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Patent US4108840 - Urea-urethane-acrylate radiation curable coating compositions and methods of ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsUrea-linked urethane-modified acrylate-capped resins provide radiation curable coating compositions of exceptional durability and flexibility and which are essentially free of volatile solvents. These resins, typically produced by controlled addition of water to an isocyanato-terminated urethane- or...http://www.google.com/patents/US4108840?utm_source=gb-gplus-sharePatent US4108840 - Urea-urethane-acrylate radiation curable coating compositions and methods of making sameAdvanced Patent SearchPublication numberUS4108840 APublication typeGrantApplication numberUS 05/787,820Publication dateAug 22, 1978Filing dateApr 15, 1977Priority dateApr 15, 1977Also published asCA1107892A1, DE2815721A1Publication number05787820, 787820, US 4108840 A, US 4108840A, US-A-4108840, US4108840 A, US4108840AInventorsCharles B. FriedlanderOriginal AssigneePpg Industries, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (10), Non-Patent Citations (1), Referenced by (31), Classifications (26) External Links: USPTO, USPTO Assignment, EspacenetUrea-urethane-acrylate radiation curable coating compositions and methods of making sameUS 4108840 AAbstract Urea-linked urethane-modified acrylate-capped resins provide radiation curable coating compositions of exceptional durability and flexibility and which are essentially free of volatile solvents. These resins, typically produced by controlled addition of water to an isocyanato-terminated urethane- or thiocarbamate-containing prepolymer moiety to form an intermediate which is reacted with a hydroxyl-containing acrylic monomer that furnishes ethylenic unsaturation crosslinking sites to the resin, are further characterized by the resin composition substantially comprising molecules wherein the urea group has directly adjacent radicals derived from the prepolymer moiety.
What is claimed is: 1. Radiation polymerizable resin comprising the reaction product of:a. a prepolymer moiety having a plurality of isocyanato groups; b. water in an amount sufficient to react with only a portion of the isocyanato groups of said prepolymer moiety to form in said reaction product at least one urea group linking two prepolymer moieties; and c. a polyfunctional compound containing at least one functional group which is reactive with an isocyanato group of said prepolymer moiety and which polyfunctional compound after reaction with said isocyanato group provides at least one ethylenic functional group in said reaction product. 2. The resin of claim 1 in which said prepolymer moiety is the reaction product of a polyol and an organic polyisocyanate.
EXAMPLE I A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and a reflux condenser is charged with 43,092 parts isophorone diisocyanate (viz., 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane), 27,216 parts phenyl Cellosolve acrylate, 19.5 parts dibutyltin dilaurate ("Niax" catalyst; Union Carbide Corp.), and 4 parts triethylene diamine ("Dabco" catalyst; Air Products Chemical Div.). With the apparatus set for total reflux and maximum agitation, the mixture is heated to a temperature of about 38� C. Over a period of 2 hours, 54,432 parts of a polycaprolactone polyol having a hydroxyl value of about 205 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added to the reaction mixture while the temperature is maintained at 36�-41� C., 27,216 parts polyol being added the first hour and 13,608 parts polyol being added in each of the remaining 30 minute segments. After the polyol is added, the reaction mixture is heated to 49�-53� C. and maintained at that temperature for 2 hours. Then the reaction mixture is heated to 60�-63� C. and maintained for about 1 hour and thereafter heated to about 72� C., at which time 19.5 parts of a polysiloxane surface tension modifying agent (DC 200; Dow Corning) is added. Over a period of 50 minutes, 861.8 parts deionized water is added to the reaction mixture. The evolution of heat and some foaming is observable, the temperature of the reaction mixture increasing to, and then held at, a temperature of about 77� C. Upon completion of the deionized water addition, the reaction mixture is held at 75�-77� C. for 1 hour and 20 minutes, after which 39 parts of di-t-butyl-p-cresol ("Ionol" inhibiting agent; Shell Oil Co.) is added. While maintaining the temperature at about 74�-76� C., 11,295 parts 2-hydroxyethyl acrylate is added to the reaction mixture over a period of 30 minutes. The reaction mixture is then held at 74�-77� C. for 1 hour and at that temperature is filtered through double-nylon bags into storage containers. A viscosity measurement, taken on a 75 percent by weight sample of the resin composition in 2-ethoxyethanol, indicates a visosity of Z+ on the Gardner-Holt viscosity scale.
EXAMPLE II A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer, and a reflux condenser is charged with 11,340 parts isophorone diisocyanate, 2,540 parts ethyl acetate and 10 parts dibutyltin dilaurate. With the apparatus set for total reflux and maximum agitation, the mixture initially at 15.5� C. is heated to a temperature of about 41� C. in 30 minutes. Over a period of 2 hours and 10 minutes, 14,016 parts of a polycaprolactone polyol having a hydroxyl value of about 206 is added to the reaction mixture with the temperature maintained at 40�-43� C. and with cooling applied to maintain the given temperature range, while about 7,031 parts polyol is added the first hour and the balance of the polyol is added in the second hour. After the polyol is added, the reaction mixture is heated to 50�-51� C. in 25 minutes and maintained at that temperature for 2 hours. Then the reaction mixture is heated to about 60� C. in 25 minutes and maintained for 1 hour and thereafter heated to about 70� C. in 15 minutes. Over a period of 30 minutes and while maintaining the temperature of the reaction mixture at 70�-74� C., 222 parts deionized water is added to the reaction mixture, after which the reaction mixture is held at about 74� C. for 1 hour. To the reaction mixture is then added 41 parts di-t-butyl-p-cresol and 0.4 part phenothiazine; 1,634 parts 2-hydroxyethyl acrylate is then added to the reaction mixture as quickly as possible. The temperature of the reaction mixture increases to about 77� C. in 15 minutes, and then 1,634 parts 2-hydroxyethyl acrylate and 7,167 parts phenyl Cellosolve acrylate are added. The reaction mixture is then held at 77�-78� C. for 2 hours and at a temperature of 71�-74� C. is filtered through double-nylon bags into storage containers. A viscosity measurement, taken on a 75 percent by weight sample of the resin composition in 2-ethoxyethanol, indicates a viscosity of T-U on the Gardner-Holt viscosity scale.
EXAMPLE III A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer, a reflux condenser and a source of nitrogen is charged with 12,701 parts isophorone diisocyanate, 3,992 parts ethyl acetate and 11.4 parts dibutyltin dilaurate. With the apparatus set for total reflux and maximum agitation, the mixture is heated under a nitrogen blanket to a temperature of about 38� C. in 45 minutes. Over a period of 2 hours and 10 minutes, 15,604 parts of a polycaprolactone polyol having a hydroxyl value of about 205 is added to the reaction mixture with about 3,901 parts polyol being added every 30 minutes. The exothermic reaction is watched carefully and the mixture is cooled as necessary to maintain the reaction mixture at about 41� C. After the polyol is added, the reaction mixture is heated to about 49� C. in 35 minutes and maintained at 49�-51� C. for 2 hours. Then the reaction mixture is heated to about 60� C. in 30 minutes and maintained at 60�-62� C. for 1 hour and thereafter heated to about 71� C. in 25 minutes. Then a mixture of 248 parts deionized water and 6 parts of a polysiloxane surface tension modifying agent is added to the reaction vessel over a period of 30 minutes while the temperature is maintained at 71�-75� C., followed thereafter by a one-hour holding period at that temperature. The nitrogen blanket above the reaction mixture is maintained while an air sparge is supplied to the reaction mixture itself. Then with the reaction mixture at a temperature of 72�-77� C. and, over a period of 45 minutes, a mixture of 0.5 part phenothiazine, 45.4 parts di-t-butyl-p-cresol and 3,674 parts 2-hydroxyethyl acrylate is added to the reaction vessel. The temperature of the reaction mixture is then held at 74�-77� C. for 1 hour and 45 minutes, and followed by the addition of 3,992 parts triethylene glycol triacrylate with a subsequent 15 minute agitation period. A viscosity measurement, taken on a 75 percent by weight sample of the resin composition in 2-ethoxyethanol, indicates a viscosity of V+. The reaction mixture is allowed to cool to about 68�-71� C., and the composition is then filtered through double-nylon bags into storage containers.
EXAMPLE IV A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer, a reflux condenser and a source of nitrogen is charged with 11,204 parts isophorone diisocyanate, 3,992 parts ethyl acetate and 11.8 parts dibutyltin dilaurate. With the apparatus set for total reflux and maximum agitation, the mixture is heated under a nitrogen blanket from an ambient temperature of about 27� to about 41� C. in 10 minutes. Over a period of 2 hours and 5 minutes 12,429 parts of a polyol derived from the reaction of 1,1,1-trimethylolpropane and propylene oxide and having a molecular weight of about 740 and a hydroxyl value of about 227 (Polyol TP 740; BASF-Wyandotte) is added to the reaction mixture, approximately one-quarter of the total polyol being added every 30 minutes. The exothermic reaction is watched carefully and the mixture is cooled as necessary to maintain the reaction mixture at about 40�-42� C. during addition of the polyol. After the polyol is added, the reaction mixture is heated to about 49� C. in 25 minutes and maintained at that temperature for two hours. Then the reaction mixture is heated to 60�-62� C. in 20 minutes and maintained for 1 hour and thereafter heated to about 71� C. in 20 minutes. Then a mixture of 147 parts deionized water and 3.2 parts of a polysiloxane surface tension modifying agent is added to the reaction vessel over a period of 30 minutes while the temperature is maintained at about 71�-74� C., followed thereafter by a 1-hour holding period at that temperature. The nitrogen blanket above the reaction mixture is maintained while an air sparge is supplied to the reaction mixture itself. With the reaction mixture at a temperature of about 74� C. and over a period of 50 minutes, a mixture of 50 parts di-t-butyl-p-cresol and 5,715 parts 2-hydroxyethyl acrylate is added to the reaction vessel. The temperature of the reaction mixture is then held at 76�-77� C. for 1 hour and 45 minutes, followed by the addition of 2,767 parts triethylene glycol triacrylate. The reaction mixture is allowed to cool to about 67� C. while agitation is continued to stir in the last component. A viscosity measurement with a sample diluted as before is made 15 minutes after addition of the triethylene glycol triacrylate; the sample gives a viscosity of X+ on the Gardner-Holt viscosity scale. The composition is then filtered through double-nylon bags into storage containers.
EXAMPLE V A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer, a reflux condenser and a source of nitrogen is charged with 58,696 parts isophorone diisocyanate, 72,032 parts 2-ethylhexyl acrylate, 844 parts methyl isobutyl ketone and 18 parts dibutyltin dilaurate. With the apparatus set for total reflux and moderate agitation, the mixture is heated under a nitrogen blanket from an ambient temperature of about 21� C. to a temperature of about 32� C. in 35 minutes. Over a period of 2 hours and 35 minutes, 38,783 parts of a polyol derived from the reaction of 1,1,1-trimethylolpropane and propylene oxide and having a molecular weight of about 440 and a hydroxyl value of about 382 is added to the reaction mixture, approximately equal incremental portions of the total polyol being added every 15 minutes. The exothermic reaction is watched carefully and the mixture is allowed to increase in temperature to 35�-38� C., with care being taken that the temperature of 40.6� C. is not exceeded. After the polyol is added, the reaction mixture is heated to about 49� C. in 35 minutes and with maximum agitation the temperature is maintained at 49�-50� C. for 2 hours. Then the reaction mixture is heated to about 66� C. in 50 minutes and maintained at 66�-67� C. for 1 hour. Then a mixture of 572 parts deionized water and 14 parts of a polysiloxane surface tension modifying agent is added to the reaction vessel over a period of 30 minutes while the temperature is increased from about 67� to about 71� C., followed thereafter by a 1-hour holding period at 71�-74� C. The nitrogen blanket above the reaction mixture is then removed. Then at a temperature of about 74� C., a mixture of 272 parts di-t-butyl-p-cresol and 26,445 parts 2-hydroxyethyl acrylate is added to the reaction vessel over a period of 30 minutes while the temperature is maintained at about 74� C. The temperature of the reaction mixture is then held at 74�-76� C. for 1 hour and a viscosity measurement taken as before indicates a viscosity of D+. Then after 15 minutes, 12 parts of dibutyltin dilaurate catalyst and 907 parts 2-hydroxyethyl acrylate are added and subsequent viscosity checks are made for about 3 hours until a viscosity value of O+ - P+ is achieved. The reaction mixture is cooled to about 54� C. over a 1 hour period and then a mixture of 30,074 parts 2-ethylhexyl acrylate and 24,630 parts hexanediol diacrylate is added to the reaction vessel. An agitation period of 30 minutes follows with the temperature being maintained at 52�-54� C. A final viscosity check yields a value of Y- and the composition is filtered through double-nylon bags into storage containers.
EXAMPLE VI A reaction vessel at ambient temperature equipped with an agitator, a heater, cooling means, a thermometer, a reflux condenser and a source of nitrogen is charged with 62,597 parts isophorone diisocyanate and 72,032 parts 2-ethylhexyl acrylate. The apparatus is set for total reflux and moderate agitation. Over a period of 3 hours, 32,931 parts of a polyol, derived from the reaction of 1,1,1-trimethylolpropane, 1,3-butanediol and adipic acid and having an equivalent weight of about 119-120 and a hydroxyl value of about 465-470, is added to the reaction mixture, approximately one-eighth of the total amount of polyol being added every 15 minutes. The temperature of the reaction mixture increases by exothermic reaction of the mixture to about 38� C. the first and second hours, and then to about 60� C. at the end of the third hour at which time maximum agitation is applied to the reaction mixture. Then the reaction mixture is heated to about 66� C. in 30 minutes and maintained for one hour at that temperature. Then a mixture of 672 parts deionized water and 14 parts of a polysiloxane surface tension modifying agent is added to the reaction vessel over a period of 30 minutes while the temperature increases to about 71� C. which is followed thereafter by a 1-hour holding period at about 68� C. An air sparge is supplied to the reaction mixture while a nitrogen blanket is provided above the reaction mixture. Then 13 parts dibutyltin dilaurate is added to the reaction mixture. A mixture of 295 parts di-t-butyl-p-cresol and 27,216 parts 2-hydroxyethyl acrylate is then added to the reaction vessel over a period of 40 minutes at a rate of about 680 parts per minute with the temperature increasing from about 68� to about 79� C. over the addition period. The temperature of the reaction mixture decreases to about 74� C. over a 1-hour period and subsequent viscosity checks are made for 2 hours, with the reaction mixture temperature ranging from 71�-77� C. The reaction mixture is cooled from about 77� to about 49� C. over a period of 1 hour and 50 minutes and then a mixture of 30,074 parts 2-ethylhexyl acrylate and 24,630 parts hexanediol diacrylate is added to the reaction vessel. An agitation period of 30 minutes follows with the temperature increasing to about 66� C. at the end of the agitation period. The final composition, having a viscosity value of Z5-, is then filtered through double-nylon bags into storage containers.
EXAMPLE VII A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer, a reflux condenser and a source of nitrogen is charged with 69,219 parts isophorone diisocyanate, 26,898 parts 2-ethylhexyl acrylate and 23 parts dibutyltin dilaurate. With the apparatus set for total reflux and maximum agitation, a nitrogen blanket is applied to the reaction mixture which is initially at a temperature of about 27� C. Under cooling conditions and over a period of 2 hours, 75,615 parts of a polyol derived from the reaction of 1,1,1-trimethylolpropane and propylene oxide and having a molecular weight of about 740 and a hydroxyl value of about 227 (Polyol TP 740; BASF-Wyandotte) is added to the reaction mixture, approximately one-eighth of the total amount of polyol being added every 15 minutes. The exothermic reaction is watched carefully and the mixture is allowed to increase in temperature to about 35� C. the first hour and to about 39� C. the second hour. After all of the polyol is added, the temperature of the reaction mixture increases over a 20 minute period to about 49� C. The reaction mixture is maintained at about 49� C. for 2 hours. Then after another holding period of 1 hour and 45 minutes, the temperature is observed to increase to about 60� C. The reaction mixture is then held at about 62� C. for 1 hour, and after another 55 minutes the temperature was observed to increase to about 72� C. Then a mixture of 907 parts deionized water and 21 parts of a polysiloxane surface tension modifying agent is added to the reaction vessel over a period of 30 minutes with the temperature increasing from about 74� to about 75� C., followed thereafter by a 11/2 hour holding period at about 74� C. An air sparge is then added to the reaction mixture while the nitrogen blanket above the reaction mixture is maintained. A mixture of 313 parts di-t-butyl-p-cresol and 38,737 parts 2-hydroxyethyl acrylate is added to the reaction vessel over a period of 30 minutes while the temperature is maintained at about 74� C. The temperature of the reaction mixture is then held at 74�-75� C. for 1 hour and thereafter a mixture of 17,146 parts of triethylene glycol diacrylate and 8,618 parts 2-hydroxyethyl acrylate is added with the temperature being observed to decrease to about 74� C. The reaction mixture is held for 2 hours at 74�-76� C. with a viscosity check giving a value of K- after the second hour. Then after another 45 minutes and with a reaction mixture temperature of about 77� C., 5,897 parts 2-hydroxyethyl acrylate is added. The reaction mixture is held for one hour while the temperature is observed to decrease to about 72� C., with another viscosity check giving a value of L+. Then after 15 minutes 5,897 parts 2-hydroxyethyl acrylate is again added to the reaction mixture which is at a temperature of about 75� C. The reaction mixture is then held at that temperature for 1 hour and cooling is subsequently applied. Over a period of two hours and 10 minutes the temperature is observed to decrease to about 71� C., at which time 1,814 parts of the Polyol TP 740 is added to the reaction mixture. The reaction mixture is held at 70�-71� C. for 30 minutes and a viscosity check is made giving a value of M+. After 1 hour and 25 minutes the temperature is observed to increase to about 74� C. and 1,814 parts of the Polyol TP 740 is again added. Then after 1 hour and 15 minutes 10 parts dibutyltin dilaurate is added and, after 3 hours and 20 minutes, the reaction mixture at a temperature of 52�-54� C. is filtered through double-nylon bags into storage containers. A final viscosity check gives a value of O+.
EXAMPLE VIII A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 111 parts isophorone diisocyanate, 70 parts phenyl Cellosolve acrylate, 0.05 part dibutyltin dilaurate and 0.01 part triethylene diamine. Under reflux conditions, constant agitation and over a period of 2 hours, 140 parts of a polycaprolactone polyol having a hydroxyl value of 205 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added dropwise to the reaction mixture which is initially at a temperature of about 27� C. As the polyol is added, heat of reaction drives the temperature of the reaction mixture to about 40� C., which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 50� C. and maintained for 2 hours, then heated to about 60� C. and maintained for 1 hour and thereafter heated to about 70� C. Then 2.25 parts ordinary tap water is added to the reaction mixture while the temperature is held at about 70� C. Upon completion of the water addition, the reaction mixture is held at about 70� C. for 2 hours. Then after addition of 0.1 part di-t-butyl-p-cresol and while maintaining the temperature at about 70� C., 31.9 parts 2-hydroxyethyl acrylate is added to the reaction mixture. The reaction mixture is held at 75� C. for 1 hour and then dispensed into storage containers. A viscosity check taken on a 75 percent by weight sample in 2-ethoxyethanol gives a value of T+1/2 on the Gardner-Holt viscosity scale.
EXAMPLE IX A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 1110 parts isophorone diisocyanate, 700 parts phenyl Cellosolve acrylate, 0.5 part dibutyltin dilaurate and 0.1 part triethylene diamine. Under reflux conditions, constant agitation and over a period of 2 hours, 1,366 parts of a polycaprolactone polyol having an hydroxyl value of 205 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added to the reaction mixture which is initially at about 29� C. As the polyol is added, the heat of reaction drives the temperature of the reaction mixture to about 40� C., which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 50� C. and maintained for 2 hours, then heated to about 60� C. and maintained for 1 hour, and thereafter heated to about 75� C. Then, after the addition of 0.2 part of a polysiloxane surface tension modifying agent (DC 200; Dow-Corning) and 0.1 part of di-t-butyl-p-cresol, and over a period of 1 hour, a mixture of 22.5 parts ordinary tap water and 290 parts 2-hydroxyethyl acrylate is added dropwise to the reaction mixture being held at about 75� C. Upon completion of the addition of this two-component mixture, the reaction mixture is held at about 75� C. for 2 hours and then dispensed into storage containers. A viscosity check made as before indicates a value of S.
EXAMPLE X A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 1110 parts isophorone diisocyanate, 350 parts ethyl acetate, 0.5 part dibutyltin dilaurate and 0.1 part triethylene diamine. Under reflux conditions, constant agitation and over a period of 2 hours, 1,365 parts of a polycaprolactone polyol having a hydroxyl value of about 206 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added to the reaction mixture which is initially at a temperature of about 28� C. As the polyol is added, heat of reaction drives the temperature of the reaction mixture to about 40� C. which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 50� C. and maintained at that temperature for 2 hours, then heated to about 60� C. and maintained for 1 hour, and thereafter heated to about 70� C. Then, after the addition of 0.2 part of a polysiloxane surface tension modifying agent, 21.7 parts ordinary tap water is added dropwise over a period of 25 minutes to the reaction mixture being held at about 70� C. Upon completion of the water addition, the reaction mixture is heated to about 75� C. and maintained for 1 hour. After the addition of 3.5 parts di-t-butyl-p-cresol, and while maintaining the temperature at about 75� C., 159.5 parts 2-hydroxyethyl ethyl acrylate is added dropwise to the reaction mixture. The reaction mixture is held at 75� C. for 15 minutes and then a mixture of 159.5 parts 2-hydroxyethyl acrylate and 700 parts neopentyl glycol diacrylate is added to the reaction mixture. At a temperature of about 75�-80� C. an air sparge is applied to the reaction vessel and maintained to aid in evaporation of the ethyl acetate for a period of 1 hour and 50 minutes. The reaction mixture is then dispensed into storage containers. A viscosity value of T-U is obtained in accordance with the method set out before.
EXAMPLE XI A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 222 parts isophorone diisocyanate, 43 parts ethyl acetate and 0.24 part dibutyltin dilaurate. Under reflux conditions, constant agitation and over a period of 2 hours, 273 parts of a polycaprolactone polyol having a hydroxyl value of about 206 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added to the reaction mixture which is initially at a temperature of about 29� C. As the polyol is added, the heat of reaction drives the temperature of the reaction mixture to about 40� C., which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 50� C. and maintained for 2 hours, then heated to about 60� C. and maintained for 1 hour, and thereafter heated to about 75� C. Then, after the addition of 0.6 part of di-t-butyl-p-cresol, and over a period of 30 minutes, 4.35 parts ordinary tap water is added dropwise to the reaction mixture being held at about 70� C. The reaction mixture is then heated to a temperature of about 75� C. and over a period of 30 minutes 69.6 parts 2-hydroxyethyl acrylate is added dropwise. After a 2-hour holding period at 75� C., 142 parts 3-chloro-2-hydroxypropyl acrylate is added to the reaction mixture as an ultraviolet light reactive diluent, and the composition is then dispensed into storage containers. A viscosity check indicates a value of U-V.
EXAMPLE XII A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and a reflux condenser is charged with 444 parts isophorone diisocyanate, 270 parts phenyl Cellosolve acrylate and 0.1 part dibutyltin dilaurate. Under reflux conditions, constant agitation and over a period of 2 hours, 560 parts of a polyester, made previously by conventional techniques from 292 parts adipic acid, 93 parts ethylene glycol, 195 parts thiodiethanol with 0.6 part butylstannoic acid and having a molecular weight of 560 and a hydroxyl value of 200, is added dropwise to the reaction mixture. The temperature of the reaction mixture is initially at about 27� C. and increases with the exothermic reaction to about 40� C. at the end of the 2-hour period. The reaction mixture is maintained at about 40� C. for 55 minutes, then heated to about 65� C. in 30 minutes, and thereafter held at 60�-65� C. for 1 hour. Then 9 parts ordinary tap water is added to the reaction mixture, which mixture is held for 2 hours at about 65� C. and then heated to about 70� C. Then 0.1 part di-t-butyl-p-cresol is added to the reaction mixture followed thereafter by dropwise addition of 116 parts 2-hydroxyethyl acrylate over a period of 1 hour with the temperature held at about 70� C. The reaction mixture is held at about 70� C. for 2 hours, then cooled and dispensed into storage containers. A viscosity check indicates a value of V-W.
EXAMPLE XIII A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 444 parts isophorone diisocyanate, 377 parts phenyl Cellosolve acrylate, 1.2 part dibutyltin dilaurate and 0.12 part triethylene diamine. Under reflux conditions, constant agitation and over a period of 2 hours, 600 parts of a polypropylene ether diol having a molecular weight of about 600 and a hydroxyl value of about 187 is added to the reaction mixture which is initially at about 29� C. As the polyol is added, the heat of reaction drives the temperature of the reaction mixture to about 40� C., which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 60� C. and maintained for 3 hours and thereafter heated to about 70� C. Over a period of 30 minutes 8.1 parts ordinary tap water is added dropwise to the reaction mixture being held at about 70� C. Upon completion of the water addition, the reaction mixture is held at about 70� C. for 1 hour. After the addition of 1.9 part di-t-butyl-p-cresol and while maintaining the temperature at about 70� C., 348 parts 2-hydroxyethyl acrylate is added to the reaction mixture. After a 15 minute period, 23 parts isophorone diisocyanate is added to the reaction mixture, which is then held for 2 hours at about 70� C. Thereafter 50 parts phenyl Cellosolve acrylate is added and the composition is then dispensed into storage containers. A viscosity check indicates a value of R-S.
EXAMPLE XIV A reaction vessel equipped with an agitator, a heater, a thermometer and a reflux condenser is charged with 333 parts isophorone diisocyanate, 210 parts phenyl Cellosolve acrylate and 0.15 part dibutyltin dilaurate. Under reflux conditions, constant agitation and over a period of 2 hours, 420 parts of a polycaprolactone polyol having a hydroxyl value of about 206 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added to the reaction mixture which is heated initially to a temperature of about 31� C. As the polyol is added, the heat of reaction drives the temperature of the reaction mixture to about 40� C., which temperature is maintained during the 2-hour reaction period by the addition of heat when necessary. The reaction mixture is heated to about 50� C. and maintained for 2 hours, then heated to about 60� C. and maintained for 1 hour, and thereafter heated to about 63� C. Then, 6.75 parts ordinary tap water is added to the reaction mixture which is then heated to about 70� C. and maintained for 2 hours. After addition of a 1.6 parts triethylene diamine, 0.81 part of di-t-butyl-p-cresol, 0.09 part methyl hydroquinone, 0.01 part phenothiazine and 0.2 part of a polysiloxane surface tension reducing agent, the reaction mixture is heated to about 95� C. Over a period of 30 minutes and while maintaining the temperature at about 95�-97� C., 57.7 parts acrylic acid is added to the reaction mixture which is then held at about 95�-97� C. for 50 minutes. The reaction mixture is heated to about 97�-100� C. and held at about 100� C. for 31/2 hours while IR and acid value samples are run on the composition, which is thereafter dispensed into storage containers. A viscosity check indicates a value of Z5-.
EXAMPLE XV A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and a reflux condenser is charged with 766 parts 2-hydroxyethyl acrylate, 684 parts ε-caprolactone, 14 parts di-t-butyl-p-cresol, 7.2 parts stannous chloride and 0.2 part phenothiazine. The mixture is heated to 115� C. over a period of 2 hours, with infrared spectra (IR) samples being taken initially and at the end of the 2-hour heating period to determine the level of unreacted caprolactone. The infrared spectra are obtained by a standard thin film procedure utilizing one drop of undiluted solution between sodium chloride plates. The mixture is then held at 115� C. for 2 more hours, with IR samples being taken at the end of each hour. At the end of the second hour of the holding period, IR data indicate that the reaction mixture is substantially free of unreacted ε-caprolactone. The resulting acrylate-caprolactone polyol adduct has a hydroxyl value of about 226, an acid value of about 6.0 and an ethylenic unsaturation equivalent weight of about 225.
A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and a reflux condenser, is charged 222 parts isophorone diisocyanate, 119 parts 2-hydroxyethyl acrylate and 3 parts di-t-butyl-p-cresol. Over a period of 2 hours, 248 parts of the previously prepared polyol adduct is added to the reaction mixture which is initially at a temperature of about 24� C. By the end of the two hour addition period the temperature is at about 40� C. The reaction mixture is heated to about 50� C., and then to about 65� C. in a period of 20 minutes. The temperature is held at about 65� C. for 1 hour and then increased to about 75� C. at which time 0.2 part of a polysiloxane surface tension modifying agent is added to the reaction mixture. Then over a period of 30 minutes, 8.1 parts ordinary tap water is added to the reaction mixture while the temperature is held at about 75� C. The reaction mixture is held for 1 hour at about 70� C. and then left to cool overnight. The following day IR samples taken of the reaction mixture indicate the presence of substantial amounts of unreacted isocyanato functional group. Then 0.4 part dibutyltin dilaurate is added to the reaction mixture which is held at about 72� C. for 2 hours and 15 minutes. Thereafter 29 parts 2-hydroxyethyl acrylate is added to the reaction mixture which is then held at 70�-72� C. for 5 hours. Data from subsequent IR samples indicate the substantial absence of unreacted isocyanato functional groups. A viscosity measurement taken without dilution of the sample indicates a viscosity of Z5+.
EXAMPLE XVI A reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and a reflux condenser is charged with 555 parts isophorone diisocyanate, 1 part di-t-butyl-p-cresol and 0.2 part dibutyltin dilaurate. The reaction mixture is heated to about 60� C. and over a period of 30 minutes 116 parts 2-hydroxyethyl acrylate is added to the reaction mixture. The reaction mixture is then held at about 60� C. for 1 hour and thereafter cooled to about 40� C. in 15 minutes. Then 1 part di-t-butyl-p-cresol is added to the reaction mixture, followed by gradual addition of 128 parts 2-hydroxyethyl acrylate over a one hour period with the temperature of the reaction mixture being held at about 40� C. The temperature is held for 1 hour at about 40� C. and then, with this temperature maintained, 534 parts of a polycaprolactone polyol having a hydroxy value of about 210 ("Niax" polyol PCP 0200; Union Carbide Corp.) is added dropwise to the reaction mixture over a period of 1 hour. Then the reaction mixture is heated to about 70� C. in 10 minutes and held at that temperature for 1 hour. Thereafter 235 parts 2-hydroxyethyl acrylate is added to the reaction mixture, followed by the sequential addition of 0.2 part of a polysiloxane surface tension modifying agent and 8.1 parts ordinary tap water, with the temperature being maintained at about 70� C. Then over a period of 2 hours and 15 minutes, the temperature of the reaction mixture is observed to rise to about 78� C. Data from IR samples indicate the presence of unreacted isocyanato functional groups. Then 0.2 part dibutyltin dilaurate is added to the reaction mixture, followed by addition of 1 part ordinary tap water and a holding period of 2 hours and 10 minutes at about 75� C. Thereafter 29 parts 2-hydroxyethyl acrylate is added to the reaction mixture which is then held at about 77� C. for 2 hours and 30 minutes. Data from a subsequent IR sample indicate that the reaction mixture is substantially free of unreacted isocyanato functionality. The resin composition is dispensed into storage containers and a viscosity measurement of P- is obtained for a 75 percent by weight sample in 2-ethoxyethanol.
EXAMPLE XVII The improved wear and chemical resistance characteristics of coating compositions containing resin of the invention can be demonstrated by comparison of the coating compositions with typical, commercially available polyurethane coating materials.
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