COMPOSITIONS CONTAINING A REACTIVE MONOMER DERIVED FROM A LACTONE

Abstract: Described herein are compositions containing a reactive monomer derived from the reaction product of a hydroxyal­ kyl acrylate or methacrylate and a lactone. These composi­ tions can be reacted with other ethylenically unsaturated monomers to produce curable oligomers and polymers than can be made into high quality industrial finishes by incorpor­ ation of various conventional crosslinking agents, plus other normally used formulating ingredients.

Description: Described herein are compositions containing a reactive monomer derived from the reaction product of a hydroxyalkyl acrylate or msthacrylate and a lactone. These compositions can be reacted with other ethylenically unsaturated monomers to pn-oduce curable oligomers and polymers that can be nade into high quality industrial finishes by incorporation of various conventional cross-linking agents, plus other normally used fonrulating ingredients. Reaction products of caprolactone with hydroxyethyl acrylate and methacrylate are described in the literature. For example, U.S. Patent 3,655,631 describes, as in Example 1 thereof, the polymerization of epsilon-caprolactone with hydroxyethyl acrylate, as initiator, in the presence of 0.18 by weight of p-toluene sulphonic acid as catalyst,the reaction being carried out at a temperature of 45 C for 4 hours. The catalyst is described as an organic acid catalyst selected fran the group consisting of halogen substituted aliphatic carboxylic acids other than trichloroacetic acid, alkane sulphonic acids, benzene suiphonic acid and lower alkyl substituted benzene suiphonic acids. The product is described in said Example I as a solid unsaturated polyester having a molecular weight of about 960. Example 8 of said patent describes the polymerization of hydroxyethyl methacrylate and epsilon-caprolactone using 0.1% by weight of p-toluene sulphonic acid catalyst. The polyester product is described as having a molecular weight of 437 and being a viscous liquid. In Examples 1 and 8 the polymerization is stated to be complete: The polyesters produced in said patent have relatively large amounts of residual acid catalyst present (i.e., about 1000 parts per million). The presence of such strong acid catalyst in the polyester induct could lead to degradation the prod. Also, its presence ray decrease the shelf life and pot life of coating systems produced from oligomers containing the polyester product and certain cross-linking agents. Also, the use of a polyester product containing such strong residual acids may generate highly colored by-groups, that may be detrinental in some coating applications. U.S. Patent 4,188,472 describes reacting (a) a lactone with an ester-containing acrylyl or alpha-substituted acrylyl group and one or two hydroxyl groups, and (b) reacting the product of (a) with an isocyanate. specifically, in Examples I to III, hydroxyethyl acrylate is added to epsilon caprolactone which was heated to 1300C (Examples I) or 1200C (Examples II and III). large amounts of a catalyst such as TPT titanate (greater than 2000 parts per million, Example I) or a mixture of stannous octanoate and dibutyltin dilurate (greater than 1500 parts per million, Examples II and III) were added to the reaction mixture. Additionally, the reaction carried out in these Examples utilizes large amounts of inhibitor, i.e., greater than 5000 parts per million. The reaction is carried out at temperatures of 130 C ftr 6 hours (Examples I) and 1200C for 8 hours (Examples II and III). The product of the reaction in these Examples is described as having a hydroxyl value of 162 (Example I), 318 (Example II) and 122 (Example III). In Example II the reaction is stated to be complete. The use of the large amounts of catalyst and inhibitor in the polymerization described in U.S. Patent 4,188,472 can have deleterious effects on the subsequent use of the lactone nodified resin in polymerization or copolymerization reactions and/or cross-linking reactions. European Patent Application No. 0044 393A2 titled "Process For Production of A (Meth) Acrylate Resin With Hydroxyl Groups and Modified By Epsilon-Caprolactone" describes the reaction of at least one monoester of acrylic or methacrylic acid with an alkane diol with 2-4 carbon atoms in the molar ratio of 1.5:1 to 1:3 with epsiloncaprolactone. The reaction is described as occurring at a temperature of 60ç130C)C in the presence of an oganotin compound. Specifically, in Example I, an adduct from 2-hydroxyethyl acrylate and epsiloncaprolactone is prepared. 2-Hydroxyethyl acrylate and dibutyltin oxide are heated to 120 C and epsilon-caprolactone is added over the course of two hours. This mixture is heated for two nore hours at 120 C. This Example was repeated and the reaction product was shown to contain greater than 25 weight percent of unreacted 2-hydroxyethyl acrylate. THE INVENTION This ineention is directed to a composition carprising: (a) 0 to 10 weight percent, preferably 0 to 5 weight percent of a lacue, (b) greater than 0 to about 20 weight percent, preferably less than 10 weight percent of hydroxyalkyl acrylate or methacrylate, (c) 2 or less weight percent, preferably 1 or less weight percent of diacrylates, (d) 10 or less weight percent, preterably b or less weight percent of products resulting fran Michael addition, acrylic polymerization, transesterification reactions, or other side reactions, (e) remainder to 100 weight percent of a reactive monomer of the following formula: : EMI4.1 wherein R, R1, R2, and R3 are independently hydrogen or methyl, R4 and R5 are independently hydrogen or alkyl or fran 1 to 12 carbon atoms, x is fran 4 to 7, and both n and the average value of n in the ccmpositian are equal to or greater than 1, and (f) less than about 200 parts per million, preferably less than about 100 Farts per million of catalyst. It has been found that the composition of this invention can be used as a comonomer in polymerization reactions with other monomers Ashen polymerized with comonomers such as acrylic, vinyl or similar monomers the composition of this invention yields oligoers andEor copolymers, which when cross-linked, yield coatings or adhesives, having high flexibility, inpact resistance, solvent resistance, hydrolytic stability, and chemical compatibility. The compositions of this invention can also be homopolymerized to yield oligomers or homopolymers having similar desirable properties. The compositions of this invention is prepared by reacting a lactone with a hydroxyalkyl acrylate or methacrylate. The lactone is characterized Ey the following formula: EMI5.1 wherein R4 and R5 are hydrogen or alkyl of fran 1 to 12 carbon arans, and x is from 4 to 7. The e preferred lactone is epsilon-caprolactone. The e hydroxyalkyl acrylates or methacrylates include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hidroxy ethyl methacrylate, 2-hydroxypropyl mehacrylate, 2-hidroxy-3-chloropropyl methacrylate, 2-hydroxy-3-chloro-propyl acrylate,2,3-dihydroxy propyl methacrylate, 2,3-dihydroxy propyl acrylate, and the like, or mixtures thereof. Hidroxyethyl acrylate or methacrylate is preferred. me composition of this invention are prepared by reacting the lactone with the hidroxyalkyl acrylate or methacrylate in the presence of less than about 200 parts per million, preferably less than 100 parts per million, of a catalyst. me catalyst which may be used herein includes one or ItDre organometallic compounds and other metallic ocmpounds such as stannic chloride or ferric chloride and other Lexis and protonic acids. Preferred catalysts include stannous octonoate, dibutyltin dilaurate, and other tin compounds; titanates such as tetraisopropyl titanate and butyl titanate; and the like. The reaction is carried out at a temperature of fran about 100 to about 140 C, preferably from about 120 to about 13cPc. The reaction nEsy be carried out at atmospheric pressure, although higher or 1eeer pressures may be used. lMe reaction is generally carried out in the presence of oxygen to inhibit polymerization of the hydroxy alkyl acrylate or methacrylate. The reaction is carried out for a period of fran about 2 to about 20, preferably fran about 3 to about 11 hours. The reaction is carried out in the presence of a suitable inhibitor to prevent polymerization of the hydroxyalkyl acrylate or methacrylate double bond. These inhibitors include the monomethyl ether of hydroquinone, benzoquinone, phenothiazine, methylhydroquinone, 2,5-di-t-butylquinone, hydroquinone, and other common free radical inhibitors know in the art. The level of inhibitor used is less than 1000 parts per million, preferably less than 800 parts per million, and nost preferably, less than 600 part per million. in a preferred embodiment, the process of this invention is carried out by adding the lactone to a reaction vessel and heating this to reaction temperature (about 100 C to about 14g C) while sparging the lactone with an inert gas such as nitrogen. The lactone nay be dried with for example conventional agents such as molecular seives before adding it to the reaction vessel. When the reaction temperature is acheived or soon thereafter, the inert gas spurge is changed to a mixture of inert gas and oxygen (such as air). Various alternatives nay be used. For example, the system may be spaied with the inert gas and oxygen mixture for a short period of time i.e., about 5 to 10 minutes, after which the sparge is discontinued, and the gas mixture then used only to flush the reactor vapor space throughout the reaction; or the inert gas sparge is stopped and the system is flushed with the mixture throughout the reaction; or the gas mixture may be sparged through the system while an inert gas is additionally used to flush the vapor space during the reaction period. Combinations of these alternatives nay be used if desired. The hydroxyalkyl acrylate or methacrylate may be mixed with the catalyst and inhibitor and this mixture added to the heated lactone. Alternatively, the inhibitor may be added to the lactone prior to heating. Also the lactone may be added to the hydroxyalkyl acrylate or rrethacrylate which has been heated,or all the reactants may be added initially to the reactor and the process carried out. Several variations in the irode of addition of the lactone, acrylate or methacrylate, catalyst and inhibitor may be used. The final reaction mixture is maintained at the reaction temperature for about 2 to about 20 hours. The reaction mixture is collected and may be used without purification. If desired the reaction mixture may be purified by conventional techniques such as vacuum stripping. The process nay also be carried out in the presence of a suitable solvent which does not contain, for example, active hydrogens or polymerizable ethylenically unsaturated groups. These solvents include ketones, ester, ethers, aromatic and aliphatic hydrocarbons, and the like, or mixtures thereof. Preferred solvents include esters, such as Cellosolve acetate. Preferably, epsilon-caprolactone is reacted with hydroxy ethyl acrylate or methacrylate according to the process described herein in the ratio of one nole of the acrylate or methacrylate tD fran one to 12 idles of the lactone. These compositions may be solid or liquid, and the most preferred capositions are liquid. The e most preferred compositions are produced by reacting epsilon-caprolactone with hydroxyethyl acrylate or methacrylate in a ratio of one mole of the hydroxyethyl acrylate or nethacrylate to t or three noles of the epsilon-caprolactone These compositions contain the reactive monomers of formula (I), 0 to 5 weight percent of lactone, less than 10 weight percent of hydroxyethyl acrylate or methacrylate, minor amounts of additional reaction product, 400 to 600 parts per million of inhibitor, and catalyst residues in amounts of about 50 parts per million. EXAMPLES The following examples serve to illustrate specific embodiments of this invention and it is not intended that the invention shall be limited by the examples. EXAMPLE I A 500 ml glass reaction flask was equipped with a stirrer, thermometer, condenser, and nitrogen inlet and outlet tubes and used as the reaction vessel. Epsilon-caprolactone was dried by contacting it with molecular sieves for about 30 minutes. Then, 228 grafts of the dried epsilon-caprolactone were introduced into the reaction vessel and heated to 140 C while sparing the system with nitrogen. the the temperature reached 1400C, the nitrogen sparge was changed to an air sparge and a mixture of 116 grams of 2-hydroxyethyl acrylate, 0.0366 grams (106 n) of stanaus octanoate and 0.027 grazes (78 ppm) of the monomethyl ether of hydroquinone was added over a ten minutes period. The reaction mixture was held at 140 C for six hours, cooled to roam temperature (about 25 C), and collected as a residue product. The product had a hydroxyl number of 148.7,an acid number of 3.41, and a Erookfield viscosity of 98 centipoise (at 25 C). EXAMPLES II A 5 liter glass reaction flask sparged as described in Example I was used as the reaction vessel. A charge of 2,736 grams of epsilon-caprolactone was introduced into the reaction vessel and heated to 140 C while sparging with nitrogen. When the temperature reached 140 C, the nitrogen sparge was changed to an air sparge which was used for about 5 minutes ard then changed to a flush of air which was continued during the reaction period. Then a mixture of 1,392 grams of 2-hydroxyethyl acrylate, 0.208 grams (50 ppm) of stannous octanoate, and 1.30 grams (315 ppm) of the monomethyl ether of hydroquinone was added over a 25 minute period. The reaction mixture was held at 1400C for five hours, cooled to room temperature (about 25 C), and collected as a residue product. The residue product had a hydroxyl number of 159, an acid number of 3.29, and a Brookfield viscosity of 115 centipoise (at 25.5 C). Carbon-13 nuclear nagnetic resonance studies indicated the final product contained 7.8% by weight 2-hydroxyethyl acrylate, an average value of n in formula I of 2.8 and nil epsilon- caprolactone. EXAMPLE III A 503 ml glass reaction flask equipped as described in Example 1 was used as the reaction vessel. A charge of 456 grams of epsilon-caprolactone was introduced into the reaction vessel and heated to 140 C while sparging with nitrogen. When the temperature reached 140 C the nitrogen sparge was changed to an air sparge, and a minute of 260 grams of 2-hydroxyethyl methacrylate, 0.036 grams (50 ppm) of stannous octanoate, and 0,217 grams (303 ppm) of the monomethyl ether of hydroquinone was added aver a 5 to 6 minute time period. The reaction mixture was held at 140 C for six hours, cooled to room temperature (abort 25 C) and stored as a residue product. The product had a hydroryl nurber of 141.7. EXAMPLE IV - VIII A suitable glass reaction vessel similar to that described in Example I was used. The ingredients used are described in Table I. Table I Example IV V VI VII VIII E-caprolactone, gm 2,046 684 912 3,529 3747 2-hidroxyethyl acrylate, gm 2,082 232 232 599 381 Stannous Octanoate grams 0.208 0.052 0.073 0.208 0.208 ppm 50 57 64 50 50 Monomethyl ether of Hydroquinone grams 1.30 0.325 0.325 1.30 1.30 ppm 315 355 284 315 315 The epsilon-caprolactone was introduced into the reaction vessel and heated to 140 C while sparging with nitrogen. When the temperature reached 140 C, the nitrogen sparge was changed to an air sparge and a mixture of the other three ingredients was added to the caprolactone. The time to feed the mixture and time held at the reaction temperature of 1400C is given in Table fl. After the reaction tie had elapsed, the product was cooled to room temperature (about 25 C), and stored as a residue product. The analysis of the residue products is given in Table II. Table II EXAMPLE "7 V VI VII VIII Feed tine, mill 20 5 4 5 1 Reaction time, hr 5 6 6 5.5 7 Hydroxyl Number 244.5 114.3 84.5 75.3 42.5 Acid Number 3.69 1.85 1.31 2.44 2.47 Viscosity, cps (room temperature) 151 189 - - appearance liquid slush solid solid solid Example IX A 5000 ml glass reaction flask was equipped with a stirrer, a thermometer fitted with a temperature controller, a condenser, and gas sparging tube. A 2052 g. charge of dry (#100 ppm H2O) epsiloncaprolactone and 0.975 g. of the monomethyl ether of hydroquinone was added to the flask. A nitro sporge was bubbled below the liquid surface as the material was heated to 130 C. The sparge was switched fran nitrogen to air and maintained below the surface far 10 min. and the sparge tube was then raised above the liquid surface and the air space was flushed with air during the remainder of the reaction. A charge of 1044 g. 2-hydroxyethyl acrylate containing 0.155 g. stannous octanoate was added over 30 min. and the reaction was then maintain ed at 130 C for about 10 hours and then allowed to cool to n temperature. A 13C trin analysis showed 7.6 weight percent of 2-hydroxyethyl acrylate, nil #-caprolactone, and an average value of n in formula I of 2.7. The viscosity of the product was 84 cps. Example X A 5000 ml glass reaction flask was equipped with a stirrer, a thermcmeter fitted with a temperature controller, a condenser, and gas sparging tube. A 2052 g. charge of dry (#100 ppm H20) epsilon- caprolactone and 1.625 g. of the monomethyl ether of hydroquinone was added to the flask. A nitrogen sparge was bubbled below the liquid surface as the material was heated to 130 C and for 30 min. after reaching 130 CL spa sparge below the surface was switched fran nitorgen to air and a nitrogen flush of the air space above the liquid surface was begun. A charge of 1044 g. of 2-hydroxyethyl acrylate containing 0.155 g. stannous octanoate was added in a single hatch. The reaction was maintained at 13R for 8 hours and then allowed to cool to room temperature. A liquid chromatographic analysis of the product showed it to be identical to that of Example III. Example XI A nitrogen flushed 50 gallon, glass-lined reactor was charged with about 242 pounds of dry (s100 ppm H2O) epsiionprolactone and 100 g. of the monomethyl ether of hydroquinone, Nitrogen was sparged into the liquid as it was heated to 100 C over about 1.5 hours. The sparge was then switched to air, and an additional flush of nitrogen was then added to the reactor vapor space during the remainder of the reaction. After sparging with air for 1.5 hours, a dharge of 124 pounds of 2-hydroxyethyl acrylate containing 8.8 g. of stannous octanoate was then heated to 125-130 C over about 2 hours. The reaction was held at this temperature for about 8.5 hours and then oooled to about 65 C over 1.5 hours before being discharged. The product mixture contained 7.7% by weight 2-hydroxyethyl acrylate, less than 4% caprolactone, and about 580 parts per million of the monomethyl ether of hyfroquinone. The average value of n in formula I was 2.7 and the product had a viscosity of 84 cps. The residues R4 and R5 are preferably alkyl C1 - C6, most preferably alkyl C1 - C4, and hydrogen, e.g. methyl, ethyl, propyl, i-propyl, butyl, pentyl, hexyl, i-hexyl.

Claims: What is Claimed is: 1. A composition comprising: (a) 0 to 10 weight percent of a lactone, (b) greater than 0 to about 20 weight percent of hydroxyalkyl acrylate or methacrylate, (c) 2 or less weight percent of diacrylates, (d) tO or less weight percent of products resulting from Michael addition, acrylic polymerization1 transester ification reactions, or other side reactions, (e) remainder to 100 weight percent of a reactive onomer of the following formula: EMI14.1 wherein R, R1, R2, and R3 are independently hydrogen or methyl, R4 and R5 are independently hydrogen or alkyl of from 1 to 12 carbon atoms, x is from 4 to 7, and both n and the average value of n in the composition are equal to or greater than 1, and .(f) less than about 200 parts per million of catalyst. 2. A composition as defined in claim l wherein component (a) is epsilon caprolactone. 3. A compositfon as defined in claims 1 or 2 wherein component (b) is hydroxyethyl acrylate or methacrylate. 4. A composition as defined in claims 1 or 2 or 3 wherein in component (e) the average value of n is 1 to 12. 5. A composition as defined in claims t or 2 or 3 wherein in component (e) the average value of n is 2 to 3. 6. A composition as defined in claim 1 which contains an inhibitor to prevent polymerization of the hydroxyalkyl acrylate or methacrylate double bond. 7. A process for preparing the composition of claim 1 which comprises reacting, in an atmosphere that con- tains oxygen,a lactone and hydroxyalkyl acrylate or methaacrylate in the presence of less than about 200 parts per million of a catalyst and less than leo00 parts per million of an inhibitor to prevent polymerization of the hydroxyalkyl acrylate or methacrylate at a temperature of from about 100 to about 1400C. 8. A composition as defined in claim 7 wherein the lactone is epsilon-caprolactone. 9. A composition as defined in claims 7 or 8 wherein the hydroxyalkyl acrylate or methacrylate is hydroyethyl acrylate or methacrylate.

Inventors: DOMEIER, LINDA ANN, KOLESKE, JOSEPH VICTOR
Applicants: UNION CARBIDE CORPORATION
Application year: 1983
Main classification: C08F299
IPC codes: C08F20, C07C67, C08G63, C09D167, C07C69, C08F299, C08F220, C08F290