PROCESS FOR THE PREPARATION OF POLYMERIC COMPOSITIONS

Abstract: Described herein is a process for the polymerization of a reactive monomer derived from the reaction product of a hydroxyalkyl acrylate or methacrylate and a lactone with other ethylenically unsaturated monomers. The resulting polymeric compositions can be made into high quality industrial finishes by incorporation of various conventional crosslinking agents, plus other normally used formulating ingredients.

Description: Technical Field This invention is directed in general to a pros for the preparation of polymeric compositions, in particular, the polymerization of a reactive monomer derived fran the reaction product of a hydroxy- all acrylate or methacrylate and a lactone with other ethylenically unsaturated monomers. The polymeric compositions can be made into high quality industrial finishes by irrpration of various conventional crosslinking agents, plus other rsnnally used forrrulating ingredients. Background Art In the field of coating csitions, efforts have been en made and are presently being trade to increase the flexibility and hardness of cured coatings and finishes in order to make them ncre suitable for such uses as automotive finishes, appliance finishes, business machine finishes, house siding, general nretal finishing and the like. The inclusion of epsilon caprolactone into coating compositions is to increase the flexibility of the coating films. See, for example, U.S. Patent Reissue 30,234 in which epsilon caprolactone is reacted with a polymer, e.g., styrene and 2-hydroxyethyl acrylate, and thereafter with a crosslinking agent, e.g., melamine formaldehyde, to give a crosslinked rrodified copolymer having desirable flexibility, hardness and chemical durability. The polymeric compositions of the present invention utilize epsilon caprolactone in noval oligomeric composition which can polymerize with other ethylenically unsaturated inners and thereafter can be crosslinked to give polymeric coating composition having a highly desirable combination of flexibility and hardness in addition to excellent adhesiveness, hydrolytic stability, chemical compatability and solvent resistance. The novel oligomeric compositions are described more fully in copening U.S. Patent Application Serial No. (D- ) filed on an even date herewith. 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 0.1% by weight of p-toluene sulphonic acid as catalyst at a temperature of 45 C for a tine of 4 burs. The catalyst is described as an organic acid catalyst selected from the group consisting of halogen substituted aliphatic carboxylic acids other than trichloroacetic acid, alkane sulphonic acids, benzene sulphonic acid and lower alkyl substituted benzene sulphonic 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 irethacrylate and epsilon-caprolactone using 0.1t by weight of the product is p-toluene sulphonic acid catalyst. The polyester product is descries as having a molecular weight of 437 and being a viscous liquid. The polyesters produced in said patent trave residual acid catalyst present in relatively large amounts (i.e., about 1000 parts per million). In les 1 and S the desibed polymerization is stated to be lete. The epsilon caprolactone . hydroxyethyl acrylate product of Example 1 was fürther copolymerized with styrene (Examples 2 and 3) and vinyl acetate (Example 4). However, the presence of such strong acid catalyst in the polyester product could lead to degradation of the product. Also, its presence may decrease the shelf life and pot life of coating systems cured fun oligaers containing the polyester product and certain cross-linking agents. The use of polyester product containing such strong residual acids nay generate highly colored by-products that may be detrimental 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 ales I to III, hydroxyethyl acrylate is added to epsilon-caprolactone which was heated to 130 C (Example I) or 1200C (Examples II and In). Large amounts of a catalyst such as TPT titanate (greater than 2000 parts per million- Example I) or a mixture of stannous octonate and dibutyltin dilaurate (Examples II and III) greater than 1500 parts per million were added to the reaction mixture. Additionally, the reaction carried art 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 for 6 hours (Examples I) and 120 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 epsilon caprolactone @ hydroxyethyl acrylate product of Examples I, II and was further reacted with a diisocyanate. However, the use of the large amounts of catalyst and inhibitor in the polymerization described in U.S. Patent 4,188,472 can have deletinus effects on the sLnt use of the lactone nodified resin in polymerization m copolymerization reactions and/or cross- linking reactions. European Patent Application No. 0044 393A2 titled "Process For Production of A (Meth) Acrylate Resin With Hidroxyl Groups and edified By Epsilon-Caprolactone" describes the reaction of at least one monoester of acrylic or methacrylic acid with an alkane dial with 2-4 carbon atans in the molar ratio of 1.5:1 to 1:3 with epsilon- caprolactone. The reaction is described as occuring at a temperature of 60-130 C in the presence of an organotin compound. Specifically, in Example I an and fran 2-hidroxyethyl acrylate and dibityltin oxide are heated to 120 C and epsilon-caprolactone is added over the course of two hours. This mixture is heated for two nore burrs at 120 C. This Example was repeated and the reaction product was shown to contain greater than 50 weight percent of unreacted 2-hydroxyethyl acrylate. The epsilon caprolactone . hydroxyethyl acrylate uct of Example 1 was further polymerized with methyl methacrylate, 2-ethylhexyl acrylate and 2-hidroxyethyl acrylate. Disclosure of the Invention The present invention is directed to a process for preparing a polymeric composition comprising polyrrerizing one or rrore ethylenically unsaturated monomers with a composition comprising: : (a) 0 to 10, preferably 0 to 5, weight percent of a lactone, (b) greater than 0 to about 20 weight percent, preferably less than 10 weight percent of hydroxyethyl acrylate or meth acrylate, (c) 2 or less, preferably 1 or less, weight pert of diacrylates, (d) 10 preferably S or less weight percent of prroducts resulting trun Michael addition, acrylic polymerization, transesterification reactions, or other side reactions, (e) remainder to 100 weight percent of a reactive monomer of the following formula: : EMI5.1 wherein R, R1, R2 and R3 are independently hydrogen or "ethyl and R4 and R5 are independently hydrogen or alkyl of from 1 to 12 carbon atoms and x is fran 4 to 7 and both n and the average value of n in the compositions are eaaal to or greater than 1, and (f) less than about 200, preferably less than abut 100 pats per inillion of catalyst. The invention is further directed to a process for preparing a crosslinked polymeric coating composition comprising: (1) polymerizing one or more ethylenically unsaturated monomers with a composition comprising: (a) O to 10, preferably 0 to 5,weight percent of a lactoin, (b) greater than 0 to about 20 weight percent, preferably less than 10 weight percent of hydroxyethyl acrylate ar methacrylate, (c) 2 or less, preferably 1 or less, weight percent of diacrylates, (d) 10 preferably 5 or less weight percent ofproducts resulting from Michael addition, acrylic polymerization, transesterification reactions, or other side reactions, (e) remainder to 100 weight percent of a reactive monomer of the following formula: EMI6.1 wherein R, R1, R2 and R3 are independently hydrogen or methyl and N and 8 are independently hydrogen-or alkyl of from 1 to 12 carbon atoms, preferably alkyl C1-C6, most preferably alkyl C1-C4, and hydrogen, e.g. methyl, ethyl, propyl, i-propyl, butyl, pentyl, hexyl, i-hexyl; ; and x is fran 4 to 7 and n both n and the average value of n in the composition are equal to or greater than 1, and (f) less than about 200, preferably less than about 100 pats per million of catalyst; and (2) cross linking the polymeric composition of (1) with an isocyanate resin or an amino resin selected from the group consisting of melamine formaldehydes, urea formaldehydes and benzoguanamine formaldehydes. The coating compositions of this invention exhibit highly desirable flexibility and stability, chemical compatibility and solvent resistance. The polymeric composition and the crosslinked polymeric coating composition prepared by the above described processes arealso part of this invention. Detailed Description The novel oligomeric compositions utilized in the process of this invention in preparing the polymeric compositions and the cross linked polymeric coating compositions are nore fully described in copending U.S. Patent Application Serial No. (D- ) filed on an even date herewith. ma oliganeric compositions are spared reacting a lactone with a hydroxyalkyl acrylate or xthacrylate. me lactone used as the starting material is characterized by the following formula: EMI7.1 herein R4 and R' are lssydr¯ or allyl of fin 1 to 12 carton atoms, and x is fran 4 to 7. The preferred lactone is epsilon-caprolactone. The hudroxyalkyl acrylates or methacrylates include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloro propyl methacrylate, 2-hydroxy-3-chloro propyl acrylate, 2,3-dihydroxy propyl methacrylate, 2,3-dihydroxy propyl acrylate, and the like, or mixtures thereof. Hydroxyethyl acrylate is preferred. The oligomeric compositions are prepared by reacting the lactone with the hydroxyalkyl acrylate or methacrylate in the presence of less than about 200 parts preferably less than 100 parts per million of a catalyst. The catalyst Which nay be used herein includes one or of organometallic compounds and other mettalic compounds such as stannic chloride; ferric chloride and other Lewis, Bronsted and protonic acids. Preferred catalysts include stannous octoate, dibutyltin dilaurate, and other tin compounds, titanates such as tetraisopropyl titanate and butyl titanate. me oligomer reaction is carried out at a temperature of from about 100 to about 140 C, preferably from about 120 to about 130 C. The reaction nay be carried cut at atmospheric pressure although higher or lower pressures may be used. The reaction is generally carried out in the presence of oxygen to inhibit polymerization of the hydroxyalkyl acrylate or methacrylate. The reaction is carried cut for a period of from about 2 to about 20, preferably from about 3 to about 11 hours. The oligomer reaction is carried out in the presence of a suitable inhibitor to prevent polymerization of the hydroxyalkyl acrylate or nethacrylate double bond. These inhibitors include the monomethyl ether of hydroquinone, benzequinone, phenothiazine, methyldroquinone, 2,5-di-t-butylquinone, hydroquinone, and other common free radical inhibitors known in the art. The level of inhibitor used is less than 1000 parts per million and preferably less than 800 parts per million, and rtost preferably less than 660 parts per million. The polymeric compositions and crosslinked polymeric coating compositions of this invention can be prepared by onventional polymerization techniques in which the novel oligomeric composition is blended with one or more ethylenically unsaturated monomers in the presence of solvents, chain transfer agents and polymerization catalysts and heated to about 1003C to 200 C for about 2 to 6 hours. Solvents which can be used in these conventional polymerization techniques are well known in the art and include for example, nethyl normal-amyl hetone (2-heptanone), normal-butyl alcohol, metyl ethyl ketone (2-butanone) and the Uke. Suitable chain transfer agents include t-dodecylmercaptan and the like. Suitbble polymerization catalysts include, for example, azo-bis-isobutyronitrile, benzoyl peroxide and the like. Suitable ethylenically unsaturated monomers which can be employed in the process of this Iinntion include among others hydroxyl functional acrylic monomers, the esters of acrylic or methacrylic acid and monohydric alcohols, alpha, beta ethylenically unsaturated carboxylic acids and vinyl hydrocarbons. The functional acrylic monomers can include 2-hydroxyethyl acrylate, 2-hydroxyethyl itethacrylate and the like. Suitable esters of acrylic or nethacrylic acid and monohydric alcohols include arrong others ethyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylheyl acrylate, hexyl acrylate, decyl acrylate, cyclohexyl acrylate, metyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, lauryl methacrylate and the like. The preferred esters are ethyl acrylate and butyl acrylate. Suitable alpha, beta ethylenically unsaturated carboxylic acids include among other acrylic acid,, nethacrylic acid, itatonic acid, crotonic acid and the like. Preferred are acrylic acid and methacrylic acid. Suitable vinyl hydrocarbons include, for example, styrene, alpha methylstyrene, vinyl toluene, t-butylstyrene, chlorostyrene and the like. The preferred vinyl hidrocarbon is styrene. Other monomers such as vinyl acetate, acrylonitrile, vinyl chloride, methacrylonitrile and the like can also be included in the polymeric compositions of this invention. me concentration of the novel oligsmers in the polymeric compositions of tis invention can range from about S to about 90 , weight percent preferably from about 20 to about 40 weight percent. The concentration of the other ethylenically unsaturated monomers in the polymeric compositions of this invention can range from about 90 to about 5 weight percent, preferably from about 60 to about 80 weight percent. The number average molecular weight of the polymeric compositions of this invention can range from 1,000 or less to about 100,000 or greater. The polymeric compositions of the present invention utilize epsilon caprolactone in novel oligomeric compositions which are reacted with other ethylenically unsaturated monomers by addition polymerization. 4silon caprolactone is not grafted into the polymeric compositions. It is believed that a unique distribution of caprolactone along the polymer backbone is obtained by addition polymerization of the oligomer as opposed to polymers prepared by the grafting reaction. Polymeric compositions prepared by either addition polymerization or grafting of caprolactone can contain the same amount of caprolactone ha the distribution of caprolactane along the polymer backbone would be different. In grafting, the caprolactone distributes along the polymer backbone in a statisitical manner whereas, in addition polymerization of a caprolactone-containing oligomer, the caprolactone is distributed in a nonstatistical manner. Unique coating properties can be obtained utilizing the polymeric compositions of the present invention as opposed to polymeric compositions grafted with caprolactone. Also in the grafting reaction caprolactone may react with any acidic monomers used in preparing the polymer, whereas by using the oligomers no reaction with acidic monomers will occur. The corsslinkable polymeric coating compositions of this invention contain an isocyanate resin or an amino resin selected from the group consisiting of melamine formaldehydes, urea formaldelhydes and benzoguanamine formaldehydes. A melamine formaldehyde resin is preferred such as hexamethoxymethyl melamine. Butylolated melamine formaldehydes can also be used. The concentration of the amino resin in the polymeric coating compositions of this invention can range from about 10 to about 50 weight percent of the total weight of the coating composition. me crossliakable polymeric coating compositions can also contain an organic solvent and a catalyst as optional components. Any of the oonventional solvents used in the coatings industry can be used at a concentration preferably below 50 weight percent of the total weight of the coating composition. While larger amounts could conceivably be used, the use of larger amounts would destroy the high solids nature of the coating; solvents are generally added in the small amounts indicated to improve flowability during application of the coating oomposition to the substrate. In sate instances an acid catalyst might be desired to improve the efficiency of the isocyanate resin or amino resin crosslinking reaction during curing. The concentration of the catalyst can vary from zero to about 10 weight percent based on the total weight of the coating compositi composition. The particular catalyst used and its concentration are dependent to a degree upon its catalytic activity and the specific wnents present in the coating composition. These catalysts are known to those skilled in the art and include hydrochloric acid sulfuric acid, p-toluene sulfonic acid, nwµh me sulfonic acid, dodecylbenzene sulfonic acid, phosphoric acid and its alkyl derivates maleic acid, trimellitic acid, phthalic acid, succinic acid, and the like. The crosslinkable polymeric coating compositions can also contain pigments, fillers, and other additives conventionally present in coating compositions in their convetional quantities. The particular cnes selected are of no consequence to the basic invention. In preparing the crosslinkable polymeric coating compositions, the ingredients are mixed by the conventional procedures used in the production of paints, inks or coating compositions. These procedures are so well know to those skilled in the art that they do not require further discussion here. The crosslinkable polymeric coating compositions are applied to a surface or substrate by oonventional means and then thermally cured by heating at a temperature of about 100 C to 375 C preferably from 125 C to 200 C for a period of time sufficient to obtain a dry film. Generally, this time will range from about one zninute to 2 hours. The components present in a particular cross- linkable polymeric coating compositions will determine the temperature and tine that will be required to obtain an adequate cure and .good film coating. The crosslinkable polymeric compositions of this invention can be high solids coating compositions and they can contain as much as 90 weight percent or more Solids therein. Generally the total Solids content of the coatings compositions of this invention range from about 25 to 90 weight percent, preferably from about 50 to 90 weight percent, of the total weight of the coating compositions. The cured coating compositions were evaluated according to the following procedures: Forward Impact Resistance: a measure of the ability of a cured film coating to resist rrrtrre from a falling weight. A Gardner Impact Tester Model IG-1120 using an eight pound dart was used to test film coatings cast and cured on steel panels, The dart was raised to a given height in inches and dropped onto the coated side of the coated steel panel. me inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the films forward impact resistanoe. Pencil Hardness: pencil leads of increasing hardness values were forced against the film coating surface in a precisely defined reeeer until one pencil lead marred the surface of the film coating. me surface hardness was considered as the hardest pencil grade which just failed to nrar the film coating surface. The leads in order of softest to hardest were reported as follows: 6B, SB, 4B 3B, 2B, B, B, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and Solvent Resistance: a treasure of the resistance of the cured film to attack by methyletbyl ketone (MEX) and was reported as the number of rubs or cycles of nethylethyl ketone soaked cheesecloth required to rerrare one half of a cured film from the test area. The test was performed by stroking the cured film with a methylethyl ketone soaked cheesecloth until that amount of film coating 'es removed. The number of cycles required to remove this amount of coating was a measure of the coating solvent resistance. Reverse Impact Resistance: a measure of the ability of a cured film coating to resist rupture from a falling weight. A Gadner Impact Tester Model IG-1120 using an eight pound dart was used to test film coatings cast and cured on steel panel. The dart was raised to a given height in inches and dropped onto the uncoated side of the coated steel penel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the films reverse impact resistance. Crosshatch Adhesion: a lattice pattern with either six or eleven cuts in each direction was made in the coating film to the substrate and pressure-sensitive adhesive tape was applied over the lattice pattern and then removed. The adhesion was evaluated by comparison with descriptions and illustrations as more fully detailed in ASTM D 3359-78. Gravelometer: standardized steel shot was projected by neans of a controlled air blast at the coated film specimens at a temperature of -10 C. The resultant chipping effect was evaluated by comparison with a set of photographic standards as more fully detailed in AS7M D 3170-74. Specular Gloss: a measure of the secular gloss of nonmetallic specimens for glossmeter geometries of 60 , 20 and 85 as more fully detailed in ASTM D 523-80. Distinctness of Image: A set of images reflected from a coated surface are carpared with a standard set of images correspond- ing to a given distirtness of image rating value. Rating values are fran 0 to 100 increasing in increments of 10. The instrument used in this test was a DOI 300 manufactured by Mechanical Design and Engineering Company, Burton, Michigan. The following examples are illustrative of the present invention and are not intended as a limitation a upon the scope thereof. As used in the examples zing herafter, the following designations, terms and abbreviations have the indicated meanings: in.-lbs. inch-pounds gram milligram C Centigrade degree F Fahrenheit degree caprolactone epsilon-caprolactone STY ate t-butyl acrylate 2-hydroxyethyl acrylate acrylic acid HEA.nCL n-mole caprolactone adduct of HEA CL caprolactone EA ethyl acrylate TBA n-buthyl acrylate MMA methyl methacrylate DA decyl acrylate CHA cyclohexyl acrylate HEMA 2-hydroxyethyl methacrylate HEMA.nCL n-mole caprolactone adduct of HEMA VCL vynil chloride VAc vinyl acetate Oligomer I A caprolactone modified hydroxyethyl acrylate oligomer having an average of two equivalents of caprolactone per equivalent of hydroxyethyl acrylate and prepared in accordance with the procedure described in copending U.S. Patent Aplication Serial Thb. tD- ) filed on an even date here with. Oligomer If: A caprolactone modified hydroxyethyl acrylate oligomer having an average of four equivalents of hydroxyethyl acrylate and prepared in accordance vith the procedure described in copending U.S. Patent Application Serial No. (D¯ ) filed on an even date wherewith. Oligomer III A caprolactone modified hydroxyethyl acrylate oligomer having an average of six equivalents of caprolactone per equivalent of hydroxyethyl acrylate and prepared in accordance with the procedure described in copending U.S. Patent Application Serial No. (D- ) filed on an even date herewith. oligomer IV A caprolactone modified hydroxyethyl acrylate oligoer having an average of ten equivalents of caprolactone per equivalent of hydroxyethyl acrylate and prepared in accordance with the procedure described in copending U.S. Patent Application Serial Ho. (D- ) filed on an even date herewith. cligooer V A caprolactone acidified hydroxyethyl methacrylate oligomer having an average of two equivalents of caprolactone per equivalent of hydroxyethyl methacrylate and prepared in accordance with the procedure described in U.S. Patent Application Serial Pb. (D- ) filed on an even date herewith. Initiator I A polymerization initiator commercially available from E.I. du Pont de Nemours and Company as Catalyst I A composition commercially available from American Cyanamid Company as Cycat 4040R. Catalyst II Stannous octoate. Catalyst III Dibutyltin dilaurate. Crosslinker I A methylolated melamine commercially available frem American Cyanamid Company as Cymel 303R. Crosslinker II A multifunctional isocyanate commercially available from Mobay Chemical Company as Desmodur N-75R. Dispersing Aid I A dispersing aid for grinding pigment corrercially available from Tenneco Chemical Company as Neosperse 657R. Catalyst IV A composition commercially available from Tenneco Chemical Company as Neosperse 657R. Example 1 Part A: Preparation of Monomer Mixture A monomer mixture was prepared by combining 110.8 grams of Oligomer I with 79.4 grams of styrene, 98.8 grams of n-butyl acrylate and 8.2 grams of acrylic acid. To the monomer mixture was added 6.8 grams of t-dodecylmercaptan, 4 grams of Initiator I dissolved in 30 grams of ethoxyethyl acetate and 65 grams of a mixture of ethoxyethyl acetate/toluene in a 2:1 weight ratio. Part B: Preparation of Resin Solution Into a one liter, three-neck reaction flask equipped with a nitrogen inlet and oulet, condenser, thermometer, stirrer and monomer mixture addition tube was added 30 grams of ethoxyethyl acetate which was heated to 115 C. At this temperature, the above monomer mixture was added into the reaction flask through the monomer mixture adition tube over a period of three hours. The addition of the mixture was regulated by means of a mechanical detering pump. After the addition of all the monomer mixture into the reaction flask, the temperature of the contents in the flask was lowered to 80 C and 1.0 grams of initiator I (post reaction) in 10 grams of ethoxyethyl acetate was added dropwise over a period of 15 minutes. The temperature was maintained t 80 C for one additional hour following the dropwise addition of initiator I and the resulting resin solution was thereafter removed from the reaction flask. The resin solution contained 61 percent w weight solids and had a hydroxyl number of > tely U7 mg KOH/gm resin. Part C: Preparation of Cured Coating Composition A coating composition was prepared containing 162.9 grams of the above resin solution, 46.8 grams of Crosslinker I, 0.83 of Catalyst I and 4.95 grams of a n-butanol. Ihe coating apposition mixed until homogeneous and then applied to Bonderite 100R treated steel panels using a drawdown blade with a 4 mil wet film clearance. The coating film was air dried for about 20 minutes and then cured by baking for 20 minutes at 150 C. The cured coating film was thereafter cooled to ambient temperature before testing for the specific properties designated in Table I. The results of the testing are given in Table I. Example 2 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts Oligomer II 150.3 grams Hydroxyethyl acrylate 30.6 grams Styrene 119.4 grams Butyl acrylate 148.5 grams Acrylic acid 12.3 grams t-Dodecylmercaptan 10.6 grams Initiator I 6.2 grams in 50 grams 2-heptanone Ihis mixture gives an average of two equivalents of caprolactone per equivalent of hydroxyethyl acrylate. The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethil a acetate were replaced with 75 grams of 2-heptanone and the post-reaction initiator used was Initiator I (1.0 grams in 28.7 grams 2-hepanone). me resulting resin solution contained 67 percent by weight solids and had a hydroxyl number of approximately 88 mg KOH/gm resin. me preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients were used in the following itouts: Above Resin Solution 149.7 grams Crosslinker I 35.2 grams Catalyst I 0.83 grams n-Butanol 4.95 grams The cured film coating was tested for the specific properties designated in Table I. Ihe results of the testing are given in Table I. Example 3 The preparation of the monomer mixture in Ewnple 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer III 93.0 grams hydroxyethyl acrylate 27.2 grams styrene 79.6 grams Butyl acrylate 99.0 grams Acrylic acid 8.2 grams t-Dodecylmercaptan . 7.07 grams Initiator I 4.2 grams in 20 grams 2-heptanone This mixture gives an average of tWD equivalents of caprolactone per equivalent of hydroxyethyl acrylate. The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 60 grams 2-heptanone and the post-reaction initiator used was Initiator I (1.0 grams in 22.3 grams 2-heptanone). Ihe resulting resin solution contained 69 percent by weight solids and had a hydroxyl number of approximately 87 mg KOH/gm resin. me preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients used used in the following amounts: Above Resin Solution 144.9 grams Crosslinker I 34.7 grams 4. Catalyst I 0.83 grams n-Butanol 4.95 grams me cured film coating was tested for the specific properties designated in Table I. me results of the testing are given in Table I. Example 4 The preparation of the monomer mixture in Example 1 was repetead with the exeception that the following ingredients were used in the following Oligomer IV 88.0 grams Hydroxyethyl acrylate 32.6 grams Styrene 79.6 grams Butyl acrylate 99.0 grams Acrylic acid 8.2 grams t-Dodecylmercaptan 7.07 grams Initiator I 4.2 grams in 20 grams 2-heptanone This mixture gives an average of two equivalents of caprolactone per equivalent of hydroxyethyl acrylate. The preparation of the resin solution in Example 1 was repetead with the exception that the 30 grams of ethoxyethyl acetate were replaced with 60 grams of 2-heptartone and the post-reaction initiator was Initiator I (1.0 grams in 22.3 grams 2-heptanone). me resulting resin solution oontained 69 percent by weight solids and had a hydroxyl number of approximately 87 mg KOH/gm resin. me preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin Solution 144.9 grams Crosslinker I 34.7 grams Catalyst 1 0.83 grams n-Butanol 4.95 grams me cured film coating was tested for the specific properties designated in Table I. me results of the testing are given in Table I. EMI24.1 Comparative Example A Part A: Preparation of Monomer Mixture A monomer mixture was prepared by combining 81.2 grams of hydroxyethyl acrylate with 158.8 grams of styrene, 197.6 grams of n-butyl acrylate and 16.4 grams of acrylic acid. Ib the mixture was added 13.6 grams of t-dodecylmercaptan and 7.95 grams of Initiator I in SO grams of 2-heptanone. Part B: Preparation of Unmodified Resin Solution Info a one liter, three-neck reaction flask equipped with EMI24.2 a nitrogen inlet and outlet, condenser, thermometer#and mixture addition tube was added 50 grams of 2-heçtanone which was heated to 115 C. At this temperature, the above monomer mixture was added into the reaction flask through the monomer mixture addition tube over a period of three hours. The addition of the monomer mixture was regulated by means of a mechanical detering pump. After the addition of all the monomer :nIxte into the reaction flask, the temperature of the contents in the flask was lowered to 80 C and 1.0 grams of Initiator I (post reaction) in 23.5 grams of 2-heptanone was added droise over a period of 15 minutes. Ihe temperature was maintained at sooc for one additional hour following the addition of Initiator I and the resulting unmodified resin solution was thereafter removed from the reaction flask. The resin solution contained 75 percent by weight solids. Part C: Preparation Of Cured Coating Composition A coating composition was prepared containing 133.0 grams of the above resin solution, 40.7 grams of Crosslinker 1, 0.83 grams of Catalyst I and 4.95 grams of n-butanol. The coating composition was mixed until homogeneous and then applied to Bonderite loOR treated steel panels using a drawdown blade with a 4 mil wet file clearance. me coating film was air dried for about 20 minutes and then cured by baking for 20 minutes at ISODC. me cured coating film was thereafter cooled tD ambient temperature before testing for the specific properties designated in Table I. me results of the testing are given in Table I. Comparative Example B Part A: Preparation of Monomer Mixture and Unmodified Resin Solution The preparation of the monomer mixture and unmodified resin solution in ccnlsrative Example A was repeated and the resulting unmodified resin solution was retained in the reaction flask. Part B: Preparation of Caprolactone Grafted Resin Solution Into the reaction flask containing 533 grams of the above unmodified resin solution was added 140 grams of caprolactone and 0.006 grams of Catalyst II. The amount of caprolactone was equivalent to the amount of caprolactone used in Example 1, i.e., two equivalents of caprolactone per equivalent of hydroxyethyl acrylate. The contents of the flask were heated to 140 C and maintained at this temperature for a period of three hours. The grafting reaction of the caprolactone cato the above unmodified resin was monitored throughout this period by gas chromatography. The resulting caprolactone nodified resin solution was thereafter removed from the reaction flask. The resin solution contained 82 percent by weight solids. Part C: Preparation of Cured Coating Composition A coating composition was prepared containing 123.0 grams of the above resin solution, 33.0 grams of Crosslinker I, 0.83 grams of Catalyst I, 4.95 grams of n-butanol and 4.75 grams of 2-heptanone. The coating compositions was mixed until homogeneous and the applied to Honderite loOR treated steel panels using a drawdown blade with a 4 mil wet film clearance. The coating film was air dried for about 20 minutes and then cured by baking for 20 minutes at 1500C. The cured coating film was thereafter cooled to ambient temperature before testing for the specific propertes designated in Table I. The results of the testing are given in Table I. Comparative Example C She preparation of the monomer mixture, unmodified resin solution, caprolactone grafted resin solution and the cured coating composition in Comparative Example B was repeated with the exception that 175 grams of caprolactona was used instead of 140 grams of caprolactone as used in Comparative Example B, i.e., 2.5 equivalents of caprolactone per equivalent of hydroxyethyl acrylate were used instead of 2.0 equivalents of caprolactone per equivalent of hydroxy- ethyl acrylate. Ihe resulting cured coating fibti was tested for the specific properties designated in Table I. Ihe results of the testing are given in The I. TABLE I COMPARISON OF METHODS FOR INTRODUCING CAPROLACTONE INTO POLYMERS AND THEIR RESULTING COATING PROPERTIES Polymer Composition Caprolactone Forward Impact Pencil Example Monomer (Mole Fraction) Content* (in./lbs.) Hardness 1 STY/BA/HEA.2CL/AA 2.0 100 F (0.387/0.392/0.164/0.058) 2 STY/BA/HEA/HEA.4CL/AA 2.0 100 F (0.382/0.386/0.0875/0.0875/0.057) 3 STY/BA/HEA/HEA.6CL/AA 2.0 80 HB (0.382/0.386/0.117/0.058/0.057) 4 STY/BA/HEA/HEA.10CL/AA 2.0 60 F (0.382/0.386/0.140/0.035/0.057) A STY/BA/HEA/AA 0.0 10 F (0.382/0.386/0.175/0.057) B Resin of Comparative Example A 2.0 40 HB grafted with caprolactone. C Resin of Comparative Example A 2.5 100 HB grafted with caprolactone *Caprolactone content reported in moles of caprolactone per equivalent of hydroxyl in polymer. Table I shows the properties obtained when caprolactone is added to a polymer by grafting (comparative examples B and C) and by addition polymerization of caprolactone modified oligomers having ethylenic unsaturation (examples 1 through 4). At equivalent caprolactone content, the forward inspect for the polymer ocwpositicns of Examples 1 through 4 is significantly higher than the forward impact of comparative Example B and also comparative Example A which was not modified with caprolactone. Pencil hardness is generally higher for the polymer composition of Examples 1 through 4 in comparison with comparative Example B at equivalent caprolactone content. In addition to the specific properties tested for in Table I, all of the final coatings prepared from the polymers in Examples 1 through 4 and comparative Examples A through C exhibited excellent crosshatch adhesion and resistance to methyl-ethyl ketone (2-butanone). The coating of Example 1 was further tested for potential chipping resistance by a gravelometer at -10 F to give the following results: Dry Coating Gravelometer Coating Identification Thickness Rating Example 1 2.5 mil. 5A, 6A Example 2 5.0 mil. 6A, 7B The results show excellent chipping resistance for the coating of Example 1. Example 5 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer I 75.0 grams styrene 26.1 grams t-Butyl acrylate 46.6 grams butyl acrylate 44.5 grams Acrylic acid 5.1 grams t-Dodecylmercaptan 4.4 grams Initiator I 2.6 grams in 21 grams of 2-heptanone t}xyethyl Acetate 44.0 grams Toluene (2:1 weight ratio) The preparation of the resin solution in Example 1 was repeated vith the exception that the 30 grams of ethoxyethyl a acetate were replaced with 50 grams of 2-heptanone and the post reaction initiator used was Initiator I (0.42 grams in 21 grams of 2-heptanone). The resulting resin solution contained 59 percent by weight solids and had a hydroxyl number of approximetely 122 mg KOH/gm resin. The preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients were used in the following amounts: Axve resin Solution 167.0 grams Corsslinker I 48.8 grams Catalyst 1 0.83 grams n-Butanol 4.95 grams The cured film coating was tested for the specific properties designated *fl Table II. The results of the testing are given in Table II. Example 6 me prepazation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer I 60.3 grams styrene 20.8 grams t-Butyl acrylate 21.4 grams Ethyl acrylate 40.1 grams Acrylic acid 4.1 grams t-Dodecylmercaptan . 3.53 grams Initiator I 2.07 grams in 10 grams of 2-heptanone The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 30 grams of 2-heptanone and the post reaction initiator was initiator I (0.5 grams in 8.7 grams of 2-heptanone). The resulting resin solution contained 69.7 percent by weight solids and had a hydroxyl number of approximately 87 mg KOH/gm resin. me preparation of the cured coating composition in Example 1 was also repeated with the exoettion that the following ingredients were used in the fallowing amounts: Above Resin solution 143.5 grams Crosslinker I 34.7 grams Catalyst I 0.83 grams n-Butanol 4.95 grams me cured film coating was tested for the specific properties designated in Table II. me results of the testing are given in Table II. Example 7 She preparation of the monomer mixture in Exanple 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer I 75.5 grams Methyl Methacrylate 26.1 grams t-Eutyl acrylate 46.6 grams n-Butyl acrylate 44.5 grams Acrylic acid 5.1 grams t-Dodecylmercaptan 4.4 grams Initiator I 2.6 grams in 20 grams of 2-heptanone The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 36 grams of 2-heptanone and the post reaction initiator was Initiator I (0.5 grams in 10 grams of 2-heptanone). Tme resulting resin solution contained 73 percent by weight solids and had a hydroxy number of approximately 97 ng KOH/gh resin The preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients were used in the falling amounts: Above Resin Solution 137.0 grams Crosslinker I 38.8 grams Catalyst I 0.83 grams n-Butanol 4.95 grams The cured film coating was tested for the specific properties designated in Table The results of the testing are given in Table II. Example 8 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer I 60.2 grams t-Butyl acrylate 67.9 grams Ethyl acrylate 23.8 grams Acrylic acid 4.1 grams 3.5 grams initiator I 2.05 grams in 11.3 grams of 2-htaone me prepration of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 30 grams of 2-heptanone and the post reaction initiator was Initiator I (0.5 grams in 10 grams of 2-heptanone). The resulting resin solution contained 72 percent by weight solids and had a hydroxyl number of approximately 76 mg KOH/gm resin. me preparation of the cured coating carpsition in Example 1 was also repeated with the exception that the following ingredients were used in the following anoints: Above Resin Solutiar 138.9 grams Crosslinker I 30.4 grams Catalyst I 0.83 grams n-Butanol 4.95 grams me cured film coating 'as tested for the specific properties designated in Table II. me results of the testing are given in Table II. Example 9 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer X 75.0 grams styrene 26.1 grams t-Butyl acrylate 46.6 grams Decyl acrylate 73.7 grams Acrylic acid 5.1 grams t-Dodecylmercaptan 2.2 grams Initiator I 2.6 grams in 20 grams of 2-heptanone The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 36 grams of 2-heptanone and the post reaction initiator was Initiator I (0.5 grams in 10 grams of 2-heptanone). The resulting resin solution contained 68 percent by wight solids and had a hydroxyl number of approximately 90 mg KOH/gm resin. The preparation of the cured coating wrposition in Example 1 was also repeated with the exception that the following ingredients were used in the following amounts: Above Pepsin Solution 147.1 grams Cro5slircer I 36.0 grams Catalyst I 0.83 grams n-Butanol 4.95 grams The cured film coating was tested the specific properties designated in Table II. The results of the testing are given in Table II. Example 10 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer I 60.2 grams Styrene 20.8 grams Cyclohexyl acrylate 58.4 grams n-Butyl acrylate 24.2 grams Acrylic acid 4.1 grams t-Dodecylmercaptan 3.53 grams Initiator I 2.07 grams in 10 grams of 2-beptanone The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 36 grams of 2-heptanone and the post reaction initiator was initiator 1 (0.5 grams in 10 grams of 2-heptanone). <RTI ID=35.11> 'Ihe resulting resin solution contained 69 percent by weight solids and had a hydroxyl number of approximately 84 mg KOH/gm resin. The preparation of the cured coating composition in Example 1 was also repeated with the ecxption that the falling ingredients were used in the following amounts: Above Resin Solution 144.7 grams Crosslinker I 33.6 grams Catalyst I 0.83 grams n-Butanol 4.95 grams me cured film coating was tested for the speeific properties designated in Table II. The results of the testing are given in Table II. Example 11 The preparation of the monomer mixture in Example 1 was repeated with the exction that the following ingredients were used in the following amounts Oligomer V 115.3 grams Styrene 79.4 grams n-Butyl acrylate 98.8 grams Acrylic acid 8.2 grams t-Dodecylmercaptan 6.8 grams Initiator T 4.0 grams in 30 grams of ethoxy ethyl acetate Ethoxyethyl Acetate/ 67.7 grams Toluene (2:1 weight ratio) me preparation of the resin solution in Example 1 was repeated. The resulting resin solution contained 63 percent t solids and had a hydroxyl number of approximately 79 mg KOH/gm resin. The preparation of the eured ooating composition in Example 1 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin Solution 80.0 gram Crosslinker I 15.8 grams Catalyst I 0.44 grams n-Butanol 2.5 grams The cured film ooatir was tested for the specific properties designated in Table II. The results of the testing are given in Table II. Example 12 The preparation of the monomer mixture in Example 1 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer V 75.5 grams Styrene 26.1 grams t-Butyl acrylate 46.6 grams n-Butyl acrylate 44.5 grams Acrylic acid 5.1 t-Dodecylmercaptan 4.4 grams Initiator I 2.6 grams in 21 grams of 2-heptanone Ethoxyethyl Acetate/ 43.6 grams Toluene (2:1 weight ratio) The preparation of the resin solution in Example 1 was repeated with the exception that the 30 grams of ethoxyethyl acetate were replaced with 50 grams of 2-heptanone and the post reaction initiator was initiator 1 (0.42 gas in 21 grams of 2-heptanone). The resulting resin solution contained 53 percent by weight solids and had a hydroxyl number of approximately 83 mg KOH/gm resin. This material was wacuan stripped to 75 percent by weight solids. The preparation of the cured coating composition in Example 1 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin Solution 133.3 grams Crosslinker I 32.2 grams Catalyst X 0.83 grams n-Butanol 4.95 grams The cured film coating was tested for the specific properties designated in Table II. TABLE II POLYMERS PREPARED WITH OLIGOMER I AND OLIGOMER V AND THEIR RESULTING COATING PROPERTIES Polymer Composition Caprolactone Forward Impact Pencil Example Monomer (Mole Fraction) Content* (in./lbs.) Hardness 5 STY/TBA/BA/HEA.2CL/AA 2.0 70 F (0.201/0.291/0.277/0.174/0.057) 6 STY/TBA/EA/HEA.2CL/AA 2.0 70 F (0.200/0.167/0.401/0.175/0.057) 7 MMA/TBA/BA/HEA.2CL/AA 2.0 70 F (0.207/0.288/0.275/0.174/0.057) 8 TBA/EA/HEA.2CL/AA 2.0 80 F (0.530/0.238/0.175/0.057) 9 STY/TBA/DA/HEA.2CL/AA 2.0 90 F (0.201/0.291/0.277/0.174/0.057) 10 STY/CHA/BA/HEA.2CL/AA 2.0 70 H (0.200/0.379/0.189/0.175/0.057) 11 STY/BA/HEMA.2CL/AA 2.0 80 F (0.387/0.392/0.164/0.058) 12 STY/TBA/BA/HEMA.2CL/AA 2.0 30 F (0.202/0.293/0.279/0.170/0.057) *Caprolactone content reported in moles of caprolactone per equivalent of hydroxyl in polymer Table II shows the properties obtained when caprolactone is added to a polymer by addition polymerization of Oligomer I or Oligomer V with other ettylenically unsaturated monomers. The final coatings prepared frrm the polymers in Examples 5 through 12 generally exhibit good or excellent forward impact and pencil herdness. In addition to the specific properties tested for in Table II, all of the final coantings prepared from the polymers in Example 5 through 12 exhibited excellent crosshatch adhesion and resistance to methylethyl ketone (2-butanone). The coating of Example 5 was further tested for potential chipping resistance by a gravelometer to give the following results: Dry Coating Gravelometer coeting Identification Thickness Rating Example 5 2.5 mil. 5A, 5B The results show excellent chipping resistance for the coating of Example 5. Example 13 Part A: Preparation of Monomer Mixture and Resin Solution A monomer mrxture was prepared in a stainless steel high pressure container cooled to -78OC by wtbining 55.4 grams of OLigomer I with 2.2 grams of vinyl acetate. To the monomer mixture was added 1.4 grams of t-dodecylmercaptan, 0.7 grams of Initiator I and 24.2 grams of 2-butanone. Into a separate reaction flask also cooled to -780C was added 51.0 grams of vinyl chloride and 101 grams of 2-butanone. me contents of the reaction flask were added into the stainless steel high pressure container which was then sealed and placed in a heating bath at sooc for a period of 24 burs. After the 24 hour period, the stainless steel high pressure container was cooled to ambient temperature, opened and the contents were removed with the aid of additional 2-butanone. me resulting resin solution was vacum stripped to give a resin solution containing 62 percent by weight solids. Part B: Preparation of Cured Coating Composition A coating composition was prepared containing 40.3 grams of the above resin solution, 8.3 grams of Crosslinker I, 0.21 grams of Catalyst I and 1.24 grams of nbutanol. The coating composition was mixed until homogeneous and then applied to Bonderite 100R treated steel panels using a drawdown blade with a 4 mil wet film clearance. me ooating film was air dried for about 20 minutes and then cured by baking for 15 minutes at 125 C. me cured coating film was after cooled to ambient temperature before tesing for the specific properties designated in Table III. The results of the testing are given in Table III. Example 14 The preparation of the monomer mixture and resin solution in Example 13 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer III 43.2 grams Vinyl Acetate 2.2 grams Vinyl Chloride 51.0 grams Hydroxyethyl Acrylate 12.4 grams Initiator 1 0.7 grm; t-Dodecylmercaptan 1.4 grams 2-Butanone 125.0 grams The resulting resin solution contained 68 percent by weight solids after vacuum stripping. The preparation of the cured coating composition in Example 13 was also repeated with the exception that the follong ingredients were used in the following amounts: Above Resin Solution 36.8 grams Crosslinker I 6.3 grams Catalyst I 0.21 grams n-Butanol 1.2 grams The cured film coating was tested for the specific properties designated in Table III. The results of the testing are given in Table III. Example 15 The preparation of the monomer mixture and resin solution in Example 13 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer IV 60.0 grams Vinyl Acetate 2.5grams Vinyl oride 60.0 grams initiator I 0.8 grams t-Dodecylmercaptan 1.5 grams 2-Butanone 181.0 grams The resulting resin solution contained 82 percent by weight solids after vacuum stripping. The preparation of the cured coating composition in Example 13 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin Solution 30.8 grams Crosslinker 1 2.2 grams Catalyst I 0.21 grams n-Butanol 1.2 grams The cured film coating was tested for the specific properties designated in Table III. The results of the testing are given in Table fli. Example 16 The preparation of the monomer mixture and resin solution in Example 13 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer 1 13.0 grins Vinyl Acetate 2.0 grams Vinyl Chloride 85.0 grams Initiator I 1.0 grams t-Dodecylmercaptan 1.4 grams 2-Butanone 93.0 grams The resulting resin solution contained 47 percent by weight solids. me preparation of the cured coating composition in Example 13 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin solution 41.0 grams Crosslinker I 1.5 grins Catalyst I 0.14 grins n-Butanol 0.8 grams Also, the coating composition was applied to Hoderite 100R treated steel panels using a dean blade with a 10 mil wet film clearance. The coating film was air dried for 15 minutes and then cured by baking for 15 minutes at 125 C. The cured film coating was thareafter cooled to ambient temperature and tested for the specific properties designated in Table III The results of the testing are given in Table III. Example 17 The preparation of the monomer mixture and resin solution in Example 13 was repeated with the exception that the following ingredients were used in the following amounts: Oligomer IV 13.0 grams Vinyl Acetate 2.0 grams Vinyl Chloride 110.0 grams Hydroxyethyl Acrylate 12.4 grams Initiator I @ 1.5 grams t-Dodecylmercaptan 1.5 grams Ethoxyethyl Acetate 92.6 grams She resulting resin solution contained 35 percent by weight solids. A pigment grind was then prepared by grinding in a sand mill to a Hegeman fineness of 7 the following: 51.0 grams of titaniun didde (rutile); 182 grams of the above resin solution; 0.5 grams of Dispersing Aid I; and 58 grams of 2-butanone. X a 10 gram We of this resinous pigment grind was added 0.868 grams of Crosslinker II and one drop of Catalyst III. The coating position was mixed until homogeneous and then applied to Bonderite 100R treated steel panels using a drawdown blade ith a 6 mil wet film clearance. be coating film was allowed to cure for three days at arrbient temperature before testing for tk specific proper ties designated in Table III. The results of the testing are given in Table III. Comparative Example D r preparation Of the monomer mixture and resin solution in ole 13 as repeated with the exception that the following ingredients were used in the following amounts: Stainless Steel High Pressure Container Hydroxyethyl Acrylate 29.0 grams Vinyl Acetate 3.5 grams Initiator I 1.0 grams 2-Butanone 8.05 grams Action flask Vinyl Chloride 79.0 grams 2-Butanone 101.0 grams The resulting resin solution contained 46 percent by weight solids. The preparation of the cured coating composition in Example 13 was also repeated with the exception that the following ingredients were used in the following amounts: Above Resin Solution 54.4 grams Crosslinker 1 12.7 grams catalyst 1 0.21 grams n-Butanol 1.25 grams Also, the coasting film was air dried for about 20 minutes and then cured by baking for 10 minutes at 125OC. The cured coating film was thereafter cooled to ambient temperature before testing for the specific properties designated in Table III. me results of the testing are given in Table III. TABLE III POLYMERS PREPARED WITH VINYL CHLORIDE AND CAPROLACTONE MODIFIED HYDROXYETHYL ACRYLATE Polymer Composition Caprolactone Forward Impact Pencil Example Monomer (Mole Fraction Content* (in./lbs.) Hardness 13 VC1/HEA.2CL/VAc 2.0 70 F (0.813/0.160/0.026) 14 VC1/HEA.6CL/HEA/VAc 2.0 45 F (0.814/0.106/0.054/0.026) 15 VC1/HEA.10CL/VAc 10.0 160 4B (0.926/0.046/0.028) 16 VC1/HEA.2CL/VAc 2.0 160 3H (0.957/0.027/0.016) 17 VC1/HEA.2CL/VAc 2.0 140 H (0.967/0.021/0.013) D VC1/HEA.VAc 0 < 10 2H (0.813/0.161/0.026) *Caprolactone content reported in moles of of caprolactone per equivalent of hydroxyl in polymer. Table III shows properties obtained when caprolactone is added to a polymer by addition polymerization of either Oligomer I, Oligomer III or Oligomer IV with vinyl chloride and other ethylenically unsaturated monomers. The forward impact for the polymer compositions of Example 13 through 17 is significantly higher than the forward impact of comparative Example D which was not modified with caprolactone. In addition to the specific properties tested for in Table III, all of the final coatings prepared from the polymers in Example 13 through 17 and comparative Example D exhibitited excellent crosshatch adhesion and resistance to methylethyl ketone (2-butanone). Example 18 A pigment grind was prepared by grinding in a sand mill to a Hegeman fineness of 7 the following: 202.13 grams of titanium dioxide (rutile); 250 grams of the resin solution prepared in Example 1; 15.74 grams of ethoxyethyl acetate and 9.19 grams of 2-heptanone. To this resinous pigment grind was added 78.64 grams of Crosslinker I, 2.55 grams of Catalyst IV, 11.6 grams of ethoxyethyl acetate, 65.9 grams of 2-heptanone and 57.85 grams of n-butanol. The resulting white coating composition had a viscosity of 31 sells using a Pb. 4 Ford cup. The coating composition was mixed until homogeneous and then applied to Bonderite 100R treated steel panels using a drawdown blade with a 4 mil wet film clearance. be coating film was air dried for 15 minutes and then cured by baking for 30 minutes at 250 F. me cured coating film was thereafter cooled to ambient temperature before testing for the specific properties designated below. me results of the testing are also given below. Forward act 140 in-lbs. Reverse Impact 80 in-lbs Pencil Hardness H Gloss at 60 C 90 at 20 C 65 Distinctness of Image 70 Gravelometer at -10 F 6A The results show good or excellent coating properties for the pigmented coating composition utilizing the resin solution prepared in Example 1.

Claims: Claims 1. A process for preparing a polymeric composition comprising poly merizing one or more ethylenically unsaturated monomers with a composition comprising: (a) O to 10 weight percent of a lactone, (b) greater than 0 to about 20 weight percent of hydroxy- alkyl acrylate or mathacrylate, (c) 2 or less weight percent of diacrylates, (d) 10 or less weight percent of products resulting fmn Michael addition, acrylic polymerization, transesterifi oation reactions, or other side reactions, (e) remainder to 100 weight percent of a reactive monomer of the following formula: : EMI49.1 wherein R, R1, R2, and R3 are independently hydrogen or methyl, R4 and are independently hydrogen or alkyl of from 1 to 12 carbon stars, x is fran 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 millicn of catalyst. 2. A prowess for praaring a crosslinked polyseric composition comprising: (1) polymerizing one or more ethylenically unsaturated monomers with a composition comprising: (a) 0 to 10 wight 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) 10 or less weight percent of products resulting from Michael addition, acrylic polymerization, trans esterificatian reactions, or other side reactions, (e) rainder to 100 weight perrent of a reactive monomer of the following formula: EMI50.1 wherein R, R1, R2, and R3 are independently hydrogen or methyl, R4 and R5 are independently hydrogen or alkyl of fan 1 to 12 carbon atans, x is fra 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; and (2) crosslinking the poly:teric composition of 11) with an isocyanate resin or a resin selected from the group consisting of melamine formaldehydes, urea formaldehydes and benzoguanamine formaldehydes. 3 A process as claimed in claim 1 or 2 wherein the one or more ethyleni cally unsaturated monomers are selected from the group consisting of styrene, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylic acid, ethyl acrylate, t-butyl acrylate, methyl methacrylate, decyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl methacrylate, vinyl chloride and vinyl acetate. 4. A process as claimed in any of the claims 1 to 3 wherein the lactone in (a) is present in a concentration of from 0 to 5 weight percent. 5. A process as claimed in any of the claims 1 to 4 wherein the hydroxy alkyl acrylate or methacrylate in (b) is present in a concentration of less than 10 weight percent. 6. A process as claimed in any of the claims 1 to 5 wherein the diacry lates in (c) are present in a concentration of 1 or less weight per cent. 7. A process as claimed in any of the claims 1 to 6 wherein the products resulting fran Michael addition, acrylic polyrnerization, transesteri fication reactions or other side reactions in (d) are present in a concentration of 5 or less weight percent. 8. A process as claimed in any of the claims 1 to 7 wherein, in the re active manager of (e), R, R1, R2, R3, R4 and R5 are hydrogen, x is five and the average value of n is two. 9. A process as claimed in any of the claims 1 to 8 wherein the catalyst in (f) is present in a concentration of less than about 100 parts per million. 10. A process as claimed in any of claims 1 and 3 to 9 wherein the one or more ethylenically unsaturated monomers are present at a concentration of fran about 5 to about 90 weight percent and the catposition compris- ing (a) through (f) is present at a concentration of from about 90 to about 5 weight percent. 11. A process as claimed in anv of the claims 2 to 9 wherein the one or more ethylenically unsaturated monomers are present at a concentration of from about 5 to about 90 weight percent, the composition comprising (a) through (f) is present at a concentration of frcn about 90 to about 5 weight percent and the isocyanate resin or amino resin is present at a concentration of f about 5 to aboot 50 weight percent. 12. A process as claimed in any of the claims 1 to 11 wherein the one or more ethylenically unsaturated nonarers are selected fran the group consisting of styrene, n-butyl acrylate, 2-hydroxyethyl acry late, methyl methacrylate, decyl acrylate, cyclohexyl acrylate, 2 hydroxyethyl acrylate, vinyl chloride and vinyl acetate.

Inventors: SMITH, DONALD FOSS, JR., WEBER, ROBERT JOSEPH, JR.
Applicants: UNION CARBIDE CORPORATION
Application year: 1983
Main classification: C08F299
IPC codes: C08G18, C08F290, C09D167, C08F299, C08F220