MXPA97010352A - Compositions of sulfopoli (ester-uretano) finished in silil, to mark the pavime - Google Patents

Abstract

The present invention relates to a pavement marker composition comprising a sulfopoly (ester-urethane) polymer which comprises in its main structure at least one terminal arylene or alkylene group comprising a pendant sulfonic acid group or a salt thereof, the polymer of the composition for marking the poviment ends in at least one hodrolysable silyl group. A method for manufactured in the composition is described. The pavement marking composition may also additionally comprise at least one of the pigments, optical elements, fillers or other adjoining materials. Particularly desirable adjuvants include optical elements, particularly retroreflective elements, particularly resistant to slippage and pigment.

Description

STJLPQPOLI sCMPOSICTQNES (ESTER-TJIiETANDi FINISHED IN SILYLOUS TO MARK THE PAVEMENT DESCRIPTION OF THE INVENTION This invention relates to water-dispersible sulphopoly (ester-urethane) compositions, terminated by silyl groups and containing solubilizing sulfonate groups which help to increase dispersibility. The sulfopoly (ester-urethane) compositions provide materials useful as components in the compositions for producing pavement.

BACKGROUND OF THE INVENTION Markers for pavement are installed on roads to delineate and provide guidance, warning and regulatory information to drivers and pedestrians. The important characteristics of pavement markers are durability, cost, method of installation, handling and installation safety and visibility. The requirements for the installation of pavement markings include the need for a short "no track" time, that is, a period of time in which the material must REF; 26542"dry" or cure so that it is not transferred to the vehicle tires that make contact with it. Due to the stricter regulations of the EPA regarding the amount of volatile organic compounds (VOC) that can be allowed in liquid materials for pavement markings, there has been research in search of new materials to replace the chlorinated and alkydic acid paints based on solvents which are widely used to mark roads. The typical VOC concentrations in these solvent-based coatings were greater than 450 grams / liter (g / 1). The new architecture and industrial maintenance coatings (AIM) rule sets a limit of 150 g / 1 for pavement marking materials in use during the years 1996 to 2004. After 2004, allowable VOC concentrations will decrease to 100 g / 1. Liquid pavement marking materials which meet these reduced VOC requirements are acrylic paints made with water, alkyd or thermoplastic hydrocarbons and two epoxy parts. Water-based paints have the advantage of a relatively low cost and easy application with conventional spray equipment, but they lack durability and very often must be applied several times a year in heavy traffic areas. Thermoplastics and epoxy resins are considered significantly more durable compared to water-based paints but are more expensive, require more expensive and specialized equipment and operators with greater training for their application. Another disadvantage of the epoxy pavement markers is their tendency to yellow in regions with a lot of sun. High temperatures (greater than 200 ° C (400 ° F)) require melting in thermoplastic material before application which constitutes a safety hazard.

BRIEF DESCRIPTION OF THE INVENTION It has now been found that sulfopoli (ester-urethanes) which end with silyl group and contain sulphonic acid solubilizing functional groups are particularly useful for forming strong, weather resistant films, which are desired for pavement markings. Briefly, the present invention provides pavement marking compositions comprised of sulfopoli (ester-urethanes) which comprise, in their main structure, at least one non-terminal arylene or alkylene group comprising a group of pendant sulfonic acid or a salt thereof. same, the polymer ends the at least one hydrolysable silyl group. In a preferred embodiment, the sulfopoli (ester-urethanes) are dispersed in water and comprise a pigment. By removing the water, the reticule polymer in a strong, insoluble polymer film, which is resistant to weathering and abrasion. For one of the polymers comprises segments containing one or more hydrophilic sulfonic acid groups or sulfonic acid salt, and at least one hydrophobic group containing one or more hydrolysable silyl groups in its terminal part. The composition of the invention preferably has an equivalent sulfonate weight of from about 500 to about 12,000, preferably from 2,000 to about 10,000 g / equivalent. Preferably, the compositions have an average number of molecular weight less than 50,000, preferably 2000, or less than 50,000, and more preferably 2000 to less than 30,000, and more preferably from 2,000 to less than 20,000. In a further aspect, the invention comprises aqueous dispersions comprising up to 70 percent by weight of sulfopoly (ester-urethane) compositions and 30 percent by weight or more of solvents such as water or organic solvents (eg, methyl ethyl ketone, acetone) and N-methylpyrrolidinone) and optionally adjuvants in amounts suitable for the desired purpose..

In a further aspect of the invention, a process for the preparation of the sulfopoli (ester urethanes) of the invention is provided. The preparation of the sulfopoli (ester-urethanes) involves the reaction of a polyol with a polyisocyanate, optionally in the presence of one of another diol, diamine or different bis-mercaptan, and preferably in the presence of a suitable catalyst, optionally in a non-reactive organic solvent. In this application: The term "aliphatic group" means straight and branched acyclic and non-aromatic chain of cyclic hydrocarbons having up to 20 carbon atoms; the groups "alkyl" and "alkylene" mean the monovalent and divalent residues which remain after the removal of one or two hydrogen atoms, respectively, of a linear or branched hydrocarbon having 1 to 20 carbon atoms; the term "aromatic group" means a group having one or more unsaturated carbon rings having 5 to 12 carbon atoms, the term "aromatic ester" means an ester group derived from an aryl or arylenecarboxylic acid and an aliphatic alcohol, the "aryl" and "arylene" groups mean residues that remain after the removal of one or two hydrogen atoms, respectively, of an aromatic compound (single ring and multiple fused rings) having 5 to 12 ring atoms and which includes substituted aromatic substances such as lower alkaryl and aralkyl, lower alkoxy, N, N-di (lower alkyl) amino, nitro, cyano, halo, and lower alkylcarboxylic ester, wherein "lower" means the term "arylene or alkylene sulfonic acid group or salt thereof" means a group containing at least one aromatic or hydrocarbon group substituted by at least one pendant sulfonic acid group or salt thereof; the groups "cycloalkyl" and "cycloalkylene" mean the monovalent and divalent residues which remain after the removal of one or two hydrogen atoms, respectively, from a cyclic hydrocarbon having 3 to 12 carbon atoms; the term "electrophilic" refers to a compound, composition or reagent that forms a bond with its reaction partner by accepting both binding electrons from that reaction partner; the term "group" means the specified portion of any group that contains the specified portion (e.g., by substitution or extension) that does not adversely affect the composition; "lower alkyl group" means an alkyl group having 1 to 4 carbon atoms; the term "molecular weight" means the sum of the atomic weights of all the atoms in a group of atoms or in a segment of a polymer and under the circumstances in which the group or segment may be mixed with two or more groups or segments, it is the average number of molecular weights of the groups or segments; the term "nucleophilic" refers to a compound, composition or reagent that forms a bond with its reaction partner by donating both binding electrons to that reaction partner; the term "polymer" includes oligomers; the term "random polymer" means similar groups which can be placed at various points along the main structure of the polymer and which do not have a sequence in a similar manner, the term "silyl group" means Si (Q) p (0Q) p , wherein p = 0, 1 or 2, wherein each Q independently can be hydrogen or a lower alkyl group having 1 to 4 atoms such that an OQ group in which Q is a lower alkyl group is the hydrolysable unit; the terms "sulfo group" or "sulphonate group" or "sulphonic acid group or salt thereof" means a group -SO3 wherein M can be H or a cation, preferably an alkali metal ion; and the term "sulfopoli (ester-urethane)" means a symmetric or asymmetric polymer or a random polymer comprising at least one sulfo group, at least one ester group and at least one urethane group, which optionally contains other functional groups such as urea and thiocarbamate. The presence of an ester containing the sulfonate moiety is useful in current polymers in that it contributes to the amorphous character, ductility and compatibility with co-reactants and adjuvants in the composition. In addition, the ester group leads directly to linear polymers, in contrast to the amide, urea or urethane portions which can lead to branching by means of an additional reaction with isocyanates. These new materials combine the safety and ease of handling of water-based paints, with the durability of epoxy-like materials and more expensive thermoplastics and provide coatings for greater work. In addition to the hardness, weather resistance and abrasion resistance of polymer films prepared from these sulphopoly (ester urethanes) finished in silyl, another significant advantage of these new materials is that it is possible to prepare high solid dispersions (for example 20 to 70 weight percent) in water. The need for a short "no track" time for liquid materials for pavement marking is well appreciated, and "trackless" time is reduced as the level of solids increases. Another advantage of sulphopoly (ester-urethanes) terminated in silyl is that these materials themselves are surface-active molecules, and can be present in the same molecule in both hydrophilic and hydrophobic groups or segments. This explains the fact that the aqueous dispersions of these materials are "self-stabilizing" and there is generally no need to add other surfactant materials or dispersing aids to generate stable dispersions. An additional advantage of these new materials is that the bonding to both pavement and reflective elements can be improved due to the presence of reactive silyl end groups such as silanol groups. The paving and reflective elements often contain components of silicon minerals which can react chemically with silanols of the present sulfopoli (ester-urethanes) due to the presence of reactive silanol groups on their surfaces. There is a continuing need for a pavement marker material which combines the durability of epoxies and thermoplastics with the safety and ease of handling of water-based paints.

DESCRIPTION DTgTAT.T.AnA TTE L S PREFERRED MODALITIES The present invention provides water-dispersible sulphopoly (ester-urethane) compositions comprising, in their main structure, at least one arylene or alkylene group which is not terminally placed, which comprises a group of pendant sulfonic acid or a salt thereof. same, the polymer ends in at least one hydrolysable silyl group. In a first embodiment, the silyl-terminated sulfopoly (ester-urethanes) of the invention of formula I, below, are prepared by reacting an isocyanate-terminated sulfopoly (ester-urethane) of formula II, below, with a silane reagent hydrolysable, nucleophilic, of formula III, below, wherein formula I can have the structure: Rr- (0) OR'OC (0) NH-R? -NH- (C (0) XZXC (0) NIIRi -) - NHC (0) YRJSi (Q) (OQ) i 0, M m P 3 -pJ, wherein R can be a trivalent or aromatic aliphatic group, in which M is a cation, preferably M is a metal cation such as Na, but M can be H, another alkali metal such as K or Li or a primary, secondary, tertiary or quaternary ammonium cation, such as ammonium, methylammonium, butylammonium, diethylammonium, triethylammonium, tetraethylammonium and benzyltrimethylammonium; each R 1 can independently be an alkylene or cycloalkylene group such as the residue that remains after the removal of the hydroxy groups of ethylene glycol, propylene glycol, neopentyl glycol, 2-butyl-2-eti 1 -1,3-propanediol, 1,6- hexanedi or 1, 1,4-cyclohexanedimethanol or a polymeric residue having a molecular weight in the range of 100 to 2000 comprising carbon, hydrogen and one or both of nitrogen and non-peroxygen oxygen atoms which remain after the removal of the hydroxyl groups of, for example, propylene glycol of molecular weight 120-2000, polyethylene glycol of molecular weight 100-2000, polyester diols such as polycaprolactone diol of molecular weight 300-2000, other polyester diols such as those obtained by reaction of alkylene diols with polymerizable lactones such as valerolactone of molecular weight 300-2000, polyether diols such as polytetrahydrofuran of molecular weight 100-2000, or the residue r emanent after the removal of the hydroxyl groups of the polyesterification product resulting from the reaction of a stoichiometric excess of a polyol with a polycarboxylic acid or the corresponding products resulting from the transesterification of lower alkyl esters of polycarboxylic acid of molecular weight 100 or 2000, or the residue that remains after the removal of the hydroxyl groups from the polycondensation product resulting from the reaction of a stoichiometric excess of a polyol with a polyisocyanate, the residue having a molecular weight of 100 to 2000; each R 2 independently can be an alkylene, cycloalkylene or arylene group such as the residue that remains after the removal of the isocyanate groups of polyisocyanates such as hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) -cyclohexane, isophorone diisocyanate and 1,3-bis (1-isocyanato-1-methylethyl) benzene, or the residue that remains after the removal of the isocyanate isocyanate groups such as those described in U.S. Patent Nos. 3,700,643 and 3,600,359 , or the residue that remains after the removal of the isocyanate isocyanate groups such as those produced by trimerization reactions of diisocyanates, for example, hexamethylene diisocyanate; each X independently can be O, S or NR4, wherein each R4 independently is a lower alkyl group, hydrogen or an alkylene bridge forming group with another X unit, such as a piperazine group, for example, each Q independently can be hydrogen or a lower alkyl group having 1 to 4 carbon atoms, with the proviso that at least one OQ is an alkoxy group, each Z independently can be selected from R-faojOR'-r- -R; - - R '(OR5C (0)) n- 1 2 SChM wherein R and R1 are as previously defined, each R5 independently can be an alkylene group, n can be an integer from 1 to 15, m can be 0 or an integer from 1 to 10, each R3 can independently be a alkylene group; each Y independently can be O, S or NR6, wherein R6 is a lower alkyl group, hydrogen or R3SÍ (Q) p) OQ) 3.p, wherein R3, Q and p are as previously defined.

Sulfopoly (ester-urethanes) terminated in isocyanate of formula II, wherein R, M, R 1, R 2, X, m and Z are as previously defined, are reaction products of a polyol sulfoester and a polyisocyanate, optionally in the presence of any other different polyol, polyamine or polythiols. The sulfoester polyols can be prepared by methods well known in the art, preferably by the reaction of one mole of sulfopolicarboxylic acid, preferably sulfoarene or sulfoalkanecarboxylic acid (or the corresponding lower alkyl esters) with at least two moles , preferably at least three moles of polyol, preferably aliphatic diol, to form the preferred sulfoester diol. The sulfoarylene and sulfoalkylene dicarboxylic acids which may be useful for the preparation of the sulfo compounds of the invention are any of the known sulfoarene and sulfoalkanecarboxylic acids. Examples thereof include sulfoalkanedicarboxylic acids such as sulfosuccinic acid, 2-sulfoglutaric acid, 3-sulfoglutaric acid and 2-sulfododecanedioic acid, sulfoarenodicarboxylic acids such as 2-sulfoterephthalic acid, 1-sulfonaphthalene-1,4-dicarboxylic acid and 5- sulfoisophthalic, which is preferred, sulfobenzylmalonic acids such as those described in U.S. Patent No. 3,821,281, and sulfofluoren-dicarboxylic diacids such as 9,9-di (2'-carboxyethyl) fluoren-2-sulfonic acid described in the patent British number 1,006,579. It is to be understood that the corresponding lower alkyl esters, halides, anhydrides and salts of the above sulfonic acids can also be used in the preparation. The aliphatic polyols useful in preparing the sulfo compounds of the invention have a molecular weight of 62 to 2000 and include, for example, monomeric and polymeric polyols preferably having two to four hydroxyl groups. Examples of the monomeric polyols include ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, 1,1-trimethylolpropane, pentaerythritol, and the like. Examples of polymeric polyols include polyoxyalkylene polyols, ie, diols, triols and tetroles of diols, triols and polyester tetroles of organic dicarboxylic acids and polyhydric alcohols, and polylactone diols, triols and tetroles having a molecular weight of 106 to about 2000. Examples of polymeric polyols include diols, thioles, and polyoxyethylene tetroles such as Carbowax ™ polyols available from Union Carbide (Danbury, CT), polyoxytetramethyl diols such as Polymeg "11 polyols available from Quaker Oast Company (Chicago, IL), polyester polyols such as poly (ethyleneadipate) polyols from Multron ™ available from Bayer Corp. (Pittsburgh, PA), and polycarprolactone polyols such as PCP1 ^ polyols, available from Union Carbide. sulfopolicarboxylic acids and polyols generally take place in the absence of solvent, at an elevated temperature, for example from 180 ° to 250 ° C, and in the presence of tin or zinc catalysts. The specific conditions and amounts are exemplified in U.S. Patent No. 4,558,149. In another embodiment of the invention, the sulfopoli (ester-urethanes) may comprise alkylene sulfonic acid units in the polymer backbone. Such sulfopoli (ester-urethanes) are typically prepared using methods other than those described for the preparation of sulfopoli (ester-urethanes) comprising aromatic sulfonic acid units described above due to the lower thermal stability of the hydroxy-terminated dicarboxylic esters of the alkylsulfonic acids. Nevertheless, preferably they can be prepared by an alternative route involving the Michael addition of a bisulfite salt to an oligomer of an unsaturated olefinic dicarboxylic acid ester. These oligomers can be prepared from esters of olefinic unsaturated dicarboxylic acids using procedures similar to those described above. Subsequent Michael addition of a bisulfite salt to the olefinic unsaturation in the presence of a free radical initiator will produce an oligomer comprising units of the alkylsulfonic acid salt in the oligomer backbone. Suitable olefinic dicarboxylic acids for preparing the sulfopoli (ester-urethanes) of the present invention include, but are not limited to, maleic acid, fumaric acid, itaconic acid, and polyunsaturated dihydric unsaturated fatty acids (ie, castor oil, etc.) or ricinoleic acid triglycerides. Representative polyisocyanates that can be used to react with the sulfoester polyols to form the isocyanate-terminated sulfopoli (ester-urethanes) are any of the well-known aliphatic and aromatic polyisocyanates. Useful polyisocyanates include hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane (3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane), 1,3-bis (isocyanatomethyl) - cyclohexane, 1,3-bis (isocyanato-1-methylethyl) benzene, 4,4'-diphenylmethane diisocyanate (MDI), 4,4 ', 4"-triisocyanatotriphenylmethane and the polymethylene polyphenylisocyanates Other polyisocyanates are well known and include those described in U.S. Patent Nos. 3,700,643 and 3,600,359, among many others. Mixtures of polyisocyanates such as Isonate ™ * 2143L, available from Dow Chemical Company, can also be used.

(Midland, MI). Aliphatic polyisocyanates are preferred. The exact nature and relative amounts of the other polyols which may be incorporated may vary to change the properties of the final films. Suitable diols include those previously mentioned as useful for preparing the sulfo compound and include ethylene glycol, propylene glycol, neopentyl glycol, 2-butyl, 2-ethyl-1,3-propanediol, propylene glycol, polyethylene glycol, polyester diols such as polycaprolactone diol and polyether diols such as polytetramethylene diol diol. Properties that may vary include ductility, water capture, tensile strength, modulus, abrasion resistance, minimum film formation temperature, and vitreous transition temperature. The larger chain polyols tend to provide materials which are more ductile and have a lower Tg, while the shorter chain polyols tend to contribute a higher modulus, higher tensile strength and have materials with high Tg. Aliphatic polyols tend to provide materials which decrease water uptake while diols containing heteroatoms in the main structure tend to exhibit increased water uptake. Useful optional polyamines include ethylenediamine, 1,6-diaminohexane, piperazine, tris (2-aminoethyl) amine and amine terminated polyethers such as those sold under the trademark Jeffamine by Huntsman Corporation (Salt Lake City, UT). Useful polythiols include 1,2-ethanedithiol, 1,4-butanedithiol, 2,2'-oxitris (ethanethiol) and di- and trimercapto propionate esters of diols and poly (oxyethylene) thiols. The reaction is optionally carried out in a water-soluble (organic) solvent that does not react with an isocyanate, such as acetone, methyl ethyl ketone (MEK), tetrahydrofuran and N-methyl-pyrrolidinone, wherein the solubility in water is at least 10 weight percent. The total concentration of sulfoester-polyol (optionally of any of the different polyols, polyamines or polythiols) and of the polyisocyanate, it is generally desirable that it be as high as for example, at least 30 weight percent, preferably greater than at least 50 weight percent . High monomer concentrations and high reaction temperatures from 50 ° to 80 ° C are desirable so that high conversions of monomers to polymer can be carried out in a reasonable time, for example, less than 8 hours, preferably less than 3 hours. hours. Catalysts that can be used such as metal salts include dibutyltin dilaurate and dibutyltin acetate and amines, such as triethylamine, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) and DABCO (1.4 -diazabicyclo [2.2.2] octane), in useful concentrations from 0.01 to 1.0 mole percent (in relation to the isocyanate reagent). In the first embodiment, the ratio of polyisocyanate to polyol is adjusted so that the product of the first reaction step is an isocyanate-terminated sulfopoly (ester-urethane) with a molecular weight of about 1000 to 25,000. The polyisocyanate moles preferably exceed the moles of polyol, preferably the molar excess is from 0.1 to 5, preferably 0.5 to 2, and more preferably from 0.8 to 1.2.

In the next step of this embodiment, the isocyanate-terminated sulfopoli (ester-urethanes) of formula II, above, are reacted with a hydrolysable, nucleophilic silane reagent of formula III.

HYR2Si (Q) p (OQ) 3.p III where Y, R2, Q and p are as previously defined. Useful nucleophilic hydrolyzable silane reagents include 3-aminopropyltriethoxysilane, 3-N-methylaminopropyltrimethoxysilane, 3-mercaptopropyltri-methoxysilane, 3-hydroxypropyltriethoxysilane and bis (3-triethoxysilylpropyl) amine. The reaction conditions are generally the same as those used in the synthesis of sulfopoly (ester-urethanes) terminated in isocyanate mentioned above, with a reaction period that extends from 0.5 to 2 hours. In still another aspect of this invention, compositions of formula II can be reacted with a polyfunctional nucleophile such as water or a polyamine in an amount less than stoichiometric, preferably less than 20 percent stoichiometric, more preferably less than 5 percent of the stoichiometric. This practice results in isocyanate-terminated compositions with higher molecular weight.

Due to the multiple possibilities of extensions and polymer branching in these reactions, the structural description is complex and can not be reduced to a simple formula. However, these products are useful and are considered to be within the scope of the present invention. The extended and branched polymers have the formulas related to the formulas I and IV. In a third step of this embodiment, water is added to convert the silyl hydrolyzable groups into silanol groups. The reaction is conveniently carried out by adding the silyl-terminated sulfopoly (ester-urethane) with at least stoichiometric water, preferably enough water to form a polymer dispersion. If an organic solvent having a boiling point of less than 100 ° C has been used in the synthesis sequence hitherto, the organic solvent can be evaporatively removed to leave an essentially aqueous polymer dispersion of the sulfur-containing (ester-urethane) terminated in silanol. The weight percent of the polymer in the final aqueous dispersion is at least 20 percent, preferably at least 30 percent, and most preferably at least 50 percent. Conversely, when an organic segment which has a boiling point greater than 100 ° C is used, the reaction sequence is carried out in a solution as concentrated as possible, for example, preferably equal to or less than 20 times percent by weight of solvent. The resulting concentrated solution containing the silyl-terminated sulfopoly (ester-urethane) can be effectively dispersed in water using microfluidization techniques. Microfluidization is a process for making uniform dispersions of size smaller than micrometers including dispersions of sulfopoli (ester-urethanes). The process uses ground, high-pressure liquid jet to combine water-dispersible polymer solutions in water. The polymers generally have a viscosity in the range of 1 to 500,000 centipoise. In this process, the polymer is injected into a stream of water and then subjected to high pressure, from 0.6 to 300 MPa (100-40,000 psi) of liquid jet milling in interaction chambers. Interaction chambers which provide a high shear zone are generally configured to be explosive expansion chambers, or use high velocity incipient currents, or contain a series of holes in series having increasingly smaller diameters. In this process, the entire liquid is forced through the interaction chamber configurations which provides a uniform shear for all the material. This provides the opportunity to produce colloidal dispersions with lower VOC levels, and / or can make particles with smaller size distributions than those produced by other processes. Reaction sequence I, below, shows the steps for preparing compositions of formulas I, II and the hydrolysis product of I, which is designated as I '.

REACTION SEQUENCE I 2 HYRJSi (Q) (OQ) j III H20 t wherein RA is independently hydrogen or a lower alkyl group and R, M, R1, R2, R3, X, Y, Z, m, Q and p can be as previously defined, and each Q1 independently can be hydrogen or a group lower alkyl having one to four carbon atoms, with the proviso that at least one of OQ 'is a hydroxyl group. In a second embodiment, the silyl-terminated sulfopoly (ester-urethanes) of the formula IV of the invention are prepared by reacting a hydroxy-terminated sulfopoly (ester-urethane), amine or thiol of formula V with a hydrolysable silane reagent , electrophilic of formula Via, VIb, VIc, where formula IV can have the structure IV in which each independently can be - CNH - • - CH2-CHCH2O- or a simple link, and where R, R1, R2, R3, M, Q, X, Z, p and m are as previously defined. In this second embodiment of the invention, hydroxy-terminated sulfopoli (ester-urethanes) are preferred and are easily obtained by adjusting the stoichiometry of the polyol / polyisocyanate ratio in the first step of the reaction sequence as described above. in the first embodiment so that the moles of polyol exceed those of polyisocyanate, the molar excess is preferably between 0.1 and 5, more preferably between 0.5 and 2, and much more preferably between 0.8 and 1.2. The product of this reaction is the composition of formula V: V wherein R, R1, R2, M, X, Z and m are as previously defined. When practicing that embodiment of the invention, the compositions of formula V are reacted in a subsequent step with a hydrolysable, electrophilic silane reagent, having any of the formulas Vía, VIb and VIc OCNR 'SM Q I < OQ) Via CIR * Yes (Q) p (OQ) Vlc where R3, Q and p are as previously defined. Useful electrophilic hydrolysable silane reagents include 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-chloropropyltriethoxysilane. For the practice of this second embodiment, the active, reaction conditions, catalysts and processes are virtually the same as those specified with the first embodiment of the invention. The reaction sequence II, below, shows the steps for preparing the compositions of formula IV or V.

Reaction Sequence II R- ClOlOROaOlNH-R'j- NHClOlXZXCíOlNHR'JjNliaOíXZXWRíSiíQ'J ^ OQ '- 0, M ml \ "where R, RA, R1, R2, R3, M, X, Y, Z, Q, Q', W, m and p are as previously defined The silyl-terminated sulfopoli (ester-urethanes) of the invention can be used as such to provide transparent and strong coatings, however, in order to improve the daytime and nighttime appearance of the pavement markers , various pigments, fillers or diluents and other adjuvants can be added.These pigments, fillers and other adjuvants are added both for economic reasons and to obtain a processing and desirable physical properties of the final coatings, such as reflectivity, viscosity , stability, color, hardness and durability To produce a white pavement marker composition, a pigment such as titanium dioxide can be added, for example, Ti-Pure * 0 * - R-706, Ti-Pure ™ R-960 ( both available from DuPont , Wilmington, DE), Kronos 2160 ™ * - or Kronos 2310MR (both available from Kronos, Inc., Houston, TX). To produce a yellow pavement marking composition, yellow pigments such as Hansa ™ 65 or 75 yellow (available from American Hoechst Corp., Somerville, NJ) can be added. The pigments typically comprise 0 to 300 weight percent relative to the sulfopoly (urethane ester).

Calcium carbonate is a common filler or diluent that is used to provide body composition at a low cost. Useful types of calcium carbonate include, for example, Omyacarb "" 5 (available from OMYA, Inc Proctor, VT) or various grades of calcium carbonate such as those available under the trademark Hubercarbm from J M Huber Corp. St. Louis, MO. Other fillers include talcs such as those available under the trademark Nytal1 ^ from R. T. Vanderbilt Co. , Norwalk, CT, clays such as those available under the trademarks Huber ™ * - or PolyplatMR from J.M. Hubert Corp., silicas such as Aerosil "" 200 and other silicas available under the trademark Aerosil ™ * from Degussa Corp., Ridgefield Park, NJ. Other useful fillers or diluents which may be incorporated into the pavement marking compositions include alumina, aluminum silicates, magnesium carbonate, calcium sulfate, and zinc oxide. Fillers typically comprise 0 to 300 weight percent relative to sulfopoly (urethane ester). These pigments and fillers can be incorporated into aqueous compositions for marking pavement by using conventional dispersion techniques and equipment, for example, three-wheel mills, ball mills, ball mills, ball mills, mills sand, high-speed disc dispersers and high-speed incidence mills. Other adjuvants which may be combined with the silyl-terminated poly (ester-urethane) compositions include dispersants such as Tamol ™ * 901 (available from Rohm and Haas Co., Philadelphia, PA), wetting aids or surfactants such as Surfynol. ™ 1 CT-136 (available from Air Products and Chemicals, Inc., Allent n, PA) or Triton ™ * - CF10 (available from Union Carbide, Danbury, CT), defoamers such as Drewplus1® L-493 (available from Ashland Chemical Co., Boonton, NJ), thixotropes or agents for controlling viscosity such as Natrosol ™ * - 250HR, HBR and Plus Grade 430 thickeners (available from Aquualon Co., Wilmington, DE), coalescing substances such as l-methyl-2-pyrrolidinone (NMP) or Texanol ™ (available from Eastman Chemical Co., Kingsport, TN), preservatives or preservatives such as Kathon ™ * LX (available from Rohm and Haas) and substances for lowering the freezing point such as methanol, ethanol or mixtures of these alcohols with propylene glycol. The effective amounts of adjuvants are preferably less than 5 weight percent of the sulfopoly (urethane ester).

To improve the visibility of pavement markings, especially under low light conditions, it is advantageous to incorporate optical elements. The optical elements preferably consist of inorganic materials which are not easily susceptible to abrasion. Suitable optical elements include glass-formed microspheres, preferably having refractive indices of from about 1.5 to about 1.9. The most widely used optical elements are made of soda-lime-silicate glass. Although the durability is acceptable, the refractive index is only about 1.5, which greatly limits its retroreflective brightness. Superior index glass elements of improved durability are described in U.S. Patent No. 4,367,919. Particularly useful optical elements, due to their durability and refractive index, are optical elements of microcrystalline ceramic. Ceramic optical elements are described in U.S. Patent Nos. 4,564,556 and 4,758,469. These optical elements are described as ceramic, non-vitreous, transparent and solid spheroids consisting of at least one crystalline phase containing at least one metal oxide. The ceramic spheroids can also be an amorphous phase such as silica. The term "non-vitreous" means that the spheroids have not been derived from a fusion or a mixture of raw materials capable of being brought to a liquid state at high temperatures, such as glass. The spheroids are resistant to scraping and peeling, are relatively hard (thicker than 700 Knoop) and are manufactured to have a relatively high refractive index. These optical elements may contain zirconia-alumina-silica or zirconia-silica. Anti-slip particles can be incorporated into the compositions of the invention in an amount suitable for their intended purpose. Typically, slip resistant particles do not play a role in retroreflectivity, because they are placed on the retroreflective and non-retroreflective pavement markings to improve the dynamic friction between the mark and the tire of the vehicle. The slip resistant particles can be, for example, ceramic materials such as quartz or aluminum oxide or a similar abrasive medium. Preferred slip resistant particles include pyrolyzed or burned ceramic spheres having a high alumina content, as described in U.S. Patent Nos. 4,937,127, 5,053,253, 5,094,902 and 5,124,178. The particles are preferred because they do not disperse before an impact such as the crystalline abrasive medium such as A1203 and quartz. Slip resistant particles typically have sizes from about 200 to about 800 microns. The silanol-terminated sulfopoly (ester-urethane) compositions of the invention are cross-linked through the reaction of the terminal silanol groups to form Si-O-Si bonds with the elimination of one molecule of water. Volatile organic compounds (VOC) are not present before or after the oligomers are cured to form the crosslinked polymer films. An additional advantage of these poly (ester-urethane) compositions terminated in silanol is that they are surfactant molecules themselves., since they have hydrophilic or hydrophobic groups or sections present in the same molecule. Accordingly, the aqueous dispersions of these materials are "self-stabilizing" and there is no need to add other surfactant materials or dispersion aids to generate stable dispersions. The objects and advantages of this invention are further illustrated by the following reaction sequences and examples, but the particular materials and amounts thereof mentioned in these examples, as well as other conditions and details, should not be considered as undue constraints of the invention.

The following reaction sequence and typical experimental procedures will serve to clarify the synthesis of the silyl-terminated poly (ester-urethane) compositions of the present invention. "Me" means methyl and "Bu" means butyl. The preparation of the PCPSSIP sulfonated diol shown below is described in greater detail in U.S. Patent No. 4,558,149.

Preparation of the PCPSSIP precursor A mixture of dimethyl 5-sodiosulfoisophthalate (DMSSIP, 25.1 kg, 85 moles, available from E.I. DuPont de Nemours, Wilmington, DE), polycaprolactone diol (PCP 0200, molecular weight average, 514, 131 kg, 255 moles, available from Union Carbide Corp., Danbury, CT) and tetrabutyl titatane (78 g, 0.23 moles, available from Aldrich Chemical Co., Milwaukee, WI), is heated at 230 ° C for four hours and the methanol by-product of the reaction is distilled from the reaction. After cooling to room temperature, an oily product is obtained which comprises an approximately equal molar ratio of a mixture of PCPSSIP and PCP 0200 that has not reacted. Reaction sequence III shows the chemical equations involved. The mixed PCPSSIP precursor has a nominal hydroxy equivalent weight of about 500 g / mole (generally in the range of 450 to 600 g / mole). The hydroxy equivalent weight for the mixed precursor may vary based on the reaction conditions (e.g. temperature, methanol removal rate, catalyst, etc.). The hydroxyl equivalent weights are determined by NMR analysis and are adjusted to a preferred value for the preparation of pavement marking compositions of the present invention, of about 475 with the addition of diethylene glycol. In the following examples, "PCPSSIP precursor" means the mixture of PCPSSIP and PCP 0200. Unless otherwise stated, the molar ratio of PCPSSI'P to PCP 200 is approximately 1.0, and "b moles" of PCPSSIP means approximately b / 2 moles of each of PCPSSIP and PCP 0200. In examples 2, 16 and 19, the PCPSSIP precursor is prepared using zinc acetate (0.24% by weight, based on diol charge), instead of tetrabutyl titanate.

REACTION SEQUENCE III Synthesis of sulfonated diol (BuO) «TÍ (tatrabutyl titanate) + residual PCP 0200 algnlflca one aagunda polymer chain according to the / subscript" 2"in the formula In all the structures in this application, which include those that show PCP 0200 and PCPSSIP, the numbers outside the parentheses refer to the average number of units. In the examples, vitreous transition temperatures are presented as the midpoint of the change in specific heat with respect to the transition interval using an average sample with a heating rate of 5 ° C / min. Tension properties were obtained from samples with gauge lengths of 1.43 cm (0.562 inches) and tensioning speeds of 2.54 cm / min (1 inch / min).

Example 1 The mixed PCPSSIP precursor is prepared as described above except that they were heated at 85 ° C 1 to 0.87 molar of a mixture of PCPSSIP and PCP 0200 (649.8 g, 0.64 mole based on a hydroxyl equivalent weight of 509 for the mixture) , Additional PCP 0200 (599.4 g, 1.16 moles), ethylene glycol (89.4 g, 1.44 moles, available from JT Baker, Inc., Phillipsburg, NJ) and methyl ethyl ketone (1338 ml), and dried by distillation with methyl ethyl ketone (445 ml) mix. After cooling to room temperature, dibutyltin dilaurate (1.53 g, 2.4 mmol, available from Alfa Chemical Co., Ward Hill, MA) was added to the solution. The dry solution was added, with stirring, to an isophorone isocyanate solution (800.2 g, 3.60 moles, available from Huís America, Inc. Piscataway, NJ) in methyl ethyl ketone (533 ml), which has been heated to 72 ° C. , at a speed such that the temperature of the reaction mixture does not exceed 85 ° C. After 1 hour, additional dibutyltin dilaurate (1.53 g) in methyl ethyl ketone (50 ml) is added to the solution and the reaction mixture is maintained at 80 ° C with stirring, for an additional 3.5 hours. Subsequently, a solution of 3-aminopropyltriethoxy-silane (159.4 g, 0.72 mol, available from Aldrich Chemical Co.) in methyl ethyl ketone (100 ml) is added to the reaction mixture, which is maintained at 80 ° C, with stirring, during 45 additional minutes. To the reaction mixture is added water (21), at 80 ° C, for a period of about 1 hour with vigorous stirring and then the methyl ethyl ketone is distilled from the mixture under reduced pressure to produce a dispersion (54% solids) of a sulfopoli (ester-urethane) terminated in silanol, in water. Calorimetric differential scanning calorimetry (MDSC) analysis and tensile properties are performed on a die-cut film of the dispersion indicating that the polymer has a Tg of 26 ° C and a tensile strength of 17.9 MPa ( 2595 psi) at an elongation of 587%. The pigments and adjuvants can be added in an amount sufficient to provide the desired color density and other characteristics.

Example 2 A silanol-terminated sulfopoly (ester-urethane) is prepared according to the procedure of Example 1, except that the reactants changed as follows: The mixed PCPSSIP precursor (37.6 g, 0.04 mol), PCP 0201 (52.4 g, 0.10 moles) (polycaprolactone diol, available from Union Carbide), ethylene glycol (7.44 g, 0.12 moles) and isophorone diisocyanate (62.2 g, 0. 28 moles). The molar proportion of the reactants was 1: 6: 6: 14 The analysis by differential scanning calorimetry modulated (MDSC) and the tensile properties were made in a film die-cut by spinning the polymer produced by this reaction sequence and indicate that the polymer has a Tg of 17 ° C and a tensile strength from 30.6 MPa to 653% elongation. In this Example and in Examples 3-5, the molar ratio is related to PCPSSIP, PCP ethylene glycol and diisocyanate, respectively. In Examples 3 to 5 below, the isocyanate used is bis (4-isocyanatohexyl) methane.

Example 3 A silanol-terminated sulfopoly (ester-urethane) is prepared substantially in accordance with the procedure of Example 1, except that the reagents are charged as follows: The mixed PCPSSIP precursor (53.3 g, 0.06 moles), PCP 0201 (47.7 g, 0.09 moles) and ethylene glycol (3.7 g, 0.06 moles and bis (4-isocyanatocyclohexyl) methane (62.9 g, 0.24 moles, H12MDI, available from Bayer Corp., Pittsburgh, PA) The molar ratio of the reactants is 1: 4 : 2: 8 Analysis by differential modulated scanning calorimetry (MDSC) and tensile properties were performed on a film die-cut by spinning the polymer produced by this reaction sequence indicating that the polymer has a Tg of 14 ° C and a tensile strength of 14.7 MPa at 502% elongation.

Example 4 A silanol-terminated sulfopoly (ester-urethane) is prepared substantially in accordance with the procedure of Example 1, except that the reagents are charged as follows: The mixed PCPSSIP precursor (56.9 g, 0. 06 moles), PCP 0201 (63.6 g, 0.12 moles) and ethylene glycol (9.3 g, 0.15 moles and bis (4-isocyanatocyclohexyl) methane) (94.3 g, 0.36 moles). The molar ratio of the reactants is 1: 5: 5: 12. The analysis by differential scanning calorimetry modulated (MDSC) and the tensile properties were performed on a film die-cut by spinning of the polymer produced by this reaction sequence indicating that the polymer has a Tg of 36 ° C and a resistance to stress from 17.4 MPa to 390% elongation.

Example 5 A silanol-terminated sulfopoly (ester-urethane) is prepared substantially in accordance with the procedure of Example 1, except that the reagents are charged as follows: The mixed PCPSSIP precursor (53.3 g, 0.06 moles), PCP 0201 (15.9 g, 0.03 mole), ethylene glycol (7.45 g, 0.12 mole and bis (4-isocyanatocyclohexyl) methane (62.9 g, 0.24 mole) The molar ratio of the reagents is 1: 2: 4: 8. The analysis by differential scanning calorimetry Modulated (MDSC) and tensile properties were performed on a spin-cut film of the polymer produced by this reaction sequence indicating that the polymer has a Tg of 80 ° C and a tensile strength of 18.2 MPa at 111% elongation.

Examples 6 to 10 These examples are prepared in a manner analogous to that described above by Example 1. In the Examples 6 to 9, isophorone diisocyanate is replaced by bis (4-isocyanatocyclohexyl) methane (also known as H12MDI, available from Bayer Corp., Pittsburgh, PA). The properties of the polymer films punched from these examples are shown in Table I below. Pigments and adjuvants can be added in an amount sufficient to provide the desired color density and other characteristics. The data indicates that the formulations of Examples 2 and 6 are particularly desirable as paints components for pavement marking.

Comparative Examples (11 to 14) The film properties of some commercially available pavement marking paints and two-part epoxy material are shown below in Table I for comparison. It will be recognized that the tensile strength, elongation and abrasion resistance of the polymer films prepared from the silanol-terminated sulfopoly (ester-urethane) compositions may exceed that of the comparative materials.

Comparative examples (commercial paintings) Relative proportions of PCPSSIP with respect to PCP with respect to polyethylene glycol; the relative amount of diisocyanate used is the sum of these three numbers plus one, that is, in Example 6, 12 parts of H12MDI were used. Taber scorch test method is ASTM C501-84.

The following example describes the preparation and reaction of a sulfonated polyester diol different from PCPSSIP.

Example 15 A mixture of DMSSIP (74.0 g, 0.25 mol), 1,4-cyclohexanedimethanol (180 g, 1.25 mol) available from Aldrich Chemical Co.), and tetrabutyl titanate (0.1 g, 0.3 mmol) is heated to 200 ° C and it is kept at this temperature, with stirring, for four hours, then it is cooled to 150 ° C, which is maintained, with stirring, for an additional 5 hours. Subsequently the temperature of the reaction mixture is increased to 180 ° C and to the reaction mixture is added, with stirring, for a period of 30 minutes € -caprolactone (228 g, 2.0 moles, available from Aldrich Chemical Co.) which contains dibutyltin dilaurate (0.2 g, 0.3 mmol). The mixture is maintained at 180 ° C, with stirring, for 3 hours, and then cooled to room temperature, to produce an oil precursor composition comprising a 1: 3 molar ratio of sulphonated diol and a diol resulting from the reaction of 1,4-cyclohexanedimethanol (1 part) with e-caprolactone (two parts). The precursor prepared in this way is converted to a silanol-terminated sulfopoly (ester-urethane) substantially in accordance with the procedure of Example 1 by reacting 55.9 g of the precursor with PCP 0201 (62.9 g, 0.12 mol), ethylene glycol (5.58 g). , 0.09 moles), isophorone diisocyanate (79.9 g, 0.36 moles) followed by reaction with aminopropyltriethoxysilane (11.7 g, 0.053 moles). The differential scanning calorimetry modulation (MDSC) analysis and stress properties performed on a spin-cut film of the polymer produced by this reaction sequence indicate that the polymer has a Tg of 29 ° C and a tensile strength of 28.6. MPa at 341% elongation. The following example describes the sulfopoly (ester-urethane) preparation of the second embodiment of the invention when first preparing a hydroxyl-terminated sulfopoly (ester-urethane), the reaction of this hydroxyl-terminated sulfopoly (ester-urethane) with a reactant of electrophilic alkoxysilane and the reaction of the sulfopoli (ester-urethane) terminated in alkoxysilane, with water.

Example 16 The mixed PCPSSIP precursor (57.33 g, 0.06 moles, with a hydroxy equivalent weight of 475), PCP 0201 (62.76 g, 0.12 moles, available from Union Carbide Corp.), ethylene glycol (9.32 g, 0.15 moles) and dibutyltin dilaurate ( 0.16 g, 0.25 mmol) in methyl ethyl ketone (85 ml) is heated at 80 ° C and a solution of isophorone diisocyanate (66.69 g, 0.3 mol) in methyl ethyl ketone (44 ml) is added to the mixture with stirring, at a high speed such that the reaction temperature does not exceed 80 ° C. Approximately 30 minutes after completing the addition of the isophorone diisocyanate solution, dibutyltin dilaurate (0.16 g) in methyl ethyl ketone (1 ml) is added to the reaction mixture and the reaction is maintained at 80 ° C with stirring, during 3.5 additional hours A solution of isocyanate propyltriethoxysilane (14.82 g, 0.06 moles) available from Huís America, Inc.) in methyl ethyl ketone (5 ml) is added to the reaction mixture and the mixture is maintained at 80 ° C, with stirring.M. , for about 1 hour. (Infrared analysis (2250 cm "1) of the reaction mixture at this point indicates that no residual isocyanate remains.) Water (260 ml) is added to the reaction mixture, with stirring, for a period of about 10 minutes and The methyl ethyl ketone is distilled from the mixture, under reduced pressure, to produce a dispersion of a silanol-terminated sulfopoli (ester-urethane), the differential scanning calorimetry modulation (MDSC) analysis and the tensile properties performed on a die-cut film. Spinning of the polymer produced by these reaction sequences indicate that the polymer has a Tg of 7 ° C and a tensile strength of 17.9 MPa at 295% elongation.

Example 17 The dispersion of various pigments, fillers and adjuvants was carried out. A sulfopoly (ester-urethane) (177 g of a 50% dispersion of solids in water) was prepared in a manner analogous to the composition of Example 2 was added to a 600 ml stainless steel beaker. The beaker was filled in a Premier Mili Model 90"" high speed disperser (available from Premier Mili Co., Reading, PA) and mixed with 2.5 cm high agitation head at 500 rpm. A TamolMR 681 dispersant (2.58 g, available from Rohm and Haas, Philadelphia, PA), Bentolite ^ ® WH rheological modifier (0.66 g of a 15% solution in water, available from Southern Clay, Gonzales, TX), surfactant was added. Surfonyl ™ CT-136 (0.85 g, available from Air Products and Chemicals, Inc., Allentown, PA), and defoamer Drewplus ^ L-493 (0.82 g, available from Ashland Chemical Co., Boonton, NJ). Subsequently, titanium dioxide (Ti-Pure ™ R-706, 39.27 g, available from DuPont, Wilmington, DE) and calcium carbonate (Omycarb ™ 5, 138.04 g, available from OMYA, Inc., Proctor, VT) was added. The mixture is stirred at 4800 rpm for 15 minutes, then the stirring speed is reduced to 500 rpm and the mixture is diluted with water (10 g), methanol (7.9 g) and N-methylpyrrolidinone (8.79 g). Subsequently Drewplus "* - L-493 (0.99 g) and Natrosol thickener" 1 * HBR250 (1.25 g of a 2.5% solution in water, available from Aqualon Co., Wilmington, DE) are added to provide a useful composition for marking pavement. The following two examples describe the preparation of a sulfopoly (ester-urethane) in l-methyl-2-pyrrolidinone (NMP) and the microfluidization of the reaction product in water.

Example 18 A solution of the mixed PCPSSIP precursor (95.0 g, 0.1 mole), PCP 0201 (78.6 g, 0.15 mole), ethylene glycol (12.4 g, 0.20 mole), dibutyltin dilaurate (0.16 g, 0.00025 mole) and NMP (57.7 g) is prepared. ) by heating the reagents together at 60 ° C. This solution is added to isophorone diisocyanate (111 g, 0.05 mole) contained in a 1000 ml flask at a rate such that the temperature is maintained between 70 ° C and 75 ° C. Five minutes after the end of the addition, another 0.16 g of butyltin dilaurate is added and the temperature is maintained between 77 ° C and 86 ° C for another 40 minutes. Subsequently, a solution of 3-aminopropyltriethoxysilane (22.1 g, 0.10 mol) in 22.1 g of NMP is added in a stream. The addition causes an immediate exotherm that raises the temperature to 94 ° C. Stirring is continued for another hour while the temperature is maintained between 85 ° C and 95 ° C, subsequently the reaction mixture is transferred to a wide-mouth glass vessel, the container is sealed and the product is allowed to cool to the room temperature.

Example 19 The apparatus that provides the high pressure liquid jet milling in this example is a Microfluidizer ^ Model M-110F (Microfluidics, Newton, MA) equipped with a 400 m expansion chamber and a 200 μm expansion chamber, in series. The maximum pressure reached is 55 MPa (8000 psi). The microfluidizer in this configuration has a flow rate of 600 ml / min. The average particle sizes of the polymer dispersions are determined by dynamic light scattering using Malvern PCS 4700 (Malvern, Southborough, MA).

A solution of NMP (95.3 g) of sulfopoly (ester-urethane) of Example 18 is pre-heated at 80 ° C and charged in a de-tapping gun. Then 240 g of deionized distilled water (85 ° C) is circulated through the microfluidizer at 55 MPa (8000 psi). The NMP solution is injected stably into the water stream, just before the high pressure pump, for a period of 10 minutes (9.53 g / min). The high shear and the intimate mixing at depth provide that the chamber immediately forms a colloidal dispersion of the sulfopoly (ester-urethane) particles after the sulfopoly (ester-urethane) and water leave the interaction chambers. The dispersion is allowed to circulate through the microfluidizer so that the solid content accumulates to its final value of 28% by weight of sulfopoli (ester-urethane) and NMP (approximately 17 of the total passes). It is determined that the particle size of this dispersion is 93 nm and is constant during the time of the experiment. further, the dispersion does not contain undispersed sulfopoli (ester-urethane) or sedimented material. In contrast, a dispersion prepared by mixing 20 g of an 80% solution of sulfopoli (ester-urethane) of Example 18 in NMP (80 ° C), with 240 g of preheated water (85 ° C) using a high dispersant Speed and a Cowles blade (3000 rpm) for 15 minutes results in poor dispersion. The dispersion contains undispersed sulfopoli (ester-urethane) which quickly settles to the bottom of the container. The sulfopoly (ester-urethane) particles that form a dispersion have an average particle size of 176 nm. This example shows the applicability of using a high pressure liquid jet grind to disperse the sulfopoli (ester-urethane) in water to form a stable, water-based dispersion with better properties than standard or conventional high shear mixing. Various modifications and alterations of this invention will become apparent to those familiar with the art without departing from the spirit and scope of this invention, and it should be understood that this invention is not unduly limited by the illustrative embodiments set forth therein. 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. Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. A composition for marking the pavement, characterized in that it comprises a sulfopoly (ester-urethane) polymer which includes in its main structure at least one arylene or alkylene group comprising a group of sulphonic acid pendant or a salt thereof, the polymer of the composition for marking the pavement ends in at least one hydrolysable group, the composition optionally further comprises at least one of a pigment, an optical element, a slip resistant particle, a filler, a diluent and an aqueous medium.

2. The composition for marking the pavement, according to claim 1, characterized in that the poly (urethane ester) is present in an amount up to 70 weight percent and the aqueous medium comprises 30 weight percent of the composition, the composition it has an equivalent weight of sulfonate in the range from 500 to 12,000 g / equivalent.

3. The composition for marking the pavement, according to claims 1 or 2, characterized in that it has the formulas I or IV, and hydrolysis products thereof, wherein the formula I is: (0) OR1OC (0) MH-ia-M- (C (0) XZXC (0) NHRa) -NHC (0) YR3SÍ (Q) p (OQ) 3 p} . wherein R is a trivalent aliphatic or aromatic group in which M is a cation, - each R1 is independently an alkylene or cycloalkylene group having an average number of molecular weight in the range from 100 to 2,000; or a polymer residue having a molecular weight in the range of 100 to 2,000 comprising carbon, hydrogen and one or both of nitrogen, both of non-peroxy oxygen; each R2 is an alkylene, cycloalkylene or arylene group; each X is independently O, S or NR4, wherein each R4 is independently a lower alkyl group, hydrogen or an alkylene group that bridges the group X; m is an integer from 0 to 10; each Z is independently selected from the group consisting of wherein R and R1 is as previously defined, each R5 independently can be an alkylene group; p is 0, 1 or 2; n is an integer from 1 to 15; each R3 is independently an alkylene group; and each Y is independently O, S or NR6 wherein R6 is a lower alkyl group, hydrogen or R3Si (Q) p (OQ) 3.p, where R3 and p are as previously defined and each Q is independently hydrogen or a lower alkyl group having 1 to 4 carbon atoms with the proviso that at least one of OQ is an alkoxy group; and in which formula IV is IV in which each W is independently O OH -NH-, -CH2 CHCH20- or a single bond, and wherein R, R1, R2, R3, M, Q, X, Z, p, and m are as previously defined.

4. The composition for marking the pavement, according to claim 3, characterized in that the hydrolysis products thereof have the formula I 'and IV, wherein the formula I' is and formula IV is wherein each Q 'independently can be hydrogen or a lower alkyl group having 1 to 4 carbon atoms, with the proviso that at least one of OQ' is a hydroxyl group; and wherein R, Ra, R2, R3, M, X, Y, Z, W, m and p are as previously defined.

5. A paint for marking the pavement, characterized in that it comprises an aqueous dispersion constituted of the composition for marking the pavement according to any of claims 1 to 4, an effective amount of at least one pigment and optionally at least one of optical elements , slip resistant particles, fillers and diluents, the dispersion is optionally produced using a microfluidization process.

6. The paint for marking the pavement characterized in that it is in accordance with claim 5, from which the aqueous medium has been removed.

7. A method, characterized in that it comprises the step of: applying to a pavement the paint to mark the pavement in accordance with claim 5, and optionally drying the paint to mark the pavement.

8. The method according to claim 7, characterized in that it additionally comprises the step of adding optical elements to the dispersion after application of the polymer to the pavement.

9. A method for preparing a composition for marking the pavement, having at least one of formulas I and I ', according to claims 3 or 4, the method is characterized in that it comprises the steps of - (a) reacting a Sulfopoly (ester-urethane) terminated in isocyanate of formula II wherein R is a trivalent aliphatic or aromatic group in which M is a cation; each R1 is independently an alkylene or cycloalkylene group having an average number of molecular weight in the range of 100 to 2,000; or a polymer residue having a molecular weight in the range of 100 to 2,000, comprising carbon, hydrogen and one or both of nitrogen and non-peroxy oxygen atoms; each R2 is independently an alkylene, cycloalkylene or arylene group; each X is independently 0, S, or NR4, wherein each R4 is independently a lower alkyl group, hydrogen or a group that forms an alkylene bridge with another unit X; Each Z is selected independently of wherein R and R1 are as previously defined, each R5 is independently an alkylene group; p is 0, 1 or 2; m is an integer from 0 to 10; with a nucleophilic hydrolyzable silane agent of formula III HYR3Si (Q) p (OQ) 3.p III wherein each R3 is independently an alkylene group; each Y is independently O, S, or NR6 wherein R6 is a lower alkyl group, hydrogen or R3Si (Q) p (OQ) 3.p where R3 is as previously defined, each Q is independently hydrogen or a lower alkyl group having 1 to 4 carbon atoms, with the proviso that at least one of OQ is an alkoxy group; and p is as previously defined, - to produce: i) the silyl-terminated sulfopoly (ester-urethane) of formula I wherein R, M, R 2, R 1, X, Z, Y, R 3, Q, m and p are as previously defined, or ii) a silyl-terminated sulfopoly (ester-urethane) having a formula related to formula I in which the polymer expressions or ramifications take place.

10. A method for producing a pavement marking composition having at least one compound of formula IV and IV according to claim 3 or 4, the method is characterized in that it comprises the steps of: (a) reacting a sulfopoly (ester) -urethane) terminated in hydroxy, amino or thiol of formula V V wherein R, R1, R2, M, X, Z and m are as previously defined, with an electrophilic hydrolysable silane reagent having any of the formulas Via, VIb and VIc OCNR3Si (Q) p (OQ) 3-p Via ? 2c H: CH2OR3YES (Q) p (OQ) 3 -p VIb CIR3Si (Q) D (OQ) 3-p VIC wherein R3, Q and p are as previously defined, to produce i) a silyl-terminated sulfopoly (ester-urethane) of formula IV: IV wherein each W is independently O OH -CNH-. -CH2 CHCH2O- or a single bond, and wherein R, R1, R2, R3, M, Q, X, Z, p and m are as previously defined, or ii) a silyl-terminated sulfopoly (ester-urethane) having a formula that it is related in the formula IV in which the polymer extensions or branches subsequent to the reaction with a polyfunctional nucleophile take place.