NORBORNYL MODIFIED POLYESTERAMIDES AND PROCESS FOR PREPARING SAME

Abstract: Polyesteramides modified by having at least one termin­ al norbornene radical have improved physical and chemical properties, such as enhanced corrosion resistance, electrical properties, and heat stability. The modified polyesteramides are prepared by a process of reacting a dicarboxylic acid, a diamine, a polyol and a norbornene compound.

Description: NORBORNYL MODIFIED POLVESTERAMIDES AND PROCESS FOR PREPARING SAME Unsaturated polyesters and polyamides are two classes of materials useful in the fabrication of a wide variety of products. By varying the starting monomers, some can be made spinnable into fibers and filaments; some are useful in casting; some are moldable; still others can be formulated into coatings. The physical and chemical properties can be changed through choice of monomers, polymerization procedures and other means. None are without one or more deficiencies, however. More recently, a class of polyesteramides has been developed. Basically, those materials have been the random interpolymerization of a dicarboxylic acid with a diol and a diamine. The products have exhibited a spectrum of properties substantially different from either polyesters or polyamides. Also recently, polyesters have been modified with dicyclopentadiene to result in products having reduced shrinkage upon curing, enhanced hydrophobicity and better economics than the corresponding unmodified polyesters. Although all of those materials have been useful in making products acceptable in the marketplace, there is room for considerable improvement in many of their properties. This invention provides a new class of modified polyesteramides having an improved spectrum of properties. The polyesteramides have at least one terminal group that is a norbornyl radical. The new polyesteramides have a central esteramide chain and have at least one terminal norbornyl radical. The central ester amide chain is composed of the polymerizate of a diamine, a polyol and an unsaturated polycarboxylic acid. The diamine is from the class of those having the formula: EMI2.1 wherein R1 and R2 are independently selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aromatic radicals or R1 and R2 taken together with the remainder of the molecule form an aliphatic ring; and R3 is a divalent organic radical selected from the group consisting of alkylene, ether-linked alkylene, ether-linked arylene, alkylene amino-linked alkylene, alkylene amino-linked cycloalkylene, cycloalkylene, polycycloalkylene, arylene, alkylarylene, bis ( alkyl ) - cycloalkylene and bis(alkyl) polycycloalkylene. Typical diamines that are useful herein are ethylene diamine, propylene diamine, hexane-1,6-diamine, piperazine, 4,4' -methylenebis(cyclohexylamine), 2,2'-bis (4-aminocyclohexyl )propane, 4,4' -diaminodiphenyl ether, bis(aminomethyl)norbornene, toluene diamine, bis(aminomethyl) dicyclopentadiene and homopiperazine. Typical polyamines are aminoethylpiperazine and diethylenetriamine. The polyol is from the class of those having the formula: HO-R3-OH wherein R3 is a divalent organic radical selected from the group consisting of alkylene, ether-linked alkylene, ether-linked arylene, cycloalkylene, polycycloalkylene, bis ( alkyl )cycloalkylene, bis ( alkyl )polycycloalkylene, and arylene. Mixtures of two or more of such polyols can be used. Representative of the useful polyols are the diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, dicyclopentadiene dimethanol, bis(hydroxymethyl)norbornane, methyl cyclohexanedimethanol, bis(hydroxypropyl)bisphenol A and other hydroxyalkylated bisphenols, pentaerythritol, sorbitol and glycerine. The ratio of diamine to polyol can be varied within wide limits. That ratio is significantly related to the solubility of the modified polyesteramide in reactive diluents, such as styrene, which are commonly employed with polyesteramides for many applications. As a general rule, the amount of diamine should not exceed about 1/3 the combined weight of the polyol and diamine. The structure and size of the diamine molecule will determine to great extent the maximum amount of diamine that can be used. The ot,B-unsaturated polycarboxylic acid is preferably maleic acid, fumaric acid, maleic anhydride or mixtures of those compounds. Such acids are readily available, have good reactivity with the polyol and diamine, and result in products of good properties. Part of the a,ss-unsaturated acid may be replaced with a saturated or aromatic polycarboxylic acid to vary the cross-linking potential and physical properties of the modified polyesteramide. Such acids include the aliphatic acids such as adipic acid and the aromatic acids such as isophthalic acid. Replacement of part of the a,-unsaturated acid with such acids is commonplace in the polyester art. Suitable selection of acid and amount to achieve a desired purpose will be known to the skilled worker and can be optimized with simple preliminary experiments. The total amount of acid varies as a function of the total pogyol, diamine and norbornyl ingredients used. The terminal group used to modify the polyesteramide is a norbornyl radical. Dicyclopentadiene (DCPD) is a most preferred norbornyl functional material to be employed in terminating one or both ends of the chain. Polycyclopentadiene (i.e., DCPD oligomers) or dicyclopentadiene monoalcohol are also preferred species. Norbornene itself can also be used. DCPD is sold commercially as a product of about 97 or greater percent purity. It is also sold as a C10 hydrocarbon concentrate prepared by dimerizing a crude C5 stream from the cracking of hydrocarbons as taught in U.S. Patent 3,557,239. A preferred DCPD source is one that is low in peroxides and hydroperoxides and in light hydrocarbons and residual cyclopentadiene. These concentrates have as the main reactive components about 70 to 90 percent by weight of dicyclopentadiene, 5 to 30 percent by weight of the mixed Diels-Alder dimers of diolefins such as butadiene, cisand trans-piperylene, isoprene, cyclopentadiene and methyl cyclopentadiene. The remainder of these concentrates generally comprise residual C5 hydrocarbons and oligomers of the above diolefins. Examples of some of the dimers which have been identified in these concentrates are the Diels Alder adducts of two moles of isoprene (isoprene dimers), the adduct of cyclopentadiene and isoprene, the adduct of cyclopentadiene and piperylene, and the like. Either the C10 concentrate or the relatively pure DCPD may be employed in preparing the modified polyester amides. The modified polyesteramides can be prepared by a variety of techniques. In a preferred method, hereinafter called the "hydrolysis method," molten a,ss-unsaturated carboxylic anhydride is partially hydrolyzed with less than the stoichiometric equivalent of water and reacted with the norbornene derivative to form a half ester of that derivative and containing unesterified acid and anhydride. This reaction may conveniently be performed in stages whereby reactants are added stepwise, thus controlling exotherms. That product mixture is then reacted with the polyol and diamine to result in the desired modified polyesteramide. In a typical procedure, molten maleic anhydride and a fraction of the stoichiometric equivalent of water is maintained at an elevated temperature of from 600 to 1300C. The initial fractional equivalents of dicyclopentadiene (DCPD) is then added and allowed to react. A second fractional equivalent of water and of DCPD is added and allowed to react. Additional fractional equivalents of DCPD are added and each allowed to react before subsequent addition of the next increment until the desired amount of DCPD has been added. The amount of maleic (or other) anhydride employed in this first esterification step may be equal to the equivalent of DCPD in which event the product is essentially all monoester. Alternatively, the amount of anhydride may be the equivalent needed to make the monoester plus that excess that is to be used in the subsequent esteramidation step. To the mixture of DCPD monoester and acid and/or anhydride is added the polyol and diamine. That addition can be a bulk addition wherein all of the polyol and diamine are added in one step. The addition can be an incremental addition wherein all of the polyol and a fractional equivalent of the diamine are added initially and allowed to react after which subsequent increments of diamine are added. In all instances, water is continuously removed during the esteramidation step. The timing of the remaining diamine additions can be easily determined by the amount of water removed by acid number or by viscosity. A convenient and practical guide is to add a diamine increment when about one fourth to one half of the expected water from the prior addition has been collected. Incremental diamine addition aids in the control of reaction exotherm when some diamines are used. After addition of the polyol and diamine is complete, the reaction can be driven to maximum yield by maintaining or increasing the temperature until the desired acid number has been reached. Typically, acid numbers of 25 to 35 are preferred, although acid numbers that are somewhat higher or lower may be tolerated, and, in some instances, may be desired for certain applications. In an equally preferred method, hereinafter called the "prehydrolyis method," molten, a,ss-unsatu- rated carboxylic anhydride is essentially totally hydrolyzed with a stoichiometric or greater equivalent of water and reacted with the norbornene derivative to form a half ester of that derivative and containing unesterified acid. This reaction may conveniently be performed in stages whereby reactants are added stepwise thus controlling reaction exotherms. That product mixture is then reacted with the polyol and diamine to result in the desired modified polyesteramide. In a typical procedure, molten maleic anhydride and the stoichiometric or greater equivalent of water are maintained at an elevated temperature of from 1200 to 1500C. The temperature is allowed to stabilize at 1200 to 1250C and the initial fractional equivalent of DCPD is then added and allowed to react. A second fractional equivalent of DCPD is added and allowed to react. Additional fractional equivalents of DCPD are added and each allowed to react before subsequent addition of the next increment until the desired amount of DCPD has been added. The amount of maleic (or other) anhydride employed in this first esterification step may be equal to the equivalent of DCPD in which event the product is essentially all monoester. Alternatively, the amount of anhydride may be the equivalent needed to make the monoester plus that excess that is to be used in the subsequent esteramidation step. The polyol and diamine are added to the mixture of DCPD monoester and acid as described in the aforementioned hydrolysis method. In a further modification of either the hydrolyis or prehydrolyis method, a polyol containing 3 or more hydroxyl groups such as pentaerythritol may be separately added to the reaction after polyesteramidation is substantially complete. This serves to rapidly increase molecular weight and viscosity by cross-linking of the esteramide chains. Modified physical properties result from this embodiment. Many other alternate methods will be recognized by the skilled worker. For example, molten maleic anhydride may be added to a mixture of DCPD and water maintained in a reactor. The polyol and diamine are added to the mixture of DCPD monoester and acid and/or anhydride as before. Finally, although less preferred, DCPD, maleic anhydride, water, glycol, and none, all or part of diamine may be simultaneously reacted. An alternate method, hereinafter called the "half ester method," for preparing the modified polyesteramides, involves preparing the central esteramide chain and subsequently capping at least one end of that chain with the norbornene derivative. Water is not used in this method. In a typical procedure, an a,-unsaturated dicarboxylic anhydride, a glycol and a diamine are reacted at an elevated temperature of 1300 to 1500C with removal of water. After substantial completion of that reaction, a fraction of the norbornene derivative, such as DCPD, is added and reacted at elevated temperature. That is followed by additional increments of DCPD with each succeeding increment added after substantial completion of the reaction of the preceding increment. After all DCPD additions are complete, reaction is continued at 2000C with continual removal of water until the desired acid number is reached. As is common in the unsaturated polyester and polyesteramide art, the modified polyesteramides of this invention may be blended with a monomer that is compatible therewith. Typical of the vinyl monomers are the alkenyl aromatics, such as styrene or vinyltoluene. Acrylic monomers, although less preferred, may also be used separately or in conjunction with the vinyl monomer. Typical of the acrylic monomers is dicyclopentadiene acrylate. Other useful vinyl monomers will be known to the skilled worker. The vinyl monomer, frequently called a reactive diluent, is.desirably employed within a wide range of concentration of from 20 to 80 percent of diluent from 80 to 20 percent of the resin. The optimum amount will depend in large measure on the polyesteramide, the diluent and the properties desired in the uncured and the cured states. Reactive diluents are employed principally to adjust the viscosity of a resin blend to permit its facile use in a given fabrication procedure. A coating formulation will usually require a lower viscosity than a molding formulation. Other additives that are conventional in the polyester and polyesteramide art may also be included in formulations based upon these modified polyesteramides. Thus, fillers, pigments and other colorants, reinforcing fibers, and other additives may be added to serve their intended function. The polyesteramides are curable by known catalyst systems. Peroxides, such as methyl ethyl ketone peroxides, can be used with or without known promoters, such as cobalt octoate or cobalt naphthenate, that function with such peroxides. Acyl peroxides, such as benzoyl peroxides can be used with or without promoters such as tertiary amines, including typically dimethyl aniline and N,N-dimethyl-p-toluidine. The concentrations of catalyst and promoter are desirably adjusted within known limits of from 0.1 to 3.0 weight percent depending on the rate of cure desired, the magnitude of the generated exotherm and for other known purposes. Known gelation retarding agents, such as p-benzoquinone, can be employed in the curing system. The modified polyesteramides have properties that make them well adapted for coating, casting, lamination, molding, filament winding and other known fabrication procedures. A preferred use is in glass fiber laminates. The compositions prepared from the polyesteramides form articles that are especially useful in corrosive environments, high temperature environments or in some electrical insulating applications, such as encapsulation of electrical components. The compositions and process of the invention are illustrated in the following examples wherein all parts and percentages are by weight. Examples 1-13 Modified polyesteramides were prepared from various diols and diamines. In each instance the amount of maleic anhydride was 2.0 moles; dicyclopentadiene concentrate was 1.2 moles; and 1.4 moles water. The DCPD concentrate contained 83.94 percent DCPD; 14.41 percent codimers; 1.11 percent lights and 0.55 percent cyclopentadiene. Example 8 used 98 percent DCPD instead of the concentrate. The composition of the diol and diamine is shown in Table I. The procedure was the hydrolysis method involving three steps, viz: (a) a hydrolysis step consisting of the reaction of a norbornene functional reactant plus maleic anhydride (MA), and water, (b) a diol/diamine addition step, (c) a polyesteramidation step. Specifically, the reaction was performed as follows: Hydrolysis Step Maleic anhydride (MA) was charged to a reactor and melted to a clear solution at 700C. A nitrogen atmosphere was continually maintained in the reactor. To this, 1.05 moles of water is added followed by 0.3 mole of DCPD after two minutes. Twenty minutes later, 0.3 mole DCPD and 0.35 mole of water are added to the reactor. After 15 more minutes, 0.3 mole DCPD is charged to the reactor. The final 0.3 mole DCPD is added 15 minutes later and the reactor is heated to 1100C and held for 30 minutes of reaction. Diol/Diamine Addition Step Two different modes of addition of the diol/diamine components were used. In the bulk diamine addition method, the total required diol/diamine stoichiometry was added to the reactor followed by heating to 1600C and removal of water via a steam condenser - Deaa Stark trap - cold water condenser assembly, and increased nitrogen sparging. A total reaction time of 2 hours is used at the 1600C temperature. In the incremental diamine addition method, the total diol stoichiometry plus some fraction of the diamine stoichiometry were added to the reactor, followed by incremental additions of the remaining diamine requirement as a function of continuing reaction (conversion). As a specific example, in Example 2, 1.17 moles of propylene glycol (PG) containing 0.13 moles of 4,4'-methylenebis(cyclohexylamine) was initially added to the reaction. After approximately 1/4 of the expected water of the reaction was removed, a second increment of diamine (0.13 moles) was added. This was followed by a third and final incremental addition of diamine (0.13 moles) after approximately 1/2 of the expected water of the reaction was removed. Polyesteramidation Step The reaction temperature was increased to 2050C and water was continually removed until the desired final acid number was attained. Acid numbers of 25 to 35 are preferred. The reaction was cooled to 1600C and 100 ppm of hydroquinone was added as an inhibitor. Comparative Examples C-i and C-2 DCPD modified unsaturated polyesters were prepared using the above method except that only the glycol reactant (no diamine) was used. Example C-i employed 1.56 moles propylene glycol. Example C-2 employed 1.56 moles DCPD dimethanol. In Table I the following abbreviations are used: PG Propylene Glycol PG/DPG Propylene Glycol/Dipropylene Glycol DCPD-DM DCPD-dimethanol Bis A/2PO bis(hydroxypropyl) bisphenol A Gamine A 4,4'-methylenebis(cyclohexylamine) Diamine B 2,2'-bis(4-aminocyclohexyl)propane Diamine C 1,6-diamino hexane Diamine D Diaminodiphenyl ether Diamine E bis(aminomethyl)dicyclopentadiene Diamine F bis(2-aminoethyl)ether Diamine G Diethylenetriamine Examples 1, 3, 5, 6 and 9 were prepared with bulk amine addition. Examples 2,4, 7, 8, 10-13 were prepared with incremental amine addition. TABLE I Example PG PG/DPG DCPD-DM Bis A/2PO 1 1.17 -- -- -2 1.17 -- -- -3 -- -- 1.248 -4 -- -- 1.248 -5 -- -- 1.248 -6 -- -- 1.248 -7 1.248 -- -- -8 1.248 -- -- -9 -- 0.624/0.624 -- -10 -- -- -- 1.248 11 -- -- 1.04 -12 1.404 -- -- -13 1.248 -- -- -- TABLE I (cont'd) Diamine Example A B C D E F G 1 0.39 -- -- -- -- -- -2 0.39 -- -- -- -- -- -3 -- -- 0.312 -- -- -- -4 -- -- 0.312 -- -- -- -5 -- 0.312 -- -- -- -- -6 -- -- 0.312 -- -- -- -7 -- -- -- -- 0.312 -- -8 -- -- -- -- 0.312 -- -9 -- -- -- 0.312 -- -- -10 -- -- -- -- 0.312 -- -11 -- -- -- -- 0.520 -- -12 -- -- -- -- -- -- 0.156 13 -- -- -- -- -- 0.312 -- The resulting polyesteramide alkyds were formulated to obtain a 43 percent styrene - 57 percent alkyd solution. These solutions were used to determine SPI gel characteristics, Brookfield viscosity (25"C), and various clear, unfilled castings were made for heat distortion temperature, tensile and flexural strength and percent elongation and corrosion resistance testing. The heat distortion bars were cured at room temperature using 0.1 percent cobalt naphthenate (6 percent), 1 percent methyl ethyl ketone peroxide, and 0.02 percent dimethylaniline. The room temperature cured bars were postcured for 2.0 hours at 93aC (2000F). Circular, clear, unfilled castings of 3.5 cm diameter and 0.5 cm thick were cured and postcured using the method described for the heat distortion bars and used in corrosion tests. Corrosion tests were performed in DI water, toluene, 5 percent sodium hydroxide, and 25 percent sulfuric acid for 7 days at 250C. Clear, unfilled castings for use in tensile and flexural strength evaluations were made using a cure system of 1 percent benzoyl peroxide and 0.01 percent dimethylaniline at room temperature followed by postcuring for 2 hours at 930C (2000F). The results are shown in the following Table II. Corrosion test results are shown in Table III. All changes are reported as percentages of original. In all of the tables in the application, the heat distortion temperatures were measured in degrees F and are reported in degrees C (from a standard conversion table). The values for tensile strength and flexural strength were determined in pounds per square inch (reported parenthetically as Pascals). Viscosity was determined in centipoises and converted to Pascalseconds. TABLE II SPI Gel - 84 C Gel Cure Max. Acid Viscosity HDT Time Time Exotherm Example Number (Pa.s) ( C) (min) (min) ( C) 1 33.7 .262 109.5 1.7 2.9 160 2 34.6 .143 111.1 3.3 5.0 167 3 33.7 .142 88.3 4.2 7.1 140 4 32.4 .089 87.2 2.5 4.7 172 5 28.1 .235 106.1 2.4 4.6 195 6 28.1 .127 99.8 0.8 2.2 99 7 32.5 .053 106.1 1.3 2.9 169 8 31.7 .090 106.1 1.4 3.1 178 9 29.4 .100 97.8 1.3 3.7 125 10 31.8 .086 66.7 3.8 8.5 103 TABLE II (cont'd) SPI Gel - 84 C Gel Cure Max. Acid Viscosity HDT Time Time Exotherm Example Number (Pa.s) ( C) (min) (min) ( C) 11 35.7 .938 71.7 3.0 8.6 111 12 39.6 .250 101.1 1.9 4.1 147 13 29.4 .070 90.0 1.9 3.7 171 C-1 33.2 .045 99 5.6 7.1 156 C-2 32.0 .091 86 5.3 9.6 165 TABLE II (cont'd) Tensile Flexural Ave. Strength Strength Barcol X 103 Elonga- X 103 Hard- psi tion psi Example ness (MPa) (%) (MPa) 1 44.0 4.095 0.96 8.705 (28.23) (60.02) 2 45.0 3.329 0.82 6.792 (22.95) (46.83) 3 46.0 6.614 1.42 10.985 (45.60) (75.74) 4 44.9 5.766 1.36 11.329 (39.75) (78.11) 5 48.4 3.799 0.87 9.532 (26.19) (65.72) 6 20.3 3.950 1.54 8.434 (27.23) (58.15) 7 45.0 5.337 1.20 10.749 (36.80) (74.11) TABLE III DI. Water Toluene 5% NaOH 25% Sulfuric Acid Change Change Change Change Change Change Change Change Example Barcol Weight Barcol Weight Barcol Weight Barcol Weight 1 +0.73 +0.23 +0.73 -0.04 0 -1.93 0 +0.15 2 +5.13 +2.21 +6.54 -0.37 +2.29 -1.81 +0.75 -1.32 3 +0.73 +0.09 -16.44 +0.57 +0.75 -1.23 +0.74 -1.75 4 +9.17 +0.09 -17.32 +0.50 +0.74 -2.37 +2.22 -1.26 5 +2.90 +0.54 -11.04 +0.42 +0.75 +0.11 +1.46 +0.09 6 +1.50 +0.09 -3.22 -5.42 +13.33 -3.92 +5.45 -1.04 7 0 +0.40 -6.16 0 0 -1.84 +4.69 -0.95 8 +1.01 +0.40 -1.40 +0.11 +1.50 -2.29 +2.27 -2.44 9 +5.5 +0.2 +2.42 -1.12 +1.52 -2.75 +3.20 -0.67 TABLE III (cont'd) DI Water Toluene 5% NaOH 25% Sulfuric Acid Change Change Change Change Change Change Change Change Example Barcol Weight Barcol Weight Barcol Weight Barcol Weight 10 -1.87 +0.40 -- --(1) 0 -1.61 -0.85 -2.44 11 +3.13 -0.05 -2.44 -1.85 +1.75 -0.10 0 0 12 +2.10 +0.14 -11.89 -0.06 -- -- -- -13 0 +0.55 +3.08 +0.03 0 0 +0.87 +0.30 C-1 -4.32 -0.23 -2.17 +0.02 -5.44 -1.59 -2.70 -1.41 C-2 +3.12 +0.03 -- -- +1.52 -1.07 +0.74 -0.31 (1) Sample fractured on 3rd day of test. Examples 14-20 Modified polyesteramides were prepared by the hydrolysis method of Examples 1-13, except that a DCPD concentrate containing 82.60 percent DCPD, 16.84 percent codimers, 0.52 percent lights and 0.04 percent trimers was used in place of the DCPD concentrate of those examples. The compositions of the diol and diamine are shown in Table IV. The resulting polyesteramide alkyds were formulated and tested using the methods of Examples 1-13. The results are shown in the following Table V. Corrosion resistance testing of the polyesteramides is shown in Table VI. All changes are in percent of original. Corrosion resistance testing of these polyesteramides was accelerated at 500C for a total of 148 hours, unless damage necessitated earlier removal. All of the polyesteramides were tested as clear, unfilled castings of 1.5 x 1.0 x 0.165 inch (38.1 x 25.4 x 4.19 mm)dimensions. A cure system of 1 percent benzoyl peroxide and 0.01 percent dimethyl- aniline was used at room temperature followed by postcuring for 2.0 hours at 930C (2000F). Twenty-four hours of sample recovery in open room temperature air was allowed prior to measurement of weight and Barcol hardness of the exposed test samples. Corrosion resistance testing of the commercially available general purpose polyester, Corezyn (Interplastics) was evaluated as a comparative standard. Comparative Example 3 The DCPD modified unsaturated polyester of Comparative Example 3 was prepared using the method of Comparative Example C-l. TABLE IV bis Aminomethyl- Ethylene (aminomethyl) Example PG piperazine diamine DCPD Piperazine 14 1.404 4.156 -- -- -15 1.404 -- 0.156 -- -16 1.404 -- 0.156 -- -17 1.248 -- 0.312 -- -18 1.248 -- 0.312 -- -19 1.248 -- -- 0.312 -20 1.404 -- -- -- 0.156 For Comparison C-3 1.56 -- -- -- - All examples, except18, were prepared with bulk diamine addition. Example 18 was prepared with incremental diamine addition. TABLE V SPI Gel - 84 C Gel Cure Max. Acid Viscosity HDT time Time Exotherm Example Number (Pa.s) ( C) (min) (min) ( C) 14 33.2 1.780 110.0 0.7 2.1 202 15 31.4 .110 111.1 1.9 3.5 230 16 22.4 2.600 117.2 1.3 2.4 203 17 34.4 .286 111.1 1.5 3.2 175 18 35.1 .762 106.1 1.4 3.5 198 19 33.7 .407 115.6 1.0 2.1 213 20 40.3 .284 111.7 2.3 3.6 220 C-3 34.7 .061 110.6 3.4 4.8 195 TABLE V (cont'd) Tensile Flexural Ave. Strength Strength Barcol X 10 Elonga- X 10 Hard- psi tion n psi Example ness (MPa) (%) (MPa) 14 48.2 4.054 0.95 11.925 (27.95) (82.22) 15 50.1 4.069 0.88 13.118 (28.05) (90.44) 16 50.6 3.858 0.86 9.855 (26.60) (67.95) 17 47.5 3.333 0.91 11.584 (22.98) ( 79.87) 18 49.0 3.742 0.85 10.945 (25.80) (75.46) 19 50.4 3.446 0.76 11.356 (23.76) (78.30) 20 46.4 2.272 0.54 11.341 (15.66) (78.19) C-3 51.5 3.440 0.79 9.951 (23.72) (68.61) TABLE VI DI. Water 5% NaOH Change Change Change Change Example Barcol Weight Barcol Weight 14 +17.11 +0.48 +2.41 +0.05 15 +6.62 +0.48 +3.21 +0.35 16 +6.02 +0.49 +4.73 +0.45 17 +4.19 +0.56 -1.76 +0.24 18 -2.33 +0.60 -10.15 +0.20 19 +3.89 +0.50 -3.68 +0.39 20 -2.03 +0.53 -9.13 +0.17 C-3 +7.50 +0.43 -1.93 +0.09 Corezyn +0.83 +0.64 -7.44 -0.26 TABLE VI (cont'd) 25% Sulfuric Acid Toluene Change Change Change Change Time to Initial Example Barcol Weight Barcol Weight Fracture (hr) 14 +11.89 +0.05 -84.1 (1) +8.23 (1) 45.3 15 +10.26 +0.35 not measured 52.8 16 +8.82 +0.36 -51.0 +4.99 148 17 +6.83 +0.37 not measured 28.8 18 +0.21 +0.40 not measured 76.8 19 +2.25 +0.36 not measured 69.3 20 +2.03 +0.33 -57.2 +5.00 None C-3 +5.57 +0.31 Not measured 21.3 Corezyn -0.21 +0.51 -100.0 (1) +7.54 (1) 28.8 (1) Measured at end of 148-hour test even though initial fracture occurred earlier. Examples 21-23 Modified polyesteramides were made by the hydrolysis method of the preceding examples using the same amount of maleic anhydride, DCPD and water. Propylene glycol and 4,4' -methylenebis (cyclohexylamine) were used in varying amounts as follows: (moles) Propylene 4,4'-methylenebis- Acid Example Glycol (cyclohexylamine) No. 21 1.17 0.390 32.7 22 1.092 0.468 34.8 23 0.78 0.78 40.1 Examples 22 and 23 were insoluble in 43 percent styrene. Example 21 had a viscosity of 0.262 Pascal-seconds, an HDT of 2290F and an SPI gel at 840C of 1.7 minutes to gel, 2.9 minutes to cure and a maximum exotherm of 1600C. Example 24 A modified polyesteramide was made by the hydrolysis method of the preceding examples using the same amount of maleic anhydride and water. Polycyclopentadiene (1.2 moles) containing 52.2 percent DCPD and tricyclopentadiene, 40.4 percent tetra- and pentacyclopentadiene and 7.4 percent hexacyclopentadiene and highers was used in place of the DCPD concentrate of the preceding examples. The diol was PG (1.248 moles) and the bis(aminomethyl) DCPD (0.312 mole) diamine was incrementally added. The resulting polyesteramide alkyd was formulated and tested for mechanical properties and corrosion resistance using the method of Examples 1-13. The following results were obtained. Acid number 34.5 Viscosity .105 HDT (OC) 103.3 SPI Gel-840C gel time (min.) 1.5 cure time (min.) 3.7 max. exotherm (OC) 172 Ave. Barcol Hardness 44.4 Tensile strength x103 psi 3.032 (MPa) (20.90) Elongation (%) 0.58 Flexural Strength x103 psi 6.549 (MPa) (45.15) Corrosion Resistance DI. Water Change Barcol 0 Change Weight +0.09 5% NaOH Change Barcol +10.74 Change Weight -2.66 25% Sulfuric Acid Change Barcol +4.76 Change Weight -1.62 Toluene Change Barcol 0 Change Weight -0.23 Example 25 A modified polyesteramide was made by the hydrolysis method of the preceding examples, except that the reaction temperature during polyesteramidation never exceeded 1650C. The same amount of maleic anhydride and water were used and norbornene (1.2 moles) was used in place of the DCPD concentrate of the preceding examples. The diol was PG (1.248 moles) and the bis(aminomethyl) DCPD (0.312 mole) diamine was incrementally added. The resulting polyesteramide alkyd was formulated and tested for mechanical properties and corrosion resistance using the method of Examples 1-13. The following results were obtained: Acid number 55.1 Viscosity .156 HDT (OC) 116.1 SPI Gel-84 C gel time (min.) 1.7 cure time (min.) 2.5 max. exotherm (OC) 160 Ave. Barcol Hardness 47.6 Tensile strength x103 psi 4.679 (MPa) (32.26) Elongation (%) 1.10 Flexural Strength x103 psi 10.620 (MPa) (73.22) Corrosion Resistance DI. Water Change Barcol +0.83 Change Weight +0.83 5% NaOH Change Barcol +1.55 Change Weight -2.69 25% Sulfuric Acid Change Barcol 0 Change Weight -1.43 Toluene Change Barcol -1.63 Change Weight -0.76 Example 26 A modified polyesteramide was made replacing the hydrolysis step of Examples 1-13 with a step consisting of the esterification of dicyclopentadiene monoalcohol with fumaric acid. The reaction was performed as follows: Fumaric acid (2.0 moles), DCPD monoalcohol (1.2 molesj and SnO catalyst (0.05 percent) were charged to a reactor and heated to 1850C under a nitrogen atmosphere. Water was continuously removed via a steam condenser - Dean Stark trap - cold water condenser assembly, and increased nitrogen sparging. A total reaction time of 2.5 hours is used at the 1850C temperature. The remaining diol/diamine addition and polyesteramidation steps were completed using the methods of Examples 1-13. The diol was PG (1.248 moles) and the bis(aminomethyl)DCPD (0.312 moles) diamine was incrementally added. The resulting polyesteramide alkyd was formulated and tested for mechanical properties and corrosion resistance using the method of Examples 1-13. The following results were obtained: Acid number 35.3 Viscosity .133 EDT (OC) 110.6 SPI Gel-840C gel time (min.) 2.2 cure time (min.) 3.6 max. exotherm (OC) 200 Ave. Barcol Hardness 45.6 Tensile strength x103 psi 4.162 (MPa) (28.69) Elongation (%) 1.02 Flexural Strength x103 psi 10.253 (MPa) (70.69) Corrosion Resistance DI. Water Change Barcol 0 Change Weight +0.24 5% NaOH Change Barcol -2.19 Change Weight -1.73 25% Sulfuric Acid Change Barcol 0 Change Weight -1.13 Toluene Change Barcol +1.36 Change Weight -0.05 Example 27 A modified polyesteramide was prepared using the half ester method. Specifically, the reaction was performed as follows: Maleic anhydride (1.0 mole), PG (0.825 mole) and 4,4'-methylenebis (cyclohexylamine) (0.275 mole) were charged to a reactor and heated to 1450C. Water was continually removed via a steam condenser - Dean Stark trap - cold water condenser assembly, and increased nitrogen sparging. After 75 minutes of reaction time, the steam condenser was shut off and a total of 0.25 mole of DCPD was added to the reactor as 0.0625 mole increments every 15 minutes for a total of 4 additions over a 45 minute period. The reactor was then held at 1450C for 45 minutes after which time the steam condenser was restarted and the reaction temperature was increased to 2000C. Water was continually removed until the desired final acid number was attained. The reaction was cooled to 1600C and 100 ppm of hydroquinone was added as an inhibitor. The resulting polyesteramide alkyd was formulated and tested for mechanical properties and corrosion resistance using the method of Examples 1-13. The following results were obtained: Acid number 31.2 Viscosity .477 HDT ( C) 104.4 SPI Gel-840C gel time (min.) 4.1 cure time (min.) 6.2 max. exotherm ( C) 112 Ave. Barcol Hardness 41.3 Tensile strength x103 psi 1.701 (MPa) (11.73) Elongation (%) 0.32 Flexural Strength x103 psi 7.141 (MPa) (49.23) Corrosion Resistance DI. Water Change Barcol -10.26 Change Weight +2.75 5% NaOH Change Barcol -8.90 Change Weight -0.05 25% Sulfuric Acid Change Barcol +0.97 Change Weight +0.07 Toluene Change Barcol C.M.(1) Change Weight C.M.(1) (1) C.M. - Sample fractured on 7th day of test. Example 28 (a) Naleic anhydride (392.24 g) was added to a reactor and heated to 700C under a nitrogen atmosphere. Water (37.84 g) was added, followed by dicyclopentadiene concentrate (79.74 g) 2 minutes later. The dicyclopentadiene concentrate contained 0.52 percent lights, 16.84 percent codimers, 82.60 percent DCPD and 0.04 percent trimers. A maximum exotherm of 1150C resulted 11 minutes later. Additional dicyclopentadiene concentrate (79.74 g) and water (12.61 g) were added to the reactor 20 minutes after the initial water addition. A third aliquot of dicyclopentadiene concentrate (79.74 g) was added 15 minutes later. Fifteen minutes later, a final aliquot of dicylcopentadiene concentrate (79.74 g) was added and the temperature controller was set at 1100C. This temperature was achieved 4 minutes later. (b) After 30 minutes, propylene glycol (213.69 g) and piperazine (26.88 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased (4 LPM), and the temperature controller was set at 1600C. The 1600C temperature was reached 18 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 40 minutes later. After 3.42 hours, a total of 67.5 milliliters of water layer and 9.5 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1690C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 30.5. Example 29 A hydrolysis step was completed in identical manner to Example 28(a). After 30 minutes, propylene glycol (189.95 g), pentaerythritol (21.24 g) and piperazine (26.88 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 10 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 23 minutes later. After 3.58 hours, a total of 68.25 milliliters of water layer and 8.5 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 32.7. Example 30 A hydrolysis step was completed in identical manner to Example 28(a) except that 98 percent DCPD was used in increments of 79.33 g. After 30 minutes, propylene glycol (213.69 g) and piperazine (26.88 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 12 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 54 minutes later. After 2.3 hours, a total of 68.5 milliliters of water layer and 5.0 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was. added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 31.2. Example 31 A hydrolysis step was completed in identical manner to Example 28(a). After 30 minutes, propylene glycol (213.69 g) and piperazine (26.88 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 15 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 45 minutes later. After 4.17 hours, a total of 68.5 milliliters of water layer and 8.5 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 27.2. Example 32 A modified polyesteramide was prepared using the prehydrolysis method. Specifically, the reaction is performed as follows: Maleic anhydride (392.24 g) was added to a reactor and heated to 1250C under a nitrogen atmosphere. Water (76.59 g) was added and induced a maximum exotherm of 1440C one minute later. Five minutes after the initial water addition, the 1250C temperature was re-established and dicyclopentadiene concentrate (106.32 g) was added. The dicyclopentadiene concentrate contained 0.52 percent lights, 16.84 percent codimers, 82.60 percent DCPD and 0.04 percent trimers. A maximum exotherm of 130at resulted one minute later and was controlled by air-cooling of the reactor. The temperature controller was set at 1100C and 15 minutes later a second aliquot of dicyclopentadiene concentrate (106.32 g) was added to the reactor. Fifteen minutes later, a final aliquot of dicyclopentadiene concentrate (106.32 g) was added. The reaction temperature was held at 1100C for 30 minutes then propylene glycol (213.69 g) and piperazine (26.88 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 20 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 20 minutes later. After 5.0 hours, a total of 103 milliliters of water layer and 17.5 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 32.5. Example 33 Maleic anhydride (137.28 g) and phthalic anhydride (88.87 g) were added to a reactor and heated to 700C under a nitrogen atmosphere. Water (18.92 g) was added, followed by dicyclopentadiene concentrate (39.87 g) 2 minutes later. The dicylcopentadiene concentrate contained 0.52 percent lights, 16.84 percent codimers, 82.60 percent DCPD and 0.04 percent trimers. A maximum exotherm of 1060C resulted 14 minutes later. Additional dicyclopentadiene concentrate (39.87 g) and water (6.31 g) were added to the reactor 20 minutes after the initial water addition. A third aliquot of dicyclopentadiene concentrate (39.87 g) was added 15 minutes later. Fifteen minutes later, a final aliquot of dicyclopentadiene concentrate (39.87 g) was added and the temperature controller was set at 1100C. This temperature was achieved 8 minutes later. After 30 minutes, propylene glycol (106.84 g) and piperazine (13.44 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 22 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 19 minutes later. After 4.0 hours, a total of 31 milliliters of water layer and 7.0 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 29.0. Example 34 A comparative DCPD modified unsaturated polyester standard was prepared as follows: (a) Maleic anhydride (196.12 g) was added to a reactor and heated to a clear solution at 700C under a nitrogen atmosphere. Water (18.92 g) was added, followed by 98 percent dicyclopentadiene (39.67 g) 2 minutes later. A maximum exotherm of 1050C resulted 17 minutes later. Additional water (6.31 g) and DCPD (39.67 g) were added to the reactor 20 minutes after the initial water addition. A third aliquot of DCPD (39.67 g) was added 15 minutes later. Fifteen minutes later, a final aliquot of DCPD (39.67 g) was added and the temperature controller was set at 1100C. This temperature was reached 7 minutes later. (b) After 30 minutes, propylene glycol (59.36 g) and diethylene glycol (82.77 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 10 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 22 minutes later. After 1.8 hours, a total of 40 milliliters of water layer and 9.0 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, pale yellow solid with a final acid number of 29.4. Example 35 A comparative DCPD modified unsaturated polyester was prepared as follows: A hydrolysis step was completed in identical manner to Example 34(a) except that DCPD concentrate was used in increments of 39.87 g. After 30 minutes, propylene glycol (118.72 g) was added to the reactor and the steam condenser was started, nitrogen sparging was increased, and the temperature controller was set at 1600C. The 1600C temperature was reached 16 minutes later. After 2 hours at 1600C, the temperature controller was set at 2050C and this temperature was achieved 20 minutes later. After 2.3 hours, a total of 41.5 milliliters of water layer and 11.0 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1640C and 100 ppm of hydroquinone was added. The polyester alkyd was recovered as a clear, light yellow solid with a final acid number of 34.7. Example 36 The physical and mechanical properties of the polyesteramides of Examples 28-33 and the comparative polyester standard of Example 34 were determined using formulations containing 57.0 percent alkyd and 43.0 percent styrene. In addition, the physical and mechanical properties of the polyesteramides of Examples 28-31 were determined using formulations containing 67.0 percent alkyd and 33.0 percent styrene. The heat distortion bars were cured at room temperature using 0.1 percent cobalt naphthenate (6 percent), 1.0 percent methyl ethyl ketone peroxide, and 0.02 percent dimethylaniline. The room temperature cured bars were post cured for 2.0 hours at 930C (2000F). Clear, unfilled castings for use in tensile and flexural strength evaluations were made using a cure system of 1.0 percent benzoyl peroxide and 0.01 dimethylaniline at room temperature, followed by post curing for 2.0 hours at 930C (2000F). The data is summarized in Table VII. TABLE VII SPI Gel - 48 C Brookfield Cure Maximum Styrene Viscosity time Time Exotherm Examople (%) (Pa.s) (min) (min) ( C) 28 33.0 1.008 3.5 4.4 160 43.0 .159 3.2 4.0 172 29 33.0 6.800 -- -- -43.0 .208 1.9 3.3 231 30 33.0 .654 -- -- -43.0 .097 2.2 3.7 229 31 33.0 4.430 -- -- -43.0 .512 2.1 3.3 232 32 43.0 .316 2.1 3.3 235 33 43.0 .151 2.7 4.8 216 For Comparison 35 43.0 .061 3.4 4.8 195 TABLE VII (cont'd) Tensile Flexural Ave. Strength Strength Barcol X 10 Elonga- X 10 HDT Hard- psi tion psi Example (C) ness (MPa) (%) (MPa) 28 110.3 50.0 3.746 0.75 8.261 (25.83) (56.96) 110 46.9 3.184 0.77 11.618 (21.95) (80.10) 29 -- 49.7 2.446 0.51 7.421 (16.86) (51.16) 109.4 47.2 3.047 0.66 9.288 (21.01) (64.04) 30 -- 48.3 2.245 0.52 11.113 (15.48) (76.62) 113.5 45.4 4.103 0.99 9.744 TABLE VII (cont'd) Tensile Flexural Ave. Strength Strength Barcol X 10 Elonga- X 10 HDT Hard- psi tion psi Example (C) ness (MPa) (%) (MPa) 31 -- 47.5 3.019 0.61 13.065 (20.81) (90.08) 108 43.9 2.812 0.70 12.490 (19.39) (86.11) 32 116 45.8 3.365 0.78 11.944 (23.20) (82.35) 33 115 47.9 5.357 1.24 12.881 (36.93) (88.81) For Comparison 35 110.6 47.7 3.113 0.71 9.951 (21.46) (68.61) Example 37 The corrosion resistance to 95 percent ethanol (2B) containing 2 percent toluene at 520C was determined for the polyesteramides of Examples 28-32, the comparative polyester standards of Examples 34 and 35, and a series of commercially available polyester standards including Corezyn, a general purpose polyester; Owens Corning Fiberglass E-720, a premium grade isophthalic polyester; Vestopal 400, a corrosion resistant polyester made from dicyclopentadiene dimethanol and fumaric acid made by Chemische Werke Huls AG; DERAKANEe 411-45 vinyl ester resin; and DERAKANEB 470-36 vinyl ester resin. The total test time was 648 hours. The percent styrene monomer utilized in each resin formulation is indicated in Table VIII. These formulations were used to prepare clear, unfilled castings from which the 1.0 inch x 1.5 inch x 0.165 inch (25.4 x 38.1 x 4.19 mm) corrosion test samples were obtained. A room temperature cure system of 1.0 percent benzoyl peroxide and 0.01 percent dimethylaniline was used, followed by post curing of the room temperature cured castings for 2.0 hours at 930C (2000F). Example 38 The tests of Example 37 were repeated in 5 percent aqueous sodium hydroxide. All tests were run at 520C for a total test time of 766 hours. The results are listed in Table vIlI. Example 39 The tests of Example 37 were repeated in toluene. All tests were run at 52OC for a total test time of 289 hours. The results are listed in Table IX. TABLE VIII 5% NaOH Ethanol Change in Change in Weight (%) Weight (%) Styrene Initial Change 30 min. Change 30 min. Example % Barcol Barcol (%) Recovery Barcol % Recovery 28 33.0 49.0 -17.4 +0.14 -80.7 +7.38 43.0 46.2 -9.3 +0.46 -71.9 +6.21 29 33.0 49.2 -15.5 +0.69 -56.5 +5.56 430 46.9 -13.2 +0.45 -64.9 +5.62 30 33.0 47.9 -14.1 -0.12 .97.5 +8.08 43.0 45.5 -20.7 +0.33 -79.2 +5.84 31 33.0 47.5 -5.7 +0.75 -67.7 +5.59 43.0 42.4 -10.1 +0.01 -73.8 +5.83 32 43.0 44.7 -14.3 +0.31 -71.1 +5.89 TABLE VIII (cont'd) 5% NaOH Ethanol Change in Change in Weight (%) Weight (%) Styrene Initial Change 30 min. Change 30 min. Example % Barcol Barcol (%) Recovery Barcol % Recovery For Comparison 34 43.0 42.7 -14.5 +0.41 -100.0 +10.16 35 43.0 46.5 -11.6 +0.24 -75.2 +5.52 not (1) not (1) Corezyn 43.0 47.2 -27.5 -1.04 measured measured OCF E-720 43.0 47.9 -20.0 -0.41(2) -65.4 +3.14 Vestopal 400 35.0 46.1 -0.37 +0.42 -85.7 +4.27 DERAKANE@ 411-45 45.0 42.1 -13.8 +0.52 -100.0 +9.39 DERAKANE@ 470-36 36.0 46.7 -10.9 +1.11 -72.4 +6.14 (1) Sample fractured after 216 hours of exposure. (2) Dry sample is opaque. TABLE IX Toluene Change in Weight % Time to Styrene Initial Change 30 min. 24 hr. Initial Example % Barcol Barcol (%) Recovery Recovery Fracture (hr) 28 33.0 49.0 -- -- -- 123 43.0 46.2 -- +12.17 +9.99 216 29 33.0 49.2 -35.8 +4.96 +4.29 None 43.0 46.9 -68.6 +10.02 +8.39 None 30 33.0 47.9 -- -- -- 69.5 43.0 45.5 -- +13.72 +10.67 258.5 31 33.0 47.5 -67.1 +9.18 +7.94 None 43.0 -- +11.89 +9.71 216 32 43.0 44.7 -- +11.59 +9.64 258.5 TABLE IX (cont'd) Toluene Change in Weight % Time to Styrene Initial Change 30 min. 24 hr. Initial Example % Barcol Barcol (%) Recovery Recovery Fracture (hr) For Comparison 34 43.0 42.7 -- -- -- 18.5 35 43.0 46.5 -- -- -- 24 Corezyn 43.0 47.2 -- -- -- 42.5 OCF e-270 43.0 47.9 -66.7 +4.58 +3.74 258.5 Vestopal 400 35.0 46.1 -- -- -- 18.5 DERAKANE@ 411-45 45.0 42.1 -- -- -- 26 surface crazing 69.5 fractured DERAKANE@ 470-36 36.0 46.7 -10.8 +0.89 +0.69 None Examples 40-49 Modified polyesteramides were prepared from various polyols and piperazine. In each instance, the hydrolysis method with bulk diamine addition was used. The composition of the reactants is shown in Table X. The DCPD concentrate used in Examples 40 and 42 contained 0.52 percent lights, 16.84 percent codimers, 82.60 percent DCPD and 0.04 percent trimers. The DCPD concentrate used in Examples 41, 43-49, and comparative polyester standard C-4 contained 0.31 percent lights, 13.64 percent codimers and 86.05 percent DCPD. In Example 49, the pentaerythritol (0.0585 mole) was added to the reactor after 3.5 hours of the polyesteramidation step had been completed. Whenever 2,5-di-t-butylhydroquinone was used as the inhibitor, it was added to the reactor just prior to the polyesteramidation step. The resulting polyesteramide alkyds, with the exception of that of Example 45, were formulated to obtain 43 percent styrene-57 percent alkyd solutions. The polyesteramide alkyd of Example 45 was formulated to obtain a 35 percent styrene-65 percent alkyd solution. These solutions were used to determine SPI gel characteristics, room temperature (250C) gel characteristics and Brookfield viscosity (250C). A cure system of 1.0 percent methyl ethyl ketone peroxide and 0.3 percent cobalt naphthenate (6 percent) was used for the room temperature gel test. Laminates of the polyesteramides, the modified polyester standard and a series of commer cm ally available polyester standards including Corezyn, a general purpose polyester; DERAKANEe 411-45 vinyl ester resin; DERAKANEe 470-36 vinyl ester resin and Dion Corres 6631T, a corrosion resistance polyester, were prepared for tensile and flexural strength testing using the following standard hand-layup procedure: A sheet of 0.005 inch (0.127 mm) Mylar film is attached to a smooth, flat surface with masking tape. An area of sufficient size is covered with a thin coating of the laminating resin and the surface C-veil (K514-236 treatment) is laid down and smoothed out. Additional resin applied and the first layer of 1.5 ounce chopped fiberglass mat (M113-K247 treatment) is applied. This is carefully rolled down with a serrated aluminum roller to exclude all trapped air. Resin is added followed by a second layer of 1.5 ounce chopped fiberglass mat. Rolling again removes any entrapped air. After adding additional resin, the final surface C-veil is applied and smoothed out. Straight steel rails of 1/8 inch square in cross -section are placed along all four sides of the laminate. A cover sheet of Mylar is rolled onto a 2-inch diameter tube long enough to bridge the rails. Additional resin is added to the laminate and the Mylar is rolled out over it. The Mylar is then stretched tightly and taped down. Any entrapped air or excess resin is squeezed out of the laminate using a wooden tongue depressor. The laminate is left until the polymerization exotherm has subsided and cooling to ambient temperature has occurred. The laminate is removed and postcured at 930C (2000F) for 2.0 hours. A cure system of 1.0 percent methyl ethyl ketone peroxide and 0.3 percent cobalt naphthenate (6 percent) was used for all of the laminates. All of the DCPD modified unsaturated polyesteramide resins, the DCPD modified unsaturated polyester standard and 43 percent styrenated Corezyn were all retarded with 100 ppm of p-benzoquinone prior to lamination. This was necessary to prevent gelation during the laminate preparation. All of the other resins were used as received. Comparative Example 4 The DCPD modified unsaturated polyester of Comparative Example 4 was prepared using the hydrolysis method with the reaction stoichiometry specified in Table X. The physical and mechanical properties of the products of Examples 40-49 and the Comparative Examples were determined as in the previous examples with the results reported in Table XI. TABLE X 2,5-di-t -butyl hydro Pentaery- HQ quinone Example MA IPA DCPD H2O PG PG/DPG NPG thritol (ppm) (ppm) 40 6.0 -- 3.6 4.2 4.212 -- -- -- 100 -41 6.0 -- 3.6 4.2 4.212 -- -- -- 100 -42 6.0 -- 3.6 4.2 4.212 -- -- -- -- 200 43 6.0 -- 3.6 4.2 3.798 -- -- 0.17 -- 200 44 5.6 0.40 3.6 4.2 4.212 -- -- -- 100 -45 7.0 -- 4.2 4.9 4.914 -- -- -- 100 -46 7.0 -- 4.2 4.9 4.797 -- -- 0.0585 100 -- TABLE X (cont'd) 2,5-di-t -butyl hydro Pentaery- HQ quinone Example MA IPA DCPD H2O PG PG/DPG NPG thritol (ppm) (ppm) 47 6.0 -- 3.6 4.2 -- 2.106/ -- -- 100 -2.106 48 7.0 -- 4.2 4.9 -- -- 4.914 -- 100 -49 7.0 -- 4.2 4.9 4.797 -- -- 0.0585 100 - For Comparison C-4 7.0 -- 4.2 4.9 5.46 -- -- -- 100 - MA = maleic anhydride DPG = dipropylene glycol IPA = isophthalic acid NPG = neopentylglycol PG = propylene glycol HQ = hydroquinone <RTI ID=57.1> TABLE XI Reaction Hydrocarbon SPI Gel -84 C time Reactives Brookfield Gel Cure Max. Acid at 205 C Efficiency Viscosity Time Time Exotherm Example Number (hr) (%) (Pa.s) (min) (min) (min) 40 26.3 4.87 98.5 -- 2.15 3.6 238 41 25.7 5.50 98.6 -- -- -- -42 25.6 6.07 98.6 .427 2.05 3.25 223 43 30.2 7.08 93.2 1.805 -- -- -44 29.9 6.67 97.9 .286 -- -- -45 24.8 5.33 98.7 1.057 -- -- -46 26.7 6.50 95.4 .236 2.2 3.5 237 47 26.7 5.75 95.9 .097 3.35 4.6 208 48 20.3 6.25 98.4 .160 3.4 4.9 222 49 26.1 6.50 98.9 .545 2.15 3.35 238 TABLE XI (cont'd) Tensile Flexural Strength Strength Average psi psi Barcol X 10 Elongation X 10 Example Hardness (MPa) (%) (MPa) 45 51.6 6.691 1.16 8.317 (46.13) (57.34) 46 51.6 6.521 1.51 10.404 (44.96) /71.73) 47 50.8 7.333 0.99 12.349 (50.56) (85.14) 48 52.4 6.997 1.10 9.441 (48.24) (65.09) 49 49.6 7.094 1.47 10.723 (48.91) (73.93) TABLE XI (cont'd) Reaction Hydrocarbon SPI Gel -84 C time Reactives Brookfield Gel Cure max. Acid at 205 C Efficiency Viscosity Time Time Exotherm Example Number (hr) (%) (Pa.s) (min) (min) (min) For Comparison C-4 24.8 5.50 97.5 0.55 -- -- - Corezyn -- -- -- .125 -- -- - DERAKANE@ 411-45 -- -- -- .470 -- -- - DERAKANE@ 470-36 -- -- -- .283 -- -- - Dion Corres 6631T -- -- -- .268 4.75 6.75 225 TABLE XI (cont'd) Tensile Flexural Strength Strength Average psi psi Barcol X 10 Elongation X 10 Example Hardness (MPa) (%) (MPa) For Comparison C-4 52.7 7.198 1.38 11.121 (49.62) (76.67) Corezyn 49.0 10.921 1.20 9.865 (75.30) (68.02) DERAKANE@ 411-45 44.7 13.221 1.75 16.134 (91.15) (111.24) DERAKANE@ 470-36 51.6 8.932 1.02 10.756 (61.58) (74.16) Dion Corres 6631T 49.5 8.833 1.08 12.606 (60.90) (86.91) The room temperature (250C) gel test gave the following results: Gel Time Cure Time Max. Exotherm Example (min) (min) 0C 40 8.0 25 108 42 3.0 15 102 49 6.0 28 105 For Comparison Dion Corres 6631T 15.0 33.0 59.5 Example 50 A modified polyesteramide was prepared using the prehydrolysis method described in Example 32 and the following reaction stoichiometry: DCPD concentrate 3.6 moles MA 6.0 moles H2O 6.375 moles PG 4.212 moles piperazine 0.468 mole The DCPD concentrate contained 0.52 percent lights, 16.84 percent codimers, 82.60 percent DCPD and 0,04*percent trimers. Hydroquinone (100 ppm) was used as the inhibitor. The resulting polyesteramide alkyd was formulated, laminated and tested for mechanical properties using the methods of Examples 40-49. The following results were obtained: Acid number 26.1 Reaction time at 2050C (hr) 5.08 Hydrocarbon Reactives Efficiency (%) 97.0 Brookfield Viscosity .186 SPI Gel-840C gel time (min.) 2.38 cure time (min.) 3.6 max. exotherm ( C) 230 Room Temp. Gel-250C gel time (min.) 11.0 cure time (min.) 23.0 max. exotherm (OC) 97 Ave. Barcol Hardness 51.6 Tensile Strength x103 psi 7.574 (MPa) (52.22) Elongation (%) 1.22 Flexural Strength x103 psi 10.458 (MPa) (72.10) Example 51 A modified polyesteramide was prepared using the hydrolysis method with bulk diamine addition, and the same reaction stoichiometry as was used in Example 45. A laminate was prepared using the method of Examples 40-49 except that no postcure was employed and no p-benzoquinone was used. The development of Barcol hardness at 250C was determined using a 934-1 Barcol Impressor. The following results were obtained: Time (hrs) Average Barcol Hardness 0 gelation 4 1.1 5 5.1 6 7,6 24 28.7 48 37,7 72 41.7 96 43,9 SPI Gel-840C gel time (min.) 2.7 cure time (min.) 3.8 max. exotherm (OC) 227 Room Temp. Gel-25 C gel time (min.) 7 cure time (min.) 25 max. exotherm (OC) 96 Example 52 A series of clear, unfilled castings measuring 2 x 2 x 0.165 inches (50.8 x 50.8 x 4.19 mm)were cured using 1.0 percent benzoyl peroxide and 0.01 percent diemethylaniline followed by 2.0 hours of postcuring at 930C (2000F). The dielectric constant and dissipation factor for each resin was determined using a General Radio Co., Type 1610 Capacitance Measuring Assembly set at a frequency of 1000 cycles per second. All measurements were made at room temperature (250C). The following results were obtained: : Dissipation 3 Dielectric Resin Factor (x 10 ) Constant DERAKANEQ 470-36 vinyl ester resin 5.57 3.57 DERAKANEe 411-45 vinyl ester resin 2.82 3.30 Corezyn (43% styrene) 5.78 3.30 Owens Corning Fiberglass E-720 (43% styrene) 4.00 3.03 DCPD modified polyesteramide of Example 31 3.45 3.03 DCPD modified polyesteramide of Example 32 3.55 2.96 DCPD modified polyester standard of Example 35 4.55 2.94 Example 53 A series of laminates were prepared using the methods of Examples 40-49. The DCPD modified unsaturated polyesteramide was prepared using the hydrolysis method with bulk diamine addition and the same reaction stoichiometry as was used in Example 45. A final acid number of 25.8 was attained after 5.5 hours of polyester amidation at 2050C. The hydrocarbon reactives efficiency was 97.5 percent. The Brookfield viscosity of the 57 percent alkyd-43 percent styrene solution was .163 Pascal second. A 2.35 minute gel time, 3.45 minute cure time and 2250C maximum exotherm were obtained in the SPI gel test. The commercially available polyester standards used to prepare laminates included DERAKANEe 411-45 vinyl ester resin, DERAKANEs 470-36 vinyl ester resin and Dion Corres 6631T, a corrosion resistant polyester resin. Samples for tensile and flexural strength testing and measurement of heat distortion temperature, were prepared from each respective laminate. The samples were placed into a forced air oven maintained at 2100C for the time intervals indicated in Table XII. The results are reported in Table XII. TABLE XII Tensile Flexural Flexural Strength Strength Modulus Hours Average Heat psi psi psi at Barcol Distortion X103 Elongation X 10 X 105 Resin 210 C Hardness Temp. ( C) (MPa) (%) (MPa) (MPa) DERAKANE@ 411-45 0 44.2 113.6 14.011 1.83 15.878 8.22 (96.60) (109.47) (5667.44) 96* 46.7 121.9 8.530 1.12 10.723 7.82 58.81) (73.93) (5391.65) 240* 50.0 123.0 7.621 0.92 10.065 7.56 (52.54) (69.39) (5212.39) 408* 49.9 107.2 7.243 1.03 9.576 6.70 (49.94) (66.02) (4619.45) 576* 49.2 107.2 6.770 0.99 9.882 7.57 (46.68) (68.13) (5219.29) DERAKANE@ 470-36 0 52.6 120.3 8.569 1.09 11.126 8.47 (59.70) (76.71) (5839.81) 96 52.2 157.2 8.000 1.00 9.941 8.02 (55.16) (68.54) (5529.55) 240 54.2 179.5 7.446 1.04 8.919 8.06 (51.34) (61.49) (5557.13) 408 50.3 179.5 7.273 1.28 8.696 7.68 (50.14) (59.96) (5295.13) 576 52.2 157.2 6.593 1.15 8.867 7.28 (45.46) (61.13) (5019.34) * Partial delamination of each sample has occured. TABLE XII (cont'd) Tensile Flexural Flexural Strength Strength Modulus Hours Average Heat psi psi psi at Barcol Distortion X103 Elongation X 10 X 105 Resin 210 C Hardness Temp. ( C) (MPa) (%) (MPa) (MPa) Dion corres 6631T 0 48.3 16.2 8.969 1.11 12.546 9.11 (61.84) (86.50) (6281.07) 96* 49.0 125.3 7.315 0.94 10.646 7.90 (50.43) (73.40) (5446.81) 240* 51.1 119.7 8.003 0.97 10.097 7.26 (55.18) (69.61) (5005.55) 408* 51.5 96.7 8.065 1.18 10.540 6.56 (55.60) (72.67) (4522.92) 576* 50.5 93.3 6.810 0.90 10.272 6.12 (46.95) (70.82) (4219.56) DCPD Modified Unsaturated Polyesteramide 0 50.7 125.3 7.623 1.40 12.720 7.75 (52.56) (87.70) (5343.30) 96 51.4 183.6 6.708 1.41 12.275 7.63 (46.25) (84.63) (5260.66) 240 51.5 186.4 7.358 1.70 12.552 6.92 (50.73) (86.54) (4771.13) 408 49.7 183.3 6.845 1.95 12.318 5.47 (47.19) (84.93) (3771.40) 576 50.1 > 187.8 6.717 1.75 11.989 5.30 (46.31) (82.66) (3654.19) * partial delamination of each sample has occurred. Example 54 Shrinkage upon curing of a clear, unfilled casting of approximately 25 cm in length was measured. A room temperature cure of 1.0 percent methyl ethyl ketone peroxide and 0.1 percent cobalt naphthenate (6 percent) was used to cure the 43.0 percent styrenated resin solutions as designated by the appropriate example number. The length of each cured casting was measured after the polymerization exotherm had subsided and ambient temperature (250C) was reached, and was used to calculate the following percent shrinkage upon curing values: Resin of Shrinkage upon Curing (%) Example 1 1.13 Example 2 1.11 Example 3 0.75 Example 7 1.12 Example 11 1.12 Example 13 0.93 Example 24 1.30 Example 25 1.68 Example 26 1.50 Comparative Example C-l 2.79 Example 55 A modified polyesteramide was prepared using the hydrolysis method with bulk diamine addition, and the following reaction stoichiometry: : DCPD concentrate - 1.2 moles MA - 2.0 moles H,O 1.7 moles PG - 1.704 moles homopiperazine - 0.156 mole The DCPD concentrate contained 0.31 percent lights, 13.67 percent codimers and 86.05 percent DCPD. The resulting polyesteramide alkyd was formulated and tested for mechanical properties using the methods of Example 36. The following results were obtained: Acid number 35.6 Reaction time at 2050C (hr) 3.50 Hydrocarbon Reactives Efficiency (%) 96.5 Brookfield Viscosity 190 SPI Gel-840C gel time (min.) 1.09 cure time (min.) 1.75 max. exotherm (OC) 229.5 Ave. Barcol Hardness 46.0 Tensile Strength x103 psi 2.317 (MPa) (15.97) Elongation (%) 0.53 Flexural Strength x103 psi 12.156 (MPa) (83.81) Example 56 Maleic anhydride (686.42 g) was added to a reactor and maintained at 1200C under a nitrogen atmosphere as a clear, stirred solution. Water (135.15 g) was added and induced a maximum exotherm of 146 C 1 minute later. Fifteen minutes after the initial water addition, a 1230C temperature was established and dicyclopentadiene concentrate (278.70 g) was added. The dicyclopentadiene concentrate contained 0.38 percent lights, 13.91 percent codimers and 85.72 percent DCPD. A maximum exotherm of 1350C resulted 2 minutes later and was controlled by air-cooling of the reactor. Fifteen minutes later, a second aliquot of dicyclopentadiene concentrate (278.70 g) was added to the reactor. Fifteen minutes later, a final aliquot of dicyclopentadiene concentrate (278.70 g) was added. The reaction temperature was held at 1200C for 30 minutes then propylene glycol (287.66 g) and piperazine (36.18 g) were added to the reactor and the steam condenser was started, nitrogen sparging was increased to 4 lpm, and the temperature controller was set at 1600C. The 1600C temperature was reached 26 minutes later. After 2 hours at the 1600C temperature, the temperature controller was set at 2050C and this temperature was achieved 30 minutes later. After 9.5 hours, a total of 132 milliliters of water layer and 56 milliliters of organic material were collected in the Dean Stark trap. The reactor was cooled to 1680C and 100 ppm of hydroquinone was added. The polyesteramide alkyd was recovered as a clear, light yellow solid with a final acid number of 31.3. The resulting polyesteramide alkyd was formulated to provide a 57.0 percent alkyd - 43.0 percent styrene solution. This solution was used to prepare a laminate and tested for mechanical properties using the methods of Examples 40-49. The following results were obtained: Brookfield Viscosity 0.160 Ave. Barcol Hardness 47.5 Tensile Strength x103 psi 8.474 (MPa) (58.42) Elongation (%) 1.56 Flexural Strength x103 psi 13.236 (MPa) (91.26) Flexural Modulus x10-5 psi 8.27 (MPa) (5701.92)

Claims: WHAT IS CLAIMED IS: 1. A norbornyl modified polyesteramide comprising an esteramide chain consisting essentially of: (a) diamino groups of the formula: EMI72.1 wherein R1 and R2 are independently selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aromatic or R1 and R2 together form an aliphatic ring, and R3 is a divalent organic radical selected from the group consisting of alkylene, ether-linked alkylene, ether-linked arylene, alkylene amino-linked alkylene, alkylene amino-linked cycloalkylene, cycloalkylene, polycycloalkylene, arylene, alkylarylene bis ( alkyl )cyclo- alkylene and bis (alkyl )polycycloalkylene; (b) bisalkoxy groups of the formula: -O-R3 -0- wherein R3 is a divalent organic radical as before defined; and (c) carboxylic acid groups at least a part of which are a,ss-unsaturated carboxylic groups with any remainder being saturated aliphatic carboxylic groups, aromatic carboxylic groups or mixtures thereof; at least one terminal group of said polyesteramide being a norbornyl radical. 2. The modified polyesteramide of Claim 1 wherein said di amino groups are from an aliphatic diamine, acycloaliphatic diamine, a polycycloaliphatic diamine, an aromatic diamine, an ether linked alkylene diamine or a polyamine. 3. The modified polyesteramide of Claim 1 wherein said bisoxo group is from an aliphatic glycol, a polycycloaliphatic glycol, bis(hydroxypropyl)bisphenol A or a mixture of an aliphatic glycol and aliphatic polyol. 4. The modified polyesteramide of Claim 1 wherein said norbornyl radical is from dicyclopentadiene, a dicyclopentadiene concentrate containing Diels-Alder dimers of diolefins, polycyclopentadiene or norbornyl. 5. The modified polyesteramide of Claim 1 wherein said a,-unsaturated dicarboxylic acid group is maleoyl, phthaloyl, isophthaloyl or fumaroyl. 6. A formulation of the modified polyesteramide of Claim 1 and an unsaturated monomer. 7. A cured composition of the formulation of Claim 6. 8. A process for making modified unsaturated polyesteramides wherein a mixture of norbornene or a norbornene derivative is reacted with an a,-unsaturated polycarboxylic acid, anhydride, or mixture thereof, a diamine, or polyamine, and a glycol, or a glycol-polyol mixture. 9. The process of Claim 8 wherein water is additionally included as a reactant. 10. The process of Claim 9 wherein: (a) an a,ss-unsaturated dicarboxylic acid anhydride and a fraction of the stoichi ometric equivalent of water are heated to a temperature of from 600 to 1300C. (b) An initial fractional equivalent of said norbornene or norbornene derivative is added and allowed to react. (c) One or more additional fractional equiva lent of water and norbornene or norbornene derivative is added and allowed to react. (d) Additional fractional equivalents of norbornene or norbornene derivative are added and each allowed to react before subsequent addition of the next incre ment until the desired amount of norbor nene or norbornene derivative has been added. (e) The diamine, or polyamine plus the glycol, or polyol or mixture thereof, are added and the temperature maintained from 1100 to 2050C with continual removal of water. 11. The process of Claim 9 wherein: (a) an a,ss-unsaturated dicarboxylic acid anhydride and at least a stoichiometric equivalent of water are heated to a temperature of from 1200 to 1250C. (b) An initial equivalent of norbornene or norbornene derivative is added and allowed to react. (c) Additional fractional equivalents of norbornene or norbornene derivative are added and each allowed to react before subsequent addition of the next increment until the desired amount of norbornene or norbornene derivative has been added. (d) The diamine, or polyamine plus the glycol, or polyol or mixture thereof are added and the temperature maintained from 1100 to 2050C with continual removal of water. 12. A modified polyester comprising a polymer chain consisting essentially of: (a) bisalkoxy groups of the formula: -O-R3-O wherein R3 is a divalent organic radical as before defined; and (b) carboxylic acid groups at least a part of which are a,-unsaturated carboxylic groups with any remainder being saturated aliphatic carboxylic groups, aromatic carboxylic groups or mixtures thereof; the improvement of which comprises (i) inclusion in the polymer chain of di amino groups of the formula: EMI76.1 wherein R1 and R2 are independently selected from the group consisting of hydrogen, aliphatic, cycloaliphatic and aromatic or R1 and R2 together form an aliphatic ring, and R3 is a divalent organic radical selected from the group consisting of alkylene, ether-linked alkylene, ether-linked arylene, alkylene amino-linked alkylene, alkylene amino-linked cycloalkylene, cycloalkylene, polycycloalkylene, arylene, alkylarylene bis(alkyl)cycloalkylene and bis(alkyl)polycycloalkylene; and (ii) at least one terminal group of said polyesteramide being a norbornyl radical.

Inventors: HEFNER, ROBERT EUGENE, JR., URODA, JAMES CLEMENT
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1983
Main classification: C08G69
IPC codes: C08G69, C09D167, C08F299, H05K1, C08F290