Q a-olcfm produced in the

presence of a catalyst composition comprising a metallocenc and an alumoxanc and having mi M^
f from about 20,000 to about 100,000; and (b) a hydrocarbon tackifier which ia aeleoted from a recited list. Exemplified are compositions consisting of 45 percent by weight of ethylene/butene-l copolymer having a apeoitlc gravity of either 0.898 gJcm^ or 0.901 g/cm\ Since the exemplified fonnulations have a viscosity greater than about 10,000 cps (100 grams/(cm-second)) at ISC"C such formulations are not only unsuitable as low application temperature hot melt adhesives, but are typically unsuitable for use on extrusion type application equipment even at an application temperature of ISCC. Furthermore, exemplified formulas contain no more than 10 percent bj" weight of a low melting point paraffin wax which has little impact on the properties of the finished adhesive other than to lower the viscosity. Even the wax containing fonnulations exliibit a viscosity greater than about 10,000 cps (100 grams/(cm"second)) and range as high as 67,000 cps (670 grams/(cm-second)) at 180°C.
U.S. Patent No. 5,548,014, issued Aug. 20 ,1996 to Tse et al., claims a hot meh adhesive composition comprising a blend of ethylene/a-olefm copolymers wherein the"first copolymer has a M^, from about 20,000 to about 39,000 and the second copolymer has a M„ from about 40,000 to about 1,00,000, Each of the hot melt adhesives exemplified comprises a blend of copolymers, with at least one of the copolymers having a polydispcrsity greater than 2.5. Fuithennore, the lowest density copolymer exemplified haa a apecific gravity of 0.894 g/cnv\ Exemplified are hot melt adhesives having a. high viscosity ranging between 4,300 cp.? (43 grainsy(cm-second)) and 180.000 Cps (1800 grams/(cm"second)), with most of the examples being at least 10,000 cps (100 grams/(cm-second)) at 180*C. such formulations being too high in viscosity for use on standard hat melt extrusion type application ecjuipment at low application temperatures.
Tse, in Application of Adhesion Model for Developing Hot Melt Adhesives Bonded to Polvolefin 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/a-olefin interpolymers show higher viscosity and inferior tensile strength, but better bond strength to polyolefm siu-faces, higher strain at break and lovkcr yield stress.
Collectively, these references do not teach the use of low density homogeneous linear or substantially linear interpolymers for low application temperature hot melt adhesives. Nor do these

"•eferences teach preferred hot melt adhcsives for the bonding of cardboard or paperbctard ftbstrates. Furthermore, the packaging industry would find advantage in a low application temperature hot melt adhesive amenable to repulping operations having high heat resistance, * improved cold temperature properties and excellent thermal stability. The present ipventors have found that when formulated jttto hot melt adhesives, certain novel homogeneous linear or substantially linear- ethylene/a-olefm interpolymers having a density from 0.850 g/cm" to 0.8"95 g/cm^ can be employed in hot melt adhesives exhibiting improved adhesive performance properties with respect to the prior art.
The present invention relates to a hot melt adhesive comprising:
a) from 20 percent to 65 percent by weight in the adhesive of at least one homogeneous
linear or substantially linear interpolymer of ethylene with at least one CyC^o a-olefin having a
polydispersity less than 2.5 and a density from 0.850 to 0.895 g/cm^;
b) from 10 percent to 60 percent by weight of at least one tackifying resin; and
c) from 0 to 40 percent by weight of a wax.
The homogeneous linear or substantially linear interpolymers preferably h^jJ^ogyigMJ" melt viscosity (using a spindle 31 and a speed of 1.5 rpm) of from 2,000 cps (20 grains/(cm"Second)) to 18,000 cps (180 gram3/(cm second)), more preferably from 5,000 to 17,000 cps (170 gramB/(cm-second)), even more preferably from 7,000 cps (70 gramfi/(cm-second)) to 16,000 cps (160 grams/(cm-second)), and most preferably from 8.000 cps (80 grams/(cm-second)) to 15,000 cps (150 grams/(cm-second)). A blend of interpolymers which individually may have viscosities higher or lower than the preferred range can be used as long as the resultant blend exhibits a viscosity within the preferred range. These interpolymers preferably have densities of less than 0.895 g/cm^, preferably less than 0.885 g/cm^ and more preferably less than 0.875 g/cm^ These interpolymers have densities of at least 0.850 g/cm\ preferably at least 0.855 g/cm\ The interpolymers may have densities higher or lower than the preferred range as long as the resulting blend has a density within the preferred range.
It is not a problem to obtain high heat resistance when employing a relatively low melt index polymer, as the molecular weight of the polymer contributes greatly to the heat resistance. However, for low application temperature hot melts, it is necessary to employ substantially less polymer or alternatively higher melt index polymers having a lower molecular weight.

Consequently, due to these polymer compromises, high heat resistance hfts been difficuh to achieve
* combination with a low viscosity. Surprisingly, the adhesives of the present invention exhibit heat resistance in comparison with standard packaging grade hot melt adliesives designed for application temperatures of 177°C, while having viscosities which are amenable to application temperatures of less than 150*C.
The resultant hot melt adhesive has a viscosity of less than about 5,000 cps (50 grams/(cm-second)) at 150"C, preferably less than 3,500 cps (35 grams/(cm-second)) at I SO^C and more preferably less than about 2,000 cps (20 grams/(cm-second)) at 150* C and can be applied at temperatures of less than about 150°C, and preferably at temperatures between 135°C and 150*C. These adhesives can be applied using standard extrusion type hot melt application equipment such as those liianufactured by Nordson Corp. in Atlanta, GA as well as by Mercer, Slautterback and
■iTw.. :■; "■- ^_!
The novel adhesive composition of the present invention is further characterized as having a low density amenable to recycling and repulping processes. The hot melt adhesive of the present invention exhibits excellent heat resistance, having peel values (PAFT) greater than 4Q""C, preferably greater than SO"C and more preferably greater than 60°C and excellent cold temperature flexibility. This combination of properties causes the adhesive compoBitions of the present invention to be a significant improvement with respect to the state of the art for low application temperature packaging adhesivas.
The subject invention fiirther pertains to a hot melt adhesive useful to adhere two cardboard or paperboard faces comprising:
(a) 25 - 100 weight percent of a homogeneous linear or substantially linear ethylene polymer having a density of 0.880 - 0.895 g/cm^ and a melt viscosity at 350*F (177*C) of from 3500 to 6000 centipoise (35 to 60 grams/(cm-second));
(b) 0-50 weight percent of a tackifier;
(c) 0 - 35 weight percent of a wax which is preferably selected from the group consisting of paraffinic wax, crystalline wax, homogenous wax having a density of 0.885-0.970 g/cm^ and a melt viscosity at 3S0*F (177*C) of from 100 to 1000 centipoise (1 to 10 grams/(cmsecond)), and combinations thereof; and

with the proviso that when the tackifier is present in an amount less than 20 weight l^ercem, the homogeneous linear or substantially linear ethylene polymer is present in an amount of at least SO weight percent.
The subject invention further pertains to a hot melt adhesive useful to adhere two faces of cardboard or paperboard, comprising;
(a) 25JO 85 weight percent of a homogeneous linear or substantially linear ethylene polymer having a density of 0.865 to less than 0.875 glcm? and a melt viscosity at 350°F (IITC) of from 3500 to 6000 centipoise (35 to 60 grams/(cmsecond));
(b) 5 to 50 weight percent of a tAckifier; and
(c) 0 to 50 weight percent of a wax which is preferably selected from the group consisting of paraffinic wax, crystalline wax, homogenous wax having a density of 0.885 to 0.970 g/cm^ and a melt viscosity at 350°F (177*>C) of from 100 -1000 centipoise (1 to 10 grams(cm*second)), and combinations thereof;
with the proviso that when the tackifier is present in an amount less tlian 20 weight percent, the polymer is present in an amount of at least 35 weight percent.
The subject invention further pertains to a hot melt adhesive useful to adhere two faces of cardboard or paperboard, comprising:
(a) 25 to 83 weight percent of a homogeneous linear or substantially linear ethylene polymer having a density of 0.860 to less tlian 0.880 g/cm^ and a melt viscosity at 350"? (177°C) of from 1500 to less than 3500 centipoise (15 to 34 grams/(cmsecond));
(b) S to 50 weight percent of a tackifier; and
(c) 0 to 50 weight percent of a wax which is preferably selected from the group consisting of paraffinic wax, crystalline wax, homogenous wax having a density of 0.885 to 0.970 g/cm" and a melt viscosity at 350"? (177°C) of from 100 -1000 centipoise (1 to 10 gtams/(cmsecond)), and combinations thereof;
with the proviso that when the tackifier is present in an amount less than 20 weight percent, the polymer is present in an amount of at least 35 weight percent.
The subject invention further pertains to a hot melt adhesive useful to adhere two faces of cardboard or paperboard, comprising:

(a) 25 to 85 weight percent of a homogeneous linear or substantially linear
f^thylcne polymer having a density of 0.860 to less than 0.880 g/cm^ and a melt viscosity at
350°F (IITC) of greater than 6000 centipoise (60 grams/(cm-second));
(b) 5 lo 50 weight percent of a tackificr; and
(c) 0 to 50 weight percent of a wax which is preferably selected from the group consisting of parafflnic wax, crysiaUine wax, homogenous wax having a density of 0.885 to 0.970 g/cm" and a melt viscosity at 350"F (177"C) of from 100 -1000 centipoise (1 to 10 grams/(cmsecond)), and combinations thereof.
The subject invention further pertains to a hot melt adlieeive useful to adhere two faces of cardboard or paperboard, comprising:
(a) 40 to 85 weight percent of a homogeneous linear or substantially linear ethylene polymer having a density of 0.880 to 0.895 g/cm" and a melt viscosity at 350"? (177°C) of from 1,500 to less than 3500 centipoise (15 to less than 35 grams/(cmsecond);
(b) 5 to 30 weight percent of a tacldfier; and
(c) 0 to 45 wt. % of a wax which is preferably selected from the group consistmg of paraffinic wax, crystalline wax, homogenous wax having a density of 0.885 to 0.970 g/cm" and a melt viscosity at 3S0*F (177*C) of from 100 -1000 centipoise (1 to 10 grams/(cmsecond)), and combinations thereof;
with the proviso that when the tackifier is less than 10 weight percent, the polymer is present in an amount of at least 50 weight percent.
The subject invention further pertains to a hot meh adhesive useflil to adhere two faces of cardboard or paperboard, comprising:
(a) 30 to 85 weight percent of a homogeneous linear or substantially linear etliylene polymer having a density of 0.875 to less than 0.885 g/cm^ and a melt viscosity at 350°F (177""C) of from 3,500 to 6,000 centipoise (35 to 60 grams/(cm.second);
(b) 0 to 50 weight percent of a wax which is preferably selected from the group consisting of paraffinic wax, crystalline wax, homogenous wax having a density of 0.885-0.970 g/cm^ and a meh viscosity at 350°F (177°C) of from 100 -1000 centipoise (1-10 greuna/(cmsecond)), and combinations thereof; and

(c) 5 to 50 weight percent of a tackjfier.
The subject invention further provides a polymerization process comprising:
ft. reacting by contacting ethylene and at least C3-C20 ot-olefms under solution polymerization conditions, in the presence of a constrained geometiy catalyst composition, in at least one reactor, to produce a solution of a homogeneous linear or substantially linear polymer which is an imerpolymer of ethylene and the at least one a-olefin, the homogeneous linear or substantially linear polymer being characterized as having a density of from 0.850 to 0.895 g/cnv^;
b. reacting by contacting ethylene and, optionally, at least C3-C20 a-olefui, under
solution polymerization conditions, in the presence of a constrained geometry
catalyst composition, in at least one other reactor, to produce a solution of a
homogeneous wax having a density of 0.920 to 0.940 g/cm^
c. combining the solution of the first reactor with the solution of the second reactor to
form a solution of a blend;
d. removing the solvent from the solution of a blend of step (c) and recovering the
blend; and
e. optionally introducing a tackifier into the reactor of step (a), tlie reactor of step (b), or
at any point subsequent to the reacting of step (b); ^
wherein the resultant composition is characterized as having a viscosity of less than 5000 centipoise(50grams/(cmsecond))at ISO^C .
The subject invention further pertains to a packaging article, comprising two adjacent faces of cardboard or paperboard which have been adhered by any of tlie hot melt adhesives of the invention, and which are characterized as having at least 80 percent initial paper tear. Most preferred packaging articles will be adhered by any of the hot melt adhesives of tlie invention, and which are characterized as having at least 80 percent 14 day paper tear at room temperature, most preferably as having at least SO percent 14 day paper tear at 50°C.
Unless indicated otherwise, the following testing procedures are to be employed:
Densitv is measured in accordance with ASTM D-792. The samples are annealed at ambient conditions for 24 hours before the measurement is taken.

Melt index (h^- "S measured in accordance with ASTM D-1238, condition !90X/2.16 kg (formally known as "Condition (E)").
Molecular weight is determined using gel permeation chromatography (GPC) on a Waters 1SCC high temperature chromatographic unit equipped with three mixed porosity colunms (Polymer Laboratories 103, 104. 105. and 106). operating at a system temperature of 140°C. The solvent is l,2,4-trichloroben2:ene, from which 0.3 percent by weight solutions of the samples are prepared for injection. The flow rate is 1.0 mL/min. and the injection size is 100 microliters.
The molecular weight determination »s deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elutlon volumes. The equivalent polyethylene molecular weights are determined by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Word in Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation:
^polyethylene " » * (Mpolystyrene)b-
In this equation, a =* 0.4316 and b «* 1.0. Weight average molecular weight, M^, is calculated in the usual manner according to the following formula: Mw = 2 wj* M[, where wj and M{ are the weight fraction and molecular weight, respectively, of the ith fraction eluting from the GPC column.
Melt viscosity of polvmer components 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 (0.1 to lOOO grams/(cm"Second)). A cutting blade is employed to cut samples into pieces small enough to fit into the 1 inch wide, 5 inches long (2.5 cm wide, 13 cm long) sample chamber. The sample is placed in the chamber, which is in turn inserted jnto 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 350°F (177*C), with additional sample being added until the melted sample is about I inch (2.5 cm) 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 tumcd on, and set to a shear rate which leads to a

torque reading in tlie range of 30 to 60 percent. Readings are taken everj" minute for about *\ 5 minutes, or until the values stabilize, which final reading is recorded.
Melt Viscosity of the hot melt adhesives were determined on a Broolctleld Thermosel Viscometer Model LVDV 2+ using a number 21 spindle.
g^cels and Shears (PAFT and SAFT) were determined by suspending Itio gram weights from the; samples in the peel mode and 500 gram weights from the samples in the sheai- mode. The temperature was ramped from a starting temperature of 25°C to an ending temperature of lOO^C at a rate of 25°C/hour. The oven automatically recorded the temperature at which the samples failed. Each sample was coated onto kraft paper by hand using glass rods or shims, The resultant coating is a one inch (2.5 cm) wide band that is 8-10 mils or 0.008 to 0.010 inches (2.0 to 2.5 cm) tliick. A minimum of 8 samples were run for each adhesive. The adhesives of the invention were compared to commercially available compositions.
Bonding Tests were conducted as follows. Adhesive bonds were made on both high performance corrugated and on clay coated chipboard cartonstock using an application temperature of about 135"C, an open time of 1.5 seconds and a set time or compression time of 1.5 seconds and a bead size of 3/32 of an inch uncompressed (2.4 imn). The resulting bonds were then conditioned at about 40"? (4.5°C) for at least 24 hours, and then separated by hand and the amount of fiber tear based on a percentage of the total bond was determined. A minimum of six samples were tested for each adhesive. The adhesive performance was compared to two different commercially available compositions.
Heat Stability Tests were conducted as follows. A 250 gram sample of each of the adhesives was placed in a glass beaker which was then placed in a forced air oven at 275°? (135"C) and allowed to sit in the oven for 96 hours. A small portion of the adhesive, from about 10 gram to about 20 gram was removed from the beaker at 24,48,72 and 96 hours. Viscosity and Molten Gardner Colors-were then recorded for each of the time intervals to monitor changes in the sample over time. The change in viscosity and Molten Gardner Color for 96 hours are reported herein.
Shear adhesion failure temperature (SAFT) fot the hot melt adhe.sives of Examples 24-93 was measured in accordance with the following procedure. A one inch (2.5 cm by 2.5 cm) by one inch lap shear bond to case cartons using the indicated hot melt adhesive in its molten state is prepared. Samples are himg vertically in an air circulating oven at 30°C with a given weight (typically a 500 gram weight) suspended from the bottom of the strip. The

oven temperature is increased by 5°C every 30 minutes umil the adhesive bond fails. The pear-fail temperature is the average of three SAFT measurements.
Peel adhesion failure temperature (cantilever-mode") (PAFT c-mode) for the hot melt adhesives of Examplea 24-93 was measured in accordance with the following procedure, A one inch by one inch (2.5 cm by 2.5 cm) lap shear bond to case cartons using the indicated hot melt adhesive in its molten state is prepared. Two metal beams are placed parallel to each other two inches apart. The prepared sample is laid across the beam with the 1 inch by 1 inch (2.5 cm by 2.5 cm) lap shear bond centered between the two beams. A 100 gnmi weight is placed on the I inch by 1 inch (2.5 cm by 2.5 cm) lap shear bond. The beams and samples ai-e placed in an air circulating oven at 30°C. The oven temperature is increased by S^C eveiy 30 minutes imtil the adhesive bond fails. The peel-fail temperature is the average of tliree PAFT measurements.
Open time is measured in accordance with the following procedure. The desired hot melt adliesive is melted at 350*F (177*C). An 11 inch by 4 inch (28 cm by 10 cm) piece of 24 pt Kraft "Post Tex Board", available from Huckster Packaging (Houston, TX), is placed clay side up. A 1 inch (2.5 cm) bead of the molten hot melt adhesive in placed onto the board. After five seconds, a 1 inch by 4 inch (2.5 cm by 10 cm) strip of the 24 pt Kraft "Post T^!X Board" is placed fiber side down onto the bead of adhesive. T^ie strip is immediately rolled with a 10 pound (3.7 kg) roller. Additional strips of the "Post Tex Board" are applied and polled every five seconds, until no bond is made. The 11 inch by 4 inch (28 cm by 10 cm) board is held securely on both sides of the board. Beginning with the first applied strip, each strip is slowly peeled, until no paper tear is achieved. The time is seconds beyond which point paper tear is not unifonuly achieved on the contacting part of the adhesive.
Close time is measured in accordance with the following procedure. The desired hot melt adhesive is melted at 3S0*F (
°C). An 11 inch by 4 inch (28 cm by 10 cm) piece of 24 pt Kraft "Post Tex Board", available from Huckster Packaging (Houston, TX), is placed clay side up. A 1 inch (2.5 cm) bead of the molten hot melt adhesive in placed onto the board. A 1 inch by 4 inch (2.5 cm by 10 cm) strip of the 24 pt Kraft "Post Tex Board" is placed fiber side down onto the bead and is immediately rolled with the 10 pound (3.7 kg) roller. After 5 seconds, the strip is peeled in the same manner as indicated in the measurement of Open Time. If paper tear is achieved, Close Time is 5 seconds or less. If paper tear is not achieved, the test is repeated, waiting 10 seconds before peeling away the strip. The test is continued until paper tear is achieved. Note, some samples have an infinite close time, such as pressure sensitive adhesives.

Paper tear is measure in accordance with the following procedure. The desired hot "melt adhesive is melted at 350*F (177°C). Aii 11 inch by 4 inch (28 cm by 10 cm) piece of 24 pt Kraft "Post Tex Board", available from Huckster Packaging (Houston, TX), is placed clay side up. A V inch (2.5 cm) bead of the molten hot melt adhesive in placed onto the board. A 1 inch by 4 inch (2.5 cm by 10 cm) strip of the 24 pt Kraft "Post Tex Board" is placed fiber side down onto the bead and is immediately rolled with the 10 poimd (3.7 kg) roller. In the case of initial paper tear, after 5 seconds, the strip is peeled in the same manner as indicated in the measvu-ement of Open Time", with the amount of paper tear being visually observed. In the case of 14 day room temperature paper tear, the sU-ip is maintained at room temperature for 14 days, and is then peeled in the same manner as indicated in the determination of initial paper tear. In the case of 14 day paper tear at SO""C, the strip is maintained at 50*C for 14 days, and is then peeled in the same manner as indicated in tlie determination of initial and 14 day room temperatiue paper tear. In each case, the value reported is the average of three measurements.
ggrcent crystallinitv may be calculated with the equation;
%C=(Ay292J/g)xl00, in which %C represents the percent ciystallinity and A represents tlie heat effusion of the ethylene in Joules per gram (J/g) as determined by differential scanning calorimetry (DSC). Differential scanning calorimetry (DSC) data may be generated by placing each sample (5 mg) in an almninum pan, heating the sample to 160°C, cooling the sample at 10°C/min and the recording the endotherm by scanning from -SO^C to 140°C at lO°C/min using a Perkin Elmer DSC 7.
FIGURE 1 is a three axis depiction of representative hot melt adhesi ves of the invention and
of comparative hot melt adhesives. "
FIGURE 2 is a graphical depiction of the average initial paper tear for representative hot meh adhesives of the invention and of comparative hot melt adhesives, with the points indicated corresponding to the points at the same relative location in the triangle of FIGURE 1.
FIGURE 3 is a graphical depiction of the average 14 day room temperature paper teai-for representative hot melt adhesives of the invention and of comparative hot melt adhesives, with ihe points indicated corresponding to the points at the same relative location in the triangle of FIGUK£1.

FIGURE 4 is a graphical depiction of liie average 14 day paper tear at 50°C for Representative hot melt adhesives of the invention and of comparative hot melt adhesives. with the points indicated corresponding to the points at the same relative location in the triangle of FIGURE 1.
FIGURE 5 is a graphical depiction of the percent crystallinity (as determined by differential scanning calorimetiy (DSC)) of the formulation, for represeiitative hot m6it adhesives of the invention and of comparative hot melt adhesives, with the points indicated corresponding to the points at the same relative location in the triangle of FIGURE 1.
FIGURE 6 is a plot of melt viscosity (centipoise) versus temperature for representative hot melt adhesives of the invention and of comparative commercial hot melt adhesives.
The hot melt adhesives of the invention comprise at leastone homogeneous linear or substantially linear polymer which is an imerpolymer of ethylene and at least one C"^-Cjf, a-olefm, and optionally at least one wax and/or tackifier.
Tlie term "intcrpolymcr" 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 inteipolymer.
The homogeneous linear or substantially linear polymer is an ethylene polymer prepared using a constrained geometry or single site metallocene catalyst. By the temi homogenous, it is meant that any comonomer is randomly distributed udthin 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 substmitially linear ethylene polymers, as determined by differential scanning caloumetry (DSC), will broaden as the density decreases and/or as the number average molecular weight decreases. However, imlike heterogeneous polymers, when a homogeneous polymer has a melting peak greater than 1 IS^C (such as is the case of polymers having a density greater than 0.940 g/cm^), such polymers typically do not additionally have a distinct lower temperature melting peak.
The homogeneous linear or substantially linear ethylene polymers are characterized
as having a narrow molecular weight distribution (Mw/Mn). For the linear and
substantially linear ethylene polymers, the M^/M^ is preferably from 1.5 to 2.5, preferably
" from 1.8 to 2.2. i

It is important to note that the ethylene polymers useful in the invention differ fton w density polyethylene prepared in a higli pressure process. In one regard, whereas low density polyethylene is an etliylene homopolymer having a density of from 0.900 to 0,935 g/cm^, the ethylene polymers useftil in the invention require the presence of a comonomer i reduce the density to the range of from 0.900 to 0.935 g/cm^.
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 polyniei backbone. When a substantially linear ethylene polymer is employed in the practice of the invention, such polymer will be characterized as having a polymer backbone substituted wi from 0.1 to 3 long chain branches per 1000 carbons.
Methods for determining the amount of long chain branching present, both qualitatively and quantitatively, are known in the art.
For qualitative methods for determination, see, e.g., U.S. Patent Nos. 5,272,236 an 5,278,272, which disclose the use of an apparent shear stress vs. apparent shear rate plot to identify melt fracuire phenomena. Substantially linear ethylene polymers will possess a ga extrusion rheology such that: (a) the critical shear rate at the onset of surface melt fracture for the substantially linear ethylene polymer is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture for a linear ethylene polymer having the sam comonomer or comonomers and having an I2, Mw/Mn and density within ten percent of th of the substantially linear ethylene polymer, and wherein the respective critical shear rates the substantially linear ethylene polymer and the linear ethylene polymer are measured at t! same melt temperature using a gas extrusion rheometer; or (b) the critical shear rate at the onset of gross melt fracture is greater than 4x10"" dynes/cm^ (0,4 MPa), as determined by gas extrusion rheometry.
For quantitative methods for determination, see, for instance, U.S. Patent Nos. 5,272,236 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297), which discusses the measurement of long chain branching using 13G nuclear magnetic resonance spectroscopy, Zimm, G.H. and Stockmayer, W.H., J. Chem. Phys., 17,1301 (1949); and Rudin, A., Modem Metliods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112, which discuss the use of gel permeation cliromatography coupled with a low angle laser light scattering detector (GPC-LALLS) and gel permeation cluomatography coupled with a differential viscometer detector (GPC-DV).

Substantially linear ethylene polymers are further characterized as having a melt ^w ratio (Ii0""l2) which may be vwied independently of the polydispersity index, that is, the molecular weight distribution M^M^. This feature accords substantially linear ethylene polymers with a high degree of processability despite a narrow molecular weight distribution.
The homogeneous linear or substantially linear ethylene polymer will be an interpolymer of ethylene with at least one a-olefm. Preferred are interpolymers of ethylene with at least one C3-C20 a-olefm (for instance, propylene, isobutylene, 1-butene, 1-pentene, l-hexene, 4-methyl-l-pentine, and 1-octene), with interpolymers of ethylene with at least one C4-C20 a-oletin, particularly at least one C^-Cj a-olefm, being most preferred.
The homogeneous linear or substantially interpolymer of ethylene useful herein ate those having a density of less than 0.895 g/cm\ preferably less than 0.885 g/cm"* and more preferably less than 0.875 g/cm^; greater than 0.850 g/cnv" and preferably greater than 0.855 g/cnv". When 1-octene is employed as the comonomer, preferably the 1-octene is present in an amount greater than 31 percent by weight in the polymer as measured by NMR in accordance with ASTM D-SOl 7. More preferably the 1-octene comonomer content of the Interpolymer is greater than 33 percent by weight and most preferably greater than 35 percent by weight.
Preferably, the adhesive composition comprises a homogeneous linear or substantially lineal" interpolymers which is characterized as having a nanow molecular weight distribution with a polydispersity (MJMn) less than about 2.5, preferably from about 1.5 to 2.5, and more preferably from 1.8 to 2.2, as determined by gel permeation chromatography.
The melt index (Ij at 190°C) of the homogeneous linear or substantially linejjr ethylene polymer is preferably from 200 to 2000 g/lG min., more preferably from 500 to ISOO g/10 min,, and most preferably from 800 to 1200 g/10 min.
The homogeneous linear or substantially linear interpolymers preferably exhibits a BrookfieldTM melt viscosity at 350°F (177°C) (using a spindle 31 and a speed of 1.5 rpm) of fioni 2,000 cps (20 grams/(cm"second)) to about 18,000 cps (180 grams/(cm-second)), preferably ftom 5,000 cps (50 grams/(cm-second)) to 17,000 cps (I70grams/(cm-second)), more preferably from 7,000 cps (70 grams/(cm"Second)) to 16,000 cps (160 grams/(cm-second)), and most preferably from 8,000 cps (80 gTanis/(cm-second)) to 15,000 cps (150 grams/(cm-second)). Melt viscosity is a preferable expression to melt index for accurately describing very high melt index polymers.

In another embodiment the present invention may comprise a blend of interpolymers ivherein the resultant blend of interpolymers has a density of less than 0.895 g/cm\ preferably less Ihan 0.885 g/cm" and more preferably less than 0.875 g/cm^; greater than. 0.850 g/cm\ and preferably greater than 0.855 g/cml The resultant blend has a viscosity from 5,000 cps (50 grams/(cm-second)) to 18,000 cps (180 grams/(cm-second)), preferably from 7,000 cps (70 grams/(cm-second)) to 16,000 cps (160 grams/(cmsecond)) and more preferably from 8,000 cps (80 grams/(cm-second)) to 15,000 cps (150 grams/(cmsecond)). Each interpolymer may therefore have a density and/or viscosity/melt index outside the preferred range provided the resultant blend of interpolymers has a density and a viscosity or melt index within the preferred range.
The homogeneous linear or substantially linear ethylene polymer, in preferred hot melt adhesive formulations, will preferably have an ultra-low molecular weight, that is, such polymers will have a number average molecular weight (Mn) of no more than 11,000.
Ultra-low molecular weight ethylene/a-olefm interpolymers are especially advantageous in the present application, as they lead to a low polymer and formulation viscosity but are characterized by a peak crystallization temperature which is greater than tliat of corresponding higher molecular weight materials of the same density. In hot melt adhesive applications, the increase in peak crystallization temperature translates to decreased close times, as the materials begins to crystallize from the hot meh more rapidly.
Homogeneously branched linear ethylene/a-olefm interpolymers may be prepared using polymerization processes (such as is described by Elston in USP 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/a-olefm interpolymers are currently available trom Mitsui Petrochemical Compatiy imder the tradename "Tafmer" and from Exxon Chemical Company under tlie tradename "Exact".
Substantially linear ethylene/a-olefm interpolymers are available from The Dow Chemical Company as Affinity™ polyolefin plastomers. Substantially linear ethylene/a-olefin interpolymer; may be prepared in accordance with the techniques described in U.S. Patent No. 5,272,236 and in U.S. Patent No. 5,278,272.

Ultra-low molecular weight polymers may be made in accordance vdih the Examples herein {d uith the proceduies set forth below.
The first polymer may be suitably prepared using a constrained geometry metal complex, such as are disclosed in U.S. Application Serial No. 545,403, filed July 3, 1990 (EP.A-416,815); U.S. Application Serial No. 702,475, filed May 20,1991 (EP-A-514,828); as well as US-A-5,470,993, 5,374,696, 5,231,106, 5,055,438, 5,057,475, 5,096,867, 5,064,802, and 5,132,380. In U.S. Serial Niunbcr 720,041, filed June 24, 1991, (EP-A-514,828) certain boranc derivatives of the foregoing constrained geometry catalysts are disclosed and a method for their preparation taught and claimed. In US-A 5,453,410 combinations of cationic constrained geometry catalysts with an alumoxane were disclosed as suitable olefin polymerization catalysts.
Exemplary constrained geometry metal complexes in which titanitmt is present in the +4
oxidation state include but are not limited to the following: (n-butylamido)dimethyKri -
tetramethylcyclopentadienyI)silanetitanium (IV) dimethyl; (n-butylamido)dimethyl(t] -tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl; (t-butylamido)dimethyl(r] -tetrametliylcyclopentadienyl)silanetitanium (IV) dimethyl; (t-butylaniido)dimetliyl(ri -tetramethylcyclopentadienyl)silane-titanimn (IV) dibenzyl; (cyclododecylamido)dimethyl(r]""-tctramcthylcyclo-pcntadicnyl)silanctitanium (IV) dibenzyl; (2,4,6-trimethylanilido)dinicthyl-(r| -tetramethylcyclopentadienyl)silanetitaniiun (IV) dibenzyl; (1 -adamantyI-amido)dimethyl(Ti -tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl; (t-butylamido)dimethyl(Ti -tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl; (t-butylamido)dimethyl(Ti -tetramethylcyclopentadlenyl)silanet{tanlum (IV) dibenzyl; (l-adamantylamido)dimethyl(iV -tetramethylcyclopentadienyl)-silanetitaniiim (IV) dimethyl; (n-butylamido)diisopropoxy(ri -tetramethylcyclo-pentadienyl)silanetitanium (IV) dimethyl; (n-butylamido)diisopropoxy(T| -tetramethylcyclopentadienyl)silanetitanium (IV) dibenzyl; (cyclododecylamido)-diisopropoxy(Ti""-"letramethylcyclopentadienyl)-silanetitaniam (IV) dimethyl; (cycIododecylamido)diisopropoxy(Ti""-tetramethyIcyolopentadienyl)-silanetitanium (IV) dibcrizyl; (2,4,6-trimethylanilido)diisDpropoxy(ii -tetramethylcyclopentadienyD-silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido)diisopropoxy(
5 "^
T] -tetramethyl-cyclopentadienyI)silanetitanium (IV) dibenzyl; (cyclododecylamido)dimethoxy(ti" -tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl; (cyclododecylamido)-dimethoxy(ri-tetramethylcyclopentadlenyl)silanetltanium (IV) dibenzyl; (l-adamantylamido)diisopropoxy(ii^-tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl; (l-adamantylamido)diisopropoxy(Ti""-tetrametbylcycIopentadienyI)-silanetitanium (IV) dibenzyl; (n-butylamido)dimethoxy(ri""-tetramethylcyclo-pentadienyl)silanetitanium (IV) dimethyl; (n-butylamido)dimethoxy-(71" "tetramethylcycIopentadienyOsilanetitanitun (IV) dibenzyl; (2,4,6-trimethylanilido)dimethoxy( ri -tetramethylcyclopentadienyI)Qilanetitanium (IV) dimethyl; (2,4,6-trimcthylaniiido)dimethoxy(r] ^-tettamethylcyclopentadienyl)silane-titanium (IV) dibenzyl; (1 -adamantylamido)dimethoxy(7i^-

tetramethylcyclo-pentadienyDsilanetitaiuum (IV) dimethyl; (l-adamaiitylamidQ)ciimethoxv(iV -
t^methylcyclopentadienyl)siIanetitatiiuni (IV) dibenzyl; (n-butylamidQ)-iitlioxymethyl(ri -
tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl; (n-butylainido)dthoxymethyl(Ti"-
tetramethylcyclopentadieny!)$ilanetitaniimi (IV) dibenzyl; (cyclododecylaniido)ethoxyme(hyl(Ti "^-tetramethylcyclopentadienyl)-silanetitamum (IV) dimethyl; (cycIododecy!amido)ethoxymethyl(ri -tetramethyi-cyclopenteidienyDsilanetitanium (IV) dibenzyl; (2,4,6-trim6thyi.aniHdo)ethoxynietbyl-( Ti""-tetraniethy}cyclopentadi?nyl)silaiietitanivm (JV) dimethyl; (2,4,6-triH>ethy!aniUsilanetitanimn (IV) dibenzyl; (cyclododecylamido)dimethyl(Ti""-tetramethylcyclopeiitadieiiyl)silane-titaniiim (IV) dimethyl; (1 -adamantylamido)-ethoxymethyl(ii 4etramethylcyclo-pentadienyl)silanetitanium (IV) dimethyl; and (l-adamantylaniidQ)ethoxymethyl(Ti" -tetrametliylcyclo-pentadienyOsilanetitantum (IV) dibenzyl.
Exemplary constrained geometry metal complexes in which titanium is present in the +3 oxidation state include but are not limited to the following: (n-butylamido)dimetliyl(Ti -tetrametiiyIcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamlno)ben2yl; (t-butylamido)dimethyl(Ti^-tetramethylcyclopentadienyl)silanetitanium(III)2-(N,N-djmcthylamino)bcnzyl; (cyclododccylamido)dimcthyl(T| -
tetramethylcyclopentadienyOsilanetitanium (III) 2-(N,N-dimethylamino)benzyl; (2,4,6-trimethylanilido)dimethyl(ii -tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (l-adamantylaniido)dimethyl(ri -tetramethylcyclopentadienyl)silanetitanlum (III) 2-(N,N-dimethylamino)benzyl; (t-butyIaraido)dimethyl(Ti -tetramethylcyclopentadienyl)silanetitanium (III) 2-("N,N. dimethylamino)benzyI; (n-butylamido)diisopropoxy(ri -tetramethylcyclopentadienyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)diisopropoxy("n -tetramethylcycIopentadienyl)-silanetitanium (ill) 2-tN,N-dimethylamino)benzyl; (2,4,6-trimetliylanilido)diiaopropoxy(ti -2-mcthyUndenyl)5ilanctitaniiim (III)2-(N,N-dimethylamino)benzyl;(l-adamantylamido)diisopropoxy(n""-tetramethylcyclopentadienyl)silanetitamum (III) 2-(N,N-dimethylamino)benzyl; (n-buiylamido)dimethoxy(ri -tetramethylcycIopentadienyl)$ilanetitanium (III) 2-(N,N-dimcthyIamino)benzyl; (cyclododecylamido)dimethoxy(r| -tetramethylcyclopentadienyl)silanetitanimn (HI) 2-(N,N-dimethylamino)beiizyl; (I-
adamantylamido)dimethoxy(ii -tetramethylcyclopentadienyl)si!anetitanium (III) 2-(N,N-diraethylamino)ben2yl; (2,4,6-trimethylanilido)dimethoxy(ti^-tetramethylcyclopentadienyI)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (n-butylamido)ethoxymethyI(Ti ^-tetramethyIcycIopentadienyI)silanetitanium (III) 2-(N,N-dimethylmnino)benzyl; (cyclododecylamido)ethoxymethyl(ii^-

tetramethyIcycIopentadienyI)silanetitanium (III) 2-(N,N-dimethylaniino)ben2yl; (2,4,6-triinethj"lanilido)ethoxymethyl(ti""-tetraiiietKylcyclopentadienyl)silanetitanium (III) 2,(N,N-imetliylamino)benzyl; and(l-adamaiitylamido)ethoxymethyl(Ti -tetramethylcyclopentadienyl)silaJietitaniiim (III) 2-(N,N-dimethylaniino)benzyl.
Exemplary constrained geometry metal complexes in wliich titanivim is present in the +2
5 oxidation state include but are not limited to the following: (n-butylamido)-dimethyl-(ri -
tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethyl(ri -tetramethylcyclopentadienyl)silanetitanium (11) 1,3-pentadiene; (t-butylamido)dimethyl(ii -tetramethylcyclopentadienyl)silane-titanium(ir) l,4-diphenyl-l,3-butadiene;(t-butylamido)dimethyl(r| -tetramethyl-cyclopentadienyl)silanetitanium(II) 1,3-pentadiene; (cyclododecylamido)dimethyl- (if-tetramethylcyclopentadienyOsiianetitaniiim (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethyl(n -
tetranietliylcyclopentadienyI)silanetitaniiim (II) 1,3-pentadiene; (2,4,6-trimethylanilido)dimethyl(
5 T] -tetramethylcyclopentadienyr)-silanetitaJiium (II) 1,4-diphenyl-l ,3-butadiene; (2,4,6-
trimethylanilido)dimethyl(r| -tetramethylcyclopentadienyl)iSilanetitanium (11) 1,3-pentadiene; (2,4,6-trimethyIanilido)dimethyl(r] -tetramethylcyclopentadienyl)silanetitanium (IV) dimethyl; (1-adamantylamido)dimethyI("n -tetramethylcyclopentadicnyl)sil£i^e-titanium (II) 1,4-diphenyl-l,3-butadiene; (l-adamantylaniido)dimethyl("n -tetramethylcyclopentadienyl)silanetitanium (II) 1.3-pentadiene;(t-butylamido)-dimethyl(Ti -tetrajnethylcyclopentadienyl)silanetitanium(ll) 1,4-diphenyl-1,3-butadiene; (t-butylamido)dimethyl(ri -tetramethylcyclopentadienyl)silanetitanium (II)
1,3-pentadiene;; (n-butylamido)diisopropoxy(r] -tetramethylcyclopentadienyD-silanetitanium (IF)
5 1,4-diphenyl-l ,3-butadiene; (n-butylamido)diisopropoxy(T| -
tetramethylcyclopentadienyI)silanetitanium (II) 1,3-pentadiene; (cyclododecylamido)-diisopropoxy(Ti -tetramethylcyclopentadienyl)silanetitamum (II) I,4-diphenyl-l,3-butadiene; (cyclododecylamido)diisopropoxy(ii -tetramethylcyclopentadienyO-silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethyianilido)diisopropoxy(T| -2-mctliyl-indenyl)silanctitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylaniIido)-diisopropoxy(Ti -tetramethylcyclopentadienyl)silanetitanium (II) 1,3"pentadiene; (I -
adamantylamido)diisopropoxy(r| -tetramethylcyclopentadienyOsilanetitanium (11) 1,4-diphenyl-
l,3-butadicnc;(l-adamantylamido)diisopropoxy(Ti -tetramethyl-cyclopentadienynsilanetitanium
(11) 1.3-pentadiene; (n-butylamido)dimethQxy(ti -tetramethylcyclopentadienyl)silanetitanJum (II)
1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethoxy(ri""-
tetramethyIcyclopentadienyl)silanetitanium (II) 1,3-pentadiene; (cyclododecylamido)dimethoxy(r)
"■-tetramethylcycIopentadienyl)-si!anetitanium(II) 1,4-diphenyl-1,3-butadlene;
5 (cyclododecylamido)dimethoxy(T) -tetramethylcyolopentadienyDailanetitanium (11) 1,3-pcntadiene:
(2,4,6-trimethylaniIido)dimethoxy(Ti -tetramethylcyclopentadienyr)silanetitanium (II) 1,4-

diphcnyl-l,3-butadiene; (2,4,6-trimcthylanilido)dimcthoxy(i-i -
tetramethylcycIopentadienyOsilanetitanium (11) 1.3-pentadiene; (1 -adamantyl-ainido)dimethoxy(Ti ^-tetramethylcyclopentadienyI)silanetitanium (II) l,4-diphenyl-l,3-butadiene; (1-adaiiiantylamido)dimethoxy(T) -tetramethylcyclopentadienyl)-silanetitanium (II) 1,3-pentadiene; (n-biitylamido)ethoxymethyl(ri^-tetramelhyIcyclopentadienyl)silanetitanium(II) l,4-diphenyl-l,3" butadiene; (n-butylamido)ethoxymethyl(i-i -tetramethyicycIopontadienyl)siIanetitaniiun (II) 1,3-pentadiene; (cycIododecylamido)ethoxymethyl(Ti -tetramethyicycIopentadienyl)siIanetitanimn (11) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)ethoxyniethyl(ti -tetramethylcyclopentadienyl)silanetitanimn(II) 1,3-pentadiene; (2,4,6-
trimetbylanilido)cthoxymcthyI(Ti -tctramcthylcyclopentadienyl)siljinctitanium(n) 1,4-diphenyl-1,3-birtadiene; (2,4.6-trimethylanilido)ethoxymethyl(T| -
tetramethylcyclopentadienyI)silanetitaniuin (II) 1,3-pentadiene; (l-adamantylaniido)ethoxymethyl( T] -tetramethylcyclopentadienyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; and (1-adamantylainido)ethoxymethyl(ii -tetramethylcyclopentadienyl)silajietitanium (II) 1,3-pentadiene.
The complexes can be prepared by use of well known synthetic techniques. The reactions are conducted in a suitable noninterfering solvent at a temperatiu"e from -100 to 300 °C, preferably from -78 to 100 °C, most preferably from 0 to 50 "C. A reducing agent may be used to cause the metal to be reduced from a higher to a lower oxidation state. Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercxjry amalgam and sodium/potassium alloy, sodium iuaphthalenide, potassium graphite, lithium alkyls. lithium or potassium alkadienyls, and Grignard reagents.
Suitable reaction media for the fonnation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtiu-as thereof; aromatic and hydrocarbyl-aubstituted aromatic compounds such as benzene, toluene, and xylene, Ci-4 dialkyl ethers, Ci-4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures ofthe foregoing are also suitable.
Suitable activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to U. S. Serial No. 07/547,718), EP-A-520,732 (equiviilent to U. S. Serial No. 07/876,268), WO 95/00683 (equivalent to U.S. Serial No. 08/82,201), and EP-A-520,732 (equivalent to U. S. Serial No. 07/884,966 filed May 1, 1992).
Suitable activating cocatalysts for use herein include perfluorinated tri(aiTl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible,

Illustrative, but not limiting, examples of boron compounds which may be used as an
activating cocatalysts are: tri-substituted ammonium salts such as: trimethylammoniuni
tetrakis(pentafluoro-phenyl) borate; triethylammonium tetrakis(pentafluofopheiiyl) borate;
tripropylammonium tetraJds(pentafluorophenyl) borate; tri(n-butyI)ammonium
tetraicis(pentafluorophenyl) borate; tri(sec-butyl)ammonium tetrakis(pentafluoro-pheny]) borate;
N,N-dimet.hylaniliniiun tetrakis(pentafluorophenyi) borate; N,N-dimethylaniliniurn
n-butyltris(pcntafluorophcnyl) borate; N,N-dimethylaniliniiun benzyltris(petitalluorQphenyl)
borate; N>N-dimethylanilimum tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate;
NjN-dimethylanilinium tetrakis(4-(triiSopropylsiIyl)-2, 3, 5, 6-tetrafluorophenyl) borate; N,N-
dimQthylanilinium pentafluorophenoxytris(pentafluorophenyl) borate; N,N-
dietliylaJiiUnium tetrakis(pentafluorophenyl) borate; N,N-dimethyl-2,4,6-trimet]iylanilinium tetTakis(pentatluotophenyl) borate; trimothylammonium tetrakis(2,3,4,6-tctrafluorophcnyl)borate; trietliylammonium 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)ammomiim tetrakis(2,3,4,6-tetrafluorophenyl) borate; N,N-dimethylanilimum tctrakis(2,3,4,6-tctrafluoraphcnyI) borate; N,N-diethylanilinium tetrakis(2,3.4.6-tetrafluorophenyl) borate; and N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl) borate;
disubstituted ammonium sahs such as: di-(i-propyl)ammonium teh-akisCpentafluoro-phenyl) borate; and dicyclohexylammonium tetrakis(pentafluorophenyl) borate;
trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorO" phenyl) borate; tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate; and tri(2,6-dimetliylphenyl)phosphonium tetrakis(pentafluorophenyI) borate;
disubstituted oxonium salts such as: diphcnyloxonium tetrakiS(pentafluoro-phenyl) borate; di(o-tolyl)oxonium tetraJds(pentafluorophenyl) borate; ajiid di(2,6-dimethyIphenyl)oxonium tetrakis(pentafluorophenyl) borate; and
disubstituted sulfonium salts such as: diphenylsulfonium tetrakis(pentafluorophenyl) borate; di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate; and bis(2,6-dimethylt>henvr>sulfoniiim tetrakis(pcntafluoroph6nyl) borate.

Other cocatalysts include, but are not limited to boron compounds which may be used as oiaic activating cocatalysts, which afe tri-substituted ammonium salts such as; Jecyldi(methyl)aitnitonium tetrakis(pentafluorophenyl) borate, dodecyldi(methyl)ammonium tetrakis(pentafluorophenyl) borate, tetradecyldi(methyl)anamonium tetrakis(pentafluorophenyl) borate, hexaadccyldi(mcthyl)antmonium tetralcis(pentafluorophenyl) borate, octadecyldi(methyl)ammomum tetrakisCpentafluorophenyl) borate, eicosyldi(methyl)amraonium tetrakis(pentafluoropheny]) borate, methyldi(decyl)ammomum tetrakis(pentafluorophqnyl) borate, methyldi(dodecyl)ammoniiim tetrakis(pentafluorophenyl) borate, methyIdi(tetradecyl)aniitionium tetrakisCpentafluorophenyl) borate, methyldi(hexadecyI)animoniuni tetrakis(pentafluorophenyl) borate, methyldi(octadecyl)ammoniuin tetraki3(pentafluorophenyl) borate, methyldJ(eicosyl)aminonium tetrakis(pentafluorophenyl) borate, tridecylammonium tetrakis(pentatluorophenyl) borate, tridodecylanimonium tetrakis(pentafluorophenyl) borate, tritetradecylammonium tetrakis(pentafluorophenyl) borate, trihexadecylammoniimi tetraki$(pentafluorophenyl) borate, trioctadecylammonium tetrakis(pentafluorophcnyl) borate, trieicosylammonium tetrakis(pet^tafluorophenyI) borate, decyldi(n-butyl)anmionium tetrakis(pentafluorophenyl) borate, dodecyldi(n-butyl)ammonium tetrakis(pentafliioroplienyl) borate, octadecyldi(n-butyl)ammonium tetrakisCpentafluorophenyl) borate, N,N-didodecylaniliniiim tetraklsCpentafluorophenyl) borate, N-methyl-N-dodecylanilimum tetrakis(pentafluorophenyl) borate, N,N-di(octadecyl)(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl) borate, cyclohexyldi(dodecyl)ammomum tetrakis(pentafluorophenyl)borate, and methyldi(dodecyl) ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate.
Suitable similarly substituted sulfoniiim or phosphonium salts such as, di(decyI)sulfonium tetrakis(pentafluorophenyl) borate, (!i-butyl)dodecylsulfonium tetrakis(pentafluorophenyl) borate, tridecylphosphommii tetrakis(pentafluorophenyl) borate, di(octadecyl)methylphosphoniiim tetrakis(pentafluorophenyl) borate, and tri(tetradecyl)phosphonium tetrakis(pentafluorophenyl) borate, may also be named.
Most preferred activating cocatalysts are trlspentafluorophenylborane and di(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate and di(octadecyl)(n-butyOammonium tetrakis(petttafluorophenyl)borate.
Alumoxanes, especially methylalumoxane or triisobutylaluminum modified methylalumoxane are also suitable activators and may be used for activating the meta! complexes.
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 trlspentafluorophenylborane and

triJsobutylalumimim modified metliylaUunoxanc, the titanium:boron;aluminiim molar ratio is typically from I : 10 : 50 to 1 : 0.5 : O.l, most typically from about 1:3:5
A support, especially silica, alumina, or a polymer (especially poly(tetratluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on nietal):support from 1:100,000 to 1:10, more preferably from 1:50,000 to 1:20. and most preferably from 1:10,000 to 1:30. In most polymerization reactions the molar ratio of catalysf.polymerizable compounds employed is from lO"^"^il to 10"^ :1, more preferably from 10"^:ltolO"^:I.
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of a dr>", inert gas such as, for example, nitrogen.
llie polymerization may be carried out as a batchwjse or a continuopa polymerization proceJJS, with continuoiis polymerizations processes being required for the preparation of substajitially 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.
In general, the homogeneous linear or substantially linear polymer may be polymerized at conditions for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, reactor pressures ranging from atmospheric to 3500 atmospheres (350 MPa). The reactor temperature should be greater than SCC, typically from lOO"C to 250T., and preferably from 100°C to 150*C, with temperatures at the higher end of the range, i.e., temperatures greater than 100°C favoring (he fomiation of lower molecular weight polymers.
In conjunction with the reactor temperature, the hydrogenrethylcnc molar ratio influences the molecular weight of the polymer, with greater hydrogen levels leading to lower molecular weight polymers. When-the desired polymer has an I2 of 1 g/10 min, the hydrogemethylene molar ratio will typically be 0:1. Wlien the desired polymer has an I2 of 1000 g/10 min„ the hydrogentethylene molar ratio will typically be from 0.45 : 1 to 0.7 : 1. The upper limit of the * hydrogen:ethylene molar ratio is typically from 2.2-2.5 :1.
Generally the polymerization process is carried out with a differential pressure of ethylene of from about 10 to about 1000 psi (70 to 7000 kPa), most preferably from about 40 to about 60 psi (30 to 300 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 140 °C.

In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10"^ ;1 to 10" .i, more preferably from 10"^.i to 10"^: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, iso-p0ntane, hexanc, 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 solventrethylene ratio (weight basis) will typically be from 2.5 :1 to 12 : 1, beyond which point catalyst efficiency suffers. The moat typical solvent;ethylene ratio (weight basis) is in the range of fromS: UolO:l.
( Thcjimeast one first polymer may further be made in a sluiry polymerization process, iising
the caraJ^Msas described above as supported in an inert support, such as silica. As a practical
limitation, slurry polymerizations take place in liquid diluents in wliich the polymer product is
substantially insoluble. Preferably, the diluent for slurry polymerization is one or more
hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane,
propane or butane may be used in whole or part as the diluent. Likewise the ot-olefm monomer or a
mixture of different a-olefm monomers may be used in whole or part as the diluent. Mos(
preferably the diluent comprises in at least major part the a-olefm monomer or monomers to Be
polymerized. "
In preparing hot melt adhesives for use in low temperature applications, the homogeneous linear or substantially linear interpolymers will preferably be present in amounts from 20 percent to 65 percent by weight in the adhesive, preferably from 25 percent to 45 percent by weight and more preferably from 30 percent by weight to 40 percent by weight.
Additionally, or in the alternative, the homogeneous linear or substantially linear interpolymer may be combined with other homopolymers, copolymers and terpolymer.s of ethylene including low density polyethylene as well as grafted and malleated versions, ethylene vinyl acetate copolymers, eUiylene n-butyl acrylate copolymers, ethylene methylacrylate copolymers; homopolymers^ copolymers and terpolymers of propylene; and rubbery block copolymers including those having the general configuration A-B-A friblocks, A-B-A-B-A-B multiblocks, A-B diblocks

and radiaJ block copolymers. These additional polymers may be used in amounts up to about 20 prsent by weight in the adhesive, and preferably up to about 10 percent by weight in the adhesive. The waxes useful herein may include paraiTm waxes, microcrystalline waxes, high density low molecular weight polyethylene waxes, by-product polyethylene waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes and functionalized waxes such as hydroxy stearamide Wiixes and fatty amide waxes. It is common in the art to use the terminology synthetic high melting point waxes to include liigh density low molecular weight polyethylene waxes, by-product polyethylene waxes and Fischer-Tropsch waxes.
Exemplary high density low molecular weight polyethylene waxes falling within this category include ethylene homopolymers available from Petrolite, Inc. (Tulsa, OK) as Polywax™ 500, PolywaxTM 1500 and Polywax™ 2000. Polywax^"^ 2000 has a molecular weight of approximately 2000, an M^^M^ of approximately 1.0, a density at 16*0 of about 0.97 g/cm^, and a melting point of approximately 126°C.
The paraffin waxes useful herein are those having a ring and ball softening point of about 55°C to about 85°C. Preferred paraffin waxes are Okerin® 236 TP available from Astor Wax Corporation located in DoraviUe, GA; Penreco® 4913 available from Pennzoil Products Co. in Houston, TX; R-7152 Paraffin Wax available from Moore & Mimger in Shelton, CT; and Paraffin Wax 1297 available from International Waxes, Ltd in Ontario, Canada.
Otlwr paraffmic waxes include waxes available from CP Hall under the product designations 1230,1236, 1240,1245,1246,1255,1260, & 1262. CP Hall 1246 paraffmic wax is available from CP Hall (Stow, OH). CP Hall 1246 paraffmic wax has a melting point of 143°F (62°C), a viscosity at 210"F (99"C) of 4.2 centipoise (0.042 grams/(cnTsecond)), and a specific gravity at 73*F (23""C) of 0,915 g/cm".
The microcrystalline waxes useful here are those having 50 percent by weight or more cyclo or branched alkanes with a length of between 30 and 100 carbons. They are generally less crystalline than paraffin and polyethylene waxes, and have melting points of greater th?in about ,70°C. Examples include Victory® Amber Wax, a 70°C melting point wax available from Pftrolite Corj). located in Tulsa, OK; Bareco® ES-796 Amber Wax, a 70°C melt point wax available from Bareco jti Chicago, IL; Okerin® 177, an 80°C meh point wax available fi"om Astor Wax Corp.; Besquare* 175 and 195 Amber Waxes and 80°C and 90""C melt point microcrystalline waxes both available from Petrolite Corp. in Tulsa, OK; Indramic" 91, a 90""C melt point wax available from

Industrial Raw Materials located in Smethport. PA; and Petrowax® 9508 Light, a 90°C melt point ""ax available from Petrowax PA, Inc. located in New York, NY.
The synthetic high melting point (HMP) waxes useful herein are high density, low molecular weight polyethylene waxes, by-product polyethylene waxes and Fischer-Tropsch waxes. Preferred waxes include Petrolite® C-4040, Polywax® 1000.2000 and 3000, low molecular weight polyethylene waxes available from Petrolite Corp.; Escomer® H-101, a modified polyethylene wax available from Exxon Chemical Co.; Marcus"" 100,200 and 300, low molecular weight by-product polyethylene waxes available from Marcu Chemical Co., a Division of H.R.D. Corp. located in Houston, TX; Paraflint® H-1, H-4 and H-8, Fischer-Tropsch waxes available from Sasol-SA/Moore & Mmiger in Shelton, CT; and Petro!ite®PX-100, a Fischer-Tropsch wax available from Bareco,
Preferred waxes, particularly when it is desired to prepare the hot melt adhesives of the invention in a dual reactor scheme, will be homogeneous waxes prepared using a constrained geometry or single site catalyst and using the procedures such as are set forth above and in the Examples below. Such polymers will be either ethylene homopolymers or interpolymers of ethylene and a comonomer which is a Cj-Cjo a-olefm, styrene, alkyl-substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, non-conjngated diene, or naphUienic, preferably a C^-Cjo a-oletln or styrene, and more preferably, a Cc-Cjo a-olefm.
The homogeneous wax will have a melt viscosity at BSO^F such as to yield the desired overall viscosity and close time of the hot melt adhesive formulation. Typically, the homogeneous wax will have a melt viscosity at 350*F (177°C) of no more than 1000 centipoise (10 gram8/(cm-second)), preferably no more than 800 centipoise (8 grams/(cm-second)), with homogeneous waxes having a melt viscosity at 350°F (177°C) of no more than 500 centipoise (5 grams/Ccm-second)) being usefiil. The homogeneous wax will typically have a melt viscosity at 350°F (177°C) of at least 100 centipoise (1 grams/(cm"second)), typically at least 120 centipoise (L2 grams/(cm"second)), more typically at least 150 centipoise (1.5 grams/cm-second), with waxes having a meU viscosity at 350°F (177"="C) of at least 200 centipoise (2 grams/(cm-second)) being particularly preferred from the standpoint of process economics.
Such polymers, in contrast to traditional waxes, will preferably have a M JM„ of from 1.5 to 2.5, preferably from 1.8 to 2.2.
The homogeneous wax will have a density of at least 0.885 g/cm^, preferably at least 0.900 g/cm"\ more preferably at least 0.920 g/cm\ The homogeneous wax will have a densit)"

of no more than 0.970 g/cm^, preferably no more thftn 0.965 g/cm^, more preferably no liore than 0.940 g/cml
Paiticularly in the case of hot melt adhesives formulated to be applied at temperatures of less than 150°C, the waxes are useful in amounts from 0 percent to 40 percent by weight in the adhesive, preferably from 15 percent to 35 percent by weight in the adhesive and most preferably from 20 percent to 30 percent by weight in the adhesive, and may be used in any combination However, waxes are useful to modify the rate of set, lower the viscosity, increase the heat resistance and improve machinabjlity of the finished adhesive. Thus, the amount and type of waux used will be detemiined based on those factors.
As used herein, the term "tackifier" means any of several hydrocarbon based compositions useful to impart tack to the hot melt adhesive composition. For instance, several classes of tackifiers include aliphatic C5 resins, polyterpene resins, hydrogenatsd resiias, mixed aliphatic-aiomatic resins, rosin esters, and hydrogenated rosin esters.
Exemplary tackifying resins uscftil herein include aliphatic, cycloaliphatic and aromatic hydi"ocarbons and modified hydrocarbons and hydrogenated versions; terpencs 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 ISO"^"C, and will typically have a viscosity at 350*F (177"C). as measured using a Brooktleld viscometer, of no more than 2000 centipoise (20 grams/cm-second). Iliey are also available with differing levels of hydrogenation, or saturation, which is another commonly used term. Useftil examples include Eastotac* H-lOO, H-115 and H-130 from Eastman Chemical Co. in Kingsport, Tennessee, which are partially hydrogenated cycloaliphatic petroleum hydrocarbon resins with softening points of 100*C, 11 S"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 HO^C. Other useful tackifying resins include Escorez* 5300 and 5400, 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. TX; Wingtack* Extra which is an aliphatic, aromatic petroleum hydrocarbon reain available from GoodyeaJr Chemical Co. in Akron, OH; Hercolite® 2100, a partially hydrogenated eloaliphatic petroleum hydrocarbon resin available fiom Hercules, Inc. in Wilminpton, DE; and Zomtac* 105 and 501 Lite, which are styrenated terpene resins made fi-om d-limonene and available from Arizona Chemical Go. in Panama City, FL.
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-lOO Lite, a pentaerythritol rosin ester from Union Camp in Wayne, NJ, Peimalyn"^ 305, a erythritol modified wood rosin available from Hercules and Foral 105 which is a highly hydrogenated pentaerythritol rosin eater also available from Hercules. Sylvatac* R-S5 and 295 aie 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 HerculeiS, Inc. Nirez V-2040 i$ 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 (16 grams/(cm-second)). Other typical tackifiers have viscosities at 350*F (I77"C) of much less than 1600 centipoise (16 grams/(cm-second)), for instance, from 50 to 300centipoise(0.5 to 3 grams/(cmsecond)).
Exemplary aliphatic resins include those available under the trade designations Escorez™, Piccotac™, Merctires™, Wingtack™, Hi-Rez^", Quintone""", Tackiro^M g^c. Exemplary polytcrpcnc resins include those available under tlie trade designations Nirez™, Piccolyte™, Wingtack™. Zonarez""""**. etc. Exemplary hydrogenated resins include thoae available under the trade designations Escorez™, Arkon™, Clearon™, etc. Exemplar}" mixed aliphatic-aromatic resins include those available under the trade designations Escorez ™, Regallte™, Hercwes™, AR"^Mmprez™, Norsolene™M, Marukarez"^^", ArkonT" M, Quintone"M, etc. Other tackifiers may be employed, provided they arc compatible with the homogeneous linear or substantially linear ethylene/a-olefm interpolymer and the wax.
In certain embodiments, the hot melt adhesive will be prepared without the use of a tackifier or vidth 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 teckifiers generally undergo degradation at elevated temperattires, hot melt adhesives wliich minimize the use of tackifiers will exhibit improved thermal stability. Hot melt adhesives having less than 20 weight percent tackifier, preferably less than 15 weight percent tackitier and more preferably less than 10 weight percent tackifier, will be preferred when it is desired to prepare the hot melt adhesive in a dual reactor configuration.
However, particularly for the hot melt adhesives of the invention which aie suitable for use at low application temperatures, the adhesive of the present invention will comprises tackifying resins present in an amount from 10 percent to 60 percent by weight in the adhckive, preferably from 20 to 55 percent by weight In the adhesive, more preferably from 25 percent to 50 percent by weight in the adhesive, mid most pycferably from 30 percent to 45 percent by weight in the adhesive.
Additives such as antioxidewts (e.g., hindered phenolics (e.g., Irganox™ 1010, Ipganox""" 1076). phosphites (e.g.. Irgafos"""^l68)), antiblock additives, pigments dyes, fluorescing agents, and fillers, can also bp ipcluded in the modified formulations, to the extent that they do not interfere with the enlianced formulation properties discovered by Applicfint.
Stabilizer and antioxidants are added to protect the adhesive from degradation caused by reactions with oxygen which are induced by such things as heat, light or residual catalyst from the raw materials. Lowering the temperature of application as in the present invention also helps to reduce degradation. Such antioxidants are commercially available from Ciba-Geigy located in Hav^^thorn, NY and include Irganox*^ 565,1010 and 1076 which are hindered phenolic antioxidants. These are primary antioxidants which act as fiee radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants like Irgafos* 168 available from Ciba-Geigy. Phosphite antioxidants are considered secondary antioxidants, are not generally used alone, and are primarily used as peroxide decomposers. Other available antioxidants are Cyanox® LTDP available from Cytec Industries in Stamford, CT and Ethanox* 1330 available from Albemarle Cotp. in Baton Rouge, LA. Many other antioxidants are available for use by themselves, or in combination with other such antioxidants. When employed, the antioxidant is typically present in an amount less than 0.5 weight percent, preferably less than 0,2 weight percent, based on the total weight of the hot melt adhesive.

Nordson Corp. of Atlanta, GA. Mercer Corp., Slautterback Corp. and ITW also manufacture Mtrusion type packaging equipment.
The adhesive formulations of the present invention are further characterized by low densities. The low density interpolymer allows for better adhesion due to better penetration into the substrates. Low densities also make them ideally suited for recycling. The low density allows for better separation in the repulptng process. The density of the homogeneous linear or substantially linear interpolymer of ethylene of the present invention is less than 0.895 g/cm\ preferably less than 0.885 g/cm\ and more preferably less than 0.875 g/cm^ and is at least 0.850 g/cm-\ preferably at least 0.855g/cml In contrast, ethylene vinyl acetate copolymers, the standard base polymer in the packaging industry, have densities greater than 0.900 g/cm^ Additionally, the most commonly used ethylene vinyl acetate copolymers have densities greater than 0.940 g/10 minutes with those with vinyl acetate contents of 28% having densities of greater than 0.950 g/10 minutes. Ethylene n-butyl acrylates and ethylene methyl acrylates also have densities greater than 0.900 g/cmThe hot melt adhesives of tlie present invention are further characterized by excellent heat resistance and excellent flexibility. The 100 gratn peel values are an illustration of the heat resistance of the adhesive composition. The peel values (PAFT) are greater than 40°C, more preferably greater than SO^C and most preferably greater than 60°C. High heat resistance in combination with good cold temperature properties is a significant improvement in the state of the art for low temperature packaging adhesives.
These hot melt adhesives are ideally suited for use in the packaging industry for case and Cc"uton sealing and for h:ay forming. These packages may be manufactured from materials such as virgin md recycled kraift, high and low density kraft, chipboard and various types of treated and coated kraft and chipboard, and corrugated versions of these materials. These adhesives may also bond composite materials such as those types of packages used for packaging of alcoholic beverages. These composite materials may include chipboard laminated witlt an aluminum foil which is further laminated to film materials such as polyethylene, mylar, polypropylene, polyvinylidene chloride, ethylene vinyl acetate and various other types of films. Such film materials may also be bonded directly to chipboard or kraft in the absence of aluminum foil. One of ordinary skill in the art would recognize that a variety of substrates are used in the packaging industry to which the hot melt adhesives of the present invention may adhere.

Examples
* The hot melt adhesive examples of the invention were prepared in the following manner.
The adliesive ingredients, other than tlie polymers, were melted in a forced air type oven between ISO^C and 175°C. The polymer was then slowly added to the melt in what is known in the art as an upright or lightening mixer such as the Stirrer Type RZRI manufactured by Caftamo in Wiarton, Ontario, Canada. The blend was kept at temperatures of between 150°C and ITS^"C using a heating mantle such as those manufactured by Glas-Col in Terre Haute, IN. The formulas were then niixe4 until smooth and homogcncQus, The antioxidant may be added either during the melting stage, tlie mixing stage or during both.
Unless othei-wise indicated, the homogeneous ethylene polymers utilized in the HMA"s of the invention were etliylene/l-octene interpolymers prepared in accordance with the procedures of U.S. Patent Nos. 5,272,236 and 5,278,272. In the case of the ethylene/octene polymers having a density of 0.858 g/cm^ and m\ l^ of 500 g/10 min. (melt viscosity at 350^(177^) of 22 JOO cps (227 grams/(cm-second))), the additive package employed was 100 ppm water as a catalyst kill apd 2000 ppm Irganox ™ 1010 hindered phenolic antioxidant (available from Ciba Geigy). In the case of the ethylene/octene polymers having a density of 0.873 g/cm^ and an Ij of 500 g/10 min (melt viscosity at 350°F of 18,750 cps (188 grams/(cm-second))), a density of 0.862 g/cm^ and an Ij of 1000 g/10 min. (melt viscosity at 3S0*F (177°C) of 10,740 cps (107 grams/(cm.second))), and a density of 0,870 g/cm3 and an Ij of 1000 g/10 min. (melt viscosity at 350°F (177*C) of 9000 cps (90 graras/(cm-second))), the additive package employed was 35 ppm water as a catalyst kill and 2000 ppm Irgaiiox ™ hindered phenolic antioxidant.


Comparative Examples A, B and C arc commercially available adhesives based on ethylene vinyl acetate which are designed for low application temperatures. The ingredients employed in Examples 1 and 2 are depicted in Table I. Examples 1 and 2 exiiibit significantly higher heat resistance as evidenced by the 100 gram oeel data (PAFT^ and lower st5ecific cavities than

commetcially available adhesives. Example 1 shows superior bonding performance at all Imperatures and is designed as an all purpose adhesive. The adhesives were applied to high performance corrugated boardstock at an application temperature of 135°C, except for Comparative Example D which wae applied at an application temperature of 177°C. The figures here represent the percent fiber tear as an amount of the total bond made. For example, if the bond is 6 inches (15 cm) long, and 3 of those inches (7.5 cm) show fiber tear then it is a 50% fiber tearing bond. Both Examples 1 and 2 exhibit superior heat stability shown by the change in viscosity and Gardner color over a % hour period.
Comparative Example 1>
Comparative Example D is conunercially available from the H.B. Fuller Co. located in St. Paul, ^AN. It is hot melt packaging adhesive which is a standard of the industry and is based on ethylene vinyl acetate and designed for application temperatures of 177*C,
The bonds were made at an application temperature of 177°C as opposed to 135*C for 9II of the other examples in Table II. Heat stability tests were also conducted at 177°C compared 10 13S^"C for the other examples.
This comparative cxeunple illuatrates the .surprisingly high heat resistance obtained with the adhesives of the present invention, The adhesives of the present invention surprisingly have heat resistance that is as high or higher, as illustrated by the 100 gram peel values (PAFT). as coimnercially available packaging adhesives designed for application temperatures of 177*"C, while having much lower viscosities.


Table III shows various formulas comprising several different grades of the homogeneous linear or siibstantially linear interpolymer of ethylene witli at least one Cj to C^o a-olefm. Each of the columns show the amount used in percent by weight in the adhesive of the various adhesive components. Column 2 depicts a homogeneous interpolymer having a density of 0.862 g/cm^ and a melt index of 1000 g/10 min.. Column 3 depicts a homogeneous interpolymer having a density of 0.870 g/cm^ and a melt index of 1000 g/10 min.. Column 4 depicts a homogeneous interpolymer having a density of 0.86 g/cm^ and a melt index of 500 g/10 min. and Colunm 5 depicts a homogeneous interpolymer having a density of 0.87 g/cm^ and a melt index of 500 g/10 min., each of which has been previously described. Eastotac® H-130R and H-IOOR are hydrocarbon resins having melt points of 130T and 1 OO"C respectively. Bareco® PX-100 is a synthetic high melting point Fischer-Tropsch wax, 195 micro is a microcrystalline wax having a melt point of 90°C and the antioxidant, is Irganox 1010 hindered phenolic antioxidant sold by Ciba-Geigy.



Table IV illustrates the physical characteristics attributable to each of the adhesive compositions shown in Tabl« HI. The peel values (PAFT) obtained for those compositions containing interpolymers having the lower densities are also lower than those compositions having interpolymers with higher densities. Even for lower density polymers, however, peel values (PAFT) which were superior over the commercially available compositions based on ethylene vinyl acetate could be obtained.


Examples 21-23 were tested for bondability to high perfomiance corrugated boardstock. Comparative Example D is a conmiercially available ethylene vinyl acetate product designed for application temperatures of about IIS^C, This product was applied to the substrate at 175*C while Examples 21 to 23 were applied at 135°C. The figures in Table VI represent fiber tear as a percent of the total bond made. These examples illustrate that superior bonding performance can be obtained with the adhesives of the current invention while applying them at much lower temperatures than standard hot melt adhesives used in the packaging industry.
Hot melt adhesives comprising ultra-low molecular weight ethylene polymers were also prepared. The procedure for preparing the ultra-low; molecular weight ethylene polymers is as follows.
Catalyst Preparation One Fartl: PrmraflQttjQtaiDME)!^
The apparatus (referred to as R-1) was set-up in the hood and purged with nitrogen; it consisted of a 10 L glass kettle with flush mounted bottom valve. 5-neck head, polytetrafluoroethylene gasket, clamp, and stirrer components (bearing, shaft, and paddle). The necks were equipped as follows: stirrer components were put on the center neck, and the outer necks had a reflux condenser topped with gas inlet/outlet, an inlet for solvent, a thermocouple, and a stopper. Dry, deoxygenated dimethoxyethane (DME) was added to the flask (approx. 5 L). In the drybox, 700 g of TiCl3 was weighed into an equalizing powder addition fuimel; the funnel was capped, removed from the drybox, and put on the reaction kettle in place of the stopper. The TiCl3 was added over about 10 minutes with stirring. After the addition was completed, additional DME was used to wash the rest of the TiCl3 into the flask. The addition funnel was replaced with a stopper, and the mixture heated to retlux. The color changed from purple to pale blue. The mixture was heated for about 5 hours, cooled to room temperature, the solid was allowed to settle, and the supernatant was decanted from the solid. The TiCl3(DME)i .s was left in R.-1 as a pale blue solid.
Part 2: Preparation of rrMe4C5lSiMe2N-t-Bu][MgCl]2

The apparatus (referred to as R-2) was set-up as described for R-l, except that flask size was 30 L. The head was equipped with seven necks; stirrer in the center neck, and the outer necks containing condenser topped with nitrogen inlet/outlet, vacuum adapter, reagent addhion tube, thermocouple, and stoppers. Tiie flask was loaded with 4.5 L of toluene. 1.14 kg of (Me4C5H)SiMe2NH-t-Bu. and 3.46 kg of 2 M i-PrMgCl in Et20. The mixture was then heated, and the ether allowed to boil off into a trap cooled to -78"*C. After four hours, the temperature of the mixture had reached 75°C. At the end of this time, the heater was turned off and DME was added to the hot, stirring solution, resulting in the formation of a white solid. The solution was allowed to cool to room temperature, the material was allowed to settle, and the supernatant was decanted from the solid. The [(Me4C5)SiMe2N-t-Bu][MgCl]2 was left in R-2 as an off-white solid.
Part 3: Preparation of f(Ti^-Me4C5"lSiMe2N-t-Bu1TiMe2
The materials in R-l and R-2 were slurried in DME (3 L of DME in R-l and 5 L in R-2). The contents of R-l were tiansfciTcd to R-2 using a trmtsfer tube connected to the bottom valve of the 10 L flask and one of the head openings in the 30 L flask. The remaining material in R-l was washed over using additional DME. The mixture darkened quickly to a deep red/brown color, and the temperature in R-2 rose ftom 2rc to 32°C. After 20 minutes, 160 mL of CH2C12 was added through a dropping funnel, resulting in a color change to green/brown. This was followed by the addition of 3.46 kg of 3 M MeMgCl in THF, which caused a temperature increase from 22*C to 5 T- The mixture was stiiied for 30 minutes, then 6 L of solvent was removed imder vacuum. Isopar""^" E hydrocarbon (6 L) was added to the flask. This vacuum/solvent addition cycle wa3 repeated, with 4 L of solvent removed and 5 L of Isopar^^ E hydrocarbon added. In the final vacuum step, an additional 1.2 L of solvent was removed. The material was allowed to settle overnight, then the liquid layer decanted into another 301 glass kettle (R-3). The solvent in R-3 was removed under vacuum to leave a brown solid, which was re-extracted with Isopar E; this material was transferred into a storage cylinder. Analysis indicated that the solution (17.23 L) was 0.1534 M in titanium; this is equal to 2.644 moles of [(tl^-Me4C5)SiMe2N-t-Bu]TiMe2. The remaining solids in R-2 were furttier extracted with Isopar™ E hydrocarbon, the solution was transfenred to R-3, then dried under vacuum and re-extracted with isopar"^w E hydrocarbon. This solution was transferred to storage bottles; analysis indicated a concentration of 0.1403 M titanium and a volume of 4.3 L (0.6032 moles [(ti^-Me4C5)SiMe2N-t-Bu]TiMe2). This gives

an overall yield of 3.2469 moles of [(ii^-Me4Cs)SiMe2N-t-Bu]TiMe2, or 1063 g. This is a 72 % yield overall based on the titanium added as TiClj.
Catalyst Preparation Two Parti: Preparation of TiChfDMEh s
The apparatus (referred to as R-1) was set-up in the hood and purged witli nitrogen; it consisted of a 10 L glass kettle with flush mounted bottom valve, 5-neck head, polytetrafluoretliylene gasket, clamp, and stirrer components (bearing, shaft, and paddle). The necks were equipped as follows: stirrer components were put on the center neck, and the outer necks had a reflux condenser topped with gas inlet/outlet, an inlet for solvent, a thermocouple, and a stopper. Dry, deoxygenated dimethoxyethane (DME) was added to the tlask (approx. 5.2 L). In the drybox, 300 g of TiCl3 was weighed into an equalizing powder addition fimnel; the Iximiel was capped, removed firom the drybox, and put on the reaction kettle in place of the Stopper. The TiCb was added over about 10 minutes with stirring. After the addition was completed, additional DME was used to wash the rest of the TiCl3 into the flask. This process was then repeated with 325 g of additional TiCl3, giving a total of 625 g. The addition funnel was replaced with a stopper, and the mixture heated to reflux. The color changed from purple to pale blue. The mixture was heated for about 5 hours, cooled to room temperature, the solid was allowed to settle, and the supernatant was decanted from the solid. The TiCl3(DME)i ,5 was left in R-1 as a pale blue solid.
Part 2: Preparation of [(Mej[.C5^SiMe2N-t-Bu1fMgCl]2
The apparatus (referred to as R-2) was set-up as described for R-1, except that flask size was 30 L. The head was equipped with seven necks; stirrer in the center neck, and the outer necks containing condenser topped with nitrogen inlet/outlet, vacuum adapter, reagent addition tube, thermocouple, and stoppers. The flask was loaded with 71 of toluene, 3.09 kg of 2.17 M i-PrMgCl in Et20,250 mL of THF, and 1.03 kg of (Me4C5H)SiMe2NH-t-Bu. The mixture was then heflted, and the ether allowed to boil off into a trap cooled to -78°C. After tliree hours, the temperature of the mixture had reached 80°C, at which time a white precipitate formed. The temperature wds then increased to 90°C over 30 minutes and held at this temperature for 2 hours. At the end of this time, tlie heater was turned off, and 2 L of DME was added to the hot, stirring solution, resulting in the formation of additional precipitate. The solution was allowed to cool to room temperature, the material was allowed to

settle, and the supernatant was decanted from the solid. An additional wash was done by adding toluene, stirring for several minutes, allowing the solids to settle, and decanting tlie toluene solution. The [(Me4C5)SiMe2N-t-Bu][MgCl]2 was left in R-2 as an off-white solid.
Part. %: Preparation of r(n5-Me4COSiMe2N.t-Ru1Tirn4.1.3-Dentadiene)
The materials in R-1 and R-2 were slurried in DME (the total volumes of the mixtures were approximately 5 L in R-1 and 12 L in R-2). The contents of R-1 were transferred to R-2 using a transfer tube connected to the bottom valve of the 10 L tlask and one of the head openings in the 30 L flask. The remaining material in R-1 was washed over using additional DME. The mixture darkened quickly to a deep redA)rown color. After 15 minutes, 1050 mL of 1,3-pentadiene and 2.60 kg of 2.03 M n-BuMgCl in THF were added simultaneously. The maximum temperature reached in the flask during tliis addition was 33 *C. The mixture was stirred for 2 hours, then approximately U L of solvent was removed under vacuum. Hcxanc was then added to the flask to a total volume of 22 L. The material was allowed to settle, and the liquid layer (12 L) was decanted into another 30 L glass kettle (R-3). An additional 15 liters of product solution was collected by adding hexane to R-2, stirring for 50 minutes, again allowing to settle, and decanting. This material was combined with the first extract in R-3. The solvent in R-3 was removed under vacuum to leave a red/black solid, which was then extracted with toluene. This material was transferred into a storage cylinder. Analysis indicated that the solution (11.75 L) was 0.255 M in titanium; this is equal to 3.0 moles of [(ti5.Me4C3)SiMc2N-t-Bu]Ti(n4-l,3-pcntadicnc) or 1095 g. This is a 74 % yield based on the titanium added as TiCb.
Polymerization of Ultra-Low Molecular Weieht Polymers and Waxes
The polymers used in tlie preparation of tlie hot melt adhesives of the Invention were prepared In accordance with the following procedure and utilizing the reaction conditions set forth in Table One.
The ethylene and the hydrogen were combined into one stream before being introduced into the diluent mixture, a mixture of Cg-Cjo saturated hydrocarbons, e.g., ISOPAR-E hydrocarbon mixture (available from Exxon Chemical Company) .and the

comonomer. The comonomer was l-octene. The reactor feed mixture was continuously injected into the reactor.
The metal complex and cocatalysts were combined into a single stream and were also continuously injected into the reactor. For Polymer A, the catalyst was as prepared in Catalyst Preparation One set forth above. For Ihe remaining polymers ar the wax, the catalyst was as prepared in Catalyst Preparation Two set forth above. For each Polymer and Wax, the co-catalyst was tris(pentafluorophenyl)borane, available as a 3 weight percent solution in Isopar""^"-E mixed hydrocarbon, from Boulder Scientific. Aluminum was provided in the form of a solution of modified methylalumoxane (MMAO Type 3A) in heptane, which is available at a 2 wt^d alttminum concentration from Akzo Nobel Chemical Inc.
Sufficient residence time was allowed for the metal complex and cocatalyst" react prior to introduction into the polymerization reactor. In each polymerization reaction, the reactor pressure was held constant at about 475 psig (3.3 MPa). Ethylene content of the reactor, in each polymerization, after reaching steady state, was maintained at the conditions specified in Table One.
After polymerization, the reactor exit stream was introduced into a separator where the molten polymer is separated from the unreacted comQnomer(s), unreactec ethylene, unreacted hydrogen, and diluent mixmre stream. The molten polymer wa subsequently strand chopped or pelletized, and, after being cooled in a water bath oi pelletizer, the solid pellets were collected. Table VIl describes the polymerization conditions and the resultant polymer properties of Polymers A, B, C, and D.


The metal complex and cocatalysts were combined into a single streiim and were also continuously injected into the reactor. The catalyst was as prepared in Catalyst Description Two set forth above; the primary cocatalyst was tri(pentafluorophenyl)borane, available from Boulder Scientific as a 3 weight percent solution in ISOPAR-E mixed hydrocarbon; and the secondary cocatalyst was modified methylaluraoxane (MMAO Type 3A), available from Akzo Nobel Chemical Inc. as a solution in heptane having 2 weight percent aluminum.
Sufficient residence time was allowed for the metal complex and cocafalyst to react prior to introduction into the polymerization reactor. The reactor pressiure was held constant at about 475 psig (3.3 MPa).

After polymerization, the reactor exit stream was introduced into a separator where the molten polymer was separated from the unreacted comonomer(s), linreacted ethylene, unreacted hydrogen, and diluent mixture 3tream, which was in turn recycled for combination with fresh comonomer, ethylene, hydrogen, and diluent, for introduction into the reactor. The molten polymer was subsequently strand chopped or pelletized, and, alter being cooled in a water bath or pelletizer, the solid pellets were collected. Tables VIII and IX describe the polymerization conditions ajid the resultant polymer properties of Polymers E, F, G, and Wax A.



The polymers, tackifier, wax, and antioxidant were simultaneously added in the amounts indicated in Table A to a Haake Rlieocord 40 mixer using a 200 g mixing bowl maintained at about 130°C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until they became molten. The antioxidant employed was Irganox™ 1010, and was employed in an amount of 2000 ppm, based on the total formulation.
Table X further sets forth various measured performance attributes of the hot melt adhesives, including melt viscosity at 3S0°F (177«C), close time, open time, PAFT, percent paper tear of the newly made hot melt adhesive (initial paper tear) for samples aged 14 days at 50*C (14 day paper tear at 50X). Each of the examples exhibited greater than 90 percent initial paper tear. Examples 25, 26, and 27 fUriher exhibited greater tlmn 90 percent 14 day paper tear. Each of the examples exhibited acceptable PAFT, and, for most applications, further exhibited suitable open and close times.



Table XI illustrates the improvement in low temperature viscosity of the hot melt adhesives of the invention as compared to that of high vinyl acetate conteni EVA-based hot melt adhesive formulations having a comparable melt viscosity at 350°F (177^C). In each column, the viscosity in centipoise is first reported, with the viscosity in grams/(cm-second) being indicated in the parentheticals.

4316. Similarly, Fuller 5754, and Examples 24 - 26 each have a melt viscosity at 350°F (177°C) which is between about 1000 and about 1300 centipoise (10 and 13 grams/cm-second). In contrast, each of Examples 24 - 26 have a melt viscosity at 275"F (135°C) which is significantly less than that of Fuller 5754. While comparative hot melt adhesives Eastman A765 and National Starch 2103 have acceptable melt viscosities at 275°F (13S*C), they are not believed to be optimal packaging adhesives, as their high level of crystaJlinity will cause embrittlement at lower temperatures.
The reduced low temperature melt viscosity of the hot melt adhesives of the invention will translate to lower operating temperamres, which is

advantageous from the perspective of economics, as well as affording itiiproved pot life. In applications where short close times are desired, the hot melt adhesives of the invention are particularly advantageous. The hot melt adhesives of the invention are further expected to create less angel hair during processing, despite |he application at low temperatures.
Varioxis hot melt adhesives which will be prefeited for bonding cardbo^d and paperboard substrates have likewise been developed, and are set forth as following.
Hot Melt Adhesives Compfisinp; A Homogeneous Ethylene Polvnier having a Melt Viscosity at 350^F (177^0 of 5000Centipoise (50 prams/fcmsecond^)and a DensitY o( 0-880 to 0.895 a/cm^
The polymers, tackifier, wax, and antioxidant were simultaneosly added in the amounts indicated in Table XH to a Haakc Rheocord 40 mixer using a 200 gram mixing bowl maintained at about ISC^C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until they became molten. The antioxidant employed was Irganox"^" lOlO hindered phenolic stabilizer, and was employed In an amount of 2000 ppm, based on the total formulation.


Preferred hot melt adhesives, that is, those which exhibit at least 80 percent initial paper tear, are characterized as corresponding to the following inequality derived from a statistical model:
Paper Tear > 83.8965*A + 18.5823*C + 114.571*B
where A, B, and C are percent composition of polymer, tackifier and wax, respectively.
Such preferred HMA"s include HMA"s corresponding to the diagram points set forth in Table Xfl: 1, lA, IC, IF, 5, 11, and 2. Such preferred HMA"fi will generally have the following formulation: greater than 25 weight percent of the homogeneous linear or substantially linear ethylene polymer, 0 to 35 weight percent wax, and 0 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 20 weight percent, the homogeneous linear or substantially linear ethylene polymer is present in an amomit of at least 50 weight percent.
More preferred hot melt adhesives, that is, those which exliibit at least SO percent 14 day room temperature paper tear, are characterised as corresponding to the following inequality derived from a statistical model:
Paper Tear S 102.902*A-9.96395*C +80.2846*B + 164.944*B*C
where A, B, and C are percent composition of polymer, tackifier, and wax, respectively.
Such more preferred hot melt adhesives include hot melt adhesives represented by the following diagram points in Table XII: 1, lA, IC, 2, 5, and J. Such preferred hot melt adhesivea will generally have the following formulation: 0 to 25 weight percent wax, 30 to 100 weight percent of the homogeneous linear or substantially linear ethylene polymer, and 0 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount leas than S weight percent, the polymer is present in an amount greater than 80 weight percent.
Most preferred hot melt adhesives, that is, those which exhibit at least 80 percent 14 day paper tear at 50°C, are characterized as corresponding to the following inequality derived from a statistical model:
Paper Tear > J02.73*A - 6.07393*C - 49.4636B - fi9,4347*A*C + 143.137*A*B + 127.72*B*C





Prefened hoi melt adhesives, i.e., those which exhibit at least 80 percent initial paper tear, are characterized as corresponding to the following inequality derived from a statistical model:
Paper Tear £ 101,746*A + 38.2428*C + 86.0133*8 - ,16.2418^*0 + S5.204l»B*C + 1350.15*A*B*C
Where A, B, and C are percent composition of polymer, tackifier, and wax respectively. Such prcfeaed hot melt adhesives include hot melt adhesives corresponding to the following diagram numbers set forth in Table D: X, IC, ID, 5, 2, 9, and 10. Such preferred hot melt adhesiv§:s will generally have the following formulation: 25 to 85 weight percent of the homogeneous linear or substantially linear etliylene polymer, 0 to 50 weight percent wax, and 5 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 20 weight percent, the polymer is present In an atnount of at least 35 weight percent.
More preferred hot melt adhesives, that is, those which exhibit greater than 80 percent 14 day paper tear at room temperature, include hot melt adhesives corresponding to the following diagram points in Table C: 1, 2, 4, 5, 7, 9, 10, and IC. Such more preferred hot melt adhesives will generally have the tbUowing formulation: 25 to 85 weight percent of the homogeneous linear or substantially linear ethylene polymer, 0 to 50 weight percent wax, and 5 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 10 weight percent, the polymer is present in an amount of at least 40 weight percent.
Most preferred hot melt adhesives, that is, those which exhibit at least 80 percent 14 day paper tear at SO^C, are characterized as corresponding to the following inequality derived from a statistical model:
Paper Tear a 102.73*A - 6.07373*0 - 49.4636*B - 69.4347*A*C + 143.137*A*B + 127,72*B*C
where A, B, and C are the weight percents of the polymer, tackifier, and wax present in ilie hot melt adhesive, respectively. Such most preferred hot melt adhesives include hot melt adhesives corresponding to the following diagram points in Table C: 2, 4, 5, 9, 10. IB, and IC. Such preferred hot meh adhesives will generally have the following formulation: 0 to 50 weight percent wax, 25 to 70 weight percent polymer, and 0 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 5 weight percent, the polymer is present in an amount greater than 50

welghi percent. It is further notable that when a polymer having a density of from 0.865 to less than 0.875 g/cm^ is employed, the range of acceptable
formulation ratios is greatly expanded over the acceptable range when a polymer having a higher density is employed.
Hot Melt Adhesives Comprising A Homop^neQUS Ethylene Polvmsr having a Melt Viscosity at 350°F (177"^ of 25Q0 Centipoise (25 grams/^cm-second")^ and a Density of 0.880 to 0.895 g/cm^
The polymers, tackifier, wax, and antioxidant were simultaneosly added in tlie amounts indicated in Table XIV to a Haake Rheocord 40 mixer using a 200 gram mixing bowl maintained at about ISO"C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until they became molten. The antioxidant employed was Irganox"^"^ 1010 hindered phenolic stabilizer, and was employed in an amount of 2000 ppm, based on the total formulation.
The resultant hot melt adhesives were evaluated for initial, 14 day paper tear at room temperature, and 14 day paper tear at SO^C, close time, open tinte, and PAFT. The formulations of the hot melt adhesives evaluated, as well as the data obtained, are set forth in Table XIV.


Preferred hot melt adhesives, that is, those which exhibit at least SO percent initial paper tear, include hot melt adhesives corresponding to the following diagram numbers set forth in Table XIV: 1 and IC. The hot melt adhesive corresponding to diagram point 1 in Table XIV contains 85 weight percent polymer, 5 weight percent tackifier, and 10 weight percent wax, The hot melt adhesive corresponding to diagram point IC contains 70 weight percent polymer and 30 weight percent tackifier. Further, the hot melt adhesives corresponding to diagram point 4 in Table XIV, while it did not achieve 80 percent initial paper tear, achieved 100 percent 14 day paper tear, both at room temperature and at 50°C, indicating acceptable performance as a hot melt adhesive of the invention. Further still, the hot melt adhesive corresponding to diagram point ID in Table E, while it did not achieve 80 percent initial paper tear, achieved 85 percent 14 day paper tear at 50°C, indicating acceptable performance as a hot melt adhesive of the invention. Such preferred hot melt adhesives corresponding to the diagram points 1, IC, ID, and 4 in Table E will generally have the following formulation: 40 to 85 weight percent of the homogeneous linear or substantially linear ethylene polymer, 0 to 45 weight percent wax, and 5 to 30 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 10 weight percent, the polymer is present in an amount greater than 50 weight percent.
Hot Melt Adhesives Comprising A Homoacneous Ethylene Polvmer having a Melt Viscosity at 350°F (177°C1 of 1800 Centipoise ri8 grams/(cm-secondY) and a Density of 0.860 to less than 0.880 p/cm^
The polymers, tackifier, wax, and antioxidant were aimultaneosly added in the amounts indicated in Table XV to a Haake Rheocord 40 mixer using a 200 gram mixing bowl maintained at about 130°C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until they became molten. The antioxidant employed was Irganox™ 1010 hindered phenolic stabilizer, and was employed in an amount of 2000 ppm, based on tlie total formulation.
The resultant hot melt adhesives were evaluated for initial, 14 day paper tear at room temperature, and 14 day paper tear at 50°C, close time, open time, and PAFT. The formulations of the hot melt adhesives evaluated, as well as the data obtained, are set forth in Table XV,


Preferred hot melt adhesives, that is, those which exhibit at least 80 percent initial paper tear, include hot melt adhesives correspondLng to the following diagram points in Table XV: 1, IB, 2, 5, 6, 7, 9, and 10. The data set forth in Table XV demonstrates the utility of hot melt adhesives having the following formulation: 25 to 85 weight percent polymer, 10 to 50 weight percent wax, and 0 to 50 weight percent tackifier, with the proviso that when the tackifier is present in an amount less than 5 weight percent, the polymer is present in an amount greater than 45 weight percent.
More preferred hot melt adhesives, that is, those which exhibit at least 80 percent 14 day room temperature paper tear, include hot melt adhesives represented by the following diagram points in Table XV: 1,2, 5, 6, 7, 9, 10, and IC. Such preferred hot melt adhesives will generally have the following fomtulation: 0 to 50 weight percent wax, 25 to 85 weight percent polymer, and 5 to 50 weight percent tackifier, with the proviso that when the wax Is present in an amount less than 10 weight percent, the polymer Is present in an amount less than 80 weight percent and more than about 60 weight percent, and when the tackifier is present in an amount greater than 40 weight percent, the polymer is present in an amount greater than 28 weight percent and less than 50 weight percent.
Most preferred hot melt adhesives, that is, those which exhibit at least 80 percent 14 day paper tear at 50°C, include hot melt adhesives represented by

the following diagram points in Table XV; 1,2, 5,6,9,10, and IC. Such preferred hot melt adhesives will generally have the following formulation: 0 to SO weight percent wax, 25 to 85 weight percent polymer, and 5 to 50 weight percent tackifier, with the proviso that when the wax is present in an amount less than 10 weight percent, the polymer is present in an amount less than 80 weight percent and more than 60 weight percent, and when the tackifier is present in an amount less than 10 weight percent, the polymer is present in an amoimt greater than 60 weight percent.
It is notable that, as in the case of the hot melt adhesives of the invention containing a polymer having a density of from 0.865 to less than 0.880 g/cm^ and a melt viscosity at 350°F (W°C) of 5000 centipoise (50 grams/(cm-second)), when a polymer having a density of from 0.865 to less than 0.880 g/cm" is employed, it is expected that the range of acceptable fonnulation ratios is greatly expanded over the acceptable range when a polymer having a higher density is employed.
Hot Melt Adhesivejf Comprising A Homofteneous Ethylene Polymer having: a Melt Viscosity at 3S0°F (177°C) of 12.000 Centiooise (120 prams/(cm"second)) and a Density of 0.880 to 0.895 g/cm^
The polymers, tackifier, wax, and antioxidant were simultaneosly added in the amounts indicated in Table XVI to a Haake Rheocord 40 mixer using a 200 gram mixing bowl maintained at about 130°C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until they became molten. The antioxidant employed was Irganox"^" 1010 hindered phenolic stabilizer, and was employed in an amount of 2000 ppm, based on the total formulation.
The resultant hot meh adhesives were evaluated for initial. 14 day paper tear at room temperature, and 14 day paper tear at 50°C, close time, open time, and PAFT. The formulations of the hot melt adhesives evaluated, as well as the data obtained, are set forth in Tabic XVI.


A preferred hot melt adhesive which exhibits at least 80 percent initial paper tear corresponds to diagram point 4 set forth in Table XVI. This hot melt adhesive further exhibits at least 80 percent 14 day paper tear at room temperature and at 50*0. The hot melt adhesive corresponding to diagram point 4 contains 43,5 weight percent polymer, 43.3 weight percent wax, and 13 weight percent tackifier. The hot melt adhesive corresponding to diagram point 11 of Table XVI, while it passed neither the initial paper tear test nor the 14 day paper tear at 50*C test, passed the 14 day paper tear at room t&nperature. The hot melt adhesive corresponding to diagram point 4, while it did not achieve 80 percent initial paper tear, it achieved 100 percent 14 day paper tear, both at room temperature and at 30°C, indicating acceptable perfonnance as a hot melt adhesive of the invention. The hot melt adhesive corresponding to diagram point 11 contains 43.4 weight percent polymer, 21.7 weight percent tackifier. and 34.7 weight percent was.
Hot Melt Adliesives Comprising A Homogeneous Ethvlene Polvmer having a Melt Viscosity at 35Q°F (117^0 of 23.000 to 25.000 Centinoise (230 - 250 grams/fcm-second)") and a Densitv of 0.86S to less tlian 0.880 e/cm^
The polymers, tackifier, wax, and antioxidant were simultaneously added in the amounts indicated in Table XVII to a Haake Rheocord 40 mix^^r

using a 200 gram mixing bowl maintained at about 130"C at 95 revolutions per minute. The ingredients were mixed for about 5 minutes, until tliey became molten. The antioxidant employed was IrganoxT^^ XQIQ hindered phenolic stabilizer, and was employed in an amount of 2000 ppm, based on the total formulation.
The resultant hot melt adhesives were evaluated for initial, 14 day paper tear at room temperature, and 14 day paper tear at 50°C, close time, open time, and PAFT, The formulations of the hot melt adhesives evaluated, as well as the data obtained, are set forth in Table XVII.

Preferred hot melt adhesives, that is, those which exliibit at least 80 percent initial paper tear, include the hot melt adhesives corresponding to the following diagram points in Table XVII: 1, 5, and 9. Each of the hot melt adhesives corresponding to diagram points 1, 5, and 9 further pass both the 14 day paper tear lest at both room temperature and at 50°C. The data set forth in Table XVII demonstrates the utility of hot meh adhesives having the following formulation: 45 to 85 weight percent polymer, 0 to 40 weight percent wax, and 3 to 30 weight percent tackifier. As no further limitations are apparent from the data set forth in Table XVII, it is expected that the range of acceptable formulations will be extended to that reported for the polymers having a density of 0.870 g/cm^ and a melt viscosity at 350°F (177X) of 5000 cemipoise (50grams/(cmsecond)), that is, 0 to 50 weight

percent wax, 25 to 85 weight percent polymer, and 5 to 50 weight percent tackifier.
Hot Meh Adhesives Comprising A Homogeneous Ethylene Polvmer having a Melt Viscosity at 35Q""F of 5.000 Centipoise and a Density of 0.875 to 0.885 g/cm^
The polymers, lackifler, wax, and antioxidant were simultaneously added in the amounts indicated in Table H to a Haake Rheocord 40 mixer uaing a 200 gram mixing bowl maintained at about 130°C at 95 revolutions per minute. The ingredients were mixed for 5 minutes, until they became molten. The antioxidant employed was Irganox™ 1010 hindered phenolic stabilizer, and was employed in an amount of 2000 ppm, based on the total formulation.
The resultant HMA"s were evaluated for initial, 14 day paper tear at room temperature, and 14 day paper tear at SO^C, close time, open time, and PAFT. TheformulationsoflheHMA"sevaluated, as well as the data obtained, are set forth in Table XVIII,


following formulation: 30 to 85 weight percent polymer, 0 to 35 weight percent wax, and 5 to 50 weight percent tacldfier, with the proviso that when the tackifier is present in an amoimt less than 10 weight percent, the polymer is present in an amount greater than 70 weight percent, and when the tackifier is present in an amount greater than 35 weight percent, the polymer is present in an amount greater than 35 weight percent and less than 60 weight percent.
More preferred hot melt adhesives, that is, those which exhibit ati least 80 percent 14 day room temperature paper tear, include hot melt adhesives represented by the following diagram points in Table XVIII: 1,7,11, and 1C. Siich preferred hot melt adhesives vnW generally have the following formulation; 0 to 50 weight percent wax, 45 to 85 weight percent polymer, and 5 to 30 weight percent tackifier, udth the proviso that when the wax is })resent in an amount less than 5 weight percent, the polymer is present in an amoimt less than about 80 weight percent and more than about 65 weight percent.
Most prefeiTed hot melt adhesives. that is, those which exhibit at least 80 percent 14 day paper tear at 50*C, include hot melt adhesives represented by the following diagram points in Table XVIII; 1,7, and IC. Such preferred hot melt adhesives will generally have the following formulation: 0 to 50 weight percent wax, 45 to 85 weight percent polymer, and 5 to 30 weight percent tackifier, with the proviso that when the tackifier is present in an amount more than 20 weight percent, the polymer is present in an amount less than 75 weight percent and more than 60 weight percent.
These and otlier embodiments will be readily ascertained by one skilled in the art. Accordingly, the subject invention is to be limited only by tlie following Claims.



We claim:
1. A process for producing a composition, said process comprising: a) reacting, by contacting, ethylene and at least one C3-C20 α-olefm, under solution polymerization conditions, in the presence of a constrained geometry catalyst composition, in at least one first reactor, to produce a solution of a homogeneous linear or substantially linear polymer, which is an interpolymer of ethylene and the at least one α-olefin, and wherein the homogeneous linear or substantially linear polymer is characterized as having a density from 0.850 to 0.895 g/cm ;
b) reacting, by contacting, ethylene, and, optionally, at least one C3-C20 α-olefm, under solution polymerization conditions, in the presence of a constrained geometry catalyst composition, in at least one other reactor, to produce a solution of a homogeneous wax, and wherein the wax has a density from 0.920 to 0.940 g/cm3;
c) combining the solution of the first reactor with the solution of the second reactor, to form a solution of a blend;
d) removing the solvent from the solution of a blend of step (c), and
recovering the blend; and
e) optionally, introducing a tackifier into the reactor of step (a), the reactor
of step (b), or at any point subsequent to the reacting of step (b), and
wherein the resultant composition is characterized as having a viscosity of less than 5000 centipoise (50 grams/(cm-second)) at 150°C.
2. The process as claimed in claim 1, wherein the polymerization temperature in the at least one first reactor is from 80°C to 250°C.

4. The process as claimed in claim 1, wherein the molar ratio of catalyst to
polymerizable compounds, in the at least one first reactor, is from 10-12 to 1 to
10-1 to l.
5. The process as claimed in claim 1, wherein for step a), the solution polymerization takes place in a solvent selected from the group consisting of mineral oils and hydrocarbons.
6. The process as claimed in claim 1, wherein for step a), the solution polymerization takes place in a solvent selected from the group consisting of pentane, isopentane, hexane, heptane, octane, nonane, mixtures of alkanes, cycloalkanes and aromatics.
7. The process as claimed in claim 1, wherein the differential pressure of ethylene
in the at least one first reactor is from 10 psi to 1000psi (70 to 7000 kPa).

Documents:

1625-mas-1997 abstract duplicate.pdf

1625-mas-1997 abstract.pdf

1625-mas-1997 assignment.pdf

1625-mas-1997 claims duplicate.pdf

1625-mas-1997 claims.pdf

1625-mas-1997 correspondence others.pdf

1625-mas-1997 correspondence po.pdf

1625-mas-1997 description (complete) duplicate.pdf

1625-mas-1997 description (complete).pdf

1625-mas-1997 drawings.pdf

1625-mas-1997 form-19.pdf

1625-mas-1997 form-2.pdf

1625-mas-1997 form-26.pdf

1625-mas-1997 form-4.pdf

1625-mas-1997 form-6.pdf

1625-mas-1997 others.pdf

1625-mas-1997 petition.pdf


Patent Number 207674
Indian Patent Application Number 1625/MAS/1997
PG Journal Number 27/2007
Publication Date 06-Jul-2007
Grant Date 20-Jun-2007
Date of Filing 21-Jul-1997
Name of Patentee M/S. THE DOW CHEMICAL COMPANY
Applicant Address 2030 DOW CENTER, MIDLAND, MICHIGAN 48674.
Inventors:
# Inventor's Name Inventor's Address
1 ROBERT A DUBOIS 15607 RIVER MAPLE LANE, HOUSTON, TEXAS 77062.
2 CYNTHIA L RICKEY 315 CARNATION, LAKE JACKSON, TEXAS 77566.
3 STEVEN W ALBRECHT 7551 SHORE CIRCLE, FOREST LAKE, MINNESOTA 55025.
4 BETH M EICHLER 520 MARSHALL AVENUE, SAINT PAUL, MINNESOTA 55102
5 THOMAS F KAUFFMAN 7144 SHERWOOD ROAD, WOODBURY, MINNESOTA 55125.
PCT International Classification Number C 09 J 123/16
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/044,909 1997-04-25 U.S.A.
2 60/022,538 1996-07-22 U.S.A.