POLYOLS, POLYURETHANE SYSTEMS AND POLYURETHANE REACTIVE HOT MELT ADHESIVES PRODUCED THEREON

Abstract: A new polyol family for the manufacture of novel polyurethane systems, preferably of polyurethane reactive hot melt adhesives is disclosed. The polyol(s) are reactive modifiers that enhance the properties of polyurethane systems. The inventive polyols are the reaction product of a monocarboxylic acid, a polycarboxylic acid and a polyhydric alcohol. The polyol of the present invention is used to produce urethane polymers, preferably polyurethane reactive hot melt adhesives by reacting the polyol with polyfunctional isocyanates. A method for producing the polyol, the urethane polymer as well as the polyurethane reactive hot melt adhesives is also provided.

Description: , D POLYURETHANE REACTIVE HOT MELT ADHESIVES PRODUCED THEREON Field of the invention The present invention relates to polyols urethane polymers comprising the polyols and reactive hot melt aαnesive compositions comprising the urethane polymers and the process of making the polyols urethane polymers and reactive hot melt adhesive comDositions Background of the Invention In conventional hot melt adhesives typically a polymer a tackifier and a selection of other additives such as antioxidants are mixed together to produce an adhesive composition These materials tend to form bonds through their rapid solidification from the melt These materials have the advantage of being relatively easy to apply However hot melt adhesives are typically not reactive in nature and therefore do not develop sufficient strength and sufficient heat and chemical resistance for certain applications In order to impart sufficient structural, heat and chemical resistance to adhesive formulations, reactive or curable compositions are conventionally used These materials tend to form durable bonds through a chemical reaction and as such are the adhesives of choice for various applications and substrates However reactive or curable compositions are typically lacking in versatility on the combined property characteristics of "green" strength and "open" time This lack of process versatility makes the compositions handling characteristics poor and limits the composition s utility in some assembly operations In polyurethane reactive hot melt adhesives (polyurethane Rhma), an isocyanate terminated urethane polymer is produced through the polymerization of polyols and excess polyisocyanate compounds Polyurethane Rhma(s) typically are cured in the presence of moisture Moisture, which is present in the ambient atmosphere reacts with the isocyanate end groups to cause chain extension and or crosslmkiπg As a result of this curing reaction, polyurethane Rhma develop temperature and chemical resistance A typical cured polyurethane Rhma would generally exhibit a degree of stiffness as well as toughness Toughness of polyurethane Rhma is attributed to long chain polyols called "soft segments" Stiffness of the polyurethane Rhma is attributed to relatively short chain, high Tg, regions called "hard segments" Typically, polyurethane Rhma(s) do not exhibit sufficient combined green strength and open time for many manufacturing processes Also, while moisture cured polyurethane Rhma exhibit good temperature resistance when compared to typical hot melt adhesives, a need exists for a polyurethane Rhma that exhibit a desirable balance of processing, thermal and mechanical attributes Those skilled in the art of formulating polyurethane Rhma(s) have used so-called "modifiers" in an attempt to improve the balance of processing, thermal and mechanical attributes of polyurethane Rhma(s) These conventional modifiers have included rosin glycerol ester, polycaprolactone diol and terpene phenolic resins These modifiers have not provided a viable solution to the formulators' needs and hence a need still exists for a modifier that can provide a useful balance of processing, thermal and mechanical attributes to polyurethane Rhma(s) Brief Description of the Invention The present invention relates to new polyols, urethane polymers made from these polyols and reactive hot melt adhesive compositions which include the urethane polymers The present invention particularly relates to polyols comprising the reaction products of a polyesteπfication process employing monocarboxylic acids, polyhydπc alcohols and dicarboxylic acids as reactants The polyol of the present invention has a glass transition temperature (Tg) in the range of about -20°C to about +45°C as determined by Differential Scanning Calorimeter (DSC) Additionally, the polyol has a hydroxyi functionality ranging from 0 1 to 4 The polyols of this invention have utility in polyurethane compositions and confer upon such compositions a desirable balance of processing, mechanical and thermal attributes, particularly when such compositions are used as reactive hot melt adhesives Brief Description of the Figures Figure 1 is a graph representing reaction time versus temperature for isocyanate addition Figure 2 is a graph representing the open time of the application process Figure 3 is a bar graph representing the Shear Adhesion Failure Temperature (SAFT) of various adhesive formulations Detailed Description of the Invention The present invention relates to new polyols, new urethane polymers made from these polyols and reactive hot melt adhesive compositions based on the new urethane polymers In one embodiment, the present invention particularly relates to polyester polyols which include the reaction products of a polyesteπfication process employing monocarboxylic acids, polyhydπc alcohols and polycarboxylic acids as reactants The preferred monocarboxylic acid reactants are rosin acids including wood, gum and tall oil rosin acids Particularly preferred rosin acids are tall oil rosin acids The rosin acids may be a mixture of rosin acids obtained by a distillation process Such distillates will comprise a mixture of various rosin acids including abietic acid and its isomers A particularly preferred commercial source of such a distillate is Pamite™ 90 tall oil rosin available from Hercules Incorporated, Wilmington, DE A hydrogenated or disproportionated rosin acid distillate may also be employed as the monocarboxylic acid component The monofunctional carboxy c acid reactant may be used in amounts of about 5% to about 70% of the total moles of reactants in the reaction product, more preferably in amounts of about 10% to about 50% of the total moles of reactants in the reaction product, and most preferably in amounts of about 20% to about 45% of the total moles of reactants in the reaction product Useful polyhydnc alcohol reactants include aliphatic polyhydnc alcohols and aliphatic ether polyhydπc alcohols For example, useful polyols include those which have the formula (HO) x R wherein x is 2, 3 or 4 If x is 2, such polyol is to be used in combination with another polyol where x is 3 or 4, and R may be a linear or branched aliphatic, a cycloaliphatic or an aliphatic ether The polyhydnc alcohol reactants preferably have more than two hydroxyl functional groups per molecule Particularly preferred are polyhydnc alcohols having three or more hydroxyl functional groups per molecule Preferred polyhydnc alcohols include pentaerythntol cyclohexane dimethanol, tπmethylol propane, dipropylene glycol, and combinations thereof When the aliphatic polyol is a diol, such as cyclohexane dimethanol and dipropylene glycol, it is desirable that the moles of hydroxyl functionality provided by these aliphatic diol reactants do not exceed about twice the moles of hydroxyl functionality provided by these polyhydnc alcohol reactant(s) having hydroxyl functionality greater than 2 The polyhydnc alcohol reactant may be used in amounts of about 5% to about 50% of the total moles of reactants in the reaction product, more preferably in amounts of about 7 5% to about 45% of the total moles of reactants in the reaction product, and most preferably in amounts of about 10% to about 40% of the total moles of reactants in the reaction product In general, useful polycarboxylic acids include those having the structure HOOC-R-COOH where R is aliphatic or aromatic For example, when R is a linear aliphatic the polycarboxylic acids included are propanedioic acid, butanedioic acid (succinic acid), pentanedioic acid (glutaπc acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid and dodecanedioic acid Combinations of polycarboxylic are useful Additionally R may also be a branched aliphatic, a cycloahphatic or a substituted aliphatic such as a halide substituted aliphatic An example of a dicarboxylic acid reactant when R is a branched aliphatic is 2-methyl-1 ,6- hexanedioic acid An example of a dicarboxylic acid reactant when R is a cycloahphatic is 1 ,4-cyclohexanedιoιc acid An example of a dicarboxylic acid reactant when R is a halide substituted aliphatic is 3,-Bromo-1 ,6-hexanedιoιc Additionally, R may be aromatic Examples are 1 ,2-benzene dicarboxylic acid (phthalic acid), 1 ,3-benzene dicarboxylic acid (isophtha c acid) and 1 ,4-benzene dicarboxylic acid (terephtha c acid) When R is aromatic, the aromatic ring may also be halogen substituted Other aromatic dicarboxylic acids may also be employed Examples include 2,7-naphthalene dicarboxylic acid and 4,4'-bιsphenyl dicarboxylic acid The preferred polycarboxylic acid reactants have an acid functionality of about two and may be aliphatic or aromatic dicarboxylic acids Preferred aliphatic dicarboxylic acids include adipic acid and preferred aromatic dicarboxylic acids include phthalic and isophthalic acids Phtha c acid is preferably used as its anhydride Particularly preferred are aliphatic dicarboxylic acids and especially adipic acid When the particularly preferred aliphatic dicarboxylic acid , adipic acid, is utilized , aromatic dicarboxylic acids such as phthalic acid and isophthalic acids may be optionally and advantageously used as well in the reactant mixture provided the moles of aromatic dicarboxylic acid does not exceed about twice the moles of aliphatic dicarboxylic acid The polycarboxylic acid reactant includes from about 5% to about 50% of the total moles of reactants in the reaction product, more preferably it includes from about 10% to about 42 5% of the total moles of reactants in the reaction product and most preferably it includes from about 15% to about 35% of the total moles of reactants in the reaction product The polyester polyols of this invention may conform to the formulation illustrated below (R-T^TOH) x where P represents a linear or branched chain structure resulting from the polyesteπfication reaction of a polycarboxylic acid and a polyhydnc alcohol, OH is a residual hydroxyl functionality derived from a polyhydnc alcohol, x may vary from about 0 9 to about 4 0, R is a rosin acid residue, y may vary from 1 to O and both OH and R may exist at chain ends and/or at terminal branch points along the chain One possible structure of a polyester polyol made in accordance with the present invention which conforms to the general formula above is described by the following formula R O CH 2 CH 3 O CH 2 O CH 2 CH 3 HOCH2— C— CH 2 0-(-CH 2 -) -CO— CH 2 — C— CH 2 — OC-(-CH 2 -) -CO— CH∑— C— CH 2 OH CH 2 CH 2 O CH 2 O O O c=o R R In this specific example, x=2, y=4, and P is a linear chain structure resulting from the polyestenfication reaction of adipic acid, pentaerythntol and tπmethylol propane The polyester polyols made in accordance with the present invention have a glass transition temperature (Tg) in a range between about -20°C and about +45 C C as determined by Differential Scanning Calorimeter (DSC) Preferably, the polyester polyol has a glass transition temperature in a range between about -15°C and about + 40°C, and most preferably the polyester polyol has a glass transition temperature in a range between about -10°C and about +35°C The polyester polyol of the invention has a melt viscosity measured at 120 degrees Centigrade with a Brookfield viscometer that preferably ranges between 100 centipoise and 20,000 centipoise and more preferably ranges between 200 centipoise and 10,000 centipoise In the polyester polyol made in accordance with the present invention, it is advantageous to limit its moisture content It is preferred that the moisture content of the polyester polyol be less than about 2% by weight absorbed water as determined by Karl Fisher titration Preferably, the moisture content of the polyester polyol be less than about 1 % by weight, more preferably less than about 0 1 % by weight, absorbed water as determined by Karl Fischer titration The polyester polyols made in accordance with the present invention have resin acids incorporated therein through an estenfication reaction It is believed that the rosin acid brings advantages to the polyol of the present invention First, the rosin's monocarboxylic acid controls the hydroxyl functionality of the polyol, which allows use of polyhydnc alcohols such as pentaerythntol, and improves structural performance of the adhesive Second, the rosin may serve to increase the glass transition temperature Moreover, presence of the rosin in combination with the other components used to make the polyol enhances the peel strength of adhesives made therefrom For example, incorporation of an effective amount of the polyols made in accordance with the present invention into a urethane adhesive enhances such physical properties as modulus, elongation, tensile strength and heat resistance The inventive polyester polyols may be produced by a number of polyestenfication processes well known to those skilled in the art Particularly preferred are melt polyestenfication processes employing small amounts of solvents that form azeotropes with water to aid in its removal from the reaction system The polyestenfication process may be conducted in one stage or in two or more stages Particularly preferred processes employ two stages The examples illustrate processes by which the inventive polyester polyols may be readily produced The polyester polyols of the present invention may be used in the manufacture of moisture curable urethane polymers or in the manufacture of multiple component polyurethane systems The moisture curable urethane polymers comprising the polyester polyols of the present invention may be used as components in polyurethane reactive hot melt adhesives and sealants Alternatively, the polyester polyols of the present invention may be used with multiple component systems to produce casting elastomers, sealants, optical products and composite structures The inventive urethane polymers are prepared by reacting the inventive polyester polyol with an excess amount of a polyfunctional isocyanate for a period of time sufficient to provide reaction between the reactive hydroxyl groups of the polyester polyol and the isocyanate group(s) of the polyfunctional isocyanate , while retaining an amount of residual isocyanate functionality such as taught in U S Patent No 4,975,523, incorporated herein by reference in its entirety The urethane polymer will preferably have from 1 5% to 2 5% by weight residual isocyanate functionality and more preferably will have about 2% by weight residual isocyanate functionality The inventive polyester polyols may be mixed with conventional polyester and polyether polyols commonly used to produce urethane polymers Representative of conventional polyester polyols are those supplied by Creanova Inc under the tradename Dynacoll™ and representative of conventional polyether polyols are those supplied by ARCO Chemical Company under the tradename ARCOL™ Blends which include the inventive polyester polyols, as well as conventional polyester polyols and or polyether polyols, are reacted with an excess amount of polyfunctional isocyanate to produce the isocyanate functional urethane polymers In such instances, the inventive urethane polymers include the inventive polyester polyols in amounts of about 10% to about 80% of the urethane polymer by weight, more preferably from about 10% to 60% of the urethane polymer by weight and most preferably from about 10% to 30% of the urethane polymer by weight Polyfunctional isocyanates of use in forming the new urethane compositions of the present invention may be aliphatic or aromatic isocyanates Useful polyfunctional isocyanates include alkane dnsocyanates such as ethylene dnsocyanate, tnmethylene dnsocyanate and hexamethylene dusocyanate alkene dnsocyanates such as 1-propylene-1 ,2-dιιsocyanate and 1-butylene-1 ,3-dιιsocyanate, alkylidene dnsocyanates such as ethyhdene dnsocyanate, isophorone dnsocyanate and propylιdene-1 ,1 -dnsocyanate, aromatic dnsocyanates such as m-phenyl-diisocyanate, 2,4 toluene dnsocyanate, 2,6-toluene dnsocyanate, 4,4' diphenyl methane dnsocyanate and other polyfunctional isocyanates such as polymethylene polyphenyl isocyanate and the like A preferred polyfunctional isocyanate is 4,4' diphenyl methane dnsocyanate The urethane polymers of the present invention may also be combined with conventional urethane polymers and or other polymers such as EVA, SBS, SIS, polyolefins, polyacrylates, and or other thermoplastic or elastomenc polymers to produce urethane polymer blends The isocyanate functional urethane polymers of this invention and or their blends with conventional isocyanate functional urethane polymers and or other thermoplastic and or elastomenc polymers may be used advantageously as moisture curable adhesives with excellent physical properties, including improved heat resistance The inventive polyurethane Rhma(s) display a heretofore unattainable balance of processing, mechanical and thermal properties Particularly surprising and beneficial is the ability of the inventive polyurethane Rhma to attain Shear Adhesion Failure Temperatures in excess of 200 degrees Centigrade Adhesives of the present invention are of use in many end uses, particularly in assembly operations Among the assembly operations are transportation uses such as, carpet bonding, door panels, instrument panel assembly, recreation vehicles, over the road trailers, heavy-duty trucks and marine uses Also among the assembly operations that adhesives of the present invention are of use in construction uses such as, window assembly, garage door assembly and structural insulated panels Also among the assembly operations that adhesives of the present invention are of use in other assembly applications such as, shoe soles, non-wovens, and profile wrapping including edge banding The present invention will be further illustrated by way of the following examples EXAMPLES METHODS AND DEFINITIONS Green Strength (Set Time) Green Strength is the amount of close time required to hold a tensile load of 45 Kg for at least 2 minutes The procedure for determining a sample's Green Strength is as follows A sample is heated in a container until the sample's temperature reaches 105°C One half of a gram of the heated sample is evenly applied over an area of one square inch (1 ιn2) of Douglas Fir plywood After ten seconds (10 sec ), a second piece of Douglas Fir plywood is applied at right angles to the first piece of Douglas Fir plywood Then the 4 5 Kg load is applied at various times after the second piece of Douglas Fir plywood has been applied to determine the minimal time needed for the sample to hold the 4 5 Kg load for a minimum of two minutes This minimal time is the sample's Set Time and is a determination of the sample's Green Strength Shear Adhesion Failure Temperature (SAFT) A one-inch wide adhesive strip is placed on a 6-ιnch wide substrate panel at 120°C so that there is one square inch of contact with the panel and a length of adhesive strip overhang at the bottom of the panel One square inch of the adhesive strip is bonded to the substrate using a 10-lb weight applied to the specimen for 15 minutes The specimens are post-cured in a controlled humidity chamber at 85°C and 65% relative humidity for 3 5 hours The specimens are removed from the chamber and stored at 21 °C and 45% relative humidity for 12 hours The bonded panel is placed in a ng so that the back of the panel is at a 2° angle with the vertical axis, allowing no peel forces to act on the adhesive bond when a one kilogram weight is hung on the unbonded end of the adhesive strip The ng is placed in a forced air oven and the temperature is ramped up from ambient at 20°C per hour The temperature at which the bond fails is recorded Eight specimens are run for each adhesive and the mean failure temperature is recorded Size Exclusion Chromatoqraphv Size Exclusion Chromatography was preformed using a Waters 590 system with differential refractive index (Hewlett-Packard model 1047A) detection The mobile phase employed was stabilized (BHT) tetrahydrofuran (Burdick & Jackson) A flow rate of 1 Oml/rnm was used Waters/Millipore UltraStyragel column set (500+500+1000+100 Angstrom pore-size) was used All molecular weight data reported above are based on a polystyrene calibration curve All samples were filtered through a 045 μm PTFE membrane filter prior to analysis Differential Scanning Calonmetry Differential Scanning Calonmetry was performed using a TH910 ROBOTIC DSC with LNCA in an open aluminum pan in a nitrogen atmosphere, using the following temperature program A typical DSC thermogram plots heat flow as a function of temperature (or time in the case of an isothermal experiment) The sample is cooled to -60°C and hold for five minutes Then the specimen is heated from -60°C to +120°C at 10°C/mιnute and held at 120°C for one minute Then the specimen is cooled from 120°C to -60°C at 10°C/mιnute and held at -60°C for five minutes Then a second heat cycle is applied The specimen is reheated from -60°C to 120°C at 10°C/mιnute When using a DSC to determine a glass transition temperature, a melting point, or the heat of fusion two heating of the sample are commonly performed with the desired information being determined from the second heating The first heating is used to impose a known thermal history on the sample The first heating erases thermal stresses in the sample which can give rise to sporadic peaks, can conform the sample to the sample pan which provides better instrument response, and can remove residual volatiles or moisture which can confuse the interpretation of the DSC results 180°C Peel Test between a cotton duck canvas and the testing substrate The Reactive Hot Melt Adhesives were tested on 1"x6" substrate panels (polycarbonate, aluminum, steel, stainless steel and EPDM) The polycarbonate and EPDM panels were wiped with isopropanol while the metal substrates were cleaned with toluene, all were air-dried for at least fifteen minutes prior to the adhesive application The metal substrates were heated to 120°C prior to the adhesive application while the polymer substrates were used at room temperature The Reactive Hot Melt Adhesives were melted in a Meltex® PUR 201 , from Nortson Corporation, at 120°C The adhesive was applied to the substrate, and the canvas was localized on top of the adhesive The adhesive strip was bonded to the substrate using a 4 5 lb mechanical rolldown device from Chemsultants International, which is applied on the canvas The specimens are stored at room temperature and 45% relative humidity for 7 days The canvas was then peeled from the tested substrate at a 180° angle in a universal testing machine The force necessary to break the bond is measured The bond area was visually evaluated for the type of failure Tensile testing of the Reactive Hot Melt Adhesives The testing machine is an Instron Model number 4201 The capacity of the load cell is 500 Newtons Sheets of polyurethane hot melt adhesive were prepared by dosing several grams of the adhesive from the Meltex® PUR201 applicator onto a PTFE film placed on top of a heated metal plate (100°C) 0 010 inch shims were placed along the edges of the PTFE film The adhesive was covered with another PTFE film and another heated plate The sandwich was then placed in a press and pressure applied (25 pounds per square inch) for one minute The thickness of the specimen was measured after the specimens had been cut into 0 5-ιnch wide strips for tensile testing Tensile tests were performed after conditioning the cured samples at room temperature and 45% relative humidity for seven days The crosshead speed was 2 00 inch/minute The gauge length was 0 5 inches Adhesive Bonding Testing System (Open Time) The Adhesive bond testing system Model 106PC is used Olinger Company produces the equipment The Olinger Bond Tester doses the hot melt adhesive onto a substrate (Polycarbonate), then presses a second substrate onto the adhesive and induces a pull force on the sandwich The following parameters were controlled during the test a ) The Open Time, which is the time between dosing the adhesive to the first substrate and the application of the second substrate b ) The Close Time, which is the time between the application of the second substrate and the breaking of the bond c ) The adhesive temperature d ) The Hopper Pressure e ) The Sample compression force The temperature, the Open time and the Close time are nominally programmable, while pressures are readily adjustable with individual regulators The force required to break the bond is measured and a visual observation of the bond failure is manually recorded When the Open time was performed, the close time was held constant (10 seconds) and the open time was varied Testing of the Moisture Content of the Polyols The AQUATEST® 8 tester from PHOTOVOLT was used to determine the amount of moisture in the samples It is a coulometric moisture analysis system (pyπdine free) The Photovolt Aquatest 8 tester is a Karl Fisher coulometric titrator for the determination of water The mechanism of determination substantially similar to that of the Karl Fisher pyπdine-based reagent Water reacts quantitatively with iodine and sulfur dioxide generating hydrogen and sulfur tnoxide Hydroxyl Number The hydroxyl number of the mateπals was determined using ASTM E 222-73, standard test method entitled, "Hydroxyl Groups by Acetic Anhydride Acetylation", Method B Percentage Isocyanate The percentage of available isocyanate in the materials was determined using ASTM D 4665-87, standard test method entitled, "Polyurethane Raw Materials Determination of Assay of Isocyanates" Acid Number The acid number of materials was determined using ASTM D 4662-87, standard test method entitled, "Polyurethane Raw Materials Determination of Acid and Alkalinity Numbers of Polyols" Viscosity The viscosity of the polyester polyols was measured with a Brookfield viscometer at 120 degrees Centigrade Example 1 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 17932 g (1 23 moles) of adipic acid, 1220 12 g (3 83 moles) of Pamite® 90 tall oil rosin (available from Hercules Incorporated) and 261 03 g (1 92 moles) of pentaerythntol and 100 ml of toluene was introduced into the reactor The reaction mixture was kept under inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135 cc/minute) At 114°C, the toluene reflux started, the riser temperature was at 84°C and the water of reaction was collected The refractive index of the water was 1 3325 after 10 minutes of reaction The heating of the reaction mixture was continued until the temperature reached 276°C When about 95% of the water was distilled, i e 866 ml, the reactor was cooled to 170°C, while maintaining the reaction mixture under inert atmosphere The reaction time of the first stage equaled about five hours The refractive index of water at the end of the first stage equaled to 1 3325 The temperature at the packing column equaled to 106°C 1220 12 g (3 83 moles) of Pamite® 90 tall oil rosin, 381 05 g (2 61 moles) of adipic acid, 514 54 g (3 83 moles) of tπmethylol propane and 30 ml of toluene were then added to the reactor, which was then reheated When the temperature reached about 148°C, the water of reaction started to distill The heating was continued until the theoretical amount of the water of reaction was removed Monitoring of the acid value of the resin and the refractive index of water was taken every thirty minutes, until the acid value was below 3 The hydroxyl number was then measured When the polyester polyol reached both a desired acid value and hydroxyl number, the reaction mixture was stripped of the toluene using a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of toluene in solution was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry, nitrogen purged and blanketed steel container 3500 g of polyester polyol was prepared The maximum polymerization temperature was 280°C The total time required for this polycondensation reaction was 20 5 hours The polyester polyol had a theoretical functionality of 2 0 and an actual functionality of 2 1 , a hydroxyl number of 58 4, and acid value of 2 9, a Gardner color of 9, a moisture content of 0 04%, a viscosity @ 120°C of 8300 cps and a glass transition temperature of +30°C Example 2 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 35 5 g (2 30 moles) of adipic acid, 986 g (0 73 moles) of dipropylene glycol, 556 3 g (386 moles) of cyclohexanedimethanol and 100 ml of xylene was introduced into the reactor The reaction mixture was kept under an inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135cc mιnute) When the reaction mixture reached 152°C, the xylene reflux started, the riser temperature was at 92°C and the water of reaction was collected The refractive index of the water was 1 3333 after 10 minutes of reaction The reaction mixture was heated until the temperature of the mixture reached 219°C When about 95% of the water was distilled, i e 78 6 ml, the reactor was cooled to 170°C, while the reaction mixture was maintained under an inert atmosphere The reaction time of the first stage was about two hours The refractive index of water at the end of the first stage was 1 3354 The temperature at the packing column was 123°C 1461 25 g (459 moles) of Pamite® 90 tall oil rosin, 6802 g (4 59 moles) of phthalic anhydride, 61623 g (4 59 moles) of tπmethylol propane and 30 ml of xylene were then added to the reactor, which was then reheated When the temperature reached about 163°C, the water of reaction started to distill The reaction mixture was heated until the theoretical amount of the water of reaction was removed The acid value of the resin and the refractive index of water were monitored every thirty minutes, until the acid value is below 3 The hydroxyl number was then measured When the polyester polyol reached both the desired acid value and hydroxyl number, the reaction mixture was stripped of the xylene with a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of xylene in solution was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry, nitrogen purged and blanketed steel container 3500 g of polyester polyol was prepared The maximum polymerization temperature was 280°C The total time required for this polycondensation reaction was 18 7 hours This polyester polyol has a theoretical functionality of 2 0 and an actual functionality of 2 1 , a hydroxyl number of 50, and acid value of 2 9, a color Gardner of 8, a moisture content of 0 04%, a viscosity @ 120°C of 8000 cps and a glass transition temperature of +27°C Example 3 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 162 32 g (1 11 moles) of adipic acid, 305 54 g (2 06 moles) of phthalic anhydride, 58 58 g (0 35 moles) of isophthalic acid, 946 36 g (7 05 moles) of tπmethylol propane and 100 ml of toluene was introduced into the reactor The reaction mixture was kept under an inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135cc/mιnute) At 128°C, the toluene reflux started, the riser temperature was at 99°C and the water of reaction was collected The refractive index of the water was 1 3333 after 10 minutes of reaction The reaction mixture was heated until the temperature reached 232°C When about 95% of the water was distilled, i e 854 ml, the reactor was cooled to 170°C, while maintaining the reaction mixture under inert atmosphere The reaction time of the first stage equaled about two hours The refractive index of water at the end of the first stage equaled to 1 3351 The temperature at the packing column equaled to 108°C 2244 07 g (7 05 moles) of Pamite® 90 tall oil rosin and 30 ml of toluene were then added to the reactor, which was then reheated When the temperature reached about 186°C, the water of reaction started to distill The reaction mixture was heated until the theoretical amount of the water of reaction was removed The acid value of the resin and the refractive index of water were monitored every thirty minutes, until the acid value was below 3 The hydroxyl number was then measured When the polyester polyol reached both the desired acid value and hydroxyl number, the reaction mixture was stripped of the toluene with a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of toluene in solution was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry, nitrogen purged and blanketed steel container 3500 g of polyester polyol was prepared The maximum polymerization temperature was 280°C The total time required for this polycondensation reaction was 20 3 hours This polyester had a theoretical functionality of 2 0 and an actual functionality of 2 1 , a hydroxyl number of 69 5, and acid value of 2 1 , a color Gardner of 8, a moisture content of 0 04%, a viscosity @ 120°C of 5775 cps and a glass transition temperature of +32°C Example 4 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 1173 85 g (8 03 moles) of adipic acid, 129 34 g (096 moles) of dipropylene glycol, 1019 g (7 07 moles) of cyclohexanedimethanol, and 100 ml of xylene was introduced into the reactor The reaction mixture was kept under inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135cc/ιmιnute) At 147°C, the xylene reflux started, the riser temperature was at 90°C and the water of reaction was collected The refractive index of the water was 1 3333 after 10 minutes of reaction The reaction mixture was heated until the temperature reached 207°C When about 95% of the water was distilled, i e 275 ml, the reactor was cooled to 170°C, while maintaining the reaction mixture under inert atmosphere The reaction time of the first stage was about four hours The refractive index of water at the end of the first stage was 1 3376 The temperature at the packing column of the reactor was 120°C 1703 94 g (5 35 moles) of Pamite® 90 tall oil rosin , 359 39 g (2 68 moles) of tπmethylol propane and 30 ml of xylene were then added to the reactor, which was then reheated When the temperature reached about 199°C, the water of reaction started to distill The reaction mixture was heated until the theoretical amount of the water of reaction was removed The acid value of the resin and the refractive index of water were monitored every thirty minutes, until the acid value was below 3 The hydroxyl number was then measured When the polyester polyol reached both the desired acid value and hydroxyl number, the reaction mixture was stripped of the xylene with a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of xylene was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry nitrogen purged and blanketed steel container 4000 g of polyester polyol was prepared The maximum polymerization temperature was 280°C The total time required for this polycondensation reaction was 31 hours This polyester has a theoretical functionality of 1 0 and an actual functionality of 1 1 , a hydroxyl number of 33, and acid value of 2 9, a color Gardner of 4 a moisture content of 0 04%, a viscosity @ 120°C of 300 cps and a glass transition temperature of -3°C Example 5 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 1181 46 g (8 08 moles) of adipic acid, 115 72 g (0 86 moles) of dipropylene glycol, 652 88 g (4 53 moles) of cyclohexanedimethanol, and 100 ml of toluene was introduced into the reactor The reaction mixture was kept under inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135cc/mιnute) At 121°C, the toluene reflux started the riser temperature was at 84°C and the water of reaction was collected The refractive index of the water was 1 3334 after 10 minutes of reaction The reaction mixture was heated until the temperature reached 190°C When about 95% of the water was distilled, i e 185 ml, the reactor was cooled to 170°C, while maintaining the reaction mixture under inert atmosphere The reaction time of the first stage was about four hours The refractive index of water at the end of the first stage was 1 3340 The temperature at the packing column was 114°C 1714 98 g (539 moles) of Pamite® 90 tall oil rosin , 72323 g (5 39 moles) of tπmethylol propane and 30 ml of toluene were then added to the reactor, which was then reheated When the temperature reached about 166°C, the water of reaction started to distill The reaction mixture is heated until the theoretical amount of the water of reaction was removed The acid value of the resin and the refractive index of water were monitored every thirty minutes, until the acid value was below 3 The hydroxyl number was then measured When the polyester polyol reached both the desired acid value and hydroxyl number, the reaction mixture was stripped of the toluene with a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of toluene was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry, nitrogen purged and blanketed steel container 4000 g of polyester modifier was prepared The maximum polymerization temperature was 280°C The total time required for this polycondensation reaction was 16 6 hours This polyester has a theoretical functionality of 2 0 and an actual functionality of 2 1 , a hydroxyl number of 65, and acid value of 2 9, a color Gardner of 4, a moisture content of 0 04%, a viscosity @ 120°C of 300 cps and a glass transition temperature of -2°C Example 6 The reactor used to produce polyols of the present invention consisted of a 5000 ml flask provided with five tubular inlets and a supply of nitrogen The reactor was also provided with a mechanical stirrer, a condenser, a packing column, a water trap, an overflow nitrogen bubbler and an overhead nitrogen bubbler A reaction mixture of 650 76 g (4 45 moles) of adipic acid, 233 04 g (1 74 moles) of dipropylene glycol, 385 3 g (2 67 moles) of cyclohexanedimethanol, 61547 g (4 59 moles) of tπmethylol propane, 243943 g (766 moles) of Pamite® 90 tall oil rosin and 100 ml of toluene was introduced into the reactor The reaction mixture was kept under inert atmosphere (nitrogen), stirred, heated and nitrogen sparged (135cc mιnute) At 155°C, the toluene reflux started the riser temperature was at 84°C, and the water of reaction was collected The refractive index of the water was 1 3334 after 10 minutes of reaction The reaction mixture was heated until the theoretical amount of the water of reaction was removed The acid value of the resin and the refractive index of water were monitored every thirty minutes, until the acid value was below 15 The hydroxyl number was then measured When the polyester polyol reached both the desired acid value and hydroxyl number, the toluene was stripped from the reaction mixture using a nitrogen sparging at a rate of 2 standard liter/minute (or vacuum strip) for 2 hours, until the concentration of toluene in solution was below 100 ppm The reactor was cooled down to 180°C and the resultant polyester polyol was discharged in a clean dry, nitrogen purged and blanketed steel container 4000 g of polyester polyol was prepared The maximum polymerization temperature was 260°C The total time required for this polycondensation reaction was 14 8 hours This polyester polyol has a theoretical functionality of 1 35 and an actual functionality of 1 4, a hydroxyl number of 76, and acid value of 14.2, a color Gardner of 5, a moisture content of 0 04%, a viscosity @ 120°C of 300 cps and a glass transition temperature of 0°C The following table provides a summary of the reactant molar ratios used to prepare the polyester polyols of Example 1 - 5 Table 1 - Reactant Molar Ratios Used to prepare the polyester polyols of Examples 1 -5 Example 7 The reactive hot melt adhesive was produced in a double-planetary, stainless steel, Ross mixer (Ross LDM-1qt) The mixer had an electronically controlled variable speed drive, and the reactor was jacketed The reactor had an integral thermocouple A manifold was connected to the mixer head, which controls the nitrogen supply, the vacuum system and the isocyanate feed system to the reactor The pot temperature was displayed on a digital readout attached to the reactor thermocouple Silicone oil is heated and circulated through the jacket with a Polystat circulator from Cole-Palmer The vacuum was generated with a single stage Welch vacuum pump, a dry ice trap was installed between the pump and the reactor A Cole-Palmer Masterflex peristaltic pump using Tygon® tubing delivers the liquefied isocyanate component to the reactor The polyol of example 6 was heated in a 100°C - 120°C convection oven 804 8 g (1 0903 number of equivalence) of the molten polyol was poured into the reactor, then 020 g of a silicone free air release agent (BYK A 500 air release agent available from Malhnckrodt Laboratory Chemicals, Phillipsburg, NJ) The reactor was installed on a mixer stand and heating oil lines were connected The temperature controller of the oil circulator was set to 135°C The reactor was then sealed and evacuated When the polyol was completely molten, the mixture was agitated Weigh 195 g (1 5600 number of equivalence) of an dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyi methane dnsocyanate, available from BASF) into an isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°C melting the dnsocyanate The vessel was connected to the feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The rate of addition of dnsocyanate was 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO The oil temperature of the reactor was allowed to cool to 120°C The total time required for the prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 1 4 and an actual functionality of 1 41 Its % NCO was equal to 1 97%, and its Brookfield viscosity @ 120°C was equal to 49000 cps The product had an isocyanate index of 1 43 Example 8 (Comparative) A polyurethane Rhma based on a highly crystalline high melting point (80°C) polyester diol (Dynacoll® 7360 polyol obtained from Creanova Inc , Piscataway, NJ) was reacted with a dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The polyester polyol was melted in a 100°C - 120°C convection oven 981 43 g (0 5248 number of equivalence) of the polyester polyol was poured a reactor, then 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ) was added The reactor was installed on a mixer stand and the heating oil lines were connected The temperature controller of the oil circulator was set to 135°C The reactor was then sealed and evacuated When the polyester polyol was melted, the agitation was started 132 34 g (1 0587 number of equivalence) of dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4 4'- diphenyl methane dnsocyanate, available from BASF) was introduced into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°C, then the dnsocyanate was melted The vessel was connected to a feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The addition of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO and in view of the measured %NCO value of the material, an additional amount of dnsocyanate was added to the material so that the %NCO approaches within approximately ± 1 % by weight of the theoretical %NCO, as calculated from the equivalent weights of the polyols and isocyanates used The additional amount added was 6 6 grams The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 2 0 and an actual functionality of 2 0 Its % NCO was equal to 2 01 %, and its viscosity @ 120°C was equal to 8000 cps The product had an isocyanate index of 2 02 Example 9 This is an example of polyurethane Rhma of the present invention It is based on a highly crystalline high melting point (80°C) polyester diol (Dynacoll® 7360 polyol obtained from Creanova Inc , Piscataway, NJ) It is also based on a polyester polyol of the present invention (Example 1) Both polyols are reacted with dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The Dynacoll® 7360 polyester polyol and the polyester polyol of Example 1 were melted in a 100°C - 120°C convection oven 669 30 g (0 3579 number of equivalence) of the Dynacoll® 7360 polyester polyol was added to the reactor, then 200 g (0 2081 number of equivalence) of the polyester polyol of Example 1 , and 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) was added to the reactor The reactor was installed on the mixer stand and connected to the heating oil lines The temperature controller of the oil circulator was set to 135°C The reactor was sealed and evacuated When the polyester polyols were melted, the agitator was started 130 50 g (1 0440 number of equivalence) of dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) was added into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°C and the dnsocyanate was melted The vessel was connected to the feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The dnsocyanate was added over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO and in view of the measured %NCO value of the material, an additional amount of dnsocyanate was added to the material so that the %NCO approaches within approximately ± 1% by weight of the theoretical %NCO, as calculated from the equivalent weights of the polyols and isocyanates used The additional amount added was 3 5 grams The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 20 and an actual functionality of 2 02 Its % NCO was equal to 2 01 %, and its viscosity @ 120°C was equal to 18300 cps The product had an isocyanate index of 1 84 Example 10 (Comparative) A highly crystalline, high melting point (80°C) polyester diol (Dynacoll® 7360 obtained from Creanova Inc , Piscataway, NJ) and a conventional reactive rosin glycerol ester modifier (Hercules Rosin glycerate, Permalyn™ 2085, hydroxyl number = 41 2, glass transition temperature = 45 degrees Centigrade and equivalent weight = 133 6) were reacted with LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The Dynacoll® 7360 diol and the conventional reactive rosin glycerol ester modifier were melted in a 100°C - 120°C convection oven 72862 g (0 3896 number of equivalence) of the Dynacoll® 7360 polyester polyol was poured into the reactor, then 215 g (0 1614 number of equivalence) of the conventional reactive rosin glycerol ester modifier was poured into the reactor along with 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) The reactor was installed on a mixer stand and connected to heating oil lines The temperature controller of the oil circulator was set to 135°C The reactor was sealed and evacuated When the polyester polyol and the rosin glycerol ester were melted, the agitation was started 133 56 g (1 0685 number of equivalence) of dnsocyanate (LUPRANATE® M (PURE diphenyl methane dnsocyanate, which contains 98% of 4,4'- diphenyl methane dnsocyanate available from BASF) was added into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set 70°C then dnsocyanate was melted The vessel was connected to the feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature was maintained and agitated for 2 hours and 30 minutes The material was sampled for %NCO and in view of the measured %NCO value of the material, an additional amount of dnsocyanate was added to the material so that the %NCO approaches within approximately ± 1 % by weight of the theoretical %NCO, as calculated from the equivalent weights of the polyols and isocyanates used The additional amount added was 5 2 grams The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 1 94 and an actual functionality of 1 94 Its % NCO was equal to 2 02%, and its viscosity @ 120°C was equal to 11600 cps The product had an isocyanate index of 1 94 Example 11 (Comparative) A highly crystalline, high melting point (80°C) polyester diol (Dynacoll® 7360 diol obtained from Creanova Inc , Piscataway, NJ) and on a highly crystalline polycaprolactone diol (CAPA™ 640 obtained from SOLVAY) were reacted with a dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The CAPA® 640 polycaprolactone diol and the Dynacoll® 7360 polyester polyol were melted in a 100°C - 120°C convection oven 692 20 g (0 3702 number of equivalence) of the Dynacoll® 7360 polyester polyol was added to the reactor, then 200 g (0 0143 number of equivalence) of the CAPA® 640 polycaprolactone diol, and 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) The reactor was installed on the mixer stand and connected to the heating oil lines The temperature controller of the oil circulator was set to 135°C The reactor was sealed and evacuated When the polyols were melted, the agitation was started 107 6 g (0 8608 number of equivalence) of dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) was added into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°C, which melts the dnsocyanate The vessel was connected to a feed pump and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The addition of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO The oil temperature of the reactor to was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 2 00 and an actual functionality of 2 00 Its % NCO was equal to 2 00%, and its viscosity @ 120°C was equal to 19600 cps The product had an isocyanate index of 224 Example 12 This is an example of a polyurethane Rhma of the present invention This example was based on a highly crystalline, high melting point (80°C) polyester diol (Dynacoll® 7360 diol obtained from Creanova Inc , Piscataway, NJ) It was also based on a polyester polyol of the present invention ( Example 3) reacted with a dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The polyester diols were melted in a 100°C - 120°C convection oven 664 30 g (0 3552 number of equivalence) of the Dynacoll® 7360 polyester polyol was added to the reactor, then 200 g (0 2478 number of equivalence) of the polyester polyol of Example 3 and 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) The reactor was installed on the mixer stand and the heating oil lines were connected The temperature controller of the oil circulator was set to 135°C The reactor was sealed and evacuated When the polyester polyols were melted, the agitation was started 135 50 g (1 0840 number of equivalence) of dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°, then the dnsocyanate was melted The vessel was connected to the feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The addition of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO and in view of the measured %NCO value of the material, an additional amount of dnsocyanate was added to the material so that the %NCO approaches within approximately ± 1 % by weight of the theoretical %NCO, as calculated from the equivalent weights of the polyols and isocyanates used The additional amount added was 11 grams The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 2.0 and an actual functionality of 2 02 Its % NCO was equal to 2.02%, and its viscosity @ 120°C was equal to 21000 cps The product had an isocyanate index of 1 80 Example 13 (Comparative) This is an example of a polyurethane Rhma based on a polyether diol (ARCOL® PPG- 2025 polyol, obtained from ARCO Chemical Company ) The polyether polyol was reacted with a dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) 875 18 g (0 8845 number of equivalence) of the ARCOL®PPG- 2025 polyether polyol was added to the reactor, then 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) was added The reactor was installed on the mixer stand and connected to the heating oil lines The temperature controller of the oil circulator was set to 135°C The reactor was sealed and agitation was started 174 62 g (1 3969 number of equivalence) of dnsocyanate was added into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°, then melting the dnsocyantate The isocyanate feed vessel was connected to a feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The addition of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 2 0 and an actual functionality of 2 0 Its % NCO was equal to 2 05%, and its viscosity @ 120°C was equal to 474 cps The product had an isocyanate index of 1 58 Example 14 This is an example of a polyurethane Rhma of the present invention It was based on a polyether diol (ARCOL®PPG -2025 polyol obtained from ARCO Chemical Company), and a polyester polyol of the present invention ( Example 1 ) reacted with a dnsocyanate (LUPRANATE® M, which contains 98% of 4,4'- diphenyl methane dnsocyanate, available from BASF) The polyester polyol of Example 1 was melted in a 100°C - 120°C convection oven 607 32 g (06138 number of equivalence) of the ARCOL®PPG - 2025 polyether polyol was poured into the reactor then 345 g (0 3590 number of equivalence) of the polyester polyol of Example 1 and then 0 22 g of a silicone free air release agent (BYK A 500 air release agent available from Mallinckrodt Laboratory Chemicals, Phillipsburg, NJ ) was introduced into the reactor The reactor was installed on the mixer stand and the heating oil lines were connected The temperature controller of the oil circulator was set to 135°C The reactor was sealed and evacuated When the polyester polyol of Example 1 was melted, the agitation was started 197 46 g (1 5796 number of equivalence) of dnsocyanate was introduced into the isocyanate feed vessel The vacuum on the reactor was broken with nitrogen The temperature controller of the oil circulator was set to 70°C then melt the dnsocyanate was melted The isocyanate feed vessel was connected to the feed pump, and the dnsocyanate was transferred to the reactor, while following the time - temperature curve (Figure 1 ) The addition of dnsocyanate was over 30 minutes When the temperature reached 115°C, the temperature and agitation was maintained for 2 hours and 30 minutes The material was sampled for %NCO The oil temperature of the reactor was permitted to cool to 120°C The total time required for that prepolymer reaction was 3 hours This reactive hot melt adhesive had a theoretical functionality of 2 0 and an actual functionality of 2 02 Its % NCO was equal to 2 22%, and its viscosity @ 120°C was equal to 2800 cps The product had an isocyanate index of 1 62 Example 15 Green Strength and Mechanical Properties of the polyurethane Rhma Table 2 Table 2 shows that the polyester polyols of this invention improve the mechanical properties of cured polyurethane reactive hot melt adhesives In contrast, a conventional rosin glycerate modifier detrimentally decreases the mechanical properties of cured polyurethane reactive hot melt adhesives In addition, the polyester polyols of this invention have a positive effect on mechanical properties while providing an acceptable time for the development of the uncured polyurethane reactive hot melt's green strength Thus, the polyester polyols of this invention enable formulations showing an improved balance of application processing and cured mechanical properties relative to the current art Table 3 Table 3 shows that the polyester polyols of this invention do not have a detrimental effect on the adhesive properties of cured polyurethane reactive hot melt formulations that are based on blends with conventional polyester diols, While Table 4 shows that the polyester polyols of this invention have a very beneficial effect on the adhesive properties of cured polyurethane reactive hot melt formulations that are based on blends with conventional polyether diols Table 4 Example 16 Open Time of Uncured Polyurethane Rhma Figure 2 shows the effect of the polyester polyols of the present invention on the uncured polyurethane Rhma's open time. The open times of Examples 9 and 12 are both greater than 600 seconds thus enabling the practicality of bonding large surfaces. In contrast, Comparative Example 8 has an open time no greater than 100 seconds and Comparative Example 11 has an open time no greater than 200 seconds. The open time of Comparative Example 10 is greater than 400 seconds but as shown in Table 2, this is obtained at the detriment of the mechanical properties of the cured polyurethane Rhma. Example 17 Shear Adhesion Failure Temperature (SAFT) of cured Polyurethane Rhma The Shear Adhesion Failure Temperature (SAFT) was measured and it was surprisingly found that the polyester polyols of this invention provide cured polyurethane reactive hot melt adhesive formulations with exceptional SAFT as shown in Table 5. Table 5 It is not intended that the examples given here should be construed to limit the invention, but rather, they are submitted to illustrate some of the specific embodiments of the invention Various modifications and variations of the present invention known to those of ordinary skill in the art can be made without departing from the scope of the invention It is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims

Claims: What is Claimed is 1 A polyester comprising, a reaction product of a polycarboxylic acid, a polyhydnc alcohol and a monocarboxylic acid, wherein the polyester formed therefrom has hydroxy functionality 2 The polyester of claim 1 , wherein the polyhydnc alcohol has a hydroxy functionality of greater than 2 3 The polyester of claim 2, wherein the polyhydnc alcohol has a hydroxy functionality of greater than 3 4 The polyester of claim 2, wherein the polyhydnc alcohol is selected from the group consisting of tπmethylol propane and pentaerythntol 5. The polyester of claim 2, wherein the polyhydnc alcohol comprises tπmethyloi propane 6 The polyester of claim 2, wherein the polyhydnc alcohol comprises pentaerythntol 7 The polyester of claim 1 , wherein the polycarboxylic acid has a carboxylic acid functionality of about 2 8 The polyester of claim 7, wherein the polycarboxylic acid is selected from the group consisting of adipic acid, isophthalic acid and phthalic 9 The polyester of claim 7, wherein the polycarboxylic acid comprises adipic acid The polyester of claim 7, wherein the polycarboxylic acid comprises isophthalic acid The polyester of claim 7, wherein the polycarboxylic acid comprises phthalic acid The polyester of claim 1 , wherein the monocarboxylic acid comprises a rosin acid The polyester of claim 12, wherein the rosin acid is selected from the group consisting of wood rosin, gum rosin, tall oil rosin, and mixtures thereof The polyester of claim 12, wherein the rosin acid comprises tall oil rosin The polyester of claim 2, wherein the polyhydric alcohol further comprises a combination of cyclohexane dimethanol and dipropylene glycol The polyester of claim 1 , wherein the monofuπctional carboxylic acid comprises from about 5% to about 70% of total moles of reactants in the reaction product The polyester of claim 16, wherein the monofunctional carboxylic acid comprises from about 10% to about 50% of total moles of reactants in the reaction product The polyester of claim 17, wherein the monofunctional carboxylic acid comprises from about 20% to about 45% of total moles of reactants in the reaction product 19. The polyester of claim 1 , wherein the polyhydric alcohol compπses from about 5% to about 50% of total moles of reactants in the reaction product. 20. The polyester of claim 19, wherein the polyhydric alcohol comprises from about 10% to about 40% of total moles of reactants in the reaction product. 21. The polyester of claim 1 , wherein the polycarboxylic acid comprises from about 5% to about 50% of total moles of reactants in the reaction product. 22. The polyester of claim 1 , wherein the polycarboxylic acid comprises from about 5% to about 35% of total moles of reactants in the reaction product. 23. The polyester of claim 1 , wherein the wherein the monofunctional carboxylic acid comprises from about 20% to about 45%, the polyhydric alcohol comprises from about 10% to about 40%, and the polycarboxylic acid comprises from about 5% to about 35% of total moles of reactants in the reaction product. 24. The polyester of claim 1 , wherein the hydroxy functionality ranges from about 0.9 to about 2.1. 25. The polyester of claim 1 , wherein the polyester has a glass transition temperature in the range of from about -20°C to about +45°C as determined by differential scanning calonmetry. 26. The polyester of claim 25, wherein the polyester has a glass transition temperature in the range of from about -15°C to about +40°C as determined by differential scanning calonmetry. 27. The polyester of claim 26, wherein the polyester has a glass transition temperature in the range of from about -10°C to about +35°C as determined by differential scanning calorimetry. 28. The polyester of claim 1 , wherein the polyester has a Brookfield viscosity at 120°C ranging from about 100 cps to about 20,000 cps. 29. The polyester of claim 28, wherein the polyester has a Brookfield viscosity at 120°C ranging from about 200 cps to about 10,000 cps. 30. A urethane polymer comprising a reaction product of: (i) a polyester comprising a reaction product of a polycarboxylic acid, a polyhydric alcohol and a monocarboxylic acid wherein the polyester has a hydroxy functionality, and (ii) a polyfunctional isocyanate, wherein the resultant urethane polymer comprises an amount, by weight, of available isocyanate. 31. The urethane polymer of claim 30, wherein the amount of available isocyantate is from about 1.5% to about 2.5% by weight of the urethane polymer. 32. The urethane polymer of claim 31 , wherein the amount of available isocyanate is about 2.0% by weight of the urethane polymer. 33. The urethane polymer of claim 30, further comprising an additional polyol. 34. The urethane polymer of claim 33, wherein the additional polyol comprises a polyester polyol. The urethane polymer of claim 33, wherein the additional polyol comprises a polyether polyol The urethane polymer of claim 33, wherein the additional polyol has a hydroxy functionality of about 2 The urethane polymer of claim 36, wherein the additional polyol comprises a polyester polyol The urethane polymer of claim 36, wherein the additional polyol comprises a polyether polyol The urethane polymer of claim 30, wherein the isocyanate comprises an aromatic isocyanate The urethane polymer of claim 39, wherein the aromatic isocyanate is selected from the group consisting of phenyl isocyanate, m-phenyl- dnsocyanate, 2,4-toluene dnsocyanate, 2,6-toluene dnsocyanate and 4,4 ' -diphenyl methane dnsocyanate The urethane polymer of claim 30, wherein the isocyanate comprises 4,4 ' -dιphenyl methane dnsocyanate An adhesive comprising, (a) a urethane polymer comprising (i) a reaction product of a polyester comprising a reaction product of a polycarboxylic acid, a polyhydnc alcohol and a monocarboxylic acid wherein the polyester has a hydroxy functionality, and (b) a polyfunctional isocyanate, wherein the urethane polymer comprises an amount, by weight, of available isocyanate and wherein the adhesive has a shear adhesion failure temperature ("SAFT") of greater than about 180°C The adhesive of claim 42, wherein the adhesive has a shear adhesion failure temperature ("SAFT') of greater than 190°C The adhesive of claim 42, wherein the adhesive has a shear adhesion failure temperature ("SAFT") of greater than 200°C The adhesive of claim 42, wherein the adhesive has an open time of greater than about 200 seconds The adhesive of claim 42, wherein the adhesive has an open time of greater than about 300 seconds The adhesive of claim 42, wherein the adhesive has an open time of greater that about 400 seconds The adhesive of claim 42, wherein the adhesive has an open time of greater than 600 seconds A method of use of an adhesive comprising obtaining an adhesive comprising, (a) a urethane polymer comprising (i) a reaction product of a polyester comprising a reaction product of a polycarboxylic acid, a polyhydric alcohol and a monocarboxylic acid wherein the polyester has a hydroxy functionality, and (b) a polyfunctional isocyanate, wherein the urethane polymer comprises an amount, by weight, of available isocyanate and wherein the adhesive has a shear adhesion failure temperature ("SAFT") of greater than about 180°C, and (c) applying the adhesive in an assembly operation, wherein the assembly operation is selected from the group consisting of carpet bonding, door panel assembly, instrument panel assembly, recreation vehicle assembly, over the road trailer assembly, heavy-duty truck assembly, window assembly, garage door assembly, structural insulated panel assembly, shoe sole assembly and non-wovens assembly. 50. A method of making a polyester polymer having hydroxy functionality comprising the step of; reacting a combination of a polycarboxylic acid, a monocarboxylic acid, and a polydydric alcohol under conditions sufficient to produce said polyester polymer.

Applicants: HERCULES INC, HERCULES INCORPORATED
Application year: 2000
Main classification: C08G18
IPC codes: C08G18, C08G63, C09J175