MXPA98006845A - Coating composition comprising a compound with functional groups bike- or spiral-ortoes - Google Patents

Abstract

The invention relates to a coating composition comprising a first compound containing at least one bicyclo- or spiro-orthoester group, and a second compound containing at least two hydroxyl reactive groups, the invention also relates to a process for curing this coating composition, more particularly, the latent hydroxyl groups of the bicyclo- or spiro-orthoester groups must be deblocked and reacted with the hydroxyl reactive groups of the second compound, if the present coating composition is to be cured; In addition, a process for producing bicyclo-orthoester compounds, from the corresponding oxetane compound, is described as polymers comprising at least one bicyclo- or spiro-orthoester group.

Description

COATING COMPOSITION COMPRISING A COMPOUND WITH FUNCTIONAL GROUPS BIKE- OR SPIRAL-ORTOESTER The invention relates to a coating composition comprising a first compound consisting of at least one bicyclo- or spiro-orthoester group. The use of compounds comprising bicyclo-orthoester groups in coating compositions is known from U.S. Patent Publication No. 4,338,240. In that patent publication, the use and preparation of compounds with bicyclo-orthoester functionality (hereinafter BikeLocus) is described. -ortoéster will be abbreviated BOE). For example, compounds with BOE functionality are described which are the adduct of two compounds comprising a hydroxyl group and a BOE group, and a compound comprising two isocyanate groups. The compounds are entangled by means of homopolymerization by cationic ring opening of the BOE groups. However, in that case, the presence of moisture must be excluded. Additionally, energy must be supplied, in the form of ultraviolet, infrared or microwave irradiation, or heat, during the polymerization process. The invention now provides a coating composition of the type mentioned above, which is free of these drawbacks. For that reason, the coating composition mentioned in the opening paragraph is characterized in that it comprises a second compound comprising at least two hydroxyl reactive groups. A coating composition comprising a compound comprising at least one bicyclo- or spiro-orthoester group (hereinafter the spiro-orthoester SOE will be abbreviated), is a composition having latent hydroxyl groups. In the presence of water or air humidity, the BOE or SOE groups will hydrolyze, forming hydroxyl groups. This reaction is also known as unblocking. During unlocking, few volatile components are released, if at all. When the BOE or SOE group is unblocked in this way, it is not possible to obtain a homopolymer of BOE or SOE groups by cationic polymerization. However, it has now been discovered that when a second compound comprising at least two hydroxyl-reactive groups in the composition is present, the unblocked hydroxyl groups can react with the hydroxyl-reactive groups to give an entangled polymer. The compounds with BOE and SOE functionality can be used as many binders or as reactive diluents in the coating compositions of the present invention. The use of compounds comprising BOE or SOE groups in coating compositions has several advantages over the use of compounds having free hydroxyl groups, such as reactive, hydroxyl-functional diluents, hydroxyl-functional main binders, for example, polyols of polyester and acrylate polyols, and even compounds in which the BOE or SOE groups have already been hydrolyzed. First, the viscosity of the compounds comprising BOE or SOE groups is lower than that of the corresponding hydrolyzed compounds. As a consequence, less viscosity reducing solvent that evaporates in the air in the coating composition is needed. Secondly, due to the stability of the compounds with BOE and SOE functionality, the pot life ratio: drying time of the compositions according to the invention is particularly favorable, since the hydrolysis is carried out only in the presence of water or of humidity. Third, in the coating compositions of the present invention, the compounds with BOE and SOE functionality have the advantage that the hydrolysis of the BOE or SOE group produces a substantial increase in the viscosity of the composition. A high viscosity will give reduced build-up of the coating composition on the substrate. Finally, it has been found that the coating compositions of the present invention give high construction performance. By BOE groups it is meant, in this context, groups that have a structure according to the formula I: wherein: X and Z, independently from each other, are selected from 0 linear or branched alkylene or alkenylene groups, with 1 to 4 carbon atoms, optionally containing an oxygen or nitrogen atom; Y is zero or independently selected from X and Z, from linear or branched alkylene or alkenylene groups, of 1 to 4 carbon atoms, optionally containing an oxygen atom or a nitrogen atom; Ri and R2 may be the same or different and are selected from the group of monovalent radicals comprising: * r hydrogen, hydroxyl, alkyl or alkenyl groups comprising 0 of 1 to 30 carbon atoms, which may be linear or branched and which may contain optionally one or more heteroatoms and groups selected from the group of oxygen, nitrogen, phosphorus, sulfone, sulfoxy and ester, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxide, amido, ether, ester , urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acyl; and divalent radicals comprising: alk (en) ylene groups having from 1 to 10 carbon atoms; groups which may be linear or branched and may optionally contain one or more heteroatoms and groups selected from the group of oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and ester, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acyl; ester groups, ether groups, amide groups, thioester groups, thioamide groups, urethane groups, urea groups and a simple ligation. Preferably, X, Y and Z are methylene, Ri and R2 in that case are linked to a divalent radical 2,6,7-trioxabicyclo [2.2.2] octane. In the case that Ri and R2 are both monovalent radicals, the BOE group, as defined by formula I, is equal to the compound with BOE functionality. The monovalent radicals Ri and R2 preferably, independently of one another, are selected from the group of hydrogen, hydroxyl and linear or branched alk (en) yl groups having from 1 to 20 carbon atoms, optionally substituted with one or more hydroxyl groups and which optionally comprise an ester group. Examples of those groups are: methyl, methylol, ethyl, ethylol, propyl, propylol, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, a -CH2-CH2-O-CO-alk (en) group ilo of 1 to 20 carbon atoms, and mixtures of them. Preferably Ri is linear or branched alkyl (en) yl having 1 to 20 carbon atoms, optionally substituted with hydroxyl, while 2 is methyl or ethyl. Alternatively, Ri can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and mixtures thereof, while R2 can be methylol, ethyl, ethylol or a group -CH2-CH2-0 -C0-alkyl (en) yl of 1 to 20 carbon atoms. When a divalent radical is selected for either or both Ri and R2 groups, compounds with high molecular weight BOE functionality can be formed. These may be adducts or polymers comprising several BOE groups. Thus, two BOE groups can form an adduct, selecting a monovalent radical for one of the two groups Ri and R2, and one radical divalent for the other. The BOE groups will then be linked together by the divalent radical. It is also possible to link the BOE groups by means of the divalent radicals, to the monomeric or oligomeric compounds. Such compounds with BOE functionality, for example, are as described in the aforementioned US Pat. No. 4,338,240. For example, two BOE groups can be linked to a dimeric fatty acid, for example, Pripol 1009 from Uniche a. Alternatively, in the configuration mentioned further back, the BOE groups may function as side groups or terminal groups, in a polymer chain. The polymers, for example, can be polyesters, polyacrylates, polyamides or polyurethanes. When the divalent radical is a simple ligation, the BOE group is directly attached to the polymer. When groups Ri and R2 are both divalent, BOE groups can be incorporated into the main chain of a polymer or can serve to link two polymer chains together. Preferably one or both of Ri and R2 groups are selected from the group of ester, ether, urethane, a single bond and alk (en) ylene groups having 10 carbon atoms, which may be linear or branched and may contain one or more ester, ether or urethane groups. The term SOE groups, in this case, refers to groups that have a structure according to formula II or III: in which: R3 and Rs are independently selected from the group consisting of linear or branched alkyl (en) yl, aryl or acyl, optionally containing one or more oxygen, nitrogen, sulfur or phosphorus atoms, optionally substituted with a halogen atom; and R4 and Re are independently selected from an alkylene group having 1 to 3 carbon atoms, optionally substituted with one or more groups selected from monovalent radicals, such as linear or branched alk (en) yl groups, aryl or acyl , optionally containing one or more oxygen, nitrogen, sulfur and phosphorus atoms; and divalent radicals, such as a simple ligation and an alkylene group having 10 carbon atoms, with or without one or more atoms and groups selected from oxygen, nitrogen, sulfur and phosphorus, and ether, ester and urethane groups. Preferably, R3 and Rs are independently selected from linear or branched alk (en) yl groups having from 1 to 4 carbon atoms, for example, a methyl or ethyl group. In the case that neither 4 nor Re is substituted with a divalent radical, the SOE group as defined by formulas II and III is equal to the compound with SOE functionality. When a divalent radical is selected as a substituent for either or both R 'and Re groups, compounds with SOE function, of high molecular weight, can be pre-prepared in the same manner as described above for the high molecular weight BOE compounds. When R 'or Rβ has a divalent radical substituent, adducts or polymers having SOE groups can be prepared as terminal groups or side groups. In formula III, R "and Rs may have both divalent radicals as substituents; in which case the SOE group can be incorporated into the main chain. The polymers can be, for example, polyacrylate, polyester, polyether, polyamide or polyurethane. Alternatively, R «may be the compound being simérate rich in point to cs, which gives an SOE compound according to the formula IV: Preferably, formula IV is: It is preferred that R. 'is ethylene, optionally substituted with a linear or branched alkyl group, having 1 to 5 carbon atoms, optionally containing one or more oxygen and nitrogen atoms. For example, R «can be: It is preferred that Rβ is propylene. In addition to the compound with BOE or SOE functionality, the coating composition according to the invention comprises a second compound comprising at least two hydroxyl reactive groups. The hydroxyl reactive groups are selected from the group of isocyanate, epoxy, acetal, carboxyl, anhydride and alkoxysilane groups. Mixtures of these groups in a compound are also included. Alternatively, the second compound can be an amino resin. Examples of compounds comprising at least two isocyanate groups are the aliphatic, alicyclic and aromatic polyisocyanates, such as trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 2,3-bune diisocyanate, hexamethylene diisocyanate. , octamethylene diisocyanate, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamelene diisocyanate, dodecamethylene diisocyanate, alpha ether diisocyanate, alpha '-dipropyl, 1,3-cyclopenne diisocyanate, 1,2-diisocyanate -cyclohexylene, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 4,4'-dicyclohexylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanato-ethane dicyclohexylene, m- and p-phenylene diisocyanate, 1,3- and 1,4-bis (isocyanatoethyl) benzene, 1,5-dimethyl-2,4-bis (isocyanato-methyl) benzene, 1,3,5 -triisocyanatobenzene, 2,4- and 2,6-toluene diisocyanate, 2,4,6-toluene triisocyanate, o-, -, and p-xylylene diisocyanate d alpha, alpha, alpha ', alpha' -tetramethyl, 4,4'-diphenylene diisocyanate-methane, 4,4'-diphenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylene diisocyanate, 1 , 5-naphthalene diisocyanate, isophorone diisocyanate and transvinylidene diisocyanate, and mixtures of the aforementioned polyisocyanates. Said compounds can also be adducts of polyisocyanates, for example, biurets, isocyanurates, allophonates, uretdiones and their mixtures. Examples of such adducts are the adduct of two molecules of hexamethylene diisocyanate or isophorone diisocyanate and a diol, such as ethylene glycol; the adduct of 3 molecules of hexamethylene diisocyanate and one molecule of water; the adduct of 1 molecule of tririethylolpropane and 3 molecules of isophorone diisocyanate; the adduct of 1 molecule of pentaerythritol and 4 molecules of toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate, obtainable from Bayer under the designation Desmodur < R > N3390, the uretdione of hexamethylene diisocyanate, obtainable from Bayer under the trade designation Desmodu R > N3400; the allophonate of hexamethylene diisocyanate, obtainable from Bayer under the trade designation DesnriodurCR) LS2101, and the isocyanurate of isophorone obtainable from Hüls under the trade designation Vestanate T1890. Additionally, the (co) polymers of isocyanate-functional monomers such as the alpha, alpha'-dimethyl-m-isopropenylbenzyl isocyanate are suitable for use. Finally, the aforementioned isocyanates and their adducts can be present in the form of blocked isocyanates, as is known to those skilled in the art. Examples of compounds comprising at least two epoxy groups are solid or liquid epoxy compounds, such as the di- or polyglyclic ethers of aliphatic, cycloaliphatic or aromatic hydroxyl compounds, such as ethylene glycol, glycerol, cyclohexanediol, mononuclear phenols di- or polyvalent, bisphenols, such as bisphenol A and bisphenol F, and polynuclear di- or polyvalent phenols; the polyglycidyl ethers of phenol-formaldehyde-novolac, epoxidized divinylbenzene, epoxy compounds comprising an isocyanurate group, an epoxidized polyalkadiene, such as epoxidized polybutadiene, epoxy hydantoin resins, epoxy resins obtained by epoxidising aliphatic and / or cycloaliphatic alkenes, such as dipentene, dicyclopentadiene dioxide and vinylcyclohexene dioxide; and resins comprising glycidyl groups, such as polyesters or polyurethanes having two or more glycidyl groups per molecule; or mixtures of the aforementioned compounds. Preferably, the cycloaliphatic compounds mentioned above are used, which comprise two or more epoxy groups. Alternatively, a (co) polymer of ethylenically unsaturated epoxy groups comprising compounds such as glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide and / or allyl glycidyl ether and, if desired, one or more ethylenically unsaturated monomers is used. , copolymerizable. Examples of compounds comprising at least two acetal groups are described, inter alia, in US Patent Publications 4,788,288, US 4,864,055, US 5,155,170 and US 5,336,807. Other suitable acetal functional compounds include the compounds obtained by reacting aminobutyraldehyde-di (m) ethylacetal 8ABDA) and the (co) oligomers or (co) polymers with carboxylic ester, isocyanate or cyclocarbonate functionality, for example, polyester, polyacrylate and polyurethane. An example of such a polymer includes the copolymer of glycerol cyclocarbonate methacrylate and styrene. It is also possible to use mixtures of compounds comprising at least two acetal groups.

Examples of compounds comprising at least two carboxyl groups include aliphatic, cycloaliphatic and aromatic polycarboxylic acids, saturated or unsaturated, such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dimeric fatty acid, acid maleic, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydrophthalic acid hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 3,6-dichlorophthalic acid, tetraalophthalic acid and mixtures thereof. Examples of anhydride-functional compounds include radical polymers of an unsaturated cyclic anhydride monomer, for example, maleic acid anhydride, itaconic anhydride or citraconic anhydride. Additionally, the copolymers of the anhydride monomers and one or more ethylenically unsaturated monomers can be used. These copolymers can contain from 10 to 50% by weight of anhydride groups. Examples of ethylenically unsaturated monomers are: styrene, substituted styrene, vinyl chloride, vinyl acetate and esters of acrylic or methacrylic acid, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (et) acrylate propyl, isopropyl (meth) acrylate, butyl (meth) acrylate, (terbutyl methacrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (met) 2,2,5-trimethylcyclohexyl acrylate and isobornyl (et) acrylate The anhydride-functional (co) polymer can contain small amounts, for example, 1 to 10% by weight, of ethylenically unsaturated carboxylic acid groups, for example, (meth) acrylic acid The molecular weight of the (co) polymer with anhydride functionality is preferably 1,000-50,000 When the coating composition according to the present invention is used, as a top coat, the ethylenically unsaturated monomer mentioned above it is used p reference in a molar ratio of 1: 1 with the anhydride monomer, as described in US 4,798,745. Alternatively, the anhydride-functional compound can be an adduct of an anhydride monomer and a polymer comprising a functional group. Examples of such adducts are: the polybutadiene adduct or a butadiene / styrene copolymer and maleic acid anhydride; the adduct of maleic acid anhydride and a styrene / allyl alcohol copolymer, esterified with an unsaturated fatty acid; terpene and maleic acid anhydride resins, polymer adducts comprising hydroxyl and anhydride monomers, for example, copolymers of hydroxyethyl (meth) acrylate or styrene / allyl alcohol and a tricarboxylic compound, capable of forming anhydride groups, such as is described in EP-A-0 025 917; the adduct of trimellitic acid anhydride and a polyol, as described in EP-A-0 134 691; and the adduct of a polymer comprising thiol groups and an unsaturated cyclic anhydride, such as maleic acid anhydride, itaconic anhydride or citraconic anhydride. It is also possible to use mixtures of compounds with anhydride functionality. Examples of compounds with alkoxysilane functionality are alkoxysilanes of the following general formula: R7 -Si- • T R7 -Si- -R « wherein T is a hydrolysable group, such as -OCH3, -OC2H5 or -OC2H4OCH3; and R7 and R1 are reactive groups independently selected from each other. Examples of such reactive groups include vinyl, aminoalkyl, epoxyalkyl and methacryloxyalkyl groups. It is also possible to use reaction products of alkoxysilane-functional compounds and mixtures of alkoxysilane-functional compounds and / or reaction products thereof. Examples of vinyl-functionalized alkoxysilanes include vinyltriethoxysilane and vinyltrimethoxysilane. As an example of a reaction product of a vinyl-functionalized alkoxysilane, mention may be made of the silicone resin formed by the reaction of (CH2: = CHSi? 3/2) x (R2SiO) y and styrene. The reaction products of alkoxysilanes with amino functionality can be prepared by reacting said silanes with inorganic acids HA: NH2 (CH2) 3Si (T) 3 + HA - >; A-NH (CH2) 3Si (T) 3 wherein A is the ion of the acid radical, or with esters of organic acids R9 (COOR? O) n, wherein n is an integer of at least 1; Rs is a linear or branched, optionally unsatur alkane radical, and Rio is a lower alkyl group, for example, an alkyl group of 1 to 4 carbon atoms, for example: NH2 (CH2) 3S1 (T) 3 + R9COOR10? RgCO-NH (CH2) 3Si (T) 3 i 2 NH2 (CH2) 3Si (T) 3 + 1 R10OOCRgCOOR10? j (T) 3Si (CH2) 3NH-OCR9CO-NH (CH2) 3Si (T) 3.

For example, the adduct of 1 mole of diethyl malonate and 2 moles of 3-aminopropyltrimethoxysilane is a suitable compound containing alkoxysilane. Also suitable for use are the reaction products of alkoxysilanes with amino functionality and the isocyanate-functional compounds. An example of a reaction product of an epoxy functional silane compound is the reaction product of beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and amines, acids and alcohols. Examples of methacryloxyalkyl trialkoxysilane reaction products are the reaction products of gamma-methacryloxypropyltrimethoxysilane and gamma-methacryloxy-propyltri (beta-methoxyethoxy) silane and vinyl functional monomers, such as styrene and methyl methacrylate. Examples of suitable amino resins are urea resins, guana ina resins and melamine resins, and mixtures thereof. Examples of urea resins are etherified methylolurea, butylurea and isobutylurea. An example of a guanamine resin is tetra (methoxymethyl) benzo-guanamine. Examples of melamine resins are hexa (methoxymethyl) melamine (HMMM) and isobutylated melamine. In addition to the compounds with BOE and SOE functionality and said hydroxyl-reactive compounds, other compounds may be present in the coating composition according to the present invention. Said compounds can be main binders and / or reactive diluents comprising reactive groups that can be entangled with the hydroxyl-functional compounds with hydroxyl function and / or the hydroxyl-reactive compounds. Examples include hydroxyl-functional binders, for example, polyester polyols such as those described in H. Wagner and co-authors Lack unstharze. 5a. edition, 1971 (Cari Hanser Verlag, Munich), polyether polyols, polyacrylate polyols, polyurethane polyols, cellulose acetobutyrate, hydroxyl-functional epoxy resins, alkyds and dendrimeric polyols, such as those described in WO 93/17060. Hydroxyl-functional oligomers and monomers, such as castor oil and trimethylolpropane, may also be present. Finally, ketone resins, asp rglyc acid esters and latent or non-latent amino-functional compounds, such as oxazolidines, ketimines, aldimines, di-ines, secondary amines and polyamines may be present. These and other compounds are known to those skilled in the art and are mentioned, in re others, in US 5,214,086. The ratio of hydroxyl-reactive groups to hydroxyl groups varies from 50 to 300 percent equivalents, preferably from 70 to 250 eq%. The invention further comprises a method for curing the coating composition of the present invention. More particularly, the latent hydroxyl groups of the compound with BOE or SOE functionality have to be deblocked and reacted with the hydroxyl reactive groups of the second compound, to allow the coating composition of the present to cure. The unblocking of the latent hydroxyl groups of the BOE and SOE compounds takes place under the influence of water in the form, for example, of air humidity or of added water. This unblocking preferably is catalyzed by a first catalyst selected from the group of Lewis acids, such as AICI3, SbCls, BF3, BeCl2, FeCl3, FeBr3, SnC n, TiC j, ZnCl2 and ZrC * and their organic complexes, for example , BF3Et2G, BF3-2CH3COOH, BF32H2O, BF3-H3PO4, BF3- (CH3) 2?, BF3-THF, BF3-2CH3OH, BF3-2C2H5OH and BF3-C6H5CH2, and Bronded acids. Preferably, the acids of Brónsted who have a pKa < 3, such as a mono- or dialkyl phosphate, a carboxylic acid having at least one chlorine and / or fluorine atom, an alkyl- or arylsulfonic acid or an (alkyl) phosphoric acid, more in particular, methanesulfonic acid, paratoluenesulfonic acid, optionally substituted naphthalenesulfonic acids, dodecylbenzenesulfonic acid, dibutyl phosphate, trichloroacetic acid, phosphoric acid and mixtures thereof. Such first catalysts can be blocked, if desired, which results in the release of the Lewis or Br? Nsted, under the influence, for example, of electromagnetic radiation (light or UV), heat or humidity. Acid-generating photoinitiators are described, among others, in G. Li Bassi and co-authors, Photoinitiators for the Simultaneous Generation of Free Radicáis and Acid Hardening Catalysts, Radcure '86 Proceedings, for example, 2-methyl-l- [4- (methylthio) phenyl] -2- [4-methylphenylsulfonyl] propan-l-one (MDTA) from Fratelli Lamberti SpA, Vese, Italy. Alternatively, Lewis acid generating compounds, such as IrgacureC > 261 by Ciba Geigy and trimethylsilylbenzenesulfonic ester.

The first catalyst can be used alone or as a mixture of catalysts in effective amounts. The term effective amount, in this case, depends on the use of the compound with BOE or SOE functionality. When the compound with BOE or SOE functionality is used as the main binder, sufficient catalyst will have to be present to hydrolyze practically all compounds with BOE or SOE functionality. However, if the compound with BOE or SOE functionality is used primarily as the reactive diluent, while other compounds are present as the main binders, the hydrolysis of at least a portion of the compound with BOE or SOE functionality will suffice. Amounts of 0 to 10% by weight may be sufficient with respect to the compounds with BOE and SOE functionality of the first catalyst. Preferably, from 0.3 to 8% by weight, more specifically, from 0.5 to 6% by weight will be present. The reaction of the unblocked hydroxyl groups, the BOE or SOE compound, the hydroxyl reactive groups of the second compound and, optionally, third compounds present in the composition comprising hydroxyl groups or hydroxyl reactive groups, preferably takes place under the influence of a second catalyst. Said catalysts are known to the skilled person. The second catalyst is used in an amount of 0 to 10% by weight, preferably 0.001 to 5% by weight, better still, in an amount of 0.01 to 1% by weight, calculated on the solid material (i.e. amount of BOE or SOE, the compound reactive to the hydroxyl and, optionally, the third compounds mentioned above). As an example of the various hydroxyl-reactive groups, the following catalysts can be mentioned. Polyisocyanates: dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, tin octoate, zinc octoate, aluminum chelate and dimethyltin dichloride. Polyepoxy compounds: tertiary amines and Lewis acids, such as BF3 or its organic complexes. Polyacetal compounds: paratoluenesulfonic acid and dodecylbenzenesulfonic acid. Polycarboxylic compounds: dodecylbenzenesulfonic acid. Polyanhydride compounds: organotin compounds, alkoxysilane compounds: organotin compounds, phosphoric acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid and tertiary amines; and amino resins: dodecylbenzenesulfonic acid. As can be seen from the foregoing, the first and second catalysts may be the same in some coating compositions. In that case, the amount of catalyst may be higher than that indicated for the first or second catalysts alone. The coating composition according to the invention can be part of a system of components, for example, a two component system. For example, a component can comprise both the compound with BOE or SOE functionality and the hydroxyl-reactive compound. The second component may comprise the catalyst for the hydrolysis of the compound with BOE or SOE functionality. Alternatively, a 3-component system may be employed. For example, a component may comprise the compound with BOE or SOE functionality. A second component can comprise the hydroxyl reactive component. A third component may comprise the catalyst for hydrolysis of the compound with BOE or SOE functionality. In addition, a coating composition such as that described may contain the usual additives, such as solvents, pigments, fillers, leveling agents, emulsifiers, antifoaming agents and rheology control agents.; reducing agents, antioxidants, stabilizers of the class of hindered amine photostabilizers (HALS), UV stabilizers, water traps, such as molecular sieves, and anti-settling agents. The application on a substrate can be carried out by any method known to those skilled in the art, for example, by roll application, spray application, brush application, flow coating, dipping or roll coating. Preferably, a coating composition such as that described is applied by spraying. The coating composition of the present invention can be applied to any substrate. The substrate can be, for example, metal, for example, iron, steel and aluminum; plastic, wood, glass, synthetic material, paper, leather or another coating layer. The other coating layer may comprise the coating composition of the present invention or it may be a different coating composition. The coating compositions of the present invention show particular utility as clear coatings (on base, water-containing and solvent-containing coatings), base coatings, pigmented finish coatings, sizing and fillers. The compositions are particularly suitable for refinishing motor vehicles and transport vehicles, and in the finishing of large transport vehicles, such as trains, trucks, buses and airplanes. The applied coating composition can be cured very effectively at a temperature, for example, 0-50 ° C. If desired, the coating composition can be baked, for example, at a temperature in the range of 50-120 ° C. The BOE functional compound of the present invention can be prepared in various ways. One such way is the transesterification of a polyol in an appropriate solvent. Examples of those polyols include glycerol, trimethylolpropane and pentaerythritol. The transesterification agent may be a trialkyl orthoester, selected from the group of triethyl orthoformate, triethyl orthoacetate and triethyl ortopropion. Preferably, solvents are used which are inert to the ransterification reaction, for example diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. The catalyst for that reaction can be a strong acid, for example, paratoluenesulfonic acid or BF3Et2 ?. Said procedure is described in T. Endo and co-authors, Polymer Journal, volume 13 (1981) p. 715. When the selected polyol is pentaerythritol, a BOE group comprising a hydroxyl group is formed. This BOE group is converted to a compound with BOE functionality by means of a transesterification reaction, or by reaction with an acid chloride. In this way, a BOE group with hydroxyl functionality can be bound, by transesterification, to a saturated or unsaturated carboxylic acid, preferably one having no more than 20 carbon atoms. The resulting BOE functionality compound has the advantage of not being volatile or hardly volatile, due to the high molecular weight; while, surprisingly, the viscosity remains low. For that reason, the compound with BOE functionality is highly suitable for use as a reactive diluent. When the carboxylic acid group is unsaturated, the coating composition of the present, comprising said compound with BOE functionality can be cured in two ways, ie, by means of the hydrolysed BOE group, as described above, and by means of the compound unsaturated In addition, the BOE group with hydroxyl functionality mentioned in the foregoing can be provided with a vinyl group, by means of a transesterification reaction with a (meth) acrylate. By polymerization under the influence of radicals, using a BOE comprising vinyl, a polyacrylate with BOE functionality can be prepared. The polyacrylate with BOE functionality can be further prepared by transesterification of a polyacrylate with a BOE group having hydroxyl functionality. Then, it is preferred to employ a polyacrylate having short chain esters, preferably esters having 1 to 4 carbon atoms. The advantage of said polylulose is that, after the transesterification reaction, the resulting alcohol groups can be isolated, for example, by distillation. In general, each polymer having an ester group as a side group, may be provided with BOE groups, by said transection. Examples of polymers include polyesters, polyethers, polyamides and polyurethanes. Alternatively, the BOE group can be provided with groups that are reactive or non-reactive, using, for example, compounds with isocyanate functionality. Additionally, two or more groups with BOE functionality can be intertwined, using a compound with polyisocyanate functionality. In this way, the BOE group can also be linked with hydroxyl functionality, for example, to hydroxyl functional polymers, for example, polyester polyols, polyether polyols and polyacrylate polyols. In addition, compounds with BOE functionality can be prepared by converting the corresponding ester-functional oxetane compounds with BF3Et2 ?, as described in E. J. Corey and coauthors, Tetrahedron Letters, 24 (1983), pp 5571-5574. The oxetane compounds have the following structure: wherein Rn, R12, R13, RIA and Ris, independently of each other, are selected from the group of hydrogen a linear or branched alkyl group having from 1 to 10 carbon atoms; and Rie is a linear or branched alkyl group having from 1 to 4 carbon atoms, substituted with a nucleophilic group selected from the group of hydroxyl, mercaptan and a primary or secondary amine and) or with an electrophilic group, selected from halogen and the methanesulfonate derivatives, p-toluenesulfonate and trifluoromethanesulfonate. Preferably Rie is hydroxymethyl, hydroxyethyl, chloromethyl or chloroethyl. The preparation of oxetane compounds comprising a hydroxyl group is described in J. B. Pattison, J. Am. Chem. Soc. 79 (1957), pp 3455-3456. Said hydroxyl-functional oxetane compounds can be converted to oxetanes comprising an ester group, by means of a transesterification reaction, with suitable esters Ri? (COORis) n, where n is an integer of at least 1, Ri? is an alkyl, aryl or acyl radical, saturated or unsaturated, having from 1 to 40 carbon atoms, optionally substituted with a reactive group, such as vinyl, carbonyl, carboxy ester, or hydroxyl; and Ris is an alkyl group having from 1 to 4 carbon atoms. Ris preferably is methyl, ethyl or propyl. The RisOH alcohols released by transesterification are isolated from the reaction mixture, for example, by distillation. Said suitable esters may be, for example, the methyl ester of a fatty acid and the fatty acid mixtures, for example, Edenor ME C6-10 of Henkel, and the dimethyl ester of a dimeric fatty acid, for example, Pripol 1009, of Unichema. Also the oxetane compounds comprising the ester group can be polymers, the oxetane compounds being terminal groups or side groups. In that case, R17 can be a polymeric group, such as polyester, polyether, polyacrylate, polyamide or polyurethane. Suitable polyesters can be obtained by nucleophilic addition of carbanions to alpha, beta-unsaturated carbonyl compounds. Polyesters terminated by an ester group, polycarboxylic acid derivatives, polyols or their ester-forming equivalents are also suitable. Preferably, the Rie groups mentioned above are used. Other examples include the adduct of the conversion of diethyl fumarate and diethyl malonate to tetraethyl ester of 1,1,2,3-propane tetracarboxylic acid and a hydroxyl-functional oxetane. In the presence of a diol or polyol, a polyester with terminal oxetane functionality is formed. It is also possible to convert the oxetane compounds with hydroxyl functionality, with the help of Ri7 (C0Cl) acid chlorides ". Preferably, Ri? is a group having a high molecular weight, such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or the polymers mentioned above. The resulting BOE compound is non-volatile or hardly volatile, due to the high molecular weight, and taking into account its surprisingly low viscosity, it is eminently suitable for use as a reactive diluent. Halogen-functional oxetanes can be converted to ester-functional oxetanes by reacting them with carboxylate salts, for example, silver or with ammonium compounds, such as substituted or unsubstituted ammonium salts. It has now been discovered that the conversion of the ester-functional oxetane compound into a compound with BOE functionality is already carried out in the presence of a catalytic amount of a strong Bronsted or Lewis acid or its organic complexes. Lewis acids are preferred. Examples of Lewis acids are: AlCls, SbCls, BF3, BCI3, BeCl2, FeCl3, FeBr3, SnCl *, TiC, ZnCl2 and ZrC, and their organic complexes, for example, BF3Et2.0M BF3-2CH3COOH, BF3-2H2O, BF3 -H3PO4, BF3- (CH3) 2 ?, BF3THF, BF3-2CH3OH, BF3-2C2Hs0H and BF3C6H5CH2. BF3Et2 ?, BF3-2CH3COOH and SnC are more preferred. Amounts of 0.001-0.1 mole of catalyst per mole of oxetane compound are preferred, better still, 0.004-0.08 mole / mole. It has further been discovered that the conversion is already carried out in the presence of a small amount of solvent, and even without solvent, if so desired. The term "solvent", in this context, refers to those solvents which are conventionally employed in the field of organic chemistry and which have been described for the conversion of oxetane compounds. The conversion is carried out on a scale of -100 to 200 ° C, preferably on a scale of 0 to 80 ° C. The conversion time is on the scale of 30 minutes to 2 days and can result in a yield of more than 90%. Various methods can be used to prepare compounds with SOE functionality. One such preparation method is the reaction of an epoxy-functional compound, such as butyl glycidyl ether, with a lactone such as caprolactone or butyrolactone. Alternatively, the SOE-functional polymers can be prepared from epoxy-functional polymers, for example, glycidyl (meth) acrylate polyacrylates, using lactones, or from polylactones using mono-epoxides. Again, catalysts such as Lewis and Bronsted acids, preferably paratoluenesulfonic acid or BF3Et2 ?. Additionally, a compound with SOE functionality can be prepared by reacting pentaeri ritol and triethyl ortopropionate in the presence of paratoluenesulfonic acid, using as a solvent a specific trimethylbenzene. Surprisingly, in that way, a compound having two SOE groups, of the following structure, was very selectively synthesized: The invention will be further illustrated with reference to the following examples.

EXAMPLES The following abbreviations are used in the examples: paratoluenesulfonic acid PTSA dibutyltin dilaurate DBTL methylacetonate MAK ethylamyl ketone EAK boron trifluoride etherate BF3Et? In the examples, the following compounds are used: Edenor < R > ME C6-10 from. Henkel, a mixture of fatty acid methyl ester, with the following chain length distribution: C6 1-8%; C8 40-60%; CIO 30-50%; C12 0-5%. Byk 333 is a surface silicone additive, by Byk Chemie.

Byk 300 is a flow additive, by Byk Chemie. Byk 322 is a flow additive, by Byk Chemie Byk 355 is a flow additive, by Byk Chemie. Disperbyk 110 is a dispersing agent of Byk Chemie. Disperbyk 166 is a dispersing agent, by Byk Chemie. Nacure 5076 is 70% DDBSA in isopropanol from King Industries. Fascat 4202 is a solution of 10% DBTL in xylene, from Air Products. Desmodur < R > N3400 is an aliphatic polyisocyanate, based on uredodione, of hexamethylene diisocyanate, Bayer. Desmodur < R > VL50 is an aromatic polyisocyanate based on diphenylmethane diisocyanate, from Bayer. Desmodur < R > N3390 is an aliphatic polyisocyanate based on the isocyanurate of hexamethylene diisocyanate, from Bayer. Desmodur < R > L75 is an aromatic polyisocyanate based on toluene diisocyanate, from Bayer. Desmodu R) LS2025 is an aliphatic polyisocyanate of bullet viscosity, based on hexamethylene diisocyanate, from Bayer. Vestanat < R > T1890E is a cycloaliphatic polyisocyanate based on isocyanurate of isophorone diisocyanate, from Hüls. Hardener MS, from Sikkens, comprises Desmodur < R > N3390 (solids content, C.S. 36%). The polyester polyol A is a high solids polyester, having a hydroxyl number of 148, an acid number of 8.8 and an Mn of 1888 (GPC, polystyrene standard). The polyester had a viscosity of 7 Pa.s in an 81% solution in butyl acetate. The polyester polyol B is based on 1,4-dimethanolcyclohexane, hexahydrophthalic anhydride, 3,5,5-trimethy1hexanoic acid, trimethylolpropane and glycidyl ester of a branched, 1,1-disubstituted decanomonocarboxylic acid. The polyester polyol has a solids content of 70%, a viscosity of 580 mPa.s at 20 ° C, a Tg of -3 ° C, an acid value of 0.2, a hydroxyl number of 160, an Mn of 1090 and a Mw of 3140 (when measured by gel penetration chromatography, using polystyrene as a rule). The polyester C of polyester is based on phthalic anhydride, hexahydrophthalic anhydride, 3,5,5- • • * trimethylhexanoic acid and trimethylolpropane. The polyester polyol has a solids content of 80.5%, a viscosity of 7.5 Pa.s at 20 * C, a Tg of -2 ° C, an acid value of 9.3, a number 5 hydroxyl of 145, an Mn of 1900 and an Mw of 4500 (when measured by gel penetration chromatography, using polystyrene as a rule). Autoclear MS2000, from Sikkens, comprises a polyacrylate polyol resin and 0.02% DBTL (on solids). The 0 solids content (C.S.) is 46%. Resin RF 4518 is a melamine resin from Monsanto. Irgazin DPP Red BO is a bright red pigment from Ciba-Geigy. Zinc Phosphate ZP10 is an anticorrosive pigment, Heubach. Tioxide TR92 is a titanium dioxide pigment, from Tioxide. Aerosil R972 is a silica compound, from Degussa. 0 Clay China Quality C is an extender, from ECC International Ltd. Blank fix N is an extender of Sachtleben Chemie GmbH. Tinuvin 1130 is a UV stabilizer from Ciba-Geigy. 5 Tinuvin 123 is a HALS stabilizer, from Ciba-Geigy. Solesso 100 is a mixture of aromatic solvents, from Exxon. 1,2,3. Thinner slow by Sikkens, is a mixture of solvents. Unless otherwise indicated, the properties of the coating compositions and the resultant films are measured as follows: The viscosity is measured in a flow cup DIN number 4, in accordance with DIN 53211-1987. The viscosity is reported in seconds. Pot life is defined as the period of time in which the viscosity of the coating composition is doubled, after the initial mixing of all the compounds. The drying time is measured in the following manner. The coating composition is applied with a spreader rod, or by spraying on a steel plate. The time until the end of the third phase of the layer drying is measured, using a BK Drying Recorder <; Rí. The term third phase refers to the drying phase during which the needle of the BK Drying Recorder < R > makes a small and strong line in the ",, • > 's does not fill in. - It is not" dry to the touch "when the mark formed empí» -' "'*. • * -, Hß appears after d3 1 or 2 minutes. The solids content (C.S.) is measured after 1 day of drying at room temperature, followed by one hour at 150 * C C.S. The theoretical maximum is C.S. to which it is assumed that the BOE or SOE will hydrolyze and bind in the dry film. The C.S. The theoretical minimum is C.S. to which the whole BOF or SOE is supposed to have evaporated from the dry film. The luster is measured according to ISO 2813: 1994. The luster is expressed in units of luster. The resistance to the solvent is measured by exposing steel panels coated with MEK. The time needed to soften the paint film to a pencil hardness 2b. Give the resistance.

EXAMPLE 1 PREPARATION OF 4-METILQL-1-METHYL-2.6.7-TRI0XABICICL0C2.2.23 OCTANE (BOE 1) It was charged into a flask equipped with stirrer, distillation column, nitrogen inlet, heating mantle and thermometer, 486 g of triethyl orthoacetate, 408 g of pentaerythritol, 300 g of diethylene glycol dimethyl ether and 0.9 g of PTSA. The mixture was gradually heated to 170 ° C over a period of 5 hours. During that time 490 g of distillate was obtained. The distillate contained mainly ethanol and small amounts of diethylene glycol dimethyl ether. The temperature was lowered to 100 ° C and the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure (30 mbar). The residue was subjected to vacuum distillation. The fraction having a boiling temperature of 126-130 ° C at a pressure of 4 mbar produced 426 g of oil. This oil solidified to a clear solid having a melting point of 99 ° C and having the following structure: EXAMPLE 2 PREPARATION OF 1.4-DIETIL-2.6.7-TRI0XABICICL0i: 2.2.2] 0CTAN0 CBOE 22 In a flask as specified in Example 1, 529 g of triethyl ortopropionate, 402 g of trimethylolpropane, 330 g of diethylene glycol dimethyl ether and 0.9 g of PTSA were charged. The mixture was heated for 0.5 hour at 140 ° C, 402 g of ethanol being distilled off. The temperature was lowered to 100 ° C and the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure. The residue was subjected to vacuum distillation. The fraction that had a boiling temperature of 54 ° C at a pressure of 0.5 mbar, produced 370 g of a clear, low viscosity liquid, which had a boiling point of 223 ° C at atmospheric pressure, and with the following structure: EXAMPLE 3 PREPARATION OF A SPIRAL-ORTOESTER (SOE 1) A 125 ml of trimethylbenzene, 89 g of triethyl ortopropionate, 68 g of pentaerythritol and 0.125 g of PTSA were charged into a flask as specified in example 1. The mixture was heated for 4 hours at 140 ° C. After just 2 hours the distillation of ethanol was stopped. In total, only 36 g of ethanol was distilled off. Only a portion of the pentaerythritol was dissolved in the reaction mixture. After cooling, the mixture was neutralized with potassium carbonate and all the solids were filtered off. Trimethylbenzene and the traces of unreacted triethyl ortopropionate were distilled off under reduced pressure and the residue was subjected to vacuum distillation. The fraction having a boiling temperature of 140-145 ° C at a pressure of 1 mbar produced 37 g of oil. After analysis by 1 H and 13 C NMR spectroscopy, it was found that the spiro-orthoester compound of the following structure was formed: EXAMPLE 4 PREPARATION OF A SPIRAL-ORTOESTER (SOE 2) It was charged into a flask equipped with stirrer, reflux condenser, dropping funnel, heating mantle and thermometer, 43 g of gamma-butyrolactone, 65 g of diethyl ether and 1.5 g of a 35% solution of BFsEtsO in diethyl ether. 93 g of butyl glycidyl ether were added to this mixture over the course of one hour. The reaction was slightly exothermic. By means of external cooling the temperature was maintained in the range of 23-28 ° C. After the addition of butyl glycidyl ether, the mixture was kept at said temperature for 3 hours, with continuous agitation. The reaction mixture was then heated to reflux for one hour. After cooling to room temperature 2 g of sodium carbonate was added and stirring was continued overnight at room temperature. The solids were filtered off and 1 g more of sodium carbonate was added. Diethyl ether was distilled off under reduced pressure at room temperature. The residue was subjected to vacuum distillation. The fraction that had a boiling point on the scale of 45-65 ° C, at a pressure of 0.1 mbar, produced 31 g of clear liquid. After analysis (NMR spectroscopy with 1H and 13C), it was found that a spiro-orthoester of the following structure had been formed: EXAMPLE 5 A: PREPARATION OF 3-ETHYL-3-HIDR0XIMETHYLXETAN0 This oxetane was prepared as described in J. B. Pattison, J. Am. Chem. Soc. 79 (1957), page 3455, and in J. V. Crivello and coauthors, J. M. S. Puré Appl. Chem .. A30 (1993), p. 189. Weighed 1023.6 g, 7.63 moles, of rimethylolpropane, 901. 3 g, 7.63 moles, of diethyl carbonate and 0.77 g of potassium hydroxide, in a 5-liter, three-necked flask. The reaction mixture was heated to reflux temperature (123 ° C). After the reaction temperature had been lowered to 105 ° C, separation by distillation of the ethanol was started. The reaction temperature was increased to 150 ° C. At the end of the distillation, a vacuum (15 mbar) was used to remove the rest of the ethanol and the diethyl carbonate from the reaction mixture. The reaction mixture was then heated to 220 ° C. Gas formation was observed and, under reduced pressure (40 mbar) at 130 ° C, a clear oil was produced, which was identified with 3-ethyl-3-hydroxymethyloxetane. The yield was 698.0 g (79%). 1 H NMR (CDCl 3) d (ppm): 0.9 (t, 3 H, 1.7 (c, 2 H), 3.1 (t, 1 H), 3.7 (d, 2 H), 4.4 (dd, 4 H).

B: PREPARATION PE LAURATE OF 3-ETIL0XETAN-3-ILMETIL0 It was weighed in a 1-liter three-necked flask equipped with Vigreux distillation column, 228.4 g, 1.0 mol of ethyl laurate, 116.0 g, 1.0 mol of 3-ethyl-3-hydroxymethyloxetane, 0.34 g of nitrous oxide. dibutyltin and 25.0 g of xylene. The reaction mixture was heated to reflux. The ethanol was distilled at 170 ° C. The reaction mixture was heated in such a way that the distillation of the ethanol proceeded uniformly.All the ethanol was distilled at a reaction temperature of 250 ° C. The xylene was removed under reduced pressure. According to NMR analysis with * H, the residue (298.7 g) was pure 3-ethyloxyethane-3-ylmethyl laurate The product solidified at room temperature NMR with * H (CDCl 3) d (ppm): 0.9 (2 xt, 6H), 1.3 (s broad, 16H, 1.65 (m, 2H), 1.8 (c, 2H), 2.4 (t, 2H), 4.2 (s, 2H), 4.45 (dd "4H).

C: PREPARATION OF 4-ETHYL-UNDECIL-2.6.7 - TRI0XABICICL0i: 2.2.2] OCTANO The reaction was carried out under a nitrogen atmosphere. 3-Ethyloxyethan-3-ylmethyl laurate was prepared as specified in Example 5B (270.0 g, 904 mmol) and mixed with BF3 Et? (1.0 g) in an Erlen eyer flask. The reaction mixture was cloudy but became clear after a certain time. After he had let himself rest during the night. The NMR analysis with 1 showed that all of the oxetane ester had been converted to the corresponding BOE compound. The reaction mixture was subjected to vacuum distillation. At 155 bC / 1 mbar 4-ethyl-l-undecyl-2,6,7-trioxabicyclo [2.2.2] octane was produced. The yield was 205 g (76%). NMR with * H (CDCl 3) d (ppm): 0.75 (t, 3H), 0.8 (t, 3H), 1.2 (broad s, 16H), 1.35 (broad m, 2H), 1.50 (t, 2H); 3.80 (s, 6H).

EXAMPLE 6 A: PREPARATION OF 3-ETHYL-3-HIDR0XIMETHYLXETAN0 Were weighed 1489 g, 11.1 moles, of trimethylolpropane, 1201 g, 13.3 moles of dimethyl carbonate and 5.38 g of potassium hydroxide, in a 5-liter, three-necked flask equipped with stirrer, reflux condenser, nitrogen inlet, heating mantle and a thermometer. The reaction mixture was heated to reflux temperature (86 ° C) and refluxed for two hours. The temperature was lowered to 80 ° C. Subsequently the temperature of the reaction mixture was increased to 155 ° C in 6 hours. At the end of the distillation, 890 g of distillate containing mainly methanol and dimethyl carbonate were obtained in a proportion of 60 to 40. The temperature was lowered to 120 ° C and under vacuum (200-40 mbar). The remaining ethanol and dimethyl carbonate were removed from the reaction mixture (about 14 g). The reaction mixture was then gradually heated to 180 ° C. Under a stream of CO2, and at reduced pressure (60-40 mbar), a clear oil was produced which was identified as 3-ethyl-3-hydroxymethyloxetane. The yield was 860 g.

B: PREPARATION OF ESTER 3-ETIL0XETAN-3-ILMETILIC0 DE CIDOS FATOS It was weighed into a 5 liter flask, equipped as in example 6A, 1268 g, 7.4 moles of Edenor (R) ME C6-10, 858.4 g, 7.4 mol, of 3-ethyl-3-hydroxymethyloxetane from Example 6A and 2.13 g of dibutyltin oxide. The reaction mixture was heated to reflux temperature. At 150 ° C methanol was distilled off. The reaction mixture was heated in 5 hours to 240 °. 197 g of distillate comprising mainly methanol (83% of theory) were obtained. The temperature was reduced to 150 ° and under vacuum (40 mbar) about 40 g of remaining distillate was separated. It was found that the residue (1834 g) had the following structure, where R is a mixture of pentyl, heptyl, nonyl and undecyl groups: C: PREPARATION OF 4-ETIL-l- (RENT OF C5-1D-2.6.7- TRI0XABICICL0C2.2.230CTAN0 (BOE 3) The reaction was carried out under a nitrogen atmosphere. The 3-ethyl oxetane-3-ylmethyl ester of fatty acids, prepared as specified in Example 6B (1834 g), was cooled to 50 ° C, and 4.59 g of BF3 -2CH3COOH was carefully added. The reaction mixture was heated to 70 ° C and maintained at that temperature for six hours. The reaction mixture was then cooled to 50 ° C and 2.45 g of triethylamine was added to neutralize the catalyst. To the resulting residue was added 1% of a filter additive, and filtered. The filtrate was 1730 g and contained about 78% BOE and 22% polymer.

D: PREPARATION OF 4-ETIL-l- (LOT OF C5-1D-2.6.7- TRIOXABICICLOC2.2.23QCTANO (BOE 3B) It was weighed in a 5 liter flask, equipped as in example 6A, 1730 g of crude BOE 3A, prepared in example 6C. The reaction mixture was heated to 140 ° C and at a reduced pressure of 40 mbar. The temperature was gradually increased to 240 ° C, with which a clear liquid appeared. 1235 g of what was found to be pure BOE 3B was collected from the following formula, wherein R is a mixture of alkyl groups of 5, 7, 9 and 11 carbon atoms.

EXAMPLE 7 A: PREPARATION OF THE DIMETHIC ESTER OF DIMERIC FATTY ACID Weight was 742 g, 1.31 moles, 2.62 equivalents of acid, of Pripol 1009, dimeric fatty acid, of Unichema, 2,000 g of methanol and 40 g of Amberlyst 15, acid ion exchange resin, from Rohm & Haas, in a flask equipped with agitator, reflux condenser, nitrogen inlet, thermocouple and heating jacket. The reaction mixture was heated to reflux temperature (65 ° C). At intervals, uesters were analyzed by infrared spectroscopy. Heating was continued until the carbonyl signal of the carboxylic acid disappeared at 1710 air *, in the infrared spectrum (about 18 hours). The reaction mixture was cooled to room temperature and the liquid from the ion exchange resin was decanted. The liquid was subjected to rotary evaporation to evaporate substantially all of the methanol. The evaporation residue was diluted with 300 g of diethyl ether. The ether solution was washed with 500 g of 10% aqueous sodium carbonate solution and subsequently with 500 g of water in three portions. 30 g of magnesium sulfate was added to the organic layer and stirred for 12 hours. The liquid was filtered and the diethyl ether was distilled off by rotary evaporation. The residue of the evaporation was the dimethyl ester of Pripol 1009, as a colorless oil (752 g »96% of theory).

B: PREPARATION OF DIET-3-ETHYLXETAN-3-ILMETILIC0 ESTER OF DIETARY FATTY ACID It was weighed in a flask equipped with stirrer, distillation column, nitrogen inlet, thermocouple, vacuum line and heating jacket, 713.5 g, 2.4 equivalents, of the Pripol 1009 dimethyl ester of Example 7A, 278.4 g, 2.4 moles, of 3 -ethyl-3-hydroxymethyloxetane of Example 6A and 1.0 g of dibutyltin oxide. The reaction mixture was gradually heated in 4 hours at 240 ° C. 47 g of methanol were expelled by distillation during that time. The temperature was reduced to 160 * C and vacuum was applied. The pressure was gradually decreased at 20 mbar for 3 hours. The residual methanol was distilled off during that time. When the distillation had ceased, the reaction mixture was cooled to room temperature. The oily, light yellow product was analyzed by infrared spectroscopy. There was no hydroxyl signal at 3400 crn-1 visible in the infrared spectrum. The yield was 914 g.

C: PREPARATION OF THE BOE DERIVATIVE OF THE ESTER DI-3-ETIL0XETAN-3- ILMETILICO OF THE DIMERIC FATTY ACID (BOE 4) Weigh into a flask equipped as in example 7A 914 g of the di-3-ethyloxyethan-3-ylmethyl ester of dimeric fatty acid, as specified in example 7B and 1400 g of butyl acetate. 9.15 g of BF3Et2 was added at room temperature. during 15 minutes. The reaction mixture was heated at 50 ° C. and kept at that temperature for 10 hours, then the reaction mixture was cooled to room temperature and 6.5 g of triethylamine was added in. A precipitate formed which was filtered off. analyzed the product by infrared spectroscopy and showed a small signal at 3400 cpr1, indicating hydroxyl functionality, 9 g of phenyl isocyanate was added to the product.After 1 hour at room temperature, infrared spectroscopy indicated the absence of hydroxyl functionality (no signal at 3400 cpr3L) and isocyanate functionality (no signal at 2270 crn-1) Part of the butyl acetate was evaporated The final product has a solids content of 82.7% and is a yellow oil.

EXAMPLE 8 A: PREPARATION OF A POLYESTER WITH OXETAN FUNCTIONALITY Weighing 686.0 g, 4.3 moles, of diethyl malonate, 358.1 g, 3.45 moles, of neopentylene glycol, 196.2 g, 1.7 moles, of 3-ethyl-3-hydroxymethyloxetane, 1.2 g of dibutyltin oxide and 100 g. of xylene, in a 2-liter, three-necked flask equipped with a distillation system. The reaction mixture was heated to reflux temperature. At 189 ° C ethanol distillation was started. The distillation rate was controlled by slowly increasing the reaction temperature. At a temperature of 210 ° C all the ethanol had been distilled. The xylene was removed from the reaction mixture under reduced pressure. The polyester with oxetane functionality had a molecular weight of Mn = 1021 and Mw = 1875 (GPC, polystyrene standard).

B: PREPARATION OF A POLYESTER WITH BOE FUNCTIONALITY This reaction was carried out under a nitrogen atmosphere. Weighed in a round bottom flask 800.0 g, 1.6 equivalents of oxetane, of the oxetane-functional polyester that was prepared in Example 8A, and about 1 g of BF3Et2 ?. An exothermic reaction occurred. The temperature of the reaction mixture was raised to 62 ° C. Then there was a cooling with a water bath. After one night, it was found that virtually all the oxetane groups had been converted to the corresponding BOE groups (BOE signal to (ppm) 4.0 in NMR with * H). The BOE functionalized polyester obtained had a molecular weight of Mn = 1658 and Mw = 7449 (GPC, polystyrene standard).

EXAMPLE 9 ft: PREPARATION OF ACRYLATE OF 3-ETHYLXETAN-3-ILMETIL0 The synthesis was carried out as described by P.

G. Gass an and coauthors, Chem. Comm. , (1989), p. 837. The reaction was carried out under a nitrogen atmosphere. It was added dropwise to a mixture of 170.6 g. 1.50 moles, of 3-ethyl-3-hydroxymethyloxetane and 153.8 g, 1.52 moles of triethylamine in 500 g of tetrahydrofuran, cooled in an ice bath, 137.5 g, 1.52 moles, of acryloyl chloride. The reaction mixture was stirred for one hour at room temperature. 500 g of water was added to the reaction mixture. The organic layer was separated from the aqueous layer. The aqueous layer was extracted with 2 x 500 ml of ether. The combined organic layers were dried with saturated NaCl solution and magnesium sulfate. After filtering the ether layer, the volatile organic compounds were removed in vacuo, using a rotary evaporator. The residue was distilled in vacuo. The 3-ethyloxyethan-3-ylmethyl acrylate was isolated at 122 ° C / 19 mbar, as a clear oil. The yield was 200.4 g (80%). NMR with * H (CDCl 3) d (pprn): 0.92 (t, 3H), 1.80 (c, 2H), 4.30 (s, 2H), 4.48 (dd, 4H); 5.88 (d, ÍH), 6.18 (dd, 1H), 6.45 (d, 2H).

B: PREPARATION OF A POLYACRYLATE THAT HAS SIDE GROUPS WITH BOE FUNCTIONALITY A mixture of 38.0 g of butyl acrylate was added, 45.0 g of tri-ethylcyclohexyl methacrylate (Nourycryl MC (R) 109), 17.0 g of 3-ethyloxyethan-3-ylmethyl acrylate, 3.0 g of t-butylperoxy-3,5,5-trimethyl hexanoate (Trigonox (R ) = 42Sm, 3.0g) and 2.0 g of dodecyl mercaptan, during a period of 2 hours, to 42.7 g of MAK at reflux. During feeding, the temperature rose from 155 ° C to 169 ° C. After feeding, there were two other additions, each for 30 minutes, of a solution of Trigonox 42S (0.25 g) in 1.0 g of MAK. The reaction mixture was cooled to room temperature. Then 0.75 g of BF3Et2 ?. The resin obtained had the following physical properties: Mn = 1736, Mw = 4567, viscosity = 1.28 Pa.s and C.S./74.7% (after 30 minutes of heating at 150 ° C.

EXAMPLE 10 AND COMPARATIVE EXAMPLE A BOE AS A MAIN AGGLUTINATOR THAT REACTS WITH A COMPOUND CONTAINING POL ISOCYANATE Desmodur (R) N3390 was mixed with (2,2-dimethylol-n-butyl) propionate (DBP) and BOE 2, respectively (130 eq% NCO, calculated on the hydroxyl (latent)), 0.15% by weight of DBTL, calculated on the solid material and 0.33% by weight of PTSA, calculated on DBP, was added to the DBP mixture, while adding 0.15% by weight of DBTL, calculated on the solid material, and 0.83% by weight of PTSA, calculated on BOE 2, to the BOE 2 mixture. The two mixtures were diluted with a 50:50 mixture of MAK / EAK at spray viscosity (± DINC4 18"). 2790 g of MAK / EAK was needed to give the DBP mixture the desired spray viscosity In contrast, the B0E2 mixture only needed 200 g.The use of BOE 2, in other words, effects a reduction of 70 g in the amount of diluent required to obtain a composition that can be The shelf life data and drying time are compiled below, shelf life is defined as the time during which the viscosity of the coating composition increased to 30"DINC4. The coating compositions were sprayed onto a steel plate to obtain a 50 μ layer after drying. It is obvious that the coating composition according to the present invention has a longer pot life and a shorter drying time; in other words, an especially favorable ratio of pot life: drying time.

A .. Pot life Drying cycle (sea) A DBP 10 min 140 9 B0E2 > 1 day 100 EXAMPLE 11 AND COMPARATIVE EXAMPLE B SOIE AS MAIN AGGLUTINATOR. THAT REACTS WITH A COMPOUND CONTAINING POLYISOCI NATO Two samples of SOE 2 were mixed with Desmodur (R) N3390 (130 eq% NCO, calculated on the latent hydroxyl), 0.3 wt.% Of DBTL, calculated on the solid material, was added to the two mixtures, while adding to the two mixtures. one of the mixtures 1.1% by weight of PTSA, calculated on SOE 2. The coating compositions were applied on a steel plate with a 100 μ extender rod. The results of C.S. are then compiled. They clearly show the effect of PTSA on the release of the hydroxyl groups in the SOE composition.

Example PTSA c. s. max. you get rich measured 11 1.1% by weight 83 .6% 80 .4% B - 83 .6% 59 .1% EXAMPLES 12-18 BOE AS MAIN AGGLUTINATOR REACTING WITH A COMPOUND WHAT POLYISOCI MATO CONTAINS 4.3 parts by weight of BOE 2 were mixed with 10.8 parts by weight of Desmodur (R) N3390 (100 eq% NCO, calculated on the latent hydroxyl), and 0.3% by weight of DBTL, calculated on the solid material, was added. Various acids were added as catalysts for the hydrolysis of BOE compound. The coating compositions were applied on steel plates with a 100 μ paver rod. The data is then compiled. The percentages of catalyst mentioned in the table are based on the amount of BOE 2. PTSA has a pKa of 0.5-1, the pKa of benzoic acid (BZ) is 4.2 and the pKa of DBF is 2-3. The C.S. after 1 day of drying at room temperature and 1 hour at 120 ° C.

Ahem. Cat. (%) C.S. C.S. C.S. Time Pelimox time. in. of geli- de drying theory. theoretical to touch 12 72.2 93.2 62.2 > 1 week 3 hrs 13 1.63 from 64.3 92.4 60.6 > 1 week 1 hrs ZnC12 14 1.63 70.2 80.2 56.6 > 1 week 2 hrs from BZ 15 0.47 from 71.4 92.4 62.0 > 1 week 4 hrs PTSA 16 1.63 from 89.4 92.4 60.6 > 1 week 3 hrs PTSA 17 1.63 from 87.5 92.4 60.6 > 1 week 4 hrs BF3E 20 18 1.63 from 88.0 92.5 60.6 > 1 week > 5 hours DBP In all cases, the life of the boat is excellent. C. S. improves with the use of a stronger acid or larger amounts of acid. Example 16 provides the best results with a high C.S. and a reasonable drying time.

COMPARATIVE EXAMPLES C AND D Example 12 was repeated. Instead of 4.3 parts of BOE 2, 3.7 parts of 2-ethyl-l, 3-hexanediol was added. Two mixtures were prepared comprising 0.005 parts by weight and 0.05 parts by weight of DBTL, calculated on the solid material, respectively. For the first mixture a pot life of 0.5 hours was measured and for the second 1 minute. The touch-dry time of the coating composition, when 0.05 parts by weight of DBTL was used, was more than 4 hours at room temperature.

EXAMPLE 19 AND COMPARATIVE EXAMPLE E BOE AS REAGENT DILUENT IN A COMPOSITION THAT COMPRISES A POLYESTER POLYOL AND A COMPOSITE WITH FUNCTIONALITY POLYISOCIANATE The dilution capacity of BOE 2 with ethylbutylpropanediol (EBP), a hydroxy-functional compound, was compared in a urethane formulation with a high solids content. 130 eq% of NCO (Desmodur (R) N3390) was used on the hydroxyl (latent). The polyester polyol A was used as the binder. The catalyst used for the hydrolysis of BOE was PTSA, the catalyst for the isocyanate-hydroxyl reaction was DBTL. You can see from the chart that, when using BOE 2, there is 65 g less solvent present per kilogram of paint (about 65 g per liter). Due to the lower equivalent weight of BOE 2 compared to EBP, it is necessary to comparatively a little more isocyanate for the interlacing. All amounts are in parts by weight.

Ahem. E Axis 19 Polyester A 40 40 BOE 2 - 8.1 EBP 8.1 - Desmodur (R) N3390 54.4 61.9 DBTL 0.12 0.06 PTSA - 0.4 (4.9% in pe calculated on BOE 2) MAK 30.8 26.3 EAK 16 9.5 Shellsol D 7.34 8.4 Viscosity (DINC4) 18.2"17.6" EXAMPLE 20 AND COMPARATIVE EXAMPLE F BOE AS A MAIN AGGLUTINER WITH A COMPOSITE OF FUNCTIONALITY POLYISOCIANATE The performance of BOE 2 was compared with that of a commercially available reactive diluent, Oxazolidine Zoldine (R) RD 20, from Angus Chemical Company (l-aza-3,7-dioxo-bicyclo-2,8-diisopropyl-5). -ethyl [3.3.0] octane). Desmodur (R) N3390 was interlaced with the two compounds (13D eq% NCO, calculated on the hydroxyl (latent)). The coating compositions were diluted with MAK: EAK (50:50) at a viscosity of 19"DINC 4. 0.1% by weight of DBTL, calculated on the solid material, and 0.57% by weight of PTSA, calculated on the BOE, was added. 2. Both compositions were sprayed on bare steel, the temperature during drying was 20 ° C, the relative humidity 70%, and then it can be seen that the life of the boat is longer when BOE 2 is used, while the drying proceeds more quickly.

Ahem. Viscosity, after Drying and 6 hrs (DINC4) .- (minutes) BOE 2 23"175 F Zoldine (R) 29" 400 EXAMPLES 21 AND 22 AND COMPARATIVE EXAMPLE G BOE AS MAIN AGGLUTINATOR. IN COMBINATION WITH A COMPOSITE WITH POLYCYOCIANATE FUNCTIONALITY AND A GENERATOR INITIATOR ACID A coating composition was prepared which contained: 5.3 parts by weight of BOE 3B 10.8 parts by weight of Desmodur (R) N3390 1.5 parts by weight of 10% DBTL in butyl acetate 1.06 parts by weight of 2-methyl-l [ 4- (methylthio) phenyl] -2- [4-methylphenylsulfonyl] propan-l-one (MDTA) from Fratelli Lamberti, SpA, Varese, Italy, in butyl acetate. The coating composition was applied with a spreader rod on two steel plates to give a film thickness of 50 μm, after drying. Five minutes after the application on the steel plate, it was irradiated by UV-A for one minute (example 21). After one hour at room temperature, the coating was dry to the touch and clear. After 5 hours, the non-irradiated coating (comparative example G) was dry to the touch, but had many problems due to the non-hydrolyzed BOE. The coating composition was stored for one week at 50 ° C. Then it was applied as described above (Example 22) Again the coating was dry to the touch after one hour The storage stability of the coating composition containing MDTA is very good.

EXAMPLE 23 AND COMPARATIVE EXAMPLE H BOE AS MAIN AGGLUTINER WITH A RESIN WITH POLYACETAL FUNCTION Two coating compositions were prepared as mentioned below (all amounts in parts by weight). The resin with polyacetal function is a copolymer of glycerol cyclocarbonate methacrylate and styrene, on which an adduct is formed with aminobutyraldehyde-dimethylacetal (C.S. = 62% in butyl acetate (equivalent weight of acetal groups = 951)). BOE 4 has a C.S. of 83% in butyl acetate, and the equivalent weight of BOE = 476. Nacure was diluted with a 10% solution in butyl acetate. As can be seen from the results cited below, the composition of the present invention has excellent can life. The coating compositions were applied with a spreader rod on a sidewalk plate, to give a film thickness of 50 μm, after drying. The touch-dry time of the coating composition of the present invention is equal to the comparative coating composition, as well as the solvent resistance of MEK.

Ex. 23 Ex. Comparat. H Resin with polyacetal function 9.5 9.5 BOE 4 4.8 BOE 4 hydrolyzed 4.8 Nacuere 5076 to 10% 1.0 1.0 Gel gel time in canister > 2 sem. 5 hours Touch drying time 10 min 10 min MEK resistance after 1 week 2 2 EXAMPLE 24 AND COMPARATIVE EXAMPLE I BOE AS MAIN AGGLUTINATOR WITH RESIN WITH FUNCTION POLIALCOXISILAN Two coating compositions were prepared as mentioned below (all amounts in parts by weight).

The resin with polyalkoxysilane function is an adduct of 1 mole of diethyl malonate and 2 moles of 3-aminopropyltrimethoxysilane, ie AMEO-T, from Wacker (CS 85.6% in xylene (equivalent weight of Si (EtO) 3 groups = 255 )). BOE 4 has a CS of 83% in butyl acetate, and the equivalent weight of BOE is 476. Nacure 5076 was diluted to a 10% solution in butyl acetate As it can green the results indicated below, the composition of the present invention has excellent can life. The coating compositions were applied with a spreader rod on a steel plate to give a film thickness of 50 μm after drying. The touch drying time of the coating composition of the present invention is equal to the comparative coating composition, as well as the solvent resistance of MEK.

Ex. 24 Ex. Comparat. I Resin with polyalkoxysiloxane functionality 5.1 5.1 BOE 4 4.8 BOE 4 hydrolyzate 4.8 Nacure 5076 at 10% 0.9 0.9 Gel time in canister > 2 sem. 1 hour Touch drying time 20 min 20 min MEK resistance after 1 week EXAMPLE 25 BOE AS MAIN AGGLUTINATOR WITH A MINE RESIN A coating composition was prepared as mentioned above (all amounts in parts by weight) Example 25 Resume RF 4518 8 BOE 3B 2 Nacure 5076 0.6 Gel time in canister < 1 hour Touch drying time 1.5 hours MEK resistance after 1 week 2 The results indicated above show that a composition comprising a melamine resin and a catalyst releases water, which results in a very rapid opening of the compound ring BOE. Consequently, the life in the boat is very short and this coating composition requires a 2K component system or a blocked catalyst. The coating composition was applied with a spreader rod on a steel plate, to give a film thickness of 50 μm after drying.

EXAMPLES 26 AND 27 COMPOSITIONS OF CLEAR COATING. SOLVENT-FREE The clear solvent-free coating compositions, which are indicated below, were prepared. The coatings were prepared according to a 3-pack system. The first component contained the BOE compound, the second component contained the polyisocyanate compound and the third component contained the acid catalyst. Solvent-free is defined as VOC < 100 g / 1.

Compound Component Axis 26 Ahem. 27 1 BOE 3B 34.2 g 30.2 g Castor oil 6.0 g DBTL 0.51 g 0.54 g Byk 333 0.41 g 0.44 g 2 Desmodur (R) N3400 63.5 g 46.5 g Desmodur (R) VL50 14.8 g 3 Nacure 5076 1.37 g 1.45 g Both compositions have a viscosity of 23" (DINC4). The light coatings were sprayed on steel panels coated with an Autobase MM basecoat, from Sikkens, with a high volume low pressure spray gun (HVLP). The coatings were cured at room temperature and at 600C. The appearance was excellent, good luster and good flow / equalization. The resistance to the pebbles, the resistance to the solvent and the adhesion were good.

EXAMPLES 28 AND 29 COMPOSITIONS OF TOP COATING. IN SOLID COLOR Two solid color topcoat compositions, based on BOE, were prepared. In the first composition the pigment was dispersed in BOE, whereas in the second composition a pigment paste based on polyester was used. Component 1 was milled in a bead mill until the particle size was less than 10 μ. Compound Compound Ahem.28 Ahem.29 1 BOE 3B 37.5 g polyester polyol B - - - 45.0 g Irgazin DPP Red BO 33.6 g 24.7 g Disperbyk 166 16.8 g 17.0 g Butyl acetate 6.1 g 6.6 g Solvesso 100 6.1 g 6.6 g 2 BOE 3B 34.8 g 28 g Desmodur ( R) N3390 141.4 g 80 g DBTL 1.08 g 0.96 g 3 Nacure 5076 1.44 g 0.56 g Solvesso 100 17.0 g 4.0 g Ethoxyethyl Propionate 17.0 g 4.0 g Both coating compositions were sprayed on steel panels repaired with a conventional sizing , as a top coating for automotive refinishing. Appearance and application behavior are good. The level of VOC is very low, approximately 250 g / 1.

EXAMPLES 30 AND 31 CLEAR COATING COMPOSITIONS Two clear coating compositions were prepared, as mentioned below. Both coating compositions have a viscosity of 16"DINC 4. The pot life of the coating composition of Example 30 is shorter than the pot life of the coating composition of Example 31, due to the presence of the hydroxy-functional polymer. in BOE 3A, both clear compositions were sprayed on steel panels with a Sikkens Autobase MM basecoat, using an HVLP spray gun.The curing at room temperature of the coating composition of Example 30 is faster than the cure of the coating composition of Example 31. The appearance and luster of both coatings are excellent.

Compound Component Axis30 Ahem.31 1 BOE 3A 40 g BOE 3B - 40 g DBTL (10% in butyl acetate / xylene (1/1)) g 4 g Byk 322, Byk 355, butyl acetate (20/15/65) 2 g 2 g Solvesso 100 / ethoxyethyl propionate (1/1) 14 g 24 g 2 Desmodur (R) N3390 67.6 9 78.5 g 3 Nacure 5076 1.14 g 1.14 g EXAMPLES 32 AND 33 CLEAR COATING COMPOSITIONS Two clear coating compositions were prepared, as indicated below. Both clear coating compositions were sprayed on steel panels prepared with a base coat Autobase MM, Sikkens, using a HVLP spray gun. Both clear coatings have excellent paint properties. The application properties are very good. The appearance and luster are excellent.

Compound Component Axis 32 Axis 33 1 BOE 3B 34 g 34 g Polyester polyol B 7.5 g Polyester polyol C 7.5 g DBTL (10% butyl acetate / xylene (1/1)) 4.0 g 4.0 g Byk 322, Byk 355, butyl acetate (20 / 15/65) 8.56 g 8.56 g Solvesso 100 5.6 g 5.6 g Ethoxyethyl Propionate 5.6 g 5.6 g Tinuvin 1130 0.1 g g Tinuvin 123 0.05 g 0.05 g 2 Desmodur (R) N3390 71.0 g 71.0 g 3 Nacure 5076 0.98 g 0.98 g EXAMPLES 34 AND 35 COMPRESSION COMPOSITIONS Two sizing compositions with extra-high solids content were prepared in the following manner. Component 1 was stirred at high speed for 15 minutes, and subsequently passed through a closed mill twice to obtain a fineness of less than 25 μm. Component 1 was then mixed with previously mixed components 2 and 3.

Compound Component Axis 34 Axis 35 1 BOE 3B 17.0 g 17.0 g Disperbyk 110 1.4 g 1.4 g Tioxide TR 92 21.0 21.0 Zinc Phosphate ZP10 13 »6 13.6 Blank fix N 11.0 11.0 Chinese clay quality C 23.5 23.5 Aerosil R972 0.8 0.8 Solvesso 100 6.0 6.0 2 Fascat 4202 0.25 0.25 Nacure 5076 0.35 0.35 Byk 300 0.8 0.8 Desmodur (R) L75 - 23.4 Vestanat (R) T1890E 25,1 Desmodur (R) LS2025 25.1 25.1 Butyl acetate 4.0 4.3 Solvesso 100 7.0 7.5 Both sizing coating compositions were applied with conventional spraying equipment, on steel panels and had a spray viscosity of about 2.0 poise (measured with a Sheen Rotothinner) at a VOC of about 290 g / 1. It was dried at room temperature (overnight) or at 60 ° C (for 30 minutes), and hard coatings and good sanding were obtained, which can be overcoated with regular top coating systems for automotive finishing and / or with coating compositions of the present invention, such as those exemplified in Examples 26-29 (pigmented top coatings, as well as base / clear systems). The advantages over sizing / loading materials Solid 2k Medium, existing, which are used in the automotive finishing market at present, are: very low VOC, prolonged boat life and high body-shaping behavior. In comparison with the existing High Solids sizing compositions, comprising imine interlayers, the advantages are, again, long can life, rapid drying at 60 ° C and the fact that there is no emission of volatile blocking components (such as aldehydes and ketones). of the interlayers, such as ceti inas, aldiminas and oxazolidiñas).

EXAMPLES 36. 37 AND 38 AND COMPARATIVE EXAMPLE J BOE 3B AS REACTIVE DILUENT IN A COMPOSITION OF CLEAR COATING A clear coating component Sikkens Autoclear MS 2000, commercially available, was diluted with different amounts of BOE 3B. The compositions are cited below. Component 1 was mixed with components 2 and 3 and sprayed on steel panels prepared with base coat Autobase MM, Si Kens, using a HVLP spray gun.

CompoCompuesto Ej. .Comp.J Ej. 36 Ej. 37 Ej. 38 nente 1 MS 2000 100 100 100 100 BOE 3B 4.4 11.1 17.8 DBTL 0.2 0.9 1.6 Acetylacetone 0.3 1.1 1.9 Nacure 5076 0.1 0.3 0.5 2 Hardener MS Standard 50 Desmodur (R) N3390 32.6 43.1 53.6 3 1.2.3.Thinner slow 9.4 33 35 35 Properties Ej.Comp.J Ej. 36 Ej. 37 Ej. 38 VOC (g / 1) 560 529 498 468 Viscosity (DINC4, sec) 18 18 19 19 NCO / OH ratio 78 100 100 100 Dry to touch (60 ° C) min. 30 10 10 10 Dry to touch (T.A) min 120 120 77 60 Pot life (min) > 180 60 60 60 Lus re 74 86 82 83 The addition of BOE 3B as a reactive diluent results in a reduction in VOC, a decrease in drying time and an increase in luster.

Claims (42)

NOVELTY OF THE INVENTION CLAIMS

1. - A coating composition, comprising a first compound comprising at least one bicyclo-orthoester group or a spiro-orthoester group, characterized in that the coating composition comprises a second compound comprising at least two groups reactive to the hydroxyl, selected of isocyanate groups, epoxy groups, acetal groups and alkoxysilane groups.

2. A coating composition according to claim 1, further characterized in that the bicyclo-orthoester group has a structure according to the formula I: wherein X and Z are independently selected from linear or branched alky (en) ylene groups, of 1 to 4 carbon atoms, optionally containing an oxygen or nitrogen atom; Y is none or independently selected from X and Z, linear or branched alk (en) ylene groups, of 1 to 4 carbon atoms, optionally containing an oxygen or nitrogen atom; Ri and R2 may be the same or different and are selected from monovalent radicals comprising hydrogen, hydroxyl, alk (en) yl groups comprising from 1 to 30 carbon atoms, which may be linear or branched and may optionally contain one or more heteroatoms , and selected oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and ester groups, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane groups , thioester, thioamide, amide, carboxyl, carbonyl, aryl and acyl; and divalent radicals comprising alk (en) ylene groups having from 1 to 10 carbon atoms; and said groups may be linear or branched and may optionally contain one or more heteroatoms and groups selected from oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and ester, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro , phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acyl groups; ester groups, ether groups, amide groups, thioester groups, thioamide groups, urethane groups, urea groups and a single ligation.

3. A coating composition according to claim 2, further characterized in that X, Y and Z are methylene.

4. - A coating composition according to any of claims 2 and 3, further characterized in that in the case of the monovalent radicals Ri and 2 are independently selected from hydrogen, hydroxyl and linear or branched alk (en) yl groups that they have from 1 to 20 carbon atoms, optionally substituted with one or more hydroxyl groups, and optionally containing an ester group.

5. A coating composition according to claim 4, further characterized in that Ri and R2 are independently selected from methyl, methylol, ethyl, ethylol, propyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and a group -CH2-CH2-0-C0-alk (en) yl of 1 to 20 carbon atoms.

6. A coating composition according to claim 2, further characterized in that one or both groups Ri and R2 is / are a divalent radical, the first compound being a polymer comprising at least one bicyclo-orthoester group.

7. A coating composition according to claim 6, further characterized in that one or both groups Ri and R2 are selected from ester, ether, urethane, a single bond and linear or branched alk (en) ylene groups, having from 1 to 10 carbon atoms, optionally containing one or more ester, ether or urethane groups.

8. A coating composition according to claim 1, further characterized in that the spiro orthoester group has a structure according to formula II or III: wherein R3 and Rβ, independently of one another, are selected from linear or branched alkyl (en) yl, aryl or acyl, optionally containing one or more oxygen, nitrogen, sulfur or phosphorus atoms, optionally substituted with a halogen atom; and R4 and Rβ are independently selected from each other, of an alkylene group having from 1 to 3 carbon atoms, optionally substituted with one or more groups selected from monovalent radicals, such as linear or branched alkyl (en) yl, aryl groups or acyl optionally containing one or more oxygen, nitrogen, sulfur and phosphorus atoms; and divalent radicals, such as a simple ligation and an alkylene group having 10 carbon atoms, with or without one or more atoms and groups selected from oxygen, nitrogen, sulfur and phosphorus atoms, and ether, ester and urethane groups .

9. A coating composition according to claim 8, further characterized in that R3 and Rs are independently selected from linear or branched alk (en) yl groups having from 1 to 4 carbon atoms.

10. - A coating composition according to any of claims 8 and 9, further characterized in that R "is ethylene optionally substituted with a linear or branched alkyl group having from 1 to 5 carbon atoms, optionally containing one or more oxygen and nitrogen atoms.

11. - A coating composition according to claim 10, further characterized in that R "is

12. - A coating composition according to any of claims 8, 9, 10 or 11, further characterized in that Rβ is propylene.

13. A coating composition according to any of claims 8 and 9, further characterized in that the first compound is a compound with spiro-orthoester functionality, according to formula IV: wherein R3 and Rs are independently selected from linear or branched alk (en) yl groups having from 1 to 4 carbon atoms.

14. A coating composition according to any of claims 8 and 9, further characterized in that one or both of the groups R4 and Rβ is (are) substituted with a divalent radical; the first compound being a polymer comprising at least one spiro-orthoester group.

15. A coating composition according to any of the preceding claims, further characterized in that the compound reactive to the hydroxyl is an aliphatic, alicyclic or aromatic compound comprising at least two isocyanate groups or their adducts.

16. A coating composition according to claim 15, further characterized in that the second compound is selected from biurets, isocyanurates, allophonates, uretdiones and their mixtures.

17. A coating composition according to any of the preceding claims, further characterized in that the coating composition additionally contains at least one compound selected from the hydroxyl-functional binders, the hydroxyl-functional oligomers and the monomers, the resins of ketone, aspargyl acid esters and compounds with latent or non-latent amino functionality.

18. A coating composition according to claim 17, further characterized in that the hydroxyl-functional binders are selected from polyester polyols, polyether polyols, polyacrylate polyols, polyurethane polyols, cellulose acetobutyrate, hydroxy-functional epoxy resins. , alkyds and dendrimeric polyols.

19. A process for curing a coating composition, characterized in that it comprises a first compound comprising at least one bicyclo-orthoester group or a spiro-orthoester group, and a second compound comprising at least two hydroxyl-reactive groups; characterized in said method because it comprises the steps of: unblocking the latent hydroxyl groups of the bicyclo-orthoester groups or spiro-orthoester groups, in the presence of water, optionally in the presence of a first catalyst, and reacting with the reactive groups on the hydroxyl of the second compound, optionally in the presence of a second catalyst.

20. A process according to claim 19, further characterized in that the first catalyst of Lewis acids and Brónsted acids is selected.

21. A process according to claim 20, further characterized in that the Lewis acid is BF3Et2 ?.

22. A process according to claim 20, further characterized in that the Brónsted acid has a pKa of less than 3.

23. A process according to claim 22, further characterized in that the acid of Brónsted is selected from a mono- or dialkyl phosphate, a carboxylic acid having at least one chlorine and / or fluorine atom, an alkyl- or arylsulfonic acid, or an acid (alkyl) phosphoric.

24. A method according to claim 23, further characterized in that the acid of Brónsted is selected from methanesulfonic acid, paratoluenesulfonic acid, optionally substituted naphthalenesulfonic acids, dodecylbenzenesulfonic acid, dibutyl phosphate, trichloroacetic acid, phosphoric acid and mixtures thereof.

25. A method according to any of claims 19 to 24, characterized in that it uses from 0 to 10% by weight of the first catalyst, calculated on the compounds with BOE functionality and with SOE functionality.

26. A method according to claim 25, further characterized in that from 0.3 to 8% by weight of the first catalyst is used.

27. A process according to any of claims 19 to 26, further characterized in that the second catalyst is selected from dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, tin octoate, zinc octoate, aluminum chelate. , di-ethyl tin dichloride, tertiary amines, Lewis acids, such as BF3, or their organic complexes; paratoluenesulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid and mixtures thereof.

28. A md according to claim 27, further characterized in that the second catalyst is present in an amount of 0.001 to 5% by weight, calculated on the solid material.

29. A coating composition, characterized in that it comprises a first compound comprising at least one bicyclo-orthoester group or a spiro-orthoester group; a second compound comprising at least two groups reactive to the hydroxyl, and as a third compound, at least one agglutinator with hydroxyl function, selected from polyester polyols, polyr polyols, polyacrylate polyols, polyurne polyols, cellulose acetobutyrate, epoxy resins with hydroxyl functionality, alkyds and rimeric dentine polyols. 30.- A coating composition for refinishing motor vehicles and transport vehicles, or for finishing large transport vehicles, such as trains, trucks, buses and airplanes, characterized in that it comprises a first compound comprising at least one group bicyclo-orthoester or a spiro-orthoester group, and a second compound comprising at least two hydroxyl-reactive groups. 31.- A coating composition for car refinishing, characterized in that it comprises a first compound comprising at least one bicyclo-orthoester group or a spiro-orthoester group, and a second compound comprising at least two groups reactive to the hydroxyl. 32. A two-component system, characterized in that a component comprises at least one bicyclo- or spiro-orthoester compound, and at least one compound reactive to the hydroxyl; and the second component comprises a first catalyst for the hydrolysis of the bicyclo- or spiro-orthoester compound. 33. A two-component system according to claim 32, further characterized in that the hydroxyl-reactive compound comprises at least two hydroxyl-reactive groups, selected from isocyanate groups, epoxy groups, acetal groups, carboxyl groups, anhydride groups and alkoxysilane groups. 34.- A three-component system, characterized in that a component comprises at least one bicyclo- or spiro-orthoester compound, a second component comprises at least one compound reactive to the hydroxyl and a third component comprises a first catalyst for the hydrolysis of the bicyclo- or spiro-orthoester compound. 35.- A three component system according to claim 34, further characterized in that the hydroxyl reactive compound comprises at least two hydroxyl reactive groups, selected from isocyanate groups, epoxy groups, acetal groups, carboxyl groups, anhydride groups and alkoxysilane groups. 36. A coating composition comprising a first compound comprising at least one bicyclo-orthoester group or a spiro-orthoester group, characterized in that the coating composition comprises a second compound which is an amino resin. 37.- A process for the preparation of a compound comprising at least one bicyclo-orthoester group, characterized in that a compound having at least one corresponding oxetane group is converted in the presence of a catalytic amount of a strong Bronsted acid or Lewis, or organic complexes thereof. 38.- A md according to claim 37, further characterized in that the Lewis acid is BF3Et2 ?, BF3-2CH3COOH and S C. 39.- A md according to any of claims 37 and 38, further characterized in that the catalyst is used in amounts of 0.001 to 0.1 mol of catalyst per mole of oxetane group. 40.- A md according to any of claims 37 to 39, further characterized in that the reaction is carried out without solvent. 41.- A procedure for the preparation of: characterized in that pentaerythritol is reacted with triethyl ortopropionate in the presence of paratoluenesulfonic acid, tri ethyl ethylbenzene being used as the solvent. 42.- A polymer selected from a polyacylate or a polyester, characterized in that it comprises at least one bicyclo-orthoester group according to formula I: -C-O-Y-C-R2 (I) in which X and Z are independently selected from linear or branched alkyl (en) ylene groups, of 1 to 4 carbon atoms, optionally containing one atom of oxygen or nitrogen; Y is none or independently selected from X and Z, linear or branched alkyl (en) ylene groups, of 1 to 4 carbon atoms, optionally containing an oxygen or nitrogen atom; one of Ri and R2 is a monovalent radical and the other is a divalent radical, or both groups are independently selected from the group of divalent radicals; the monovalent radicals comprising: hydrogen, hydroxyl, alk (en) yl groups comprising from 1 to 30 carbon atoms, which may be linear or branched and which may optionally contain one or more heteroatoms; and groups selected from the group of oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and ester, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acyl groups; and divalent radicals comprising alk (en) yl groups having from 1 to 10 carbon atoms, and said groups may be linear or branched and may optionally contain one or more heteroatoms and groups selected from the group of oxygen, nitrogen, sulfur, phosphorus , sulfone, sulfoxy and ester, optionally substituted with epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl groups and acyl; ester groups, ether groups, amide groups, thioester groups, thioamide groups, urethane groups, urea groups and a simple ligation.