MXPA99010538A - Polyurethane compositions made from hydroxy-terminated polydiene polymers - Google Patents

Abstract

This invention provides a process for producing a polyurethane resin from a hydrogenated polydiene diol or polyol having a functional group equivalent weight of 750 to 10000, a reinforcing agent having a functional group equivalent weight of 30 to 200, and a polyisocyanate. In a preferred embodiment, the process comprises reacting at least one of a polydiene diol or a reinforcing diol or triol with the polyisocyanate at an NCO/functional group molar ratio of 0.4 to 0.7 or a functional group/NCO molar ratio of 0.25 to 0.55 to form a stable reaction product, adding to this reaction product an additional sufficient amount of the polyisocyanate and, as needed, one or both of the polydiene diol or the reinforcing agent to bring the NCO/OH functional group ratio up to from 0.9 to 1.1 and to achieve a polydiene agent content of 35 to 80 wt.%(on solids basis) and a reinforcing agent content of 2 to 17 wt.%(on solids basis), and reacting this final mixture to form a cross-linked polyurethane product. This process can also be carried out at an OH/NCO ratio of 0.9 to 1.1 using a blocked polyisocyanate wherein the intermediate reaction product is a stable polyurethane resin.

Description

POLYURETHANE COMPOSITIONS PREPARED FROM POLYDYENE POLYMERS WITH HYDROXY FINISHES DESCRIPTION OF THE INVENTION The present invention relates to new crosslinkable compositions comprised of polydiene polymers with hydroxy terminations, polyisocyanates and reinforcing agents. More especially, the present invention relates to the use of hydrogenated diene polymers with particular dihydroxy terminations, with polyisocyanates to produce products that are useful in coating compositions and in adhesive compositions and sealants. Polydiene polymers with hydroxy functional groups (polydienodiols) are well known. U.S. Patent No. 5,393,843 discloses that formulations containing these polymers, a melamine resin and an acid catalyst, can be cured by cooking under normal cooking conditions. This same patent also discloses that these polymers can be mixed with isocyanates, to obtain compositions that cure at room temperature. It is known that, for example, hydrogenated polybutadiene diols (EB diol) can be crosslinked by reacting them with polyisocyanates at almost stoichiometric ratios of 1: 1 NCO / OH (NCO represents the isocyanate functional group which is active in REF .: 31905 the reaction of crosslinking and OH represents the hydroxyl functional group, however, for economic reasons, it is only practical to prepare hydrogenated polydiene diols of relatively high hydroxyl equivalent weight (Pe OH), however, these compositions based on polydiene polymers with cured hydroxy functional groups With a crosslinking agent, they are very smooth because the polymers have a relatively high hydroxyl equivalent weight, ie, above about 750 Pe OH (the hydroxyl equivalent weight is the number of average molecular weight divided by the number of functional groups per molecule) and, in this way, they are elastomeric and rubbery in nature and, although they can be very useful in some applications, they are too soft and have a cohesive force too low to be widely useful in applications such as hard coatings. Attempts to increase the hardness and adhesion by crosslink density simply by mixing the polydienodiols and the polyisocyanate with a refrigating agent, such as a low molecular weight diol or triol, were unsuccessful because the reinforcers are relatively polar and therefore both are incompatible with the relatively non-polar polydiene polymers. The incompatibility of the components causes poor properties, as in the luster, in the cured composition or, even worse, the compositions can be separated into phases when stored before curing. It has been discovered that this problem of incompatibility can be solved by synthesizing polyurethane resins based on a polydienodiol, a reinforcing diol or triol and a polyisocyanate, at appropriate NCO / OH ratios that are not close to 1: 1. Essentially, this involves carrying out a limited reaction between the three components, in order to make them more compatible. The present invention provides a process for producing a polyurethane resin from a hydrogenated polydienodiol or polyol, having an hydroxyl equivalent weight of 750 to 10000, a reinforcing agent, preferably a diol or triol, having a functional group of hydroxyl preference, an equivalent weight of 30 to 200, and a polyisocyanate. In a first preferred embodiment, the process comprises reacting at least one of the polydienodiols (or polyol) or the reinforcing agent, with the polyisocyanate at a molar ratio of NCO / functional group (NCO refers to the isocyanate functional group of the polyisocyanate and "functional group" refers to the functional group of the polydienodiol or polyol and the reinforcing agent) from 0.4 to 0.7, to form a stable reaction product, adding to this reaction product a sufficient additional amount of polyisocyanate and, as necessary, one or both of the polydienodiol (or polyol) and the reinforcing agent, to bring the NCO / functional group ratio up to a value of 0.9 to 1.1 and to achieve a polydienodiol (or polyol) content of 35 to 80% p (based on solids) (% p means weight percent) and a reinforcing agent content of 2 to 17% p (based on solids), for example 14% p and reacting this final mixture to form a cross-linked polyurethane product. The present invention also provides a novel polyurethane resin, which is the reaction product of the first stage of the process. In a second preferred embodiment, the process comprises reacting at least one of the polydienodiol (or polyol) and the reinforcing agent, with the polyisocyanate at a NCO functional group ratio of 0.25 to 0.55, to form a finished reaction product. stable isocyanate, adding to this stable reaction product a sufficient additional amount of one or both of the polydienodiol (or polyol) and the reinforcing agent, and as necessary, the polyisocyanate to bring the functional group / NCO ratio up to a value from 0.9 to 1.1 and up to a polydienodiol (or polyol) content of 35 to 80% p (based on solids) and a reinforcing agent content of 2 to 17% p (based on solids), eg 14% p and reacting this final mixture to form a cross-linked polyurethane product. The present invention also provides a novel polyurethane resin, which is the reaction product of the first stage of this process. In a third preferred embodiment, the process comprises mixing the polydienodiol (or polyol), the reinforcing agent and a blocked polyisocyanate curing agent, such that the molar ratio of the functional group to the completely unblocked NCO would be from 0.9 to 1.1. , the content of polydienodiol or polyol is from 35 to 80% p (based on solids) and the content of the reinforcing agent is from 2 to 17% p, eg 14% p, and then these components are reacted at a temperature, preferably from 80 to 150 ° C and for a time, preferably from 0.5 to 5 hours, sufficient to sufficiently unblock the polyisocyanate, in such a way as to form a partially stable reaction polyurethane resin and, finally, the remainder of the blocked polyisocyanate is unblocked and reacted with the partially reacted polyurethane resin, to form a cross-linked polyurethane product. The present invention also provides a new polyurethane resin, which is the reaction product of the polydienodiol or polyol, the reinforcing agent and the unblocked portion of the blocked polyisocyanate, in the second stage of the process. Polydienes with hydroxy functional groups are preferred for use herein, as are reinforcing agents that are diols or triols. The first stage of the process of the first embodiment described above, produces a stable polyurethane resin composition which can be used in the above process or can be stored for later use. This composition comprises from 40 to 90% p of the polydienodiol or polyol, from 2 to 25% p of the reinforcing agent and is reacted with the polyisocyanate at a molar ratio of NCO / functional group of 0.4 to 0.7. The first stage of the process of the second embodiment described above produces a polyurethane resin composition with isocyanate termination. This comprises from 10 to 75% p of the polydienodiol or polyol, from 1 to 10% p of the reinforcing agent and is reacted with the polyisocyanate at a molar ratio of the functional group / NCO of 0.25 to 0.55. This product can also be prepared without the reinforcing agent. The following table provides examples of the actual quantities (at the bottom of the table) of the components in stage (a) of the first and second modalities, for different coating formulations.

LP O Cn tn I or Cn t 8 Polydiene polymers with hydroxy functional groups and other polymers containing an ethylenic unsaturation can be prepared by the copolymerization of one or more olefins, particularly diolefins, by themselves or with one or more aromatic alkenyl hydrocarbon monomers. The copolymers, of course, can be random, glued, block or a combination thereof, as well as linear, radial or star. Polydiene polymers with hydroxy functional groups can be prepared using anionic initiators or polymerization catalysts. Such polymers can be prepared using bulk, solution or emulsion techniques. When polymerizing at a high molecular weight, the polymer will usually be coated as a solid, such as a lump, a powder or a pellet. When polymerized at low molecular weight, it may be coated as a liquid, such as in the present invention. In general, when using anionic solution techniques, copolymers of conjugated diolefins, optionally with aromatic vinyl hydrocarbons, are prepared by contacting the monomer or monomers to be polymerized, simultaneously or sequentially, with an anionic polymerization initiator, such as metals of group la, their alkyl derivatives, amides, silanolates, naphthalides, biphenyls or anthracenyls. It is preferred to use an alkaline organometallic compound (such as sodium or potassium) in a suitable solvent at a temperature in the range of -150 to 300 ° C, preferably at a temperature in the range of 0 to 100 ° C. Particularly effective anionic polymerization initiators are organolithium compounds having the general formula: RLin wherein R is an aliphatic, cycloaliphatic, aromatic or aromatic hydrocarbon radical substituted with alkyl groups, having from 1 to about 20 carbon atoms and n is a integer from 1 to 4. Conjugated diolefins, which can be anionically polymerized, include those conjugated diolefins containing from about 4 to about 24 carbon atoms, such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-l, 3-hexadiene and 4,5-diethyl-l, 3-octadiene. Isoprene and butadienes are the preferred conjugated diene monomers for use in the present invention, because of their low cost and easy availability. Alkenyl aromatic hydrocarbons (vinyl) which can be copolymerized, include vinyl aryl compounds such as styrene, various styrenes substituted with alkyl groups, styrenes substituted with alkoxy groups, vinyl naphthalene, vinyl naphthalenes substituted with alkyl groups and the like. The hydroxy terminated polymers of the present invention are generally diols wherein the polymer is linear, but linear polyols are also useful herein. Radial and star polymers are also contemplated herein and, in such a case, the polymers would be polyols wherein a hydroxy group is located at the ends of most or all of the branches of such polymers. The polydiene polymers with hydroxy functional groups can have an average molecular weight of 500 to 50,000. The lower molecular weights require excessive crosslinking, while the higher molecular weights cause a very high viscosity, making the process very difficult. Preferably, the polymer is one that has an average molecular weight number of 1,000 to 20,000. More preferably, the polymer is a predominantly linear diol having an average molecular weight number from 1,500 to 10,000 (hydroxyl equivalent weight of 750 to 5,000, because it is a diol and has two hydroxyl groups), because it offers the best balance between the cost of the polymer, good behavior in the process and achieving the correct balance of mechanical properties in the final cured polyurethane. Hydrogenated polybutadiene diols are preferred for use in the present, because they are prepared with ease, have a low vitreous transition temperature and have an excellent wettability. The diols, dihydric polybutadienes are synthesized by anionic polymerization of conjugated hydrocarbon diene monomers with lithium initiators. Polyols can be synthesized in the same way. This process is well known and, for example, is described in U.S. Patent Nos. 4,039,593 and Re. 27,145. Polymerization begins with a monolithium, dilithium or polylithium initiator, which constructs a polymer leaving framework at each lithium site. Typical structures of conjugated hydrocarbon diene monomers containing monolithium leaving polymer structures are: X-B-Li X-B! -B-Li X-A-B-Li X-A-B? -B2-Li • X-A-B-A-Li wherein B represents the polymerized units of one or more conjugated diene monomers such as butadiene or isoprene, A represents polymerized units of one or more vinyl aromatic monomers such as styrene and X is the residue of a monolithium initiator such as sec- Butyllithium B can also be a copolymer of a conjugated diene and an aromatic vinyl compound. Bi and B2 are formed from different dienes. The dihydric polydiene diols used in the present invention can also be prepared anionically as described in US Pat. Nos. 5,391,663; 5,393,843; 5,405,911 and 5,416,168. The dihydric polydiene polymer can be prepared using a dilithium initiator, such as the compound formed by the reaction of two moles of sec-butyllithium with one mole of diisopropenylbenzene. This diinitiator is used to polymerize a diene in a solvent typically composed of 90% p of cyclohexane and 10% p of diethyl ether. The molar ratio of the diinitiator to the monomer determines the molecular weight of the polymer. The protruding polymer, then, is capped with two moles of ethylene oxide and terminated with two moles of methanol, to obtain the desired dihydroxy polydiene. The dihydric polydiene polymers can also be prepared using a monolithium initiator containing a hydroxyl group that has been blocked, such as silyl ether. This process is also known to those skilled in the art. The details of the polymerization process can be found in U.S. Patent No. 5,376,745. A suitable initiator is hydroxypropyl lithium, in which the hydroxyl group is blocked as in tert-butyl di-ethylsilyl ether. This monolithium initiator can be used to polymerize isoprene or butadiene in a hydrocarbon or polar solvent. Then, the protruding polymer is capped with ethylene oxide and terminated with methanol. Then, the silyl ether is removed by acidic catalytic cleavage in the presence of water, obtaining the desired polymer. An unsaturated dihydroxy polybutadiene polymer within the scope of the present invention can have any butadiene microstructure. A polymer of dihydroxypolibutadiene to be used after hydrogenation, can also have any butadiene microstructure. However, it is preferred that it has not less than about 30% 1,2-butadiene addition because, after hydrogenation, the polymer would be a solid wax at room temperature if it contained less than about 30% addition of 1, 2-butadiene and, when used in the process of the present invention, a paste would be obtained at room temperature instead of a low viscosity solution. Therefore, compositions based on a hydrogenated polybutadiene diol having less than about 30% addition of 1,2-butadiene, would have to be coated on a substrate while the composition was at a temperature high enough that the composition it was a homogeneous liquid of low viscosity. Alternatively, the composition could be dispersed in water while hot and then handled as an aqueous dispersion. Although a hydrogenated polybutadiene having an addition of 1,2-butadiene greater than about 30% will produce compositions within the present invention that are liquid at room temperature, it is preferred that the 1,2-butadiene content be between 40 and 60% to minimize the viscosity of the hydrogenated polybutadiene diol. When one of the conjugated dienes is 1,3-butadiene and it is to be hydrogenated, the anionic polymerization of the conjugated diene hydrocarbon is typically controlled with structure modifiers such as diethyl ether or glyme (1,2-diethoxyethane), to obtain the desired amount of addition 1.4. As described in Re 27,145, the 1,2-addition level of a butadiene polymer or copolymer, can greatly affect the elastomeric properties after hydrogenation. Hydrogenated polyisoprene diol polymers can also be used in these compositions. A polymer of dihydroxy polyisoprene within the scope of the present invention can have any microstructure of isoprene. However, it is preferred that it has more than 80% 1,4-isoprene addition, preferably greater than 90% 1,4-isoprene addition, in order to minimize the viscosity of the polymer. Polyisoprene diols of this type can be prepared by anionic polymerization in the absence of microstructure modifiers that increase the 3,4-addition of isoprene. The diene microstructures are typically determined by C nuclear magnetic resonance (NMR) in chloroform. Another method for preparing the polymers of the present invention involves the use of lithium initiators having the structure: (2) wherein each R is a methyl, ethyl, n-propyl or n-butyl radical and A "is an unsubstituted or alkyl-substituted propyl bridge group, including -CH2-CH2-CH2- (1,3 -propyl), -CH2-CH (CH3) -CH2- (2-methyl-l, 3-propyl) and -CH2-C (CH3) 2-CH2- (2,2-dimethyl-l, 3-propyl) or an unsubstituted or alkyl-substituted octyl bridge group, including -CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2- (1,8-octyl), because these initiators will initiate the polymerization of the polymers anionic at surprisingly high polymerization temperatures, with surprisingly low amounts of dead initiator (higher efficiency) compared to similar initiators where A "is replaced by unsubstituted or alkyl-substituted butyl, pentyl or hexyl bridging groups, such as - CH2-CH2-CH2-CH2- (1,4-butyl), -CH2-CH2-CH2-CH2-CH2- (1, 5-pentyl) or -CH2-CH2-CH2-CH2-CH2-CH2- (1 , 6-hexyl). Certain hydroxylated polydiene polymers useful in the present invention have the structural formula (I) HO-A-OH or (HO-A) nX wherein A is a homopolymer of a conjugated diolefin monomer, a copolymer of two or more monomers of diolefin conjugates or a copolymer of one or more diolefin monomers conjugated to a monoalkenyl aromatic hydrocarbon monomer, wherein n > l and X is the residue of a coupling agent. During the preparation of these hydroxylated polydiene polymers, it is possible to prepare some monofunctional polymers having the structural formula HO-A, either by incomplete capping of the protruding polymer; or, by incomplete coupling through the coupling agent. Although it is preferred that the amount of this monofunctional polymer be minimal, satisfactory crosslinked compositions within the present invention can be achieved even when the amount of the monofunctional polymer is as high as 70% p of the hydroxylated polymer in the composition. Other hydroxylated polydiene polymers useful in the present invention have the structural formula (II) HO-A-S2-B-OH or (HO-A-Sz-B) nXO HO-Sz-.AB-Sy-OH or ( HO-Sz-AB) nX wherein A and B are polymer blocks which may be homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers , where S is a block of aromatic vinyl polymer and where y and z have a value of 0 or 1, where n is greater than or equal to 2 and where X is the residue of a coupling agent. These polymers can contain up to 60% by weight of at least one aromatic vinyl hydrocarbon, preferably styrene. Blocks A and blocks B can have an average molecular weight number of 100 to 500,000, preferably 500 to 50,000 and more preferably 1,000 to 20,000. The S block can have a number average molecular weight of 500 to 50,000. Either block A or block B can be capped with a polymer miniblock, with a number average molecular weight of 50 to 1000, of a different composition, to compensate for any initiation of bonding due to unfavorable copolymerization rates or difficulties in the crowned The molecular weights of the polymers are conveniently measured by gel permeation chromatography (CPG), where the CPG system has been properly calibrated. The polymers can be characterized from the chromatogram data by calculating the average molecular weight number (Mn) and calculating the average molecular weight (Mw) or by measuring the "peak" molecular weight. The peak molecular weight is the molecular weight of the main species shown in the chromatogram. For anionically polymerized linear polymers, the polymer is monodisperse cas.i (the Mw / Mn ratio approaches unity) and it is generally descriptive to report the peak molecular weight of the narrow molecular weight distribution observed. As usual, the peak molecular weight value is between Mn and Mw. The molecular weights reported herein are the average molecular weight number calculated from the chromatograms. The materials used in the CPG columns are styrene-divinylbenzene gels or silica gel. The solvent is tetrahydrofuran and the detector is a refractive index detector. The polydienodiol is typically hydrogenated in accordance with procedures known to those skilled in the art. For example, the polydienodiol can be hydrogenated in the manner described in the US Pat. Reissue 27,145. The hydrogenation of these polymers and copolymers can be carried out by a variety of well-established processes, including hydrogenation in the presence of catalysts such as Raney nickel, noble metals such as platinum and palladium, soluble transition metal catalysts and catalysts. of titanium, as in U.S. Patent No. 5,039,755. The polymers can have different diene blocks and these diene blocks can be selectively hydrogenated in the manner described in U.S. Patent No. 5,229,464. The reinforcing agent is a low molecular weight material having at least two functional groups that will react with the polyisocyanate crosslinker. The average molecular weight number is preferably from 60 to 600, more preferably from 60 to 120. Suitable functional groups include the primary and secondary alcohols, dicarboxylic acids, aminoalcohols, mercaptans and primary and secondary amines. Preferred functional groups are hydroxyls. For convenience, all NCO / functional group ratios hereafter will be referred to as NCO / OH or OH / NCO, but OH may be substituted by amines, mercaptans and dicarboxylic acids. The equivalent weight of the reinforcing agent will generally be between about 30 and about 200 g per working group, preferably between about 50 and 150 g per functional group. The functionality of the reinforcing agent should be at least 2 and can be as high as desired, taking into account that the increase in functionality increases the polarity, which adversely affects the compatibility of the reinforcing agent with the polydienodiol. However, if the reinforcing agent can be mixed or cooked in the composition, the functionality is acceptable. Preferred reinforcing agents for use in the present invention include branched aliphatic diols having from 5 to 30 carbon atoms, especially aliphatic diols substituted with alkyl groups such as 2-ethyl-l, 3-hexanediol (PEP diol), , 2,4-trimethyl-l, 3-pentanediol (TMPD diol) and 2-ethyl-2-butyl-1,3-propanediol (BEPD diol), because they are branched diols substituted and, as such, are not as polar and therefore are not as incompatible with polydiene polymers compared to straight chain unsubstituted diols. Triols such as trimethylolpropane or triethylolpropane can also be used. The isocyanate used in the present invention is an isocyanate having an average functionality of two or more isocyanate groups per molecule. To prepare the preferred thermosetting coatings of the present invention, the functionality must be greater than 2. Preferred isocyanates are those that are less polar because they are more compatible with the polydiene polymer. Examples of suitable diisocyanates are 2,4-toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDl), mixtures of diphenylmethane diisocyanate isomers, para-phenyl diisocyanate, isophorone diisocyanate (IPDI), bis ( 4-isocyanatocyclohexyl) -methane (HMDI), naphthalene diisocyanate and hexamethylene diisocyanate (HDI). The polyisocyanates can be prepared from these diisocyanates, by dimerization or trimerization of the diisocyanates, using appropriate catalysts to obtain biurets, isocyanurates, and the like. The blocked isocyanates prepared by reacting these diisocyanates and polyisocyanates with blocking agents are also useful. Suitable blocking agents are phenols, alcohols such as butanol, hexanol, etc., oximes such as butanone oxime and caprolactam. The particular blocking agent used determines the temperature at which the blocking agent will be unblocked. Specific commercially available isocyanates that can be used in the present invention include those found in the following table: Mondur, Desmodur and Vestament are registered trademarks.

The IPDI isocyanurate is especially useful and is preferred for use herein, because it exhibits especially good compatibility with the preferred polybutadiene diols of the present invention, has a functionality of 3 NCO groups per molecule, which facilitates the compatibility of the polydienodiol with the reinforcing diol more than with an isocyanate, and it has an excellent stability, which allows the preparation of polyurethane products having an excellent durability. The polymerization process can be carried out in the presence of catalysts. Useful catalysts for accelerating the NCO / OH reaction are tertiary amines such as tetramethylbutanediamine and triethylamine, pyridine, 1,4-diaza (2, 2, 2) bicyclo-octane and organometallic compounds such as tin dioctoate and dibutyltin dilaurate. These catalysts are used at levels ranging from 0.001 to 1.0% by weight. Simple Two-Component Polyurethane The two-component curing polyurethanes at room temperature consist of an "A" side and a "B" side. The "A" side usually contains everything except the isocyanate (polyols, catalysts, fillers, stabilizers, etc.) and the WB side "is usually only the isocyanate." When it is time to apply the polyurethane, the components A and B are mixed and the reaction begins.Indeed, mix an "A" side composed of a hydrogenated polybutadiene diol having an hydroxyl equivalent weight of 1700, a catalyst and a solvent, with a "B" side composed of an aliphatic triisocyanate such as DESMODUR Z-4370 at a 1: 1 stoichiometry of NCO / OH, produces a cross-linked polyurethane film which is soft and elastomeric.It is not surprising that the film is soft, since the film cured at 1: 1 NCO / OH, contains approximately 85% p of gum (polymeric diol in this case) due to the relatively high hydroxyl equivalent weight of the hydrogenated polybutadiene diol.Even elastomeric products are necessary in many applications, the prepa With this formulation of simple polybutadiene diol and triisocyanate, they will be too soft and will have too low tear strength to be of wide utility in applications such as strong wear resistant coatings or adhesives that require high cutting resistance. This work uses this procedure to increase the hardness and strength of compositions based on such polymers, including a low molecular weight (MW) booster diol or triol, together with higher concentrations of the isocyanate required to maintain the 1: 1 stoichiometry of NCO / OH. This stoichiometry, or a very close one, is necessary to achieve the maximum crosslink density in the final cured polyurethane, which produces the optimum properties of the polyurethane. This approach of using a mixture of a polybutadiene diol and a low molecular weight diol or triol on the A side is complicated by the fact that many candidate low molecular weight diols and triols are too polar to be compatible with the polybutadiene. relatively non-polar dioles, so that they do not form a stable mixture on the A side. Another complication is that many candidate low molecular weight triols and triols are crystalline solids that are not soluble in the solvents used for the A side. The PEP diol was used to illustrate the approach of including a reinforcing diol or triol on the A side, since it has a relatively good compatibility with the hydrogenated polybutadiene diol (hereinafter referred to as EB diol) and because it is soluble in the required solvents. The structures of the materials used in this work are given in Table 1. The solvents were dried on 4Á molecular sieves. All polymers and reinforcing diols were vacuum dried before use. Initially, the booster diols were dried in a vacuum oven overnight at 80 ° C. However, some reinforcing diols sublimated and plugged the vacuum line. The diols NPG and TMPD were particularly bad in this respect. Another procedure was attempted in which the EB diol and the booster diol were placed in the resin vessel and heated to 130 ° C. The vessel was purged with dry nitrogen for about 1 hour. After purging, isobutyl acetate was added to the vessel and refluxed to rinse the reinforcing diol that had been sublimed and returned to the mixture. The best procedure for drying the diols was with an apparatus in which the diol was heated in a vacuum-filled balloon flask through a w-nock out glass container. "Using this apparatus, the diols were dried for 2 hours at 120 ° C under vacuum Unless otherwise indicated, the coatings were applied to cold-rolled steel panels (panels QD412 of Q-Panel Corp.) using a No. 52 wire rod and cured under ambient temperature conditions, the coatings were also applied to thermoplastic polyolefin (TPO) plates (DEXFLEX® 777 or 880, from D &; S Plastics). In the tables it is observed that these coatings in TPO were cured at room temperature or baked at 121 ° C. The overall appearance of the coatings, such as their luster, clarity, wear resistance, etc., were qualitatively qualified. Quantitative measurements of the coating properties were made using the standard methods for oscillation hardness (ASTM D2134), scratch-hardness (ASTM D3363), mechanical rub resistance (ASTM D2794) and cross-hatch adhesion (ASTM D2794).

TABL 1 Identification of Ingredients Component Supplier Description Polydiene Polymers Ma = Average molecular weight number f = Number of OH groups per polymer 1,2-Bd = Vinyl content in weight percent EW = hydroxyl equivalent weight '(M , / f) EB DIOL A SHEL HO-EB-OH, a hydrogenated polybutadiene diol Mn = 4000, f = 1.94, 1.2-Bd = 38%, EW = 2062 EB DIOL B SHELL HO-EB-OH, a hydrogenated polybutadiene diol a = 2660, f = 1.91, 1,2-Bd = 50%, EW = 1393 EB DIOL C SHELL HO-s / EB-OH, a hydrogenated poly- (styrene / butadiene) diol a = 3500, f = 1.86, styrene content = 26% p, EW = 1882 EB DIOL D SHELL HO-EB-OH, a hydrogenated polybutadiene diol a = 3300, f = 1.92, 1.2-Bd = 53%, EW = 1720 Isocyanate crosslinkers Bayer Polyisocyanate based in IPDI, DESMODUR Z-4370 70% p in xylene, NCO EW = 365 DESMODDR Z-4470 Bayer Polyisocyanate based on IPDI, 70% p in Aromatic 100, NCO EW = 359 DESMDDDR N-3390 Bayer Polyisocyanate based on HDI, 90% p in butyl acetate / Aromatic 100, NCO EW = 216 DESMODÜR N-3400 Bayer Polyisocyanate based on IPDI, 100% solids, ^ JCO EW = 193 MONDÜR MR Bayer Polyisocyanate based on MDl, 100% solids, NCO EW = 134 Reinforcing agents PEP Aldrich 2-ethyl-l, 3-hexanediol, mp = -40 ° C BEPD Perstorp 2-ethyl-2-butyl-l, 3-propar? Xaiol, m.p. = 39 ° C NPG Eastman 2,2-dimeti 1-1,3-propanediol, m.p. = 125 ° C TMPD Eastman 2,2,4-trimethyl-l, 3-pentanediol, m.p. = 46-55 ° C HBPA Shell bis-phenol-A, m.p. 165 ° C HDD Henkel Dimer diol, HO-C36-OH, p. eq. = BDO DuPont 1,4-butanediol, m.p. = 19 ° C ZOLDINE »RD-4 Angus Reagent diluent of oxazolidine-aldima type, EW = 89, f = 3, liquid (aminoalcohol) Polyol DESMOPHENS) 670-80A Bayer Polyester saturated polyol, 80% p in n-butyl acetate, PE OH = 500 DABCC® T-12 Air catalytic converter Dibuty 1-tin dilaurate Products Solvents Eastman Isobutyl acetate Urethane grade, eg = 112-119 ° C Xylene Aldrich e.g. = 137-144 ° C Aromatic 100 Exxon Aromatic solvent, boiling range 185-206 ° C Methylamyl ketone Aldrich p.e. = 150 ° C Stabilizers IRGANOXS) 1076 CIBA Antioxidant of phenol type hindered TINUVINS) 400 CIBA Absorbent UV of triazine type TINÜVINÍy 123 CIBA UV stabilizer of hindered amine type Pigment TiPure?) R-706 DuPont Soft pigment of rutile titanium dioxide, size of particle 0.27 microns Silano SILQÜESTS 'A-189 OSI Mercaptopropyltrimethoxy s 1 anus EXAMPLE 1 (comparative) Table 2 shows the results of the mixture of EB diol A and PEP diol on the A side of 2-component polyurethane coatings.

TABLE 2 Coatings of two Components at 1.1 NCO / OH with the Side «Aw Modified Composition Side Mixing Mixture Mixture Mixture Mixture "A", pbw * A-l A-2 A-3 A-4 A-5 EB DIOL A 1700 612 281 119 70 PEP diol 47 61 68 70 DABCO T-12 2.0 0.9 0.6 0.5 0.4 Xylene 729 262 120 51 30 Solution Side "A" EB DIOL A / PEP 100/0 93/7 82/18 64/36 50/50 Transparency transparent- lightly slightly opaque opaque Stability of stable stable stable separate phases Phase Composition Side "B" pbw DESMODUR Z-4370 401.5 401.5 401.5 401.5 401.5 Composition of C-1 C-2 C-3 C-4 C-5 coating A + B dry,% p EB diol 85.7 65.1 45.0 25.4 16.5 PEP diol 5.0 9.8 14.5 16.6 Triisocyanate 14.2 29.9 45.1 60.0 66.7 Caulking 0.1 0.1 0.1 0.1 0.1 0.1 Properties8 on steel (QD412) Thickness, mil 1.1 1.2 1.4 (pp? (0.028) (0.030) (0.036) Scratch hardness 4B H 2B Adhesion at 0 0 0 cross scratches General Appearance Light tack None none High high gloss Transparent transparency Rentente Adhesion to the very defimuy defimuy defiacero ciente ciente ciente Parts in weight - it is equal in all the tables properties after 1 week of curing at room temperature.

The coating C-1 is simply the EB diol cured with the triisocyanate at a slight excess of NCO (1.1: 1, NCO / OH), obtaining a coating containing approximately 85% p of EB diol. Since the mixture of side A A-l is simply a solution of EB diol and catalyst in xylene, it is clear and of stable phase. When mixed with the B side, the composition is cured to obtain a glossy, transparent polyurethane film, which feels slightly tacky and has poor adhesion to the steel. Coatings C-2 and C-3 are compositions that incorporate 5% p and 9.8% p of PEP diol in the cured and dried final coating. The PEP diol and the resulting increase in isocyanate required to maintain the 1.1: 1 ratio of NCO / OH, cause the concentrations of EB diol to decrease to 65% p and 45% p, respectively. The mixtures of side A, A-2 and A-3, of the EB diol, PEP diol and catalyst in xylene, are of stable phase but slightly turbid. When mixed with the B side, they provide coatings that are somewhat harder and that are not sticky to the touch. Both are pleasant and glossy coatings that have poor adhesion to steel. The C-2 coating is transparent, but the C-3 coating is opaque. In coatings C-4 and C-5, sufficient PEP diol was included on the A side to obtain cured coatings containing 25% p and 16% p of EB diol, respectively. Due to the incompatibility of the EB diol and the PEP diol, the mixtures of side A, A-4 and A-5 were of stable phase and separated when resting. Therefore, coatings were not made with these compositions. The . examples of Table 2 show the limited ability to combine the polydienodiol and the reinforcing diol in a simple physical mixture, without using the partial reaction as taught in the present invention. Example 2 (Comparative) The other approach to preparing the coatings with these three components is to incorporate either the EB diol, or the PEP diol, with the isocyanate on the B side, instead of on the A side. PEP diol was incorporated into the B side, the B side would become more polar and would be more likely to be incompatible with the EB diol when the A and B sides were mixed. Therefore, the EB diol was incorporated into the B side. Thus, side B contains the triisocyanate, the EB diol (which was coated with the triisocyanate, catalyst and solvent.The A side is simply PEP diol.Table 3 shows formulations demonstrating this approach of modifying the isocyanate with the EB diol on side B. TABLE 3 Coatings of two Components to 1.1 NCO / OH with Side B "Modified Composition Side Mix Mixture Mixture Mixture Mixture "B" pbw B-l B-2 B-3 B-4 B-5 EB DIOL A 1700 612 281 119 70 DESMODUR Z-4370 401.5 401.5 401.5 401.5 401.

DABCO T-12 2.0 0.9 0.6 0.5 0.4 Xylene 729 262 120 51 30 Solution Side "B" NCO / OH 1.1 3.1 6.7 15.7"26.8 Very opaque transparency very opaque very opaque Stability of not stable stable stable stage carried out Composition Side "A" pbw PEP diol 0 47 61 68 70 Composition of C-1 C-2 C-3 C-4 C-5 Coating A + B dry,% p EB diol 85.7 65.1 45.0 25.4 16.5 PEP diol 5.0 9.8 14.5 16.6 Triisocyanate 14.2 29.9 45.1 60.0 66.7 Catalyst 0.1 0.1 0.1 0.1 0.1 Properties3 on steel (QD412) Luster little bit little Opaque opaque opaque transparency Adhesion to brittle brittle brittle steel Resistance to deficient poor deficient wear Properties after 1 week of curing at room temperature. The solutions gelled rapidly when PEP was mixed in the "B" side solutions.

The mixtures of side B, Bl and B-2 could not be prepared at this solids content, because the EB diol and the triisocyanate on the B side are stoichiometrically so close that they would form high molecular weights and have very high viscosities. elevated.

It was possible to prepare stable B-side mixtures with B-3, B-4 and B-5, but they were very opaque. When the PEP diol was mixed in these B side blends, they gelled very quickly and the coatings were opaque and possessed very little luster. The little success found when combining the EB diol and the PEP diol on the A side or combining the EB diol and the triisocyanate on the B side, suggests that the mutual incompatibility of the EB diol / diol booster / crosslinker is a significant problem in polyurethane compositions. Therefore, in accordance with the present invention, additional work on cooking in the resin vessels was performed to find limited reaction conditions that could provide stable phase resins that could be cured to obtain coatings having a better hardness and gloss and adhesives that have better resistance to cutting and tearing. Resin Cooking Technology In this resin cooking, the polyurethane polymers are synthesized by the reaction of the EB diol, the booster diol and the isocyanate in the presence of a small amount of catalyst and some solvent to control the viscosity. The extent of the reaction between the EB diol, the booster diol and the crosslinker must be carefully controlled. There must be enough reaction to resolve the incompatibility of the components. But there must not be so much reaction as to form molecules of high molecular weight, thus producing high viscosities. When blocked isocyanates are used as crosslinkers, it is relatively easy to control the extent or degree of the reaction, because the reaction can be stopped at any point only by cooling the resin to room temperature or by adding a little n-butanol, which suppresses the reaction and becomes part of the solvent system. This works well for one component resins to prepare cooked cured coatings. However, in the preparation of intended resins for two components, the curing at room temperature of the compositions can not be stopped and will continue until either the OH groups or the NCO groups are consumed. Thus, the only method to control the extent or degree of the reaction between the EB diol, the reinforcing diol and the isocyanate, is to control the stoichiometry. This is illustrated as follows. Table 4 shows recipes calculated for two-component polyurethanes based on EB diol, BEPD diol and DESMODUR Z-4370. The first entry does not contain BEPD diol, it uses 1 equivalent of OH reacting with 1 equivalent of NCO. Since DESMODUR Z-4370 is a triisocyanate, for each molecule of EB diol, there is 2/3 of the triisocyanate molecule. So that, based on weight, the formulation contains 87% p (percent by weight) of EB diol and 13% p of triisocyanate. Progressing down the table, the concentration of EB diol in the composition is reduced by incorporating BEPD as the reinforcing diol and increasing the triisocyanate to maintain the 1: 1 ratio of NCO / OH. For example, to prepare a polyurethane containing 40% p of EB diol, it is estimated that 12% p of BEPD is required. The amount of triisocyanate required in the formulation to react with all OH is 48% p. Thus, for each molecule of EB diol, there would be 7 molecules of the booster diol and 5.3 molecules of triisocyanate. TABLE 4 Recipes for Thermosetting Polyurethane Compositions (1: 1 NCO / OH) Component Weight eq. EB Diol 1700 BEPD Diol 80 DESMODUR Z-4370 365 Composition (1: 1 Composition (1: 1 NCO / OH), E EB diol / NCO / OH), moles EB diol BEPD Triiso BEPD, p / p EB diol BEPD Triiso 87. 0 0.0 13.0 100/0 1 0 0.67 80. 0 1.8 18.2 98/2 1 0.5 1.0 70. 0 4.3 25.7 94/6 1 1.4 1.6 60. 0 6.9 33.1 90/10 1 2.7 2.5 50. 0 9.4 40.6 84/16 1 4.4 3.6 40. 0 12.0 48.0 77/23 1 7.0 5.3 . 14.6 55.5 67/33 1 11.3 8.2 . 0 17.1 62.9 54/46 1 19.9 14.0 To prepare this polyurethane containing 40% p of EB diol as a two component system, the EB diol and the BEPD diol would usually be dissolved on the A side and the triisocyanate used as the B side. However, the incompatibility of the EB diol and the BEPD diol in the A-side solution, can cause phase separation of the solution or produce opaque coatings or coatings with little luster. The approach taken in this work to solve this incompatibility, is to effect a limited reaction between these components to synthesize either a polyurethane resin with OH endings, or a polyurethane resin with NCO terminations, which could be used subsequently in a system of two components or in a wet curing system. Figure 1 shows a graph of the concentration of the EB diol in the final cured polyurethane composition versus the stoichiometry of the mixture of EB diol, reinforcing diol and triisocyanate. The vertical line in the center of the figure is the 1: 1 point of NCO / OH. The compositions that fall in this line have an equal number of OH groups and NCO groups. These are compositions for crosslinked polyurethanes having a maximum crosslink density. The compositions to the left of this central line contain less than the stoichiometric amount of NCO. Therefore, these compositions can produce polyurethane resins with OH endings which can subsequently be used as side A of a two component system. The compositions to the right of this central line contain less than the stoichiometric amount of OH. Therefore, these compositions can produce polyurethane resins with NCO terminations that can be subsequently used as the B side of a two component system or as a wet curing system. There are four regions shown in Figure 1. Region 4 shows compositions that are close enough to the stoichiometry that they will gel in a two component system. The compositions of region 3 are far enough from the stoichiometry so that they do not gel. However, they are close enough to the stoichiometry that high molecular weight polyurethane molecules are formed when they are mixed in solution, which produces high viscosity solutions. The compositions of region 3 will not be useful due to their high viscosity, region 2 indicates compositions that are useful in this work and that fall within the scope of the present invention. The stoichiometry is sufficient to produce a sufficient reaction to obtain transparent stable phase resins. However, the compositions are sufficiently far from the stoichiometry for the polyurethane molecules that are formed to have a sufficiently low molecular weight, which produces tolerable viscosities. In region 1, the degree or extent of the reaction is too low to obtain clear stable phase resins. In region 1 on the left side, there is not enough triisocyanate to bind enough EB diol molecules and booster diol molecules to obtain stable phase resins. In region 1 on the right side, there is such a large excess of triisocyanate that again the EB diol and reinforcing diol molecules will not bind through the triisocyanate molecules. Thus, the compositions of region 1 are not useful in this work. The boundaries of the regions in Figure 1 are not fixed and distinguishable. The stoichiometry needed to reach region 2 will depend to some degree on the particular ingredients, especially of the particular reinforcing diol used in the composition. The positions of the boundaries of region 2 are the best estimates from the data presented here for the reinforcement diols and diols used herein. The procedure for making the resin preparation depends on whether the resin was a polyurethane with hydroxyl endings or a polyurethane with isocyanate terminations. For a resin with OH endings, it was found that the best procedure (procedure 1) was to charge the diols, the catalyst and about 70% of the solvent in the first resin vessel, heat to 80 ° C under a dry nitrogen purge and slowly add the isocyanate, diluted with 30% of the solvent. For a resin with NCO terminations containing just EB diol and triisocyanate, the best procedure (procedure 2) was to charge the isocyanate, the catalyst and approximately 70% of the solvent in the first vessel, heat to 80 ° C under a purge of dry nitrogen and slowly add the diol, dissolved in 30% of the solvent. For a resin with NCO terminations containing EB diol, reinforcing diol and triisocyanate, the best procedure (procedure 3) was to charge the EB diol, the reinforcing diol, the isocyanate and the solvent in the first resin vessel, heat at 80 °. C under a dry nitrogen purge and add the catalyst in the form of a 10% p solution in the solvent. In all three procedures, the resin was maintained at 80 ° C for approximately another 2 to 4 hours after all the ingredients had been added. Subsequently, it was emptied into a bottle for later use. Synthesis of Polyurethane Resins with Hydroxyl Terminations EXAMPLE 3 Effect of NCO / OH - Table 5 shows examples of the synthesis of polyurethane resins with hydroxyl endings to be used on the A side of a two component polyurethane. These resins contain mixtures of EB diol and reinforcing diol. To resolve the incompatibility between these two components, they are reacted together with the appropriate amount of triisocyanate in a resin vessel, to obtain Resin Preparation Side "A". The amount of triisocyanate used in the preparation is expressed by the NCO / OH ratio.

TABLE 5 Effect of the NCO / OH Ratio on the Resin Preparation EB DIOL / DIOL Booster / 4370 Pre-Mixing Preparation Preparation Preparation Preparation Preparation Preparation of Resin Side "A", Al A-2 A -3 A-4 A-5 A-6 A-7 pbw EB DIOL B 48 38.9 28.2 26.4 32.7 28.2 15.8 TMPD diol 12 9.7 7. 1 6.6 10.5 BEPD diol 8.2 7.1 DESMODUR Z-4370 11.4 24.7 27 19.1 24 .7 33.6 IO » DABCO T-12 0.06 0.06 0.06 0.06 0.06 0.06 0.06 I Acetate 40 '40 40 40 40 40 40 isobutyl Properties of the prepared resin EB diol B / diol 80/20 80/20 80/20 80/20 80/20 80/20 60/40 reinforcement IJ tn L? Ui Nc? /? Ii 0.2 0.6 0.7 -0.4 0.6 Appearance 0.6 not performed separately opacity separate opacity transparent opacity very light very light very light Carposition Side "B", Pbw DE9401UR Z-4370 77.0 51.1 20.8 12.7 33.4 21.2 Composition of 28.0 C-1 C-2 Coating C-3 C-4 C-5 6 A + B secor íp C-7 EB diol 42.1 42.0 43.4 41.8 booster diol 22.7 10.5 10.6 10.8 10.5 Triisocyanate 15.1 47.3 47.4 45.7 47.6 Catalyst 62.1 0.053 I 0.089 0.099 0.089 Properties' 0.086 < 1 C-2 on steel C-4 C-5 (QD412) £ -§ C-7 Stickiness, thousand 1.1 1.2 (pm) (0.028) (0.030) Hardness of 10 11 oscillation I J I fi o t l (J1 hit or:? to rayadinas Resi st pirin al frot e pr «< -Anico 12 Adhesion to cross-hatchlings P ^ o Jdades Oscillation hardness 12 15 Scratch hardness < 4B < 4B I * > Resistance to mechanical rubbing 29 13 Adhesion to the crossed scratches General appearance Stickiness none none none L sLte Transparency Adhesion to steel Adhesion to TPO Resistance to desuaste Characteristics of the Fellula Propi ages after 1 week of The results of preparations A-2 and A-5 show that, at 80/20 of EB diol / booster diol, triisocyanate at 0.2 and 0.4 NCO / OH does not produce a sufficient reaction to obtain stable phase resins. The increase of triisocyanate up to 0.6 NCO / OH (A-3 and A-6) - it produces a sufficient reaction to obtain very pleasant stable phase resins. Triisocyanate at 0.7 NCO / OH (A-4) produces a nice resin, but the viscosity a 60% p in isobutyl acetate is very high. These polyurethane resins with stable phase hydroxyl functional groups can be cured in the form of a two component system, by mixing them with more triisocyanate at about 1.0 to 1.1 NCO / OH. The results of Table 5 show that resins using 80/20 of EB diol / reinforcement diol (producing cured coatings containing approximately 42% p of EB diol), produced cured coatings C-3, C-4 and C- 6, which have a good luster, good transparency and good film characteristics (which means they are films that are flexible and resistant). These results also demonstrate that the C-7 coating, which used 60/40 EB diol / reinforcement diol (producing cured coatings containing approximately 23% p of EB diol), produced a cured coating that was brittle. Thus, the useful compositions will contain at least about 30% p of EB diol in the final cured coating, in order to obtain good flexibility and hardness. EXAMPLE 4 Table 6 shows resins with hydroxyl functional groups prepared with much lower concentrations of the reinforcing diol (NPG in these examples). TABLE 6 Effect of the NCO / OH Ratio on Resin Preparation EB DIOL / NPG / 4370 Resin Preparation Preparation Preparation Side "A", pbw A-l A-2 A-3 EB DIOL B 54.3 45.5 37.9 NPG diol 1.9 3.1 DESMODUR Z-370 5.7 12.6 19 DABOO T-12 0.06 0.06 0.06 Isobutyl acetate 40 40 40 Properties of prepared resin EB DIOL BNPG 100/0 96/4 92/8 NDO / OH 0.4 0.5 0.6 Clear Transparent, Cloudy Appearance Composition Side "B" pbw DESMODUR Z-4370 9.4 13.9 13.9 Coating composition C-1 C-2 C-3 A + B dry, tp EB diol 83.6 69.0 59.1 - so ¬ NPG 2.9 4.8 Triocyanate 16.3 28.1 36.0 Catalyst 0.092 0.091 0.094 Properties on steel (QD412) Resistance to mechanical rubbing > 100 80 > 100 Adhesion to scratches 0 0 1 crossed Properties to on TPO (DEXELEX 777) Resistance to mechanical rub 54 > 100 > 100 l o Adhesion to scratches or crossed General Appearance Light r-inguna no glue High high high luster Transparent transparent transparent Adhesion to poor deficient steel regular Poor poor TPO adhesion very poor Poor wear resistance6 very good regular Characteristics of elastic elastic hard Film Pleasant surface fine cracks fine cracks 0 Properties after 1 week of curing / drying at room temperature. It could be cut through the film with the fingernail.

Preparation A-1, which does not contain NPG, shows that EB diol can be prepared with triisocyanate at 0.4 NCO / OH without greater penalty for viscosity. However, coating C-1, prepared with the Al preparation and cured with more triisocyanate at 1.1 NCO / OH, has the same properties as a simple two-component mixture of EB diol as side A and all of the triisocyanate as side B. When the EB diol / triisocyanate resin was prepared at 0.7 NCO / OH, the reaction mixture became so thick in about 20 minutes that the stirrer rod rose as it approached gelation. Coating C-2 of Table 6 uses only a small amount of NPG as a reinforcing diol. Resin Side A Preparation A-2, prepared at 0.5 NCO / OH was stable phase. The properties of the C-2 coating made with the A-2 preparation cured with more triisocyanate at 1.1 NCO / OH, shows that even this small amount of reinforcing diol was sufficient to remove the slight tackiness of the C-1 coating and to improve the Wear resistance to a point where it can not be easily cut through the lining with the nails. The resin side. A preparation A-3, at 0.6 NCO / OH, was stable but opaque. However, when cured with more triisocyanate, the C-3 coating was clear.

EXAMPLE 5 Effect of Type of Diol Reinforcement - resin preparations side A were conducted with a series of diols reinforcement in two formulations, one of which the cured coating end to 1.1 NCO / OH it contained about 59% w EB diol and in another of which the final coating contained approximately 39% p of EB diol. The results are presented in tables 7 and 8, respectively. Table 7 Effect of type Diol Reinforcement Preparation of Resin EB DIOL / DIOL Reinforcement / 4370 Diol PEP BEPD TMPD HBPA NPG BDO reinforcement ComDosición A-l A-2 A-3 A-4 A-5 A-6 Preparation of Resin Side "A", pbw EB DIOL. B 37.6 3_.e 27.e 37.6 37.9 3".9 Diol of 4.1 4.3 4.1 5.8 3.1 2.7 reinforcement DESMDDUR z- 18.1 17.e 18.1 16.6 19 19.3 4370 DABCO T-12 0.06 0.06 0.06 0.06 0.06 0.06 Acetate 40 40 40 40 40 40 isobutyl Properties of the prepared resin EB diol B / diol 90/10 90/10 90/10 87/13 92/8 reinforcement 93/7 N30 / OH 0.6 0.6 0.6 0.6 0.6 0.6 Trans-trans-trans-trans-trans-gelling sensibility can be seen from the front Copying Side "B", pbw DE? MODUR Z- 13.3 13.1 13.3 12.1 13.9 4370 Composition of C-1 C-2 C-3 coating C-4 C-5 C-6 A + B dry, p EB diol 59.1 59.3 59.1 59.1 59.1 diol of 6.4 6.7 6.4 9.1 booster 4.8 Triisocyanate 3 33.9 34.4 31.6 36.0 Catalyst 0.094 0.094 0.094 0.094 0.094 Properties * Steel (QD412) Thickness, mil 1 * 5 1-4 1-4 1.3 1.5 (m) (0,038) (0,036) (0,036) (0,033) (0,038) Hardness of oscillation 6 6 7 7 Resistance to 26 26 22 24 mechanical rub 31 Adherence to 0 0 Crossed scuff Properties * TPO fDEXFLEX 880) Hardness of 7 July oscillation resistance 33 39 34 29 46 mechanical rub adhesion scratch cross ADariencia General Stickiness none none none none none high gloss high high high high adhesion to defidefidefidefidefiacero sufficient enough enough enough enough enough Adhesion to TPO defidefidefidefideficiente enough enough enough resistance regulating defi- very regularly determined regularly wear sufficient elastic elastic elastic feature ficient elastic elastic s film Properties after 1 week cure / dry at room temperature.

The results in Table 7 show that all the reinforcing diols except the BDO, produced resins with stable phase hydroxyl endings and transparent when prepared with triisocyanate at 0.6 NCO / OH. The properties of the coatings cured with more triisocyanate at 1.1 NCO / OH, show that all the resins produced coatings with 59% p of EB diol, which were glossy, non-tacky and pleasant elastic films. In fact, the differences between the resins are very small.

The results of table 8 show that, again, transparent stable phase resins with all reinforcing diols except BDO could be prepared at a ratio of 0.6 to 0.7 NCO / OH. The cured coatings contained 39% p of EB diol and were hard and, in the case of TMPD and HBPA, a little brittle. TABLE 8 Effect of Type of Bound Diol on Resin Preparation EB DIOL / Boost Diol / 4370 Diol of PEP BEPD TMPD HBPA BDO BDO Reinforcement Comoosition of Al A-2 A-3 A-4 A-5 A-6 Preparation of Resin Side "A", pbw EB DIOL B 24.0 25.7 24.0 24.0 24 25.9 Dol of 7.0 8.1 7.0 10.1 4.7 5.1 reinforcement DESMDDUR Z- 29.0 26.2 29.0 25.9 31.3 28.9 4370 DABCO T-12 0.06 0.06 0.06 0.06 0.06 0.06 Acetate 40 40 40 40 40 40 isobutyl Properties of prepared resin EB DIOL B / diol 77/23 76/24 77/23 70/30 84/16 84/16 reinforcement NCO / OH 0.6 0.6 0.6 0.6 0.6 0.6 Transp appearance transp. transp. transp. gelifi- separac each Composition Side "B", pbw DESMDDUR Z- 13.7 19.2 13.7 12.2 4370 Ccumulation of C-1 C-2 C-3 C-4 coating A + B dry,% p EB diol 39.4 39.2 29.4 29.4 diol of 11.5 12.3 11.5 reinforcement 16.6 Triisocyanate 49.0 48.4 49.0 43.9 Catalyst 0.098 0.091 0.098 0.099 Properties in steel (QD412) Hardness of 14 17 13 osci-lation 18 Resistance to < 20 > 100 < 20 mechanical rub < twenty Adhesion to the 5 5 2 cross scratches Properties "in TPO (DEXFLEX 777) Hardness of 11 18 12 osci-lation 14 Resistance to 42 > 100 < 20 mechanical rub < twenty Adhesion to cross-hatchings General appearance Resistance to very-very-very-de-wasteful-fickle-fickle-fickle Feature cracked cracked from film a Properties after 1 week of curing / drying at room temperature.

All these resins with hydroxyl functional groups were prepared with procedure 1 described above, using vacuum-dried diols, except for the two prepared with HBPA. Vacuum drying HBPA is difficult due to its high melting point and its tendency to sublimate. Therefore, the following procedure was used to prepare the resins with HBPA. The EB DIOL B and HBPA were loaded into the resin container and heated to 170 ° C. Dry nitrogen was purged through the vessel for 4 hours with stirring. This mass was cooled to approximately 100 ° and 70% isobutyl acetate was added. This mixture was heated to 130 ° C, causing the solvent to reflux and wash the HBPA that had been sublimated in the walls of the vessel and down again to the reaction mixture. This mixture was cooled to 110 ° C and the catalyst was added. Subsequently, the isocyanate diluted with 30% isobutyl acetate was added, slowly with a dropping funnel, over a period of 55 minutes. The dough was held for an additional 1.5 hours at 110 ° C and then emptied into a jar for later use. EXAMPLE 6 Effect of Solvent Type - The results of Resin Preparations A-1 and A-2 in Table 9, show that the preparations can be carried out satisfactorily using either isobutyl acetate, or xylene as solvent. Both solvents produce resins that are transparent and of stable phase and, when cured with DESMODUR Z-370, both produce coatings C-1 and C-2, which have almost identical properties. TABLE 9 Effect of Solvent Type in Resin Preparation EB DIOL / BEPD / 4370 aration Preparation Preparation Resin Side "A", pbw A-l A-2 A-2 EB DIOL B 37.8 37.9 37.9 BEPD diol 4.3 3.1 3.1 DESMDDUR Z-4370 17.8 19.0 19.0 DABCO T-12 0.06 0.06 0.06 Isobutyl Acetate 40 Xylene 40 40 Properties of the Prepared Resin EB DIOL B / NPG 90/10 90/10 90/10 NCO / OH 0.6 0.6 0.6 Transparent transparent phase stability / transparency Composition Side "B", pbw DESMODUR Z-4370 13.1 13.1 none Coating composition C-1 C-2 C-3 A + B dry, zp EB diol 59.3 59.7 69.7 BEPD 6.7 4.9 5.7 Triisocyanate 33.9 35.4 35.0 Catalyst 0.094 0.094 0.110 Properties "in steel (QD412) Thickness, thousand 1.4 1.2 1 (pm) (0.036) (0.030) (0.025) Oscillation hardness 6 5 0 Resistance to mechanical rub 26 19 0 Adhesion to cruciate scratches 0. 0 0 zadas Properties * in TPO (DEXFLEX 777) Oscillation hardness 7 7 0 Resistance to mechanical rubbing 39 29 5 Adhesion to cross-hatch scratches 0 2 0 General Appearance Tightness none none High luster High clear transparent transparency Adhesion to poorly deficient steel Regular regular wear resistance Characteristics of elastic film elastic a Properties after 1 week of curing / drying at room temperature .

The coating C-3 of table 9, offers interesting information about the characteristics of the polyurethane resin with hydroxyl endings that was prepared using xylene. In this example, the resin preparation itself was emptied without adding the remainder of DESMODUR Z-4370 required to obtain a 1.0 NCO / OH crosslinked coating. The uncured resin preparation produces a dry coating that has surprising integrity. Although the coating film is not very strong, it does have sufficient strength to be removable from the steel substrate and is not sticky. However, as shown in the properties of table 9, it has very low hardness and low mechanical rub resistance. The comparison of coatings C-2 and C-3 shows that the crosslinking of the polyurethane resin with hydroxyl endings clearly increases the hardness and resistance to mechanical rubbing.

Synthesis of Polyurethane Resins with Isocyanate Terminations Effect of the OH / NCO Ratio - Table 10 shows examples of polyurethane resins prepared with EB diol, reinforcing diol and a molar excess of triisocyanate, obtaining polyurethanes having terminations with isocyanate groups. These resins can be used as side B of the two-component polyurethanes or can be used as one-component wet curing systems. The well-known mechanism of wet curing is one in which part of the isocyanate reacts with water from the atmosphere. This generates CO2 and converts the isocyanate into an amine. These amines can react rapidly with isocyanates that have not yet reacted with water, generating urea bonds and curing the composition. f J o in o in TABLE 10 Effect of the concentration of EB diol in the resin preparation EB DIOL / BEPD / 4370 for wet curing í "gB", £ «JWa-sa-ffg. "?" ?, n r "^ ac, on r" 'p? "cl' r" ^ "cl6" "" • «« * > ^ «* '-» «« * - «• - *. Bl l2 B B-4 B-5 B-6 B-7 B-8 EB DIOL D 27.97 30. IB 23. 15 23.23 18.4 18.45 18.54 13.95 BEPD diol 0.59 0.93 1.16 1.57 2.15 2.17 DEI * WtjR 2-4.170 22.03 19.82 26.26 25.84 30.44 29.98 29.31 33.88, DABCO T-12 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 1 Isobutyl acetate 50 50 50 50 50 50 50 1 50 Properties of the prepared resin EB Diol B / BEPD 100/0 100/0 97/3 96/4 94/6 92/8 - 90/10 87/13 N00 / OH 3.0 2.5 3.0 2.5 3.0 2.5 2.0 2.5 OH / NCO 0.33 0.40 0.33 0.40 0.33 0.40 0.50 0.40 Transp. transp. transp. transp. transp. transp. transp. transp. Ccposition "A" side. pbw H2O H2O Copying of Cl C-2 C-3 coating A * B CH C-5 C-6 C-7 C-8 dry, p EB diol 64.4 68.4 54.9 54.9 45.0 44.9 44.9 BEPD 35.0 0.0 0.0 1.4 2.2 2.8 3.8 5.2 5.4 Triisocyanate 35.5 31.5 43.6 42.8 52.1 51.1 49.7 Catalyst 59.4 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Properties on steel (QD412) Thickness, thousand 1.1 1.2 1.0 1.1 1.2 1.2 1.2 I (tpn) 1.3 at (0.028) (0.030) (0.025) w 0.028 ) (0.030) (0.030) I (0.030) Oscillating hardness (0.033) 7 5 12 13 16 18 17 Resistance to rubbing 23 86 86 mechanical 36 36 42 18 32 6 Adhesion to cross-hatching Prpp ages_ 'in C-1 C -2 C-3? PO DEXFLEX 880) C-4 C-5 C-6 C-7 C-8 Oscillation hardness 10 10 11 11 M ln Cn Resistance .il rub M00 > 100 mechanical 60 52 61 40 30 25 Ad) to the scratches «j crossed General Appearance Stickiness none none none no Luster no any bu or good good good good good good Transparency good transp. transp. transp. transp. transp. transp. transp. Mies i n to steel transp. Poor deficient Adhesion to the TPO b na good Resistance to poor deficient wear ££ ", .._ • ^ pi ages after the day of cure to aggressive text.

The Resin Preparations Side B, B-1 and B-2 of Table 10 are simply the triisocyanate containing less than a stoichiometric amount of the EB diol. Preparation B-1 was carried out at 0.33 OH / NCO. This corresponds to 2 moles of triisocyanate per mole of EB diol. Thus, the average molecule in this resin is the EB diol that has been covered with a triisocyanate molecule at both ends. Preparation B-2 was made at 0.4 OH / NCO, giving the same chain extension and a little more viscosity. After wet curing, both the C-1 and C-2 coatings produced glossy, transparent, and pleasant coatings. Process 2 (described above) was used to prepare these EB diol / triisocyanate resins. For example, to perform preparation Bl of Table 10, 77.10 grams of DESMODUR Z-4370, 108.40 grams of anhydrous isobutyl acetate and 1.53 grams of a 10% p solution of DABCO T-12 in a solvent, were charged. a resin container of 500 ml. The vessel was purged with dry nitrogen as it was heated to 80 ° C. The purge was stopped and 163.11 grams of a 60% p solution of EB DIOL B in isobutyl acetate were added by dripping over a period of 1 hour. The dough was kept at 80 ° C for another 1.5 hours and then emptied into a bottle for later use.

The resin preparations B-3 to B-8 of Table 10 were made using EB diol, BEPD diol and triisocyanate. Stable phase clear resins with these components could be prepared at an OH / NCO ratio of from about 0.3 to about 0.5. After wet curing, all of the compositions produced clear, glossy and pleasant coatings. Coatings C-3 to C-7 contain about 55% p and about 45% p of EB diol and have good flexibility, but coating C-8 containing 35% p of EB diol was brittle after wet curing. Process 3 was used to prepare these resins of EB diol / BEPD diol / triisocyanate. For example, to carry out preparation B-3 of table 10, 64.42 grams of EB DIOL B, 4.09 grams of anhydrous BEPD diol, 106.49 grams of DESMODUR Z-4370 and 162.13 grams of isobutyl acetate were charged to the resin container. and the agitation began. The vessel was heated to 80 ° C under a dry nitrogen purge. The purge was then stopped and 14.31 grams of a 10% solution of DABCO T-12 in solvent was added. The dough was kept at 80 ° C for 2 hours and then emptied into a bottle for later use.

EXAMPLE 7 Table 11 represents formulations for polyurethane resins with isocyanate terminations prepared with EB diol, NPG and triisocyanate. The three resins were prepared at 0.5 OH / NCO and all three were transparent and stable phase. Instead of using these resins as single-component wet curing systems, they were used as the B side of a two-component polyurethane, using a stoichiometric amount of ZOLDINE RD-4 ALDIMINE OXAZOLIDIN 8 from Angus Chemical), alpha, alpha, 4, 4-tetramethyl-2- (1-methylethyl) -N- (2-methylpropylidene) -3-oxazolidinetanamine, as the side-curing agent A. TABLE 11 Effect of the Concentration of EB DIOL on Resin Preparation EB DIOL / NPG / 4370 laxation Preparation Preparation Resin Side "B", pbw B-l B-2 B-3 EB DIOL B 36.3 27.2 15.7 NPG diol 0.3 1.2 2.4 DESMDDUR Z-4370 23.4 31.6 41.9 DABCO T-12 0.06 0.06 0.06 Isobutyl Acetate 40 40 40 Properties of the Pre-copied Resin EB DIOL B PG 99/1 96/4 87/13 NCO / OH 2.0 2.0 2.0 OH / CO 0.5 0.5 0.5 Transparent transparent t-transparent appearance Composition Side "A", pbw Zoldine RD-4 2.9 3. .8 5.1 Coating composition C-1 C -2 C-3 Dry A + B,% p EB diol 64.9 50 .0 29.9 NPG 0.5 2., 2 4.6 ZOLDINE RD-4 5.1 7., 1 9.7 Triisocyanate 29.3 40.66 55.8 Catalyst 0.1 0. .1 0.1 Steel properties (QD412) Oscillating hardness 6 11 9 Resistance to mechanical rub > 100 > 100 > 100 Adhesion to scratches 2 2 crosswise Properties * in TPO (DE2CFLEX 777) Oscillating hardness 6 11 Resistance to mechanical rub 98 > 100 peeling Adhesion to scratches cru0 or shedding zadas General Appearance Stickiness none none none High high high luster Transparent transparent transparent transparency Adhesion to poor deficient steel regular Adhesion to deficient TPO very poorly detached Regular regular wear resistance very poorb Characteristics of the hard elastic brittle film Pleasant pleasant surface to Properties after 1 week of curing / drying at room temperature. D The coatings were easily deduced as if they had a weak surface layer The results of Table 11 show that the three formulations produced clear, glossy and pleasant coatings. The Ci coating containing approximately 65% p of EB diol was an elastic coating, the C-2 coating containing 50% p of EB diol was a flexible and hard coating, but the C-3 coating containing 30% p of EB Diol was brittle. These data show that the partially reacted isocyanate compositions were useful for preparing coatings as well as intermediates for preparing other coatings in accordance with the process of the present invention. Process 3 is considered the best way to prepare the resins of Table 11. However, they were prepared by a different route in which the diols were charged to the first reactor and then the isocyanate was added rapidly with vigorous stirring. For example, the following procedure was used to prepare Resin Preparation B-2 from Table 11. 95.23 grams of EB DIOL B, 4.38 grams of vacuum-dried NPG, 2.09 grams of a 10% solution were charged to the container. of DABCO 5-12 and 140.03 grams of anhydrous isobutyl acetate. The vessel was purged with dry nitrogen as it was heated to 70 ° C. The purge was stopped and 110.71 grams of DESMODUR Z-4370 were added rapidly with vigorous stirring. This is a critical step because the isocyanate must be mixed uniformly and rapidly in the polyol, to avoid chain extension as the OH-rich mass progresses to NCO rich. The dough was kept for 6 hours at 70 ° C and then emptied into a bottle for later use. EXAMPLE 8 Table 12 shows two-component coatings using polyurethane with isocyanate terminations, based on triisocyanate and EB diol as side B and a solution of reinforcing diols as side A.

TABLE 12 Resin with Isocyanate Terminations Cured with Preparation of Reinforcing Diol Solution Composition of Preparation Preparation of Resin Side "A", pbw Bl EB DIOL B 27.97 DESMODUR Z- 22.03 4370 DABCO T-12 0.05 Acetate of 50 isobutyl Properties of Resin Prepared NCO / OH 3.0 OH / NCO 0.33 Appearance transp. Composition Side "A" Concentration H2O BEPD TMPD PEP BEPD HDD of the insoluble environment diol 5.9 6.4 21.5 reinforcement pbw Composition of C-1 C-2 C-3 C-4 C-5 C-6 coating A + B dry, * p EB diol 64.5 60.37 60.00 51.66 Diol 6.34 6.91 19.84 Trusocyanate 35.5 33.29 33.09 28.49 Catalyst 0.1 0.1 0.1 0.1 Properties in steel (QD412) Hardness of 6 2 oscillation Resistance to 41 20 18 20 Mechanical rub Adhesion to the 0 crossed scratches Properties a in TPO (DEXFLEX 777) 7-degree hardness Resistance to 40 18 21 45 Mechanical rub Adhesion at 0-2 1-4 cross-hatch General Appearance Stickiness none none none very light Luster high high high Transparency transp. transp. transp. transp.

Adhesion to very demuy dedefimuy deacero deficient ficiente enough cientiente Adhesion to good TPO regular defiregular cient (b) Resistance to regulate regular regular defidesgaste ciente Elastic Elastic Elastic Elastic Feature s of the film a Properties after 1 week of curing / drying at room temperature. b The adhesion was very good in some points but only from regular to deficient in others. There was no pattern.

In coating C-1, no reinforcing diol was used and the polyurethane was only allowed to cure wet. BDO and TMPD could not be used because they are not soluble at 50% p in isobutyl acetate. The PEP, BEPD and HDD were soluble and behaved well. The results of coating C-1 of table 12 show that wet curing produced a lustrous, pleasant, transparent, elastic coating. The C-4 and C-5 coatings cured with PEP and BEPD, produced practically the same properties as the wet cured coatings. It would be appropriate to cure the polyurethane with isocyanate terminations in low humidity environments.

Due to its relatively high hydroxyl equivalent weight, the HDD did not serve as a booster diol. Instead, it produced a much softer coating, the C-6 coating, than the wet-cured coatings and also exhibited some stickiness. EXAMPLE 9 Table 13 compares the approaches for curing a resin with hydroxyl endings using a triisocyanate, versus curing an isocyanate terminated resin using a reinforcing diol, both having the same final cured coating composition. TABLE 13 Comparison of Resins with Hydroxy Terminations and Resins with Isocyanate Terminations Composition of PrepaPrepaPrepaPrepaPrepaPreparation of Resin Ration Ration Ration Ration Ration Side "A or B", pbw A-l A-2 B-l B-l B-l EB DIOL B 37.8 37.8 27.97 27.97 27.97 PEP diol 4.1 BEPD diol 4.3 DESMODUR Z-4370 18.1 17.8 22.03 22.03 22.03 DABCO T-12 0.06 0.06 0.05 0.05 0.05 Isobutyl acetate 40 40 50 50 50 Properties of Prepared Resin EB Diol 90/10 90/10 B / NCO / OH 0.6 0.6 3.0 3.0 3.0 OH / NCO 0.33 0.33 0.33 Transp appearance transp. transp. transp. transp.

Composition Side "A or B", Dbw DESMODUR Z-4370 12.1 11.9 H2O ambient PEP diol 5.9 BEPD diol 6.4 Composition of C-1 C-2 C-3 C-4 C-5 coating A + B dry, «p EB diol 60. 60.1 64.5 60.4 60.0 diol 6.5 6.8 6.3 6.9 Triisocyanate 33.5 33.1 35.5 33.3 33.1 Catalyst 0.1 0.1 0.1 0.1 0.1 Properties ° in steel (QD412) Thickness, one thousand 1.3 1.3 1.5 1.7 1.3 (rrpi) (0.033) (0.033) (0.038) (0.043) (0.033) Oscillation hardness 8 6 6 8 8 Resistance to rubbing 21 84 21 41 20 Mechanical Adhesion to cross scratches Properties ° in TPO (DEXE EX 880) Oscillation hardness 8 7 7 8 8 Resistance to mechanical rub 31 50 46 59 33 Adhesion to scratches = crossed General Appearance Stickiness none none none none none Luster high high high high high Adhesion to the defidefidefidefidefideficient steel cient ciente ciente ciente Adhesion to TPO defidefidefidefidefient cient ciente ciente ciente Resistance to regulate regular regulate regulate regular wear Characteristics of elastic elastic elastic elastic elastic film 5 Properties after 1 week of curing / drying at room temperature.

Coatings C-1 and C-2 used Resin Preparations A-1 and A-2 with hydroxyl endings, containing PEP and BEPD diols and using DESMODUR Z-4370 as the curing agent. Coatings C-4 and C-5 used the preparation of resin B-1 with isocyanate terminations and solutions of PEP and BEPD diols as curing agents. The C-3 coating is the wet cured coating of the B-1 resin with isocyanate terminations. The results show very little difference between any of the five coatings. EXAMPLE 10 It is also possible to use a polyurethane resin with hydroxyl endings as the A side and to use a polyurethane resin preparation with isocyanate terminations as the B side of a 2 component polyurethane cured at room temperature. This is shown in table 14.

TABLE 14 Resin Cure with Terminations Hydroxyl with Resin with Isocyanate Terminations Side "A" Side "" B "PreparePreparation Composition of Al Bl Resin Preparation, pow EB DIOL B 31.8 27.97 BEPD diol 6.2 DESMODUR Z- 22 22.03 4370 DABCO T- 12 0.06 0.05 40 50 iso-butyl acetate Properties of the Resin Pre-paraaa EB diol B / diol 84/16 reinforcement NCO / OH 0.6 3.0 OH / NCO 0.33 Appearance Transp transp Composition of C-1 C-2 C -3 C-4 C-5 C-6 Coating, E = f Preparation of 2491 2491 2491 Resin Side "A" Preparation of 2485 2485 2485 2485 Resin Side "B"?? DESMODUR. 'Z- 401.5. 4370 n-Butanol 200 H2O ambient BEPD diol 80 Composition of C-1 C-2 C-3 C-4 C-5 C-6 coating A + B dry, tp EB diol 60.5 50.0 64.5 64.5 60 61.7 diol 11.8 9.7 6.9 6.4 Triisocyanate 27.8 40.3 35.5 35.5 33.1 31.8 Catalyst 0.1 0.1 0.1 0.1 0.1 0.1 Properties in steel (QD412) Thickness, thousand 1.0 1.4 (pm) (0.025) (0.036) Hardness "of 4 3 6 7 oscillation Resistance to 39 <20 41 18 46 Mechanical rub Adhesion to cross scratches Properties * in TPO (DEXFLEX 880) - Oscillation hardness Resistance to 80 40 40 21> 100 mechanical rubbing Adhesion at 0 0 0-2 1-4 2 cross scratches Appearance C-1 C-2 C-3 C-4 C-5 C-6 General Stickiness none none none none none none Luster high high high high high high Transparency transp. transp. transp. transp. transp. transp.

Adhesion to the defidefidefidefidefidefiacero cient cient ciente ciente ciente ciente Adhesion to TPO very much de fi x i- regulate regular2 regularity enough cientient Resistance to def i- def i- defi- regular regular defidesgaste cient ciente ciente Elastic elastic feature strong elastic elastic elastic s hard hard dura-film foundation ° Properties after 1 week of curing / drying at room temperature. 1 The adhesion was very good in some points but only from regular to deficient in others. There was no pattern.

In the Resin Preparation side A, A-l, EB diol and BEPD diol were used with triisocyanate at 0.6 NCO / OH. The Preparation of Ream side .B, B-1, contained EB diol coated with two molecules of triisocyanate. Several coatings were prepared in order to deepen the meaning of the components. The coating C-1 is only the resin preparation side A, A-l with terminations OH emptied and dried as such, without crosslinker. The coating C-2 is the preparation of resin side A, A-l cured with DESMODUR Z-4370 in a polyurethane of two components at 1.1 NCO / OH. The coating C-3 is the preparation of resin side B, B-l with NCO to 3.0 endings of NCO / OH after it has been completed by a reaction with n-butanol. The C-4 coating is a single-component wet cured polyurethane. The C-5 coating is a two-component polyurethane which uses the resin preparation B side, B-l cured with BEPD diol (in the form of a 50% solution in solvent) at 1.0 NCO / OH. The C-6 coating is a two component polyurethane that uses the resin preparation side A, A-l and the resin preparation B side, -B-1, at 1.0 NCO / OH. The properties are shown in Table 14. Although the quantitative properties of the C-1 coating were not measured, the qualitative evaluation shows that the non-crosslinked film had surprising integrity. In fact, compared to the gel permeation chromatograms of EB DIOL B and coating C-1, it shows that a substantial amount of polymer of high molecular weight was formed, even though the NCO / OH content was only 0.6. The comparison of the qualitative properties of coatings C-1 and C-2 shows that the properties do not change substantially when the film is crosslinked. The C-3 coating is the EB diol coated with two molecules of triisocyanate and terminated with n-butanol. It is not expected to find high molecular weight polymer in this sample andIn fact, the film had little integrity, showing permanent marks when stretched. The crosslinking of this B-side resin preparation with moisture (coating C-4), with BEPD diol (C-5) or with the resin preparation side A (C-6) becomes an elastic film with greater hardness and generally better resistance to mechanical rubbing. EXAMPLE 11 Effect of Isocyanate Type - Multifunctional isocyanates based on HDI are of lower viscosity and higher reactivity than DESMODUR Z-4370. Table 15 shows attempts to prepare resins with isocyanate terminations with EB diol using two isocyanates based on HDI, DESMODUR N-3390 and N-3400. It is thought that these isocyanates have functionalities of 3.0 and 2.5, respectively. TABLE 15 Res Preparations a Using Isocyanates Based on HDI for Wet Curing Composition of Pre-Prepared- Prepared- Prepared- Prepared- Prepared-parac on of Res t ationin g tion tion side "B", pbw Bl B-2 B-3 B-4 B-5 EB DIOL B 34.1 32.39 37.12 39.13 39.69 DESMODUR N-3390 15.9 17.61 DESMODUR N-3400 12.88 10.87 10.31 DABCO T-12 0.05 0.05 0.05 0.05 0.05 Acetate 50 50 50 50 50 Isobutyl Properties of the Prepared Resin NCO / OH 3.0 3.5 2.5 2 1.9 OH / NCO 0.33 0.29 0.40 0.50 0.53 Appearance gelled transp. opaca ligemen transp. dulling the appearance of coating A + B dry,? p Water environment environment ambient ' Composition C-1 C-2 C-3 C-4 C-5 EB diol 70.4 67.1 74.2 78.2 79.3 Triisocyanate 29.5 32.8 25.7 21.7 10.6 Catalyst 0.1 0.1 0.1 0.1 0.1 Properties in steel (QD412) Thickness, thousand 0.9 1.2 (mm) (0.023) (0.030) Resistance to 80 29 mechanical rubbing Adhesion to cross stingrays Properties * in TPO (DEXFLEX 880) Resistance to 69 50 Mechanical rub Adhesion to cross-streaks General Appearance High regular luster Transparency transp. txansp.

Adhesion to poor deficient steel Poor deficient TPO adhesion Good Debt Resistance Good Elastic Characteristics Elastic Film Color None None 3 Properties after 1 week of curing / drying at room temperature.

The result in the Preparation of Resin B-l showed that with DESMODUR N-3390, the incorporation of EB diol at 0.33 OH / NCO was stoichiometrically too close, causing the resin to gel. However, preparation B-2 at 0.29 OH / NCO produced a transparent and pleasant resin. The results with the resin preparations B-3, B-4 and B-5 show that the EB diol can be incorporated in the DESMODUR N-3400 at higher concentrations than the DESMODUR N-3390, due to the lower functionality of DESMODUR N-3400 In order to obtain a transparent and pleasant resin, the EB diol had to be incorporated at 0.53 OH / NCO. Coatings C-4 and C-5, which contain approximately 79% p of EB diol in the cured coating, are wet cured to obtain elastic, glossy and transparent films. EXAMPLE 12 Aromatic isocyanates are much lower cost than aliphatic isocyanates and are suitable for use in applications where their brown color is not a problem and do not require good weather resistance. The results of Table 16 of Resin Preparations Bl and B-2, show that resins with stable and transparent base isocyanate terminations can be prepared, incorporating either EB diol or an S / EB diol in MONDUR MR at 0.33 OH / NCO These resins can be wet cured (coating C-1 and C-3) or can be used as the B side in a two component polyurethane, with a solution of BEPD diol as side A (coatings C-2 and C-4) ). These four compositions based on MONDUR MR produced elastic films, glossy and transparent, which have a distinctive brown color.

TABLE 16 Resin Preparations Using Isocyanate Based on MDl for Moisture Cure or with BEPD Diol Composition of Preparation-Preparation Preparation Preparation of Resin Side "B" pbw B-l B-l B-2 B-2 EB DIOL B 46.5 46.5 EB DIOL C / EB diol 49.4 49.1 MDNDUR MR 13.5 13.5 10.6 10.6 DABCO T-12 0.03 0.03 0.03 0.03 Isobutyl acetate 40 40 40 40 Properties of the Prepared Resin NCO / OH 3 3 3 3 OH / NCO 0.33 0.33 0.33 0.33 Transp appearance transp. transp. transp Composition Side "A", pbw Water ambient environment BEPD 5.4 4.2 Dry coating composition A + B,% p 'EB diol 77.5 71.1 82.4 77.0 Triisocyanate 22.5 20.6 17.6 16.5 BEPD diol 8.2 7.5 Catalyst 0.050 0.046 0.050 0.047 Properties "in steel (QD 12) Thickness, thousand 1.2 1.2 1.2 1.2 (m) (0.030) (0.030) (0.030) (0.030) Oscillation hardness 6 4 2 2 Resistance to rub me > 100 13 53 14 Cyanic Adhesion to scratches 0 0 0 0 crossed Properties "in TPO (DEXELEX 880) Toughness of oscillation 6 5 Resistance to rubbing me-> 100 42 caries Adhesion to crossed scratches General appearance Luster high high high high Transparent transparent transparent transparent transparent Adhesion to steel very defi- very de fi cient insufficient deficient enough adhesion to poor TPO deficient deficient deficient Resistance to wear good good very good good Characteristic of the Elastic Elastic Elastic Peel Elastic Color Coffee Coffee Coffee Brown Properties after 1 week of curing / drying at room temperature.

EXAMPLE 13 Properties of Baking Cured Coatings - One of the main advantages of a two-component coating is that it will cure at room temperature, as needed in maintenance coatings for wood, concrete, and so on. However, there are numerous applications wherein the coating will be cured at elevated temperature to accelerate the reaction and reduce the time required for curing to take place. A prime example of this is automotive coatings, where the painted part is baked, typically for 30 minutes at 121 ° C, to dry and cure the paint. Table 17 compares the properties of two-component coatings when cured at room temperature and when cured by baking for 30 minutes at 121 ° C on a TPO substrate that is used for buffers. (i O L? tn TABLE 17 Effect of Curing Temperature on Adhesion to TPO Composition of Preparation Al A-2 A-3 A-4 Resin Side "A", pbw EB DIOL B 60 24.0 25.7 24.0 PEP diol 7.0 BEPD diol 8. 1 HBPA diol 10.1 DESMODUR Z- 370 29.0 26.2 25.9 I DABCO T-12 0.06 0.06 0.06 00 co • t: Isobutyl acetate 40 40 40 40 Properties of the Prepared Resin EB diol B / reinforcing diol 100/0 77/23 76/24 73/30 NCO / OH 0.7 0.6 0.7 Transparent transparent nsparent appearance tp O Ui Cn Coating Option C-1 C-2 C-3 C-4 C-5 C-6 Wet, -p, Carposicián Side "A", C-7 pbw Preparation of Resin Mixture Al 84.72 56.65 36.86 57.31 37.72 51.69 32.29 Preparation of Resin Mixture A-2 28.99 49.39 Preparation of Resin Mixture A-3 26.98 46.23 Preparation of Resin Mixture A-4 26.51 43.33 Isobutyl acetate 9.04 12.98 Carposition Side "B", pbw DESMODUR Z-4370 17.3 13.8 13.1 15.1 15.5 12.2 10.9 | 1 Coating position A + B C-1 C-4 C-5 dry, p £ .2 C 3 03 C-6 C-7 «JO 1 EB diol 83.2 70.0 60.0 70.0 60.0 70.0 60.0 reinforcement diol 3.5 6.1 3.7 6.5 5.0 8.8 Triisocyanate 16.8 26.5 33.9 26.3 33.5 25.0 31.2 - Catalyst 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Properties a in TPO After 1 week at 25 ° C Oscillation hardness f-J tn or tp duiera a raya-turas 3B < 4B < 4B 4B < 4B 4B Mechanical rub resistance < 4B > 100 57 37 78 75 70 Adhesion to cross scratches 30 2 5 1 0 2 2 Qualitative adhesion 2 deficient * f¿ÜLu * sufficient * flc, «nt« * ,? «* very deficient Properties' in TPO d» * p " A «A > 30 deficient minutes at 121 * C ~ Oscillating hardness 2 2 6 4 6 Scratched hardness 3 5 B < 4B < 4B B < 4B 2B < 4B Mechanical rub resistance > 100 65 65 > 100 > 100 Adhesion to cross hatchings > 100 100 5 5 5 5 5 Qualitative adhesion 5 5 good nu good very good poor good I Appearance &? N.M.t very good deficient or i Excellent luster good good regular regular Good transparency good transp. transp. transp. transp. transp. Adhesion to steel tranap. tranap «" "Very poor wear resistance deficient Good good surface« c? .i (iepce regular DEXFLEX 880 TPO In these experiments, mixture A-1 of EB diol in solvent was prepared and three preparations of resin A-2, A-3 and A-4 were prepared, using PEP, BEPD and HBPA as reinforcing diols. The Al diol solution was mixed with each of the three resin preparations in suitable proportions, such that when cured with DESMODUR Z-4370 as the "B" side, the coatings had a content of 70% p (C -2, C-4 and C-6) and 60% p (C-3, C-5 and C-7) of EB diol in the final cured coatings. One set of coatings on TPO was cured for 1 week at room temperature and the other set was baked for 30 minutes at 121 ° C. It was found that the overall appearance of the coatings cured at room temperature was the same as that of those cured by baking. In fact, the only property that showed a strong dependence on the curing conditions, was adherence to the TPO. Coatings cured at room temperature could be easily peeled off from TPO, while baked ones showed much better adhesion to TPO. The coating C-1 of table 17 produced a very pleasant coating, which adhered well to the TPO when it was baked. However, since it does not contain reinforcing diol, it could easily be cut with the nails and is probably too soft to be used in practical applications. Coatings C-2 and C-3 containing PEP diol, were very pleasant coatings. Qualitatively, the adhesion of the C-3 coating to the TPO after being cured by baking was excellent and its wear resistance was good. Coatings C-4 and C-5 containing BEPD diol were good coatings, although their surfaces showed some flaking. Their adhesion to TPO after being cured by baking was good, but they could still be detached manually from the TPO without difficulties. He coating C-6 containing HBPA, was very similar to the C-2 coating, both in appearance and adhesion. the C-7 coating was a pleasant coating which, after being cured, showed no loss of adhesion in the cross-hatch adhesion test. Without However, it could be detached from the TPO very easily. It was released by a stick / move type mechanism, so that it left a slip pattern or irregular surface in the TPO as it was detached. The cladding C-3 of table 17 seems to be the best candidate to be used as a coating for TPO, for automotive shock absorbers. EXAMPLE 14 Curing with Blocked Isocyanate - Two-component coatings should be mixed ? F, immediately before use and then applied to the substrate before the reaction progresses to a degree where they become too thick for handling. For coatings that will be cured by baking, a blocked isocyanate can be used as a curing agent in a one component coating and have no concern about the shelf life of the coating. In a blocked isocyanate, the NCO groups of the WB-type crosslinker "have reacted with a blocking agent such as a phenol, butanone oxime or caprolactam." A stoichiometric amount of the blocked isocyanate is mixed with the "A" side polyol, but does not occur no reaction at room temperature After the coating is applied to the substrate and heated in the furnace, the blocking agent is unblocked and volatilized from the film, regenerating the NCO groups which, then, react with the polyol. at which unblocking occurs depends on the particular blocking agent.Two blocking isocyanates that are commercially available, are the DESMODUR BL-3175A and BL-4165, based on HDI and IPDI, respectively.It is believed that both are blocked with butanone oxime The recommended baking temperature is 150 ° C. Table 18 shows formulations for the curing of a resin preparation "A" side Al, with an amount stequiometric of these two curing agents. With the DESMODUR BL-4165, the etria stequium was also varied. The results show that DESMODUR BL-3175A, based on HDI, produced a turbid mixture with the polyol resin preparation, which indicates limited compatibility. However, the good result in the mechanical rub resistance test in the C-1 coating demonstrates that it is still an effective crosslinker for the polyol. As expected, the blends of the polyol resin preparation A-1 with DESMODUR BL-165 were clear, indicating good compatibility. Once again, the good results in the mechanical rub resistance test in coatings C-2, C-3 and C-4, showed that this isocyanate is a good crosslinker for the polyol. TABLE 18 Resin Preparation Cure EB DIOL / PEP / 4370 with Blocked Isocyanate Preparation Preparation Preparation Resin Pbw EB DIOL B 32.1 PEP diol 5.7 DESMODUR Z-4370 22.2 DABCO T-12 0.06 Isobutyl acetate 40 Properties of Prepared Resin EB Diol B / PEP diol 85/15 NCO / OH 0.6 Transparent appearance Wet coating Copolyption pbw C-1 C-2 C-3 C-4 Prepared resin 2468 2468 2468 2468 DESMDDÜR EL-3175A 370 DESMODUR BL-4165 519.0 467.0 '571.0 DABCO T-12 0.9 0.9 0.9 0.9 Transparent Transparent Cloudy Cloudy Mix Appearance Coating dry coating% p EB diol 49.7 47.9 48.9 46.9 PEP diol 8.8 8.5 8.7 8.3 IPDI Triisocyanate 24.1 43.6 42.4 44.7 HDI 17.4 Triisocyanate Catalyst 0.09 0.09 0.09 0.09 Properties "in steel (QD412) after 1 hour at 150 ° C Thickness, thousand (prn) 1.4 (0.036) 1.5 (0.038) 1.4 (0.036) 1.6 (0.041) Oscillation hardness 3 9 8 10 Resistance to rub me > 100 > 100 > 100 > 100 panic Poor wear resistance Poor Poor Poor The recommended bake temperature of 150 ° C, it is probably too high to cure TPO coatings, because the TPO can distort at 150 ° C. Therefore, the coatings in Table 18 were only applied to steel panels and the adhesion of the cured coatings was poor. EXAMPLE 15 Resin Preparations with Blocked Isocyanates - In the work described above, the resins were synthesized in preparations using a stoichiometric sufficiently far from 1.0 NCO / OH, so that the resins had manageable viscosities at reasonable solids conte For example, polyurethane resins with hydroxy functional groups at 0.6 NCO / OH were prepared. Afterwards, these resins were used as the "A" side of a two-component coating, the WB side being "the rest of the isocyanate needed to bring the stoichiometry up to 1.0 NCO / OH. If the coating is intended for applications in which I will be When the curing is done by baking, then the resin preparation can be done using a blocked isocyanate.The EB diol, the reinforcing diol and the blocked isocyanate can be loaded into the resin container at 1.0 NCO / OH and the time and temperature of preparation or baking can be adjusted to obtain a sufficient reaction to obtain a single-component stable phase resin.Then, this resin can be coated and cured by baking, without having to add any more reageThe formulations to test the feasibility of This approach is presented in Table 19. TABLE 19 Resin Preparations Made with Blocked Isocyanates Prepare PreparedPreparatePreparationPreparation on Correctness of PreAB-1 AB-2 AB-3 AB-4 AB-5 Resin para pbw EB DIOL B 24.4 24.4 24.4 26.4 26.4 BEPD diol 3.5 3.5 3.5 4.7 4.7 DESMODUR BL-165 32.1 32.1 32.1 DESMODUR BL-3175A 28.9 28.9 DABCO T-12 0.06 0.06 0.06 0.06 0.06 Acetate 40 40 40 40 40 isobutyl Cooking time, 6 6 1.5 8 4 hours Cooking temperature 120 120. 100 140 tion, cc Properties of the Pre-heated Resin EB Diol B / BEPD diol 87/13 87/14 87/15 85/15 85/16 NCO / OH 1.0 1.0 1.0 1.0 1.0 Phase Stable separate stable stable separate separated Transparency transp. transp.

Color burgundy orange yellow red dark red dark Oviposition of ReC-l C-2 C-3 C-4 C-5 dry clothing. % p EB diol 50.0 50.0 50.0 50.0 50.0 BEPD diol 7.3 7.3 7.3 9.0 9.0 Triisocyanate 42.8 42.8- 42.8 41.0 41.0 Catalyst 0.10 0.10 0.10 0.10 0.10 Properties a steel (QD412) cured 1 hour at 150 ° C Thickness, 1.5 1.5 1.5 (prn) (0.038) (0.038) Regular regular luster Resistance to desmuy defimuy defigaste ciente ciente In Preparation of Resin AB-1 was used EB diol, BEPD diol and blocked triisocyanate based on IPDI, DESMODUR BL-4165. Since the proper combination of cooking time and temperature were not known, the resin was baked arbitrarily for 6 hours at 100 ° C. However, these conditions did not give a sufficient reaction since the resin separated when cooled to room temperature. Therefore, in the next preparation, the resin was baked for 6 hours at 120 ° C. As shown in Table 19, these conditions produced a stable resin (AB-2). However, the blocking agent caused the resin to turn an intense burgundy color. Thus, the resin preparation was repeated except that it was cooked only 1.5 hours at 120 ° C. These conditions were sufficient to obtain a stable phase resin, which only had a yellow color (AB-3). When it was coated in steel and baked for 1 hour at 150 ° C, the coating composition C-3 cured well, to obtain a non-tacky coating having a good luster. Two attempts were made to prepare resins using EB diol, BEPD diol and DESMODUR BL-3175A, the blocked triisocyanate based on HDI. It was anticipated that this preparation would be more difficult than with the DESMODUR BL-4165 due to the limited compatibility with the DESMODUR BL-3175A observed in the curing experiments described in the previous section. In the first preparation with DESMODUR BL-3175A, the resin was baked for 8 hours at 100 ° C. As shown in Table 19, this preparation of AB-4 resin was separated when cooled to room temperature. Another preparation was made, except that it was cooked for 4 hours at 140 ° C. Once again, the resin (preparation AB-5) separated when cooled. Since a stable phase resin was not obtained even under these very severe conditions, no further work was done with the DESMODUR BL-3175A.

EXAMPLE 16 Wear Resistance - Throughout this work, it was observed that these polyurethane coatings often had poor wear resistance when scratched with a fingernail. Good wear resistance would certainly be necessary in a surface coating, but it might not be necessary in the base coat of a basecoat / clearcoat system, as the clearcoat will protect the basecoat against wear. . However, it would be important to understand the reasons for the poor wear resistance. To study the influence of the composition on wear resistance, the formulations in Table 20 were prepared. TABLE 20 Wear Resistance and Gel Content Ratio Mixture Preparation-Preparation Preparation Copulation of Pre-Al A-2 A-3 of Resin Side "A", pbw EB DIOL B 60 37.8 25.74 BEPD diol 4.3 8.08 DESMODUR BL-165 17.8 26.18 DABCO T-12 0.06 0.06 Acetate 40 40 40 isobutyl Properties of the prepared resin EB Diol B / BEPD diol 90/10 76/24 NCO / OH 0.6 0.6 Appearance transp. transp Composition of ReC-1 C-2 C-3 C-4 C-5 Wet Dressing Side "A", pbw Mixture Al 2317 1605 626 Preparation of 942 2240 2209 675 Resi-na A-2 Preparation of 585 1631 Resin A-3 DABCO T-12 0.8 0.9 1.0 0.98 0.83 Acetate 624.0 670.0 734.0 719 622 Isobutyl Copying Side "B", pbw DESMODUR Z-4370 401.5 401.5 401.5 401.5 401.5 Copper coating A + B dry, tp EB diol 83.2 75.0 65.0 55.0 45.0 BEPD diol 2.3 5.2 8.0 10.7 Triisocyanate 16.8 22.7 29.8 37.0 44.3 Catalyst 0.1 0.1 0.1 0.1 0.1 Properties' in MYIAR of 2 thousand (0.051 prn) Gel Content, 99.2 96.4 92.6 84.1 80.1 -p Defective resistance0 regular regular deficient0 deficient spend (c) a Properties of coatings at 1.2 thousand (0.030 pro) dry thickness, after 10 days of curing at room temperature. D The coating is weak and can be easily cut with the nails.

"The coating had a weak surface layer, which could wear easily.

The Al mixture of EB diol in solvent was prepared and the two resins were hydrogenated with hydroxy functional groups preparation A-2 and A-3, shown in Table 20. These were then mixed in suitable proportions to obtain the polyols side A "such that when cured with DESMODUR Z-4370 to 1.1 NCO / OH, they were final cured coatings with a content of 83, 75, 65, 55 and 45% p of EB diol. to C-5) were applied on polyester film and cured during days at room temperature. Subsequently, its wear resistance was evaluated qualitatively, scratching the. surface with the fingernails. The results in Table 20 show that the wear resistance of the reverse side C-1, which does not contain reinforcing diol, is poor. The reason for this is that the coating is too soft for a nail to cut easily. The results in coatings C-2 and C-3 show that, as expected, by including the reinforcing diol in the formulation the coating was harder and, therefore, improved the wear resistance. However, the results in coatings C-4 and C-5 show that by including an even greater amount of reinforcing diol, the wear resistance decreased. When the C-4 and C-5 coatings are scraped, it is evident that there is a thin layer of something on the surface of these coatings, which wears easily. These cured coatings were subjected to extraction twice with toluene for 10 minutes at 125 ° C, to determine their gel / sol content. The results of Table 20 show that, in order to obtain good wear resistance, the formulation must contain a sufficient amount of reinforcing diol to make the coating hard enough to resist cutting, but not so hard that the gel content drops below 90% p. EXAMPLE 17 Adhesion to EPDM - A 1.5 mm (55 mil) thick roll of an EPDM sheet was used in this experiment. This material is sold to be used as a roof membrane. The weakest point in the water barrier provided by the EPDM sheet, is the overlap where the sheets are glued in place on the roofs. Since the EPDM sheet is vulcanized and not polar, it is very difficult to adhere to it. To determine whether a two-component polyurethane based on the EB diol could be used as an overlap adhesive, the formulations in Table 21 were tested. TABLE 21 Resin Preparations as Adhesives for EPDM Sheets Mixture Mixture Prepara- Prepara- Preparation Copying of PreA-l A-2 A-3 A-4 B-5 Resin setting Sides "A or B", obw EB DIOL B 37.8 37.8 27.97 PEP diol 50 4.1 BEPD diol 50 4.3 DESMODUR BL-165 18.1 17.8 22.03 DABCO T-12 0.6 0.6 3.0 Acetate 50 50 40 40 50 Isobutyl Properties of the prepared resin EB Diol B / 90/10 diol 90/10 NCO / OH reinforcement 0.6 0.6 3.0 OH / NCO 0.33 Transp appearance transp. transp.

Wet Adhesive C-1 C-2 C-3 C-4 C-5 Composition Side "A", pbw Ambient humidity PEP mixture To 146 BEPD mixture A-2 160 Preparation of 3019 Resin A-3 Preparation of 3068 Resin na A-4 DABCO T-12 1.2 1.3 1.3 2.1 2.1 Copying Side "B", pbw Preparation of 2485 2485 2485 Resi-na B-5 DESMODUR Z-4370 365.0 365 Copolymerization of C-1 C-2 C-3 C-4 C-5 adherent A + B dry, 2S EB diol 64.5 60.4 60.0 60.0 60.1 PEP diol 6.3 6.5 BEPD diol 6.9 6.8 Triisocyanate 35.5 33.1 33.1 33.5 33.1 Catalyst 0.1 0.1 0.1 0.1 0.1 Properties * in sheets of EPDM "T" detachment 8.4 13.5 7.6 7.2 after 1 week "T" detachment 13 18 12t 8.5 after 3 weeks a The adhesive was applied with a brush on the EPDM to approximately 3 thousand (0.076? Tm) of dry thickness. b All samples failed adhesively at the EPDM / Adhesive interface, except this one, which failed due to partial cohesive failure of the EPDM rubber itself.

Adhesive C-1 of Table 21 (wet cure of the Resin Preparation with NCO B-5 functional groups), had 65% p of EB diol in the final cured adhesive. The other four had 60% p of EB diol in the final cured adhesive. The adhesives C-2 and C-4 have the same composition and the adhesives C-3 and C-5 have the same composition. These differ in that the adhesives C-2 and C-3 use the approach of a resin preparation "B" side cured with a solution of diol reinforcement; while the adhesives C-4 and C-5 use the approach of a resin preparation "A" side cured with DESMODUR Z-4370. The EPDM sheet was cut into 1 inch (2.54 cm) wide strips and the talc of the surface was cleaned. The adhesive was applied by brush on one side of two strips and after approximately 15 minutes of evaporation of the solvent, the strips were bonded from adhesive to adhesive. The strips were placed between two glass plates to dry and cure. Adhesion was determined by measuring the "T" release on an Instron machine at a crossing speed of 12 inches (30.5 c) per minute at 23 ° C. The results of Table 21 show that after 1 week of curing at room temperature, the "T" release was about 7 pounds per inch wide (1225 N / m). However, during the detachment measurement it was observed that the mixtures still had solvent odor. Therefore, the samples were allowed to dry for another two weeks and the "T" release was measured again. As shown in Table 21, the five adhesives met or exceeded 7 pli (1225 N / m), which is considered the minimum acceptable value. The best results were obtained with the resin preparation "B" side with isocyanate functional groups (B-5). In fact, the C-2 adhesive showed a cohesive failure of the EPDM sheet itself in the release test. The butyl rubber-based contact adhesive that is now used commercially produced a value of 11.8 pli (2065 N / m) of "T" release. Other potential applications are coatings that can be pigmented to obtain a desired color, to hide the black color of EPDM, for roofing or automotive applications or coatings that can reduce the coefficient of friction, for example, for automotive sprays.

EXAMPLE 18 Silane Wrapped Polyurethane It was previously shown that resin preparations • side "B" such as the EB diol covered with 2 moles of DESMODUR Z-4370 can be cured by a reaction with atmospheric moisture. The other well-known wet cure chemistry is through the condensation of silyl ethers to form Si-O-Si bonds. One way to cover a diol with a silane is by a reaction with isocyanatosilane such as isocyanatopropyltriethoxysilane (SILQUEST A1310 from OSI). This would produce a diol transformed to have a silane at each end. Another way to cover a diol with a silane is first covering with two moles of difunctional or trifunctional isocyanate and then covering again with 2 or 4 moles of mercaptosilane (SILQUEST A-189). This will produce a converted diol to have one or two silanes at each end. Another way is to cover with two moles of triisocyanate and then cover with an inosilane, such as a secondary aminodisilane (SILQUEST A-1170). This would put four silanes at each end of the polymer. Polyurethanes wrapped with silane like these would be especially useful for applications in wet-cured sealants as well as in adhesives and coatings.

TABLE 22 Preparation of Polyurethane Coated with Silane for Wet Cured Coatings Preparation Composition of Preparation of B-l B-2 Resin, pbw EB DIOL B 28.0 24.2 DESMODUR Z-4370 22.0 19.0 ? ILQUEST A-189 6.8 DABCO T-12 0.05 0.05 Isobutyl acetate 50 50 Composition of Resin Preparation, eq. EB DIOL B 1.0 1.0 DESMODUR Z-4370 3 3 SILQUEST A-l89 2 Composition of resin preparation, moles EB DIOL B 1 1 DESMODUR Z-4370 2 2 SILQUEST A-189 4 Composition of Dry coating,% p EB DIOL 64.5 54.5 Triisocyanate 35.5 30.1 Mercaptosilane 14.1 Catalyst 0.10 0.10 Com -Dysition C-1 C-2 EB diol 64.5 54.5 Triisocyanate 35.5 30.1 Mercaptosilane 14.1 Catalyst 0.10 0.10 Properties a in steel (QD412) Thickness, one thousand (mm) 1.1 (0.028) 1.0 (0.025) Hardness of oscillation 7 5 Resistance to mechanical rubbing 86 70 Adhesion to scratches crossed 0 days Properties a in TPO (DEXFLEX 880) Oscillating hardness 7 6 Resistance to mechanical rub > 100 > 100 Adhesion to scratches cross 3 days General Appearance Luster Wear resistance Adhesion to TPO Properties after 1 week of curing / drying at room temperature.

The results of table 22 compare the wet cure of a NCO coated polyurethane, the ream B-1 preparation and a polyurethane covered with silane, the B-2 resin preparation. The polyurethane coated with NCO was prepared by the reaction of 1 mole of EB diol with 2 moles of DESMODUR Z-4370. Thus, the average molecule in this composition is EB diol with 1 mole of triisocyanate at each end, leaving two NCO groups at each end. The resin coated with silane in Table 22 was prepared by coating this NCO-covered polymer with 4 moles of gamma-mercaptopropyltrimethoxysilane. This forms a molecule that has on average two Si (OCH3) 3 groups at each end of the polymer. The actual procedure for preparing the B-2 resin preparation in Table 22 was as follows: 500 ml 66.63 grams of DESMODUR Z-4370, 126.11 grams of isobutyl acetate (dried over 4X Sieve) were loaded into a resin container of 500 ml. Molecular) and 1.36 grams of a 10% p solution of DABCO T-12. The vessel was purged with dry nitrogen as it was heated to 80 ° C. Then 151.21 grams of a 60% solution p of EB DIOL B in isobutyl acetate was added dropwise over a period of about 1.2 hours. This mass was maintained at 80 ° C for one hour to complete the coverage of the EB diol with the triisocyanate. At 80 ° C, this "prepolymer" was transparent and with moderate viscosity. Then 23.8 of SILQUEST A-189 was quickly added to the vessel and the mass was maintained for another 1.3 hours at 80 ° C to complete the coverage of the prepolymer with mercaptosilane. The product was transparent and of low viscosity at 80 ° C. Afterwards, the product was emptied into a bottle for later use. Table 22 shows the results of coatings C-1 and C-2 in steel and in TPO, after 1 week of wet curing at room temperature. The results of the mechanical rub resistance test show that both compositions were in fact wet cured. Both compositions produced glossy and pleasant coatings, which did not adhere well to steel, but which adhered better to TPO. A particularly attractive feature of the polymer coated with silane is that it had a very good wear resistance. EXAMPLE 19 A polyurethane resin with hydroxy functional groups was prepared using the following procedure. The NCO / OH ratio for this resin is 0.6. Component Preparation of resin A-l9, pbw EB diol D 1116.0 2-ethyl-l, 3-hexanediol 127.2 DESMODUR Z-4470 612.0 DABCO T-12 1.0 Butyl acetate 1236.0 All components except DESMODUR Z-4470 and half butyl acetate were weighed into a 5 liter flask and heated to 80 ° C. DESMODUR Z-4470, dissolved in half of the butyl acetate, was added to the flask slowly with a dropping funnel, in a period of about 1 hour. The reaction mixture was maintained for another 3 hours at 80 ° C with continuous stirring, to complete the reaction. Subsequently, the resin was stored at room temperature for later use as the \ A "side of a two-component polyurethane. >; This resin (Preparation of Resin A-19) was formulated in a white coating using the following procedure. The following dispersion was prepared using a high speed disperser equipped with a Cowles blade and mixing for about 30 minutes. Dispersion pbw Preparation of Resin A-19 583.2 Ti-Puro R-706 350.9 Xylene 98.3 The following decreaser was prepared. The term "decreaser" refers to decreasing the viscosity (by spraying) by the addition of a diluent. Decrease pbw DABCO T-12 0.18 TINUVIN 400 (25% in xylene) 28.10 TINUVIN 123 (25% in xylene) 28.10 IRGANOX 1076 (25% in xylene) 7.10 Xylene 836.0 The reducer was mixed with the dispersion to obtain the "A" side of the two component polyurethane coating. When ready to apply the coating, the "A" side was mixed with the appropriate amount of DESMODUR Z-4470, to obtain an NCO / OH ratio of 1.05 (2.6 grams of DESMODUR Z-4470 per 100 grams of coating). Sufficient Aromatic 150 was added to reduce the coating viscosity to about 50 centipoise. This composition is required as coating 19-1. This 19-1 coating of two component polyurethane was applied by spraying approximately 2 mil (0.051 mm) dry film thickness onto steel panels that had been primed with an electrodeposited epoxy primer (E-coat, GM ED5000 specification) . The coating was cured by baking for 1.5 hours at 121 ° C. The coating had an excellent adhesion to this epoxy primed steel, obtaining a value of 5 (without loss of adhesion) in the cross-hatch adhesion test. EXAMPLE 20 The following two-component polyester-urethane was prepared to be used as a clear coating on the white coating 19-1 used as the base. Component pbw DESMOPHEN 670A-80 500.0 DABCO T-12 0.6 TINUVIN 400 (25% in butyl acetate) 48.4 TINUVIN 123 (25% in butyl acetate) 48.4 IRGANOX 1076 (25% in butyl acetate) 12.0 Xylene 251.7 When ready to spray the coating, enough DESMODUR N-3390 was added to obtain an NCO / OH ratio of 1.05 (26.4 grams per 100 grams of coating) and enough methylamyl ketone was added to reduce the viscosity to about 50 centipoise. This coating is referred to as coating 20-1. Coating 19-1 was sprayed on polyolef thermoplastic (TPO, DEXFLEX 880) and on steel primed with the E-coat at a dry film thickness of approximately 2 mil (0.051 mm). Then, the coating 20-1 was sprayed onto the coating 19-1, wet on wet, at a dry film thickness of about 1.5 mil (0.038 mm). The coatings were cured by baking for 1.5 hours at 121 ° C. Excellent adhesion of the clear coat was found to the base coat and the base coat to the TPO and to the epoxy-primed steel substrate, all the coatings giving a value of 5 in the cross-hatch test. EXAMPLE 21 The following polyurethane resin with isocyanate functional groups was prepared. The NCO / OH ratio for this resin was 3.0. Component Preparation of resin B-21, pbw EB diol D 1130.0 DESMODUR Z-4470 730.0 DABCO T-12 0.8 Butyl acetate 1860.0 The isocyanate, the catalyst and the butyl acetate moiety were placed in a 5 liter flask and heated to 80 ° C. The EB diol, dissolved in half of the butyl acetate, was added. to the flask slowly with a dropping funnel over a period of about 1 hour. The resin (resin preparation B-21) was maintained for a further 3 hours at 80 ° C with continuous agitation, to complete the reaction. Then, this resin was stored for later use as a wet-cured urethane or as the "B" side of a two-component polyurethane. A white wet cured polyurethane coating, referred to as coating 21-1, was prepared in the following manner. The following dispersion was prepared with a high speed stirrer equipped with a Cowles blade. Dispersion pbw Preparation of Resin B-21 620.0 Ti-Pure R-706 91.7 The following decreaser was prepared. Decrease pbw DABCO T-12 0.13 TINUVIN 400 (25% in xylene) 5.40 TINUVIN 123 (125% in xylene) 5.40 IRGANOX 1076 (25% in xylene) 1.37 The decreaser was mixed with the dispersion and enough xylene was added to reduce the viscosity to about 50 centipoise, to obtain the coating 21-1. Coating 21-1 was sprayed onto a simple EPDM roofing membrane at a dry film thickness of 2 mil (0.051 mm). The coating was allowed to cure by reaction with atmospheric moisture. After one month under ambient conditions, the cured composition produced a white lustrous coating. Its adhesion to EPDM was sufficient to remain attached when the EPDM was stretched and folded. EXAMPLE 22 Coating 21-1 was used as the "B" side of a two-component polyurethane, the WA side being "2-ethyl-1,3-hexanediol (PEP diol)." When the coating was ready to be sprayed , enough PEP diol was mixed with coating 21-1 to obtain an NCO / OH ratio of 1.05 (2.6 grams per 100 grams of coating) and enough xylene was added to reduce the viscosity to about 50 centipoise. as coating 22-1, coating 22-1 was sprayed onto an EPDM roofing membrane at a dry film thickness of approximately 2 mil (0.051 mm) After a month of curing under ambient conditions, the cured composition produced a glossy white coating, its adhesion to EPDM was sufficient to remain attached when the EPDM was stretched and flexed or folded.

The coating 22-1 was sprayed on steel primed with E-coat epoxy to a dry film thickness of approximately 2 mil (0.051 mm), to produce a white base coating. The clear polyester-urethane coating, coating 20-I on coating 22-1, wetted wet, was then sprayed at a dry film thickness of approximately 1.5 mil (0.038 mm). The coatings were cured by baking for 1.5 hours at 121 ° C. Excellent adhesion of the base coat to the epoxy-primed steel and of the clear coat to the base coat was found, both coatings giving a value of 5 in the cross-hatch adhesion test. EXAMPLE 24 Coating 22-1 was sprayed onto a rubber foam seal typically used in apparatuses at approximately 1 mil (0.025 mm) of dry film thickness. The coating 20-1 was sprayed onto the wet-wet coating 22-1 at a dry film thickness of approximately 1.5 mil (0.038 rom). The coatings were cured by baking for 1.5 hours at 121 ° C. Excellent adhesion of the base coating to the rubber foam and clear coating to the base coat was found. The coatings exhibited excellent flexibility, showing no cracking or loss of adhesion when the rubber foam was scraped and flexed or bent. The coatings dramatically reduced the coefficient of friction of the foam and the base coat concealed the black color of the rubber foam joint. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (15)

1. CLAIMS Having described the invention as an antecedent, the content of the following claims is claimed as property: 1. A process for producing a polyurethane resin from a polydienodiol or hydrogenated polyol having an equivalent hydroxyl weight of 750 to 10,000, a reinforcing agent having an equivalent functional group weight of 30 to 200 and a polyisocyanate curing agent, characterized in that it comprises: (a) reacting at least one of the polydienodiol (or polyol) or the reinforcing agent, with the polyisocyanate at a molar ratio of NCO / functional group of 0.4 to 0.7, to form a stable reaction product, (b) add to the product of part (a) a sufficient additional amount of the polyisocyanate and, as necessary, one or both between the polydienodiol (or polyol) and the reinforcing agent, to bring the NCO / functional group ratio up to a value of 0.9 to 1.1 and until reaching a polydienodiol content or polyol of 35 to 80% p (based on solids) and a content of reinforcing agent of 2 to 17% p (based on solids), and (c) reacting the mixture of part (b) to form a cross-linked polyurethane product.
2. 2. A process for producing a polyurethane resin from a polydienodiol or hydrogenated polyol having an equivalent hydroxyl weight of 750 to 10,000, a reinforcing agent having an equivalent functional group weight of 30 to 200 and a curing agent of polyisocyanate, characterized in that it comprises: (a) reacting at least one of the polydienodiol (or polyol) "or the reinforcing agent, with the isocyanate at a functional group / NCO ratio of 0.25 to 0.55, to form a product of finished stable isocyanate reaction, (b) adding to the product of part (a) a sufficient additional amount of one or both of the polydienodiol (or polyol) or the reinforcing agent and, as necessary, of the polyisocyanate, to carry the functional group / NCO ratio to a value of 0.9 to 1.1 and to achieve a polydienodiol or polyol content of 35 to 80% p (based on solids) and a reinforcing agent content of 2 to 17% p (with base in the s lidos), and (c) reacting the mixture of part (b) to form a crosslinked polyurethane product.
3. 3. A process for producing a polyurethane resin from a polydienodiol or hydrogenated polyol having an hydroxyl equivalent weight of 750 to 10,000, a reinforcing agent having an equivalent functional group weight of 30 to 200 and a hydroxylating agent. cured polyisocyanate curing, characterized in that it comprises: (a) mixing the components in such a way that the molar ratio of the functional group to completely unblock the NCO groups is from 0.9 to 1.1, the content of polydienodiol or polyol from 35 to 80% p (based on solids) and the content of the reinforcing agent from 2 to 17% p (based on the solids), (b) reacting the components at a temperature and for a time sufficient to unblock a sufficient amount of the blocked polyisocyanate, so that a stable, partially reacted polyurethane resin is formed, and (c) ) unblocking the remainder of the blocked polyisocyanate and reacting it with the partially reacted polyurethane resin of part (b), to form a cross-linked polyurethane product.
4. 4. The process according to claim 3, characterized in that the components are reacted at a temperature of 80 to 150 ° C and for a time of 0.5 to 5 hours.
5. 5. The process according to any of claims 1 to 4, characterized in that the reinforcing agent is a branched aliphatic diol or triol.
6. 6. The process according to any of claims 1 to 5, characterized in that the polydienodiol or polyol is a polybutadiene diol.
7. 7. The process according to claim 6, characterized in that the polybutadiene diol has a vinyl content of at least 30%.
8. The process according to any of the preceding claims, characterized in that no more than 10% by weight of the reinforcing agent is used.
9. 9. A crosslinkable polyurethane resin composition, characterized in that it comprises from 40 to 90% p (based on solids) of a polydienodiol or polyol having an equivalent hydroxyl weight of 750 to 10,000, 2 to 25% p of a reinforcing agent having an equivalent functional group weight of 30 to 200 and reacted with a polyisocyanate at a molar ratio of NCO / functional group of 0.4 to 0.7.
10. 10. A crosslinkable polyurethane resin composition with isocyanate terminations, characterized in that it contains from 10 to 75% p (based on solids) of a polydienodiol or polyol having an equivalent hydroxyl weight of 750 to 10,000, from 0 to 10 % p (based on solids) of a reinforcing agent having an equivalent functional group weight of 30 to 200 and reacted with a polyisocyanate, wherein the molar ratio of the functional group / NCO is 0.25 to 0.55.
11. The composition according to claim 10, characterized in that the reinforcing agent comprises from 1 to 10% p of the composition.
12. 12. A polyurethane resin composition characterized in that it comprises from 35 to 80% p (based on solids) of a polydienodiol or polyol having an equivalent hydroxyl weight of 750 to 10,000, from 2 to 17% p (based on in solids) of a reinforcing agent having an equivalent functional group weight of 30 to 200 and an amount of a blocked polyisocyanate, which when unblocked would produce a molar ratio of NCO / functional group of 0.9 to 1.1, where the mixture has reacted at a temperature and for a time sufficient to obtain a stable, partially reacted polyurethane resin composition.
13. A roofing membrane characterized in that it comprises an EPDM sheet coated with the composition prepared by the process according to any of claims 1 to 8.
14. 14. A polyurethane composition covered with silane, characterized in that it is prepared by reacting the resin of polyurethane according to claim 9, with at least a stoichiometric amount of an isocyanatosilane.
15. 15. A polyurethane composition coated with silane, characterized in that it is prepared by reacting the polyurethane resin according to any of claims 10 or 11, with at least a stoichiometric amount of a mercaptosilane or an aminosilane.