WO2000069943A1 - Polyurea composition - Google Patents

Abstract

A polyurea composition is disclosed. The composition is one which can be maintained for long periods of time without the polyurea gelling. The composition comprises an oligomeric aminobenzoic acid ester or amide or an aromatic diamine derivative, a polyisocyanate and a stabilizing carrier.

Description

POLYUREA COMPOSITION

BACKGROUND OF THE INVENTION

Related Prior Application

This application is a conversion and continuation-in-part of provisional application no. 60/133,981, filed May 13, 1999.

1. Field of the Invention: This invention relates to a polyurea composition and more particularly, to such composition comprising a first component selected from an oligomeric amino benzoic acid ester or amide and an aromatic diamine derivative, a second component of a polyisocyanate and a stabilizing carrier.

2. Description of the Prior Art:

Reactions between diisocyanates, particularly the toluene diisocyanates, and amines containing active hydrogens proceed at a very rapid rate to form what is generally known as polyurea resins. These resins are particularly useful as castings, moldings, coatings and in the manufacture of rubber since they are extremely tough and tenacious. These polyurea resins can also be formed by any of the conventional foaming methods to produce a tough foam resin. Heretofore these resins have found little use in the foams, coatings, moldings, etc. due to the fact that the reaction between the amine and the isocyanate takes place before the resinous mix prepared from the above reactants can be cast, molded, shaped, or other-wise utilized. For example, when it is desired to apply a coating composition comprising essentially a polyisocyanate terminated compound and an amine or a polyamine containing active hydrogens, the isocyanate groups tend to react with the hydrogen atoms of the amines or polyamines while the coating is still in the pot. Thus a sharply reduced pot life of the resin mix is obtained. When it is desired to use the reaction products of such components to form films or molds, the rapid cross-linking occurring between these components prevents them from being utilized in such systems because these systems will cure before they can be applied as a film or before they are molded into a final shape.

Attempts to overcome this problem involve utilizing the conventional, thermally reversible, blocking agents for blocking isocyanates such as butyrolactam, propiolactam, phenyl methyl pyrazolone, aceto acetic ester, acetoacetone, valerolactam, benzimidazole, and many other compounds which include various oximes, phenols, imides, etc. Although these compounds have been reported to be successful in other reactive isocyanate systems as thermally reversible blocking agents, they have proven inadequate when utilized as a thermally reversible blocking agent for isocyanates in a system which contains amines or polyamines having at least one active hydrogen.

U.S. Patent No. 3,245,961 reveals completely reacting isocyanates with a prolactam to form adducts of the isocyanates so that all of the free isocyanate groups are blocked with caprolactam. When such completely blocked isocyanates are heated to temperatures above about 100°C, the isocyanate is regenerated and now made available for reaction with the active hydrogen containing amine or polyamine compound.

Another approach has been the use of a moderating solvent such as a ketone or an aldehyde, e.g., acetone, methyl ethyl ketone, cyclohexanone, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, etc., to slow down the reaction between the isocyanate and the active hydrogen present. In this regard, U.S. Patents Nos. 3,892,696 and 5,104,930 reveal such use. Other techniques employ the use of imino functional reactants, as disclosed in U.S. Patent No. 4,794,128, and finely divided solids to form powders of reactants, such as in U.S. Patent No. 5,418,311.

What is desired is a polyurea composition and process for its preparation which does not utilize blocking agents and thus heating at elevated temperatures, and which composition can be stored for months and not only for minutes, hours, or days. This storage time is presently not available when blocking agents and/or moderating solvents are employed. SUMMARY OF THE INVENTION

This invention relates to a polyurea composition and, more particularly, to such compostion comprising a first component of an (la) oligomeric aminobenzoic acid ester or amide, or an (lb) aromatic diamine derivative, a second component of a polvisocyanate and a stabilizing carrier.

The oligomeric amino benzoic acid ester or amide has the formula

where n is an integer form 2 to 4; each x is one or two; each benzoyl nucleus is para, meta, or di meta amino-substituted; each Z is -O- or -N- ; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000. The stabilizing carrier comprises a stabilizing solvent combined with at least one polyol.

DETAILED DESCRIPTION

A suitable first component is selected from among an oligomeric amino benzoic acid ester or amide and an aromatic diamine derivative. The oligomeric amino benzoic acid ester or amide has the formula

wherein n is an integer of from 2 to 4, each x is one or two; each benzoyl nucleus is para-, meta or di-meta amino substituted; each Z is

H

-O- or -N- ; and G is an n-valent radical which may be obtained by the removal of hydroxyl groups or amino groups, respectively, from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000. It will be appreciated that the characterization of radical G (as an n-valent radical which may be obtained by the removal of hydroxyl groups or amino groups, respectively, from an n-valent polyol or polyamine) is set forth for convenience in defining the nature of radical G per se, notwithstanding that abstraction or removal of hydroxyl or amino groups from such polyol or polyamine is not mechanistically involved in the synthesis or production of the oligomeric aminobenzoic acid esters and amides thereof.

It will be seen from inspection of the formula I set forth hereinbefore that the oligomeric aminobenzoic acid esters utlized in the present invention comprise di-, tri- and tetra-(aminobenzoate) esters of oligomeric polyol materials where n is, respectively, 2, 3 or 4. Correspondingly, oligomeric aminobenzoic acid amides comprise di, tri- and tetra-(aminobenzoic acid) amides of oligomeric polyamine materials where n is respectively 2, 3, or 4. Inasmuch as the aromatic rings of the benzyol moieties of the esters and amides each contain one or two amino groups, the oligomeric amino benzoic acid esters and amides may be termed oligomeric polyamines. Accordingly, the term "oligomeric polyamine" can be utilized in reference to the essential aminobenzoic acid ester or amide components of the polyaddition product and process of the present invention.

The oligomeric aminobenzoic acid esters utilized in the practice of the polyaddition process of the present invention are aminobenzoate esters of oligomeric polyol materials and can be conveniently provided by reaction of a nitro-substituted benzoyl halide, or a nitro-substituted benzoic acid, with a suitable polyol, such as polyalkylene ether or ester polyol, followed by reduction of the nitro groups of the resulting product to the corresponding amino groups. Thus, for example, an oligomeric di-(p-aminobenzoate) ester useful herein can be prepared by reaction of two moles of p-nitrobenzoyl chloride with one mole of a dihydric alcohol such as poly(ethylene giycol) having a molecular weight in the range of from about 400 to about 6,000 and by reduction of the resulting polyethylene giycol di-(p-nitrobenzoate), etc.

In like manner, oligomeric aminobenzoic acid amides useful herein can be provided by reaction of a nitro-substituted benzoyl halide, or a nitro-substituted benzoic acid, with a suitable polyamine, followed by a reduction of the benzoyl halide or benzoic acid nitrosubstitutes to corresponding amino groups. For example, an oligomeric di- (p-aminobenzoic acid) amide useful herein can be prepared by reaction of two moles of p-nitrobenzoic acid with one mole of an oligomeric diamine such as propoxalated propylene diamine having a molecular weight in the range of from about 400 to 6,000 and by reduction of the nitro groups to amino groups.

The nature of radical G of the aminobenzoic acid esters and amides can vary and will depend upon the nature of the oligomeric polyol and polyamine materials utilized in the preparation thereof. As indicated previously, the radical G will be derived from a polyol or polyamine material having a molecular weight of from about 400 to about 6,000. Preferably, the polyol or polyamine will have a molecular weight in the range of about 650 to 2,000. The radical G can comprise an n-valent saturated or unsaturated, straight chain or branched chain hydrocarbon radical which can be interrupted by oxygen ether atoms. For example, where a polyether polyol or a polyether polyamine is utilized in the preparation of an oligomeric aminobenzoic acid or amide, the corresponding G radical will comprise repeating oxygen ether atoms. Preferably, radical G will include such oxygen ether atoms.

It will be appreciated from inspection of the hereinbefore described representative formula I that the nature of n-valent radical G will vary with the value of integer n. Thus, where n is two, radical G will be a divalent radical -G- obtained by removal or abstraction of two hydroxyl or amino groups, respectively, from an oligomeric polyol or polyamine having a molecular weight of from about 400 to about 6,000. In the case where n is three, G will represent a trivalent radical

-G-,

obtained by removal of three hydroxyl or amino groups from a polyol or polyamine having a molecular weight in the same range. Similarly, when n is four, radical G will represent a tetravalent radical.

-G-

obtained by removal of four hydroxyl or amino groups from a polyol or polyamine having a molecular weight in the same range.

The Z moieties of the oligomeric aminobenzoic acid ester and amide compounds hereof can independently be oxygen or imino groups and, accordingly, each Z is defined as being

H

-O- or -N- ;

While the utilization of, for example, an oligomeric polyol or polyamine having, respectively, only hydroxyl or amino groups will be preferred from the standpoint of convenience and ease of preparation, compounds having both hydroxyl and amino groups can be utilized for the preparation of mixed aminobenzoic acid ester/amide compounds hereof. A number of polyol materials can be suitably employed for the preparation of the oligomeric aminobenzoic acid esters utilized herein. Examples of such polyols, which provide divalent, trivalent or tetravalent G radicals include oligomeric diols, such as polyalkyleneether glycols and polyalkylene-arylene-ether glycols; oligomeric triols, such as the polyalkyleneether glycerols or mixed polyalkyene-arylene-ether glycerols; and oligomeric tetrols, such as the polyalkylene ether pentaerythriols or mixed polyalkylene-arylene-ester pentaerythritols.

A preferred class of polyol materials useful in the preparation of the aminobenzoic acid esters herein comprises the polyalkyleneether glycols which provide a divalent G radical and which may be represented by the formula HO(RO)_a wherein R is an alkylene radical containing up to ten carbon atoms and a is an integer sufficient to provide a molecular weight within the range of from about 400 to 6,000, and preferably, from about 650 to about 2,000. Preferably R is an alkylene radical of from 2 to 4 carbon atoms. Examples of polyalkyleneether glycols useful herein include polyethyleneether giycol, polypropylene ether giycol, polyhexyleneether giycol, polytetramethyleneether giycol, polydecamethyleneether giycol, poly-1, 2-dimethyl ethyleneether giycol and the copolymer of tetrahydrofuran and l-allyloxy-2,-3-epoxypropane. The polyalkyleneether glycols herein can be readily obtained, for example, by polymerization to suitable molecular weight of an alkylene ether, e.g., ethylene oxide, tetrahydrofuran, propylene oxide, or, an admixture thereof, in the presence of water or other low molecular weight alcohol or hydrogen-donor compound.

The polyalkylene-arylene-ether glycols can also be employed for the preparation of oligomeric p-aminobenzoic acid esters utilized herein. These glycols, similar in structure to the polyalkyleneether glycols, additionally contain arylene radicals. Thus, arylene groups such as phenylene, naphthylene and anthralene radicals can be present in the polyalkylene-aryleneether glycols. In general, the arylene groups will be present in minor proportion relative to the alkylene groups. Normally, the giycol will contain at least one polyalkyleneether radical of molecular weight of about 500 for each arylene radical. Another class of polyol materials suited to the preparation of oligomeric aminobenzoic acid esters useful herein comprises the class of hydroxy-containing hydrocarbon polymer materials having a molecular weight in the range of from about 400 to 6,000. Accordingly, the radical G derived therefrom will comprise an n-valent saturated or unsaturated, straight or branched chain hydrocarbon radical which may be obtained by removal of hydroxyl groups from a saturated or unsaturated straight or branched chain hydrocarbon polymer having a molecular weight within the previously set forth range. Preferably, the n-valent G radical will be an aliphatic hydrocarbon radical derived from an aliphatic hydrocarbon polyol. Examples of suitable hydrocarbon polyol materials include the polyols obtained from the polymerization of polymerizable ethylenically unsaturated monomers, such as 1 ,4-butadiene, and by the introduction of hydroxyl groups in known manner. Such polyol materials are known and can be prepared, for example, by free-radical initiated polymerization of a polymerizable ethylenically unsaturated monomer to provide a dicarboxylate-substituted hydrocarbon polymer, for example, a dicarboxylate-terminated polymer. Reduction in known manner provides an aliphatic hydrocarbon polvol, for example, an aliphatic hydrocarbon diol. A suitable method for the production of such polyol materials is described in greater detail in U.S. Patent No. 2,888,439.

As indicated previously, the polyol materials useful for the preparation of the oligomeric aminobenzoic acid esters utilized herein also include polyols capable, by abstraction, respectively, of three or four hydroxyl groups, of providing a trivalent or tetravalent radical G. Thus, polyalkyleneether polyols and mixed polyalkylene-arylene-ether polyols derived from such polyhydric alcohols as glycerol, trimethylolpropane, pentaerythritol and the like can be employed. Such materials can be obtained by oxyalkylation as, for example, by reaction of glycerol or pentaerythritol with ethylene oxide, propylene oxide or a mixture thereof. The resulting trifunctional and tetrafunctional ethers may be advantageously employed for the preparation of oligomeric tri- and tetra-(aminobenzoate) esters which can be suitably employed for the production of polymers having increased cross-linking. A variety of polyamines can be utilized for the preparation of oligomeric aminobenzoic acid amides useful herein. Examples of such polyamines, which provide divalent, trivalent or tetravalent G radicals include oligomeric diamines, triamines and tetramines. For example, oligomeric diamines useful for the provision of oligomeric aminobenzoic acid amides include polyamines of the formula

wherein each of R and R is a divalent saturated or unsaturated, straight chain or branched chain hydrocarbon radical; c is zero or an integer; d is an integer; and the combined value of c and d is such as to provide a molecular weight for the polyamine of

1 from about 400 to about 6,000. Preferably, each of R and R is an aliphatic, straight or branched chain divalent hydrocarbon radical, e.g., an alkylene radical of from 2 to 10 carbon atoms, and more preferably from 2 to 4 carbon atoms. Suitable polyamines are known and commercially available and can be obtained, for example, by polymerization of an alkylene oxide and conversion of terminal hydroxyl groups to amino groups by know amination techniques.

The polyol and polyamine materials from which the n-valent G radical is derived can contain substituent moieties where such substituents do not interfere with the desired reaction of the aminobenzoic acid ester or amide with an isocyanate. Alkyl or halo substituents, for example, can be suitably present. The n-valent G radical can also contain repeating oxygen ether atoms as will be the case where the polyol or polyamine from which radical G is derived comprises, for example, a polyalkyleneether giycol, a polyalkyleneether glycerol, a polyalkyleneether pentaerythritol, a mixed polyalkylene-arylene-ether polyol or an amine-terminated polyalkylether. The polvol and polyamine materials can additionally contain ester linkages. Thus, polyol materials of suitable molecular weight, i.e., in the range of from about 400 to 6,000, ester linikages as may be obtained, for example, by reaction of a polycarboxylic acid and a polyhydric material can be suitably exrnployed. Example of such polyol is having ester groups include the oligomeric polyester polyols such as may be obtained by the condensation of adipic acid and ethylene giycol.

The oligomeric aminobenzoic acid esters utilized herein for the production of polymeric products include the di-(aminobenzoate) esters (obtained, for example, by reaction of two moles of a nitro-substituted benzoyl chloride with one mole of an oligomeric giycol having a molecular weight of about 400 to about 6,000, followed by reduction of nitro-to-amino-groups); and the tri-(aminobenzoate) esters (from three moles of nitro-substituted benzoyl chloride and one mole of an oligometric triol of molecular weight of about 400 to about 6,000, followed by reduction of nitro-to-amino-groups). Similarly, the oligomeric aminobenzoic acid esters include the tetra- (aminobenzoate) esters derived from four moles of a nitro-substituted benzoyl chloride per mole of an olilgomeric tetrol of molecular weight of about 400 to about 6,000, followed by a suitable nitro-to amino group reduction. These oligomeric aminobenzoate esters can conveniently be represented by the following formulas:

0 0 i l

-C-0-G-O-C- Formula

(H_:N)i m?

c=o Formula III

Formula IV

Similarly, the oligomeric aminobenzoic acid amides utilized herein for the

production of polymeric products include the di-(aminobenzoic acid) amides, the tri-

(aminobenzoic acid) amides and the tetra-(aminobenzoic acid) amides. These oligomeric

aminobenzoic acid amides can conveniently be represented by the following formulas:

0 H H 0

, I

// -C-N-G-N-C— Formula V

(H₂N); (NH_: Formula VI

Formula VII

In the formulae shown for the oligomeric aminobenzoate esters hereof (Formulae II, III, and IV) and the oligomeric aminobenzoic acid amides (Formulae V, VI, and VII), G will represent, respectively, a divalent, trivalent or tetravalent radical derived from a polyol or polyamine having a molecular weight in the range of about 400 to about 6,000, and preferably, in the range of from about 650 to about 2,000. As will be apparent from inspection of each of the formulae set forth hereinbefore, the phenyl group of each benzoyl moiety contains one or two amino groups depending upon the value of each x as one or two. The amino groups are positioned such that each benzoyl nucleus is para-amino-substituted, a meta-amino-substituted or di-meta-amino-substituted. Accordingly, the oligomeric aminobenzoic acid esters and amides hereof are inclusive of para-amino-benzoic acid esters and amides, meta-aminobenzoic acid esters and amides; and di-meta-aminobenzoic acid esters. It will be appreciated that each benzoyl moiety of an oligomeric aminobenzoic acid ester or amide hereof, while para-, meta- or di-meta- amino-substituted, need not be indentically substituted. Preferred oligomeric aminobenzoic acid esters and amides herein are those wherein the benzoyl moieties are each para-amino substituted. In addition to the amino-group substitution of the benzoyl moieties, the benzoyl groups can be substituted with non-intefering groups. Accordingly, the benzoyl moieties of the aminobenzoic acid ester and amide compounds hereof can be substituted with halogen, alkyl or other substituents which do not interfere with the desired polyisocyanate addition process.

Examples of oligomeric aminobenzoic acid esters useful herein and represented by Formula I include the following wherein a and b are integers having values corresponding to molecular weights for the polyols from which they are derived of from about 400 to about 6,000.

— 0 0

H₇N— ^{' ■}C-0tCH.-CH-0.7C" ^■NH,; A.

r-^ 0 0

HnN- ^■C-θ(CH--CH -CH,- ^•cH₂-o2C— ; ^•NH-

An example of a compound of Formula (II) B., above, is VERSALINK™ PI 000, commercially available from Air Products & Chemicals, Inc. which has the formula

Where m = 13-14, with a molecular weight of 1238.

Other commercially available products include VERSALINK™ P650, having an average molecular weight of 830, and VERSALINK™ 485, having an average molecular weight of 485.

Examples of oligomeric aminobenzoate esters useful herein and represented by Formula III include the following wherein a and b are integers having values corresponding to the molecular weights for the polyols from which they are derived of from about 400 to about 6,000.

An example of an oligomeric aminobenzoate ester represented by Formula IV includes the following wherein each a is an interger having a value corresponding to a molecular weight for the polyalkyleneether pentaerythritol from which the aminobenzoate ester is derived of from about 400 to about 6,000.

Examples of oligomeric aminobenzoic acid amides useful herein and represented by Formula V include the following wherein each c is an integer having values corresponding to molecular weights for the polyamines from which they are derived of from about 400 to about 6,000.

An example of an oligomeric aminobenzoic acid amide useful herein and represented by Formula VI is the following wherein each c has a value corresponding to the molecular weight for the polyamine from which the amide is derived of from about 400 to about 6,000.

An example of an oligomeric aminobenzoic acid amide represented by Formula VII includes the following wherein c is an integer having a value corresponding to a molecular weight for the polyamine from which the amide is derived of from about 400 to about 6,000.

The above-described oligomeric aminobenzole acid esters and amides and their preparation is described in U.S. Patent Nos. 4,328,322; 5,039,775 and EP 0630666 which are incorporated by reference hereinto in their entirety for all purposes.

Examples of other aminobenzoate esters or amides include, polyethyleneglycol bis(4-aminobenzoate); polyethyleneglycol bis(2-aminobenzoate); polyethyleneglycol bis(3-aminobenzoate); polytetramethyleneglycol bis(4-aminobenzoate); polytetramethyleneglycol bis(2-aminobenzoate); polypropyleneglycol bis(4-aminobenzoate); polypropylenegylycol bis(2-aminobenzoate); poly(oxypethylene-oxypropylene)-glycol bis(4-aminobenzoate); polyoxybutyleneglycol bis (4-aminobenzoate); polytetramethyleneglycol bis(3,5-diaminobenzoate); polypropyleneetherglycerol tris(4- aminobenzoate); polypropyleneetherpentaerithritol tetrakis(4-aminobenzoate); polyoxyethylene bis(4-aminobenzamide); polyoxypropylene bis(4-aminobenzamide); polyoxypropylene bis(3,5-diaminobenzamide); and polyoxypropyleneetherglycerol tris(4-aminobensamide); as revealed in U.S. Patent No. 5,319,058, incorporated by reference hereinto in its entirety.

A suitable aromatic diamine derivative include (a) an aromatic diamine of the formula:

where each Y is independently from one another H, loweralkyl, loweralkoxy, halogen and CF₃, where the term "lower" means the group it is describing contains from 1 to 6 carbon atoms; where the term "alkyl" refers to a straight or branches chain hydrocarbon containing no unsaturation, e.g. methyl, ethyl, isopropyl, 2-butyl, neopentyl, n-hexyl, etc; where the term alkoxy" has the formula lower alkyl-0-; and t is an integer of 1 to 4; some suitable diamines of the formula include, 4,4'methylene bisaniline; 4,4'methylene bis(2-chloroaniline); 4,4'methylene bis(2,3-dichloroaniline) TCDAM); 4,4'methylene bis(2,5-dichloroaniline); 4,4'methylene bis(2-methylaniline); 4,4'methylene bis(2-ethylaniline); 4,4'methylene bis(2-isopropylaniline); 4,4'methylene bis(2,6-dimethylaniline); 4,4'methylene bis(2,6-diethylaniline); 4,4'methylene bis(2-ethyl-6-methylaniline); 4,4'methylene bis(2-chloro-6-methylaniline); 4,4'methylene bis(2chloro-6-ethylaniline);

4,4'methylene bis(3-chloro-2,6 -diethylaniline); 4,4'methylene bis(2- trifluoromethylaniline); 4,4'methylene bis(2-methyoxycarbonylaniline); and the like; (b) a diphenyl ether derivative of the formula

where Y and t are as previously defined; some suitable diamines of the formula (2) include 4,4'diaminodiphenyl ether; and 4,4'diamino-3,3'dichlorodiphenyl ether; (c) a diphenyl sulfone derivative of the formula

where Y and t are as previously defined; some suitable sulfone derivatives of formula (3) include, 4,4'-diaminodiphenyl sulfone; 4J'-diamino-3,3'-dichlorodiphenyl sulfone; bis(4aminophenoxyphenyl) sulfone; l,2-bis(2-aminophenylthio)ethane; bis[2-(2-aminophenylthio)ethyl]terephthalate; and the like; (d) a diaminotoluene, such as 2,4-diaminotoluene; 2,6-diaminotoluene;

3,5-diethyl-2,4-diaminotoluene; 3,5-diethyl-2,6 diaminotoluene;

3,5-dimethylthio-2J-diaminotoluene; 3,5-dimethylthio-2,6-diaminotoluene and the like; (e) a diaminodiphenyl-propane derivative of the formula

where Y and t are as previously defined; such as 2,2-bis(4-aminophenyl)propane; 2,2-bis(4-amino-3-methylphenyl)propane; 2,2-bis(4-amino-3-isopropylphenyl) propane; 2,2-bis(4-amino-3,5-dimethylphenyl) propane; 2,2-bis(4-amino- 3,5-diethylphenyl) propane; 2,2-bis(4-amino-3,5-diisopropylphenyl) propane; 2,2 -bis(4-amino-3-ethyl-5-methylphenyl) propane and the like; (e) an ester of an amino benzoic acid of the formula

where the term "alkylene" refers to a bivalent radical of the lower branched or unbranched alkyl group it is derived from, having valence bonds from the terminal carbons thereof, e.g. ethyl (-CH₂CH₂-), propyl (-CH₂CH₂CH₂-), isopropyl (CH₃CH-CH₃), etc.; where R is H and

where Y and t are as previously defined; (g) 3,3'diaminobenzophenone; (h) m-or p-phenyl diamine; (i) m- or p- xylylenediamine; and (j) aromatic tetramine compounds such as 3,3', 4J'-tetraaminodiphenyl ether; 3,3', 4,4'-tetraaminobiphenyl and the like; and so on. These aromatic polyamine compounds can be used either singly or as a combination of two kinds or more according to need and are disclosed in U.S. Patent No. 5,319,058, incorporated hereinto by reference in its entirety.

A suitable polyisocyanate is selected. A suitable polyisocyanate is one which is conventionally employed in the production of polyurethanes.

Examples of monomeric polyisocyanates useful herein include polyisocyanates and polyisothiocyanates which are PAPI- 1 (a polyaryl polyisocyanate as defined in U.S. Patent No. 2,683,730), tolylene diisocyanate "TDI", triphenylmethane-4,4'4"-triisocyanate, benzene-1 ,3,5-triisocyanate, toluene-2,4,6-triis ocyanate, diphenyl-2JJ'-triisocyanate, hexamethylene diisocyanate, xylylene diisocyanate. chlorophenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene- 1 ,5-diisocyanate, xylene-alpha, alpha'-diisothiocyanate, 3,3'-dimethyl- 4,4'biphenylene diisocyanate, 3-3'dimethoxy-4J -biphenylene diisocyanate, 2',3,3'-dimefhyl-4,4'-biphenylene diisocynate, 5,5'-tetramethyl-4J'biphenylene diisocyanate, 2,2',5,5'-tetramethyl-4,4'biphenylene diisocyanate, 4J'mefhylenebis(phe nylisocyanate), 4,4'-sulfonylbis (phenylisocyanate), 4,4'-methylene di-orthototylisocy anate, ethylene diisocyanate, ethylene diisothiocyanate, trimethylenediisocyanate and the like. Mixtures of any one or more of the above mentioned organic isothiocyanates or isocyanates may be used as desired.

Additionally, suitable are mixtures of TDI such as a mixture (80/20 by weight) of 2,4-toluene diisocyanate and 2,6 toluene diisocyanate or a mixture (65/35 by weight) of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate; xylene diisocyanate; 1 ,5-napththylene diisocyanate; 1 ,4-phenylene diisocyanate; 4,4'-'diphenylmefhane diisocyanate (MDI)

(Upjohn's ISONATE® 125M); 4,4'4"-triphenylmethane triisocyanate; and 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate. Aliphatic diisocyanates such as the

C3₆ aliphatic diisocyanate derived from the dimer of ricinoleic acid can be suitably employed and are commercially available, for example, as DDI-1410 (Henkel Corporation,

Resin Division, Minneapolis. Minn.). The polyisocyanates hereof are known polyisocyanates in the field of polyurethane technology and can be employed singly or in admixture. Other examples of such polyisocvanates can be found, for example, in The

Development and Use of Polyurethane Products, E. N. Doyle, McGraw-Hill Book

Company, page 27 (1971) and Polyurethane Handbook, Gunter Oertel Hauser, Gardner

Press (1994).

Preferred polyisocyanates for employment in the process of the present invention are polyisocyanate materials in a liquid form at ambient temperatures e.g. a liquid MDI product as disclosed in U.S. Patent No. 3,394,164. These materials facilitate the production of polymeric products from normally liquid oligomeric aminobenzoic acid esters or amides and obviate the requirement of melting a solid polyisocyanate as a prerequisite to providing a suitable reaction mixture. Suitable liquid polyisocyanate materials are known and include, for example, polymeric MDI (4,4'-diphenylmethane diisocyanate) products obtained as by-products from the synthesis of MDI.

In the production of MDI by the condensation of aniline with formaldehyde and the conversion of amino to corresponding isocyanate groups, a content of the initially formed bis-adduct of aniline and formaldehyde reacts further with the reaction mixture to form polymeric aniline derivatives which are in turn converted to isocyanates. Typically, such polymeric derivatives will have a functionality of from about 4 to about 15, for example, about 10 isocyanate groups per molecule. Products containing such polymeric polyiscocyanates in the form of a pot residue after removal of pure MDI by distillation can be utilized. Similarly, polyisocyanate products comprising such polymeric polyisocyanate species in admixture with pure MDI, i.e., the undistilled reaction mixture, can be employed. Polymeric MDI products can be employed herein to advantage and are commercially available under such trade designations as RURBINATE® M, RUBINATE® LF-168 and RUBINATE®

LF-209 (available from Rubicon Chemicals Inc., Geisman, La.) and PaPI 27, PaPI

135, PaPI 580 and PaPI 901 (available from the Upjohn Company, Kalamazoo,

Mich.).

Another liquid polyisocyanate material which can be employed where crosslinking is desirably introduced into the polymeric products hereof comprises an admixture of MDI and a tri-functional cycloaddition product of MDI. An admixture of MDI and a trifunctional cycloadduct having the following structure, where R is

can be employed.

N-R-NCO

OCN-R-N-

(6)

N.

O^' R-NCO

Such an admixture is available under the designation "Liquid MDI, Isonate 143L (The Upjohn Company, Kalamazoo, Michigan).

To reiterate, in addition to the preferred MDI, modified forms of monomeric MDI or MDI-containing resins, any suitable organic diisocyanate may be used in the process of this invention such as, for example, aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, and heterocyclic diisocyanates including such as, for example, ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclopentylene-l,3-diisocyanate, cyclohexylene- 1 ,4-diisocyanate, cyclohexylene- 1 ,2-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2 -diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1 ,4-napthylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'diisocyanate, azobenzene-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, tetramethylene diisocyanate, pentametylene diisocyanate, hexamethylene diisocyanate, l-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate, triphenyl methane triisocyanate and the like.

Other examples of suitable organic diisocyanates include 1 ,4-tetramefhylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-l,6-hexamethylene diisocyanate, lJ2-dodecamethylene diisocyanate, cyclohexane-lJ-and- 1 ,4-diisocyanate, 1 -isocyanato-2-isocyanatomefhyl cyclopentane, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 2,4'dicyclohexyl- methane diisocyanate, 1,3- and l,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, ,α,α',α'Jetramethyl- 1,3-1 - isocyanato-l-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4-,- 1,3- and/or 1,.4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4- and/or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof. Aromatic polyisocyanates containing 3 or more isocyanate groups such as 4,4',4"-triphenylmefhane diisocyanate.

In accordance with the present invention, the polyisocyanate component can be in the form of an NCO prepolymer or a polyisocyanate adduct, more preferably a polyisocyanate adduct. Suitable polyisocyanate adducts are those containing, isocyanurate, uretidone, biuret, urethane, allophanate, carbodiimide and/or oxadiazinetrione groups. The polyisocyanates adducts have an average functionality of 2 to 6 and an NCO content of 5 to 30% by weight. The isocyanato-isocyanurates generally have an average NCO functionality of 3 to 3.5 and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.

Preferred polyisocyanate adducts are the polyisocyanates containing isocyanurate groups, biuret groups or mixtures of isocyanurate and allophanate groups.

The NCO prepolymers, which may also be used as the polyisocyanate component in accordance with the present invention, are prepared from the previously described monomeric polyisocyanates or polyisocyanate adducts, preferably monomeric diisocyanates, and organic compounds containing at least two isocyanate-reactive groups, preferably at least two hydroxy groups. These organic compounds include high molecular weight compounds having molecular weights of 400 to about 6,000, preferably 800 to about 3,000, and optionally low molecular weight compounds with molecular weights below 400. The molecular weights are number average molecular weights (M_n) and are determined by end group analysis (OH number).

With regard to the organic diisocyanates, the prepolymers and the polyisocyanate adducts, reference is made to U.S. Patent No. 5,516,873, which is incorporated by reference hereinto in its entirety.

The suitable stabilizing carrier is selected. A suitable stabilizing carrier is one which will completely dissolve the selected aminobenzoic acid ester or amide or the aromatic diamine derivative and the selected polyisocyanate when they are combined to form a reaction solution but which will prevent the resultant polymeric reaction product, i.e. the polyurea, from solidifying or gelling out of the reaction solution. In other words, the stabilizing carrier either prevents the normally near instantaneous reaction between the isocyanate group and the amino group or prevents the resultant reaction product, e.g. polyurea, from solidifying or gelling until such time as a portion of the stabilizing carrier or solvent is removed from the resultant solution, e.g., as by evaporation.

A suitable stabilizing carrier comprises a stabilizing solvent selected from (a)an aldehyde or ketone of the formula

O

F ^■ C-R, (7)

where R and R5 are independently of each other hydrogen and lower alkyl or R and R5 are joined to form a five or six membered ring; where the term "lower" is as previously defined; and where the term "alkyl" is as previously defined; (b) an ester having the formula o

CH₂-C-OR_s (2)

R₇

where R₆ and R7 are loweralkyl (as previously defined) and R₇ additionally is H and loweralkoxy where the term "lower" is as previously defined and the term "alkoxy" is as previously defined (c) ortho, meta- or para- dimethylbenzene; (d) N-methylpyrrolidone; (e) Solvesso solvent; (f) a petroleum hydrocarbon; (g) a lactone of the formula

O O-C (8)

I I

(loweralkylene)

where "lower" and "alkylene" is as previously defined; such as y-butyrolactone; and a mixture of any of the foregeoing solvents; combined with at least one polyol of the formula

HO— loweralkylene-OH (9)

where "lower" and "alkylene" is as previously defined.

Some suitable aldehydes and ketones, for example, include acetone, methyl ethyl ketone, methylisobutylketone, N-methylcyclohexanone, acetaldehyde, propionaldehyde, butryaldehyde and isobutyraldehyde. Some suitable solvents of formula (b) include methyl acetate, ethyl acetate, butyl acetate, methoxy propyl acetate. Some suitable polyols include, for example, polyglyols of the formula

H(OCH ,CH₂)_pOH _{{ 10)}

where p is an integer equal to 1 to 14, as for example when p is equal to 1 to 3, such compounds as ethylene giycol, propylene giycol, butylene glycols, such as 1,3-, 1,4-, and 2-3-butylene giycol, and alkylene glycols having 5 to 9 carbon atoms; when n is 4 or greater, polyglycols of an average molecular weight of about 600, such as polyethylene giycol 200, polyethylene giycol 400 and polyethylene giycol 600, It is to be understood that a mixture of the stabilizing solvents, e.g. aldehydes and ketones, can be employed, as well as a mixture of polyols, e.g., a mixture of ethylene giycol and propylene giycol.

The selected oligomeric aminobenzoic acid ester or amide or aromatic diamine derivative and the selected polyisocyanate components are added to the stabilizing carrier solution to form a reaction solution. Conventionally, these reaction components, are combined in the stabilizing carrier in solution in substantially equivalent proportions, that is in amount of the polyisocyanate of about 0.9 to 1.2 equivalents per equivalent of the first component of oligomeric aminobenzoic ester or amide or aromatic diamine derivative, based upon the isocyanate groups and amino groups, respectively, of the polyisocyanate and oligomeric aminobenzoic acid ester or amide or diamine derivative reactants. Typically, from about 1.0 to about 1 J 5 equivalent of polyisocyanate material per equivalent of the first component e.g. oligometric aminobenzoic acid ester or amide is employed.

Preferably, the primary reactants, e.g. the ester or amide (Formula I), and the polyisocyanate are combined in a volume ratio whereby the isocyanate is in excess to the ester or amide or diamine and is expressed in the following manner:

100 x 1_ x

0.95 Total Equivalent percent volume of

Weight of the first component the polyisocyanate e.g. the oligomeric ester or amide second component. which gives the parts of the polyisocyanate per 100 parts of the first reactant e.g. the oligomeric aminobenzoic acid ester or amide.

The amount of carrier agent employed is one which is sufficient to dissolve the first reactant e.g. the oligomeric aminobenzoic acid ester or amide reactant, and the polyisocyanate second reactant and maintain the reaction product thereof, i.e., the polyurea, in solution without the precipitation out or gelling of the polyurea product. Typically, the amount of stabilizing carrier employed is about 10 to 80% of the total reaction solution volume. Typically the amount of the stabilizing solvent, e.g. aldehyde and/or ketone of formula (7), employed with at least one polyol of formula (9) is in the ratio of 10 to 80 parts of solvent to one part of polyol. The amount of stabilizing solvent, e.g. acetone, is adjusted depending upon the viscosity desired for specific application requirements, e.g. for maximum penetration and an ultrathin coating thickness for glass, plumbing fixtures, furniture coatings, to a heavy gauge coating thickness for substrates having heavy chemical or environmental corrosion exposure. Typically, the reaction product viscosity will range from about 3.5 centipoise to about 1800 centipoise at room temperature.

The ester or amide in the stabilizing carrier typically reacts with the polyisocyanate at room temperature, however, the reaction solution can be heated to affect reaction.

The resultant reaction solution is a "single pot" polyurea composition which can be stored for a long period of time, e.g., 6-9 months at 25°C without exhibiting any instability or gelling out of the polyurea. Accordingly, this single pot composition can be applied in any manner for a synthetic polymer process, e.g., casting, molding, spraying, etc., where, after application, the single pot composition is treated, e.g. by heating, vacuum evaporation, etc., to remove at least a portion of the stabilizing carrier, leading to the formation of a solid, cured polyurea material. The single pot composition of the invention can be employed to obtain cast polyurea materials. In this regard, the single pot composition is cast into a mold and at least a portion of the stabilizing solvent is removed, e.g., by evaporation, whereby a solid thermosetting or thermoplastic polymeric material is obtained. The single pot composition can be employed with conventional casting and molding operations, including extrusions, rotation molding and the like operations. While the single pot composition can be employed in the production of cast pieces or fabrications formulated to suit the requirements of hard, abrasion-resistant, flexible pieces of thermosetting or thermoplastic character as desired, the single pot composition can be utilized in the production of cellular or non-cellular polymeric coatings or films. These coatings or films can be provided by coating the single pot composition, in neat form, into a coatable substrate and removing at least a portion of the stabilizing carrier to permit the gelling of the desired polymeric film or coating.

While the process and the single pot formulation permits the production of polymeric materials without the use of blocking agents, end-capping chemical modifications or thrmally activated catalysts, e.g. caprolactum, B-carbonyl compounds (such as ethyl aceto acetate, ethyl malonate), alcohols and oximes; polymerization additives of various types employed in the manufacture of polymeric products can desirably be employed. For example, such polymerization agents as catalysts, ultraviolet absorbers, fillers, plasticizers, blowing agents, etc., can be employed where desired.

Typically a flow and leveling agent polymerization additive is employed. Preferably such additive comprises a glycidyl ester of neo decanoic acid, of the formula

R₁₂

| O

R -C-C-OCH->CH-CH'. (11 )

I " \κ ^'

where the Rio, Rn, Rι are independently of each other H and lower alkyl where the sum of each alkyl group of Rio, Rn, and Rι₂ does not exceed 8 carbon atoms. Other flow and leveling agents include the diglycidyl either of 1,4-butane diol, the diglycidyl ether of neopentyl giycol, the poliglycidyl ether of aliphatic polyols, phenyl glycidyl ether, nonyl phenyl glycidyl ether, C₉-Cι₈ glycidyl ethers, polyglycidyl ether of castor oil, trimethyol ethane of triglycidyl ether and the ester forms of the aforementioned ethers. These ethers and esters are commercially available from the Shell Chemical Company and are designated as HELOXY. The glycidyl neodecanoate is commercially available from Exxon Chemical Company and is known as GLYDEXX N-10.

Additionally, employed is an ultraviolet (UV) light absorber such as benzotriazoles, e.g. benzotriazoles revealed in U.S. patents 3,004,896 and 3,189,615. Such benzotriazoles are commercially available from Ciba Geigy as Tinuvin® products, such as Tinuvin® P, (2-(2H-benzotriazol-2yl))-4-methylphenol); Tinuvin® 1130, comprising about fifty-two weight percent of poly(oxy-l ,2-ethanediyl), oc-(3-(3- (2H-benzotriazol-2-yl)-5-(lJ-dimethylethyl)-4-hydroxyphenyl)- 1 -oxopropyl)-τιτ-hydroxy, of the formula

having an average molecular weight of 637, about thirty five weight percent of poly(oxy- 1 ,2-ethanedlyl), oc-(3-(3-2H-benzotriazole-2-yl)-5-( 1 , 1 -dimethylethyl)-4-hydr oxyphenyl)-l-oxopropyl-ω-(3-(3-2H-benzotriazol-2-yl)-5-(l J-diamethylethyl)-4— hydro xyphenyl)-l-oxopropyoxy), of the formula

having an average molecular weight of 975, and the remainder (about thirteen weight percent of polyethylene giycol (300 molecular weight), which is used to functionalize the Tinuvin® 1 130; Tinuvin® 292 and Tinuvin® 328, [2-(2'-hydroxyl-3,5'-di-tert-amylphenyl)benzotriazole].

Finally, an antioxidant is employed. A preferred antioxidant is 3,5-di-tert-butyl-hydroxycinnamate, known as IRGANOX 1076, commercially available from Ciba Geigy.

A preferred UV stabilizer/antioxidant additive composition comprises about 70-75 weight percent of Tinuvin® 1 130, 10- 15 weight percent IRGANOX 1076 and 10-20 weight percent of Tinuvin® 328.

The concentration of the additives, e.g. UV stabilizer, antioxidant, leveling agent, etc. of the total formulation will, of course, depend upon the desired use of the formulation and will be varied accordingly in a manner well known to those skilled in the art. Typically, where the reactants are VERSALINK® P-1000 and ISONATE® 2143L, the carrier solvent is acetone and the leveling agent GLYDDEX® N-10 is employed ("FORMULATION"), the polyol component of the stabilizing carrier in the reaction solution and the FORMULATION is present in an amount which is in the ratio of the oligomeric aminobenzoic acid ester to the polyol of 5 to 2.66 to 1, preferably between 4.25 and 1.75 to 1, and, most preferably 4.0 to 1.

If a mixture of polyols is employed in the FORMULATION, e.g., ethylene giycol and propylene giycol, each polyol preferably should be present in equal amounts. If each polyol of the mixture of polyols is not present in equal amounts in making up the ratio of ester to polyol in the FORMULATION, then the cure time and storage time will vary. For example, where a mixture of ethylene giycol ("EG") and propylene giycol ("PPG") is emploed in the FORMULATION and the ratio of EG/ISONATE® 2143L to

PPG/ISONATE® 2143L ("RATIO") is greater than 1 , then the following cure times are obtained:

Additionally, typically, for the FORMULATION, the ratio of N-l 0/2143L is equal to or less than the ratio of EG + PPG/2143L. If it is greater, then the dry times of the coatings resulting form the reaction solution are lengthened. When the ratio is less than 1, the flow and spreadability of the reaction solution is reduced. The ratio range is typically 0.72 to 1.3, preferably 0.85 to 1.15, and most preferably 1.0 for N-10/2143L to EG + PPG/2143L.

Finally, for the FORMULATION, the ratio of EG + N-10/2143L to PPG + N- 10/2143L is typically 1, whereby an optimum drying time of about 45 minutes to one hour and fifteen minutes at 25°C is obtained. Ratios of less than or more than 1 typically produce reaction solutions with proportionate increases in drying times.

Another ratio which is considered with the FORMULATION is the ratio of EG/N- 10 and PPG/N-10 which typically are equal to each other as well as equal to twice that of (EG + PPG)/2143L. Typically, the ratio of EG/N-10 to PPG/N-10 is 0.8 to 1.42, preferably 0.92 to 1.2 and most preferably 1.0.

It is hypothesized that the resultant single pot polyurea formulation having a very long shelf life without any solidification or gelling of the polyurea, e.g., 9 to 12 months at a temperature of 5 to 45°C, is due to an in situ ionic shielding action. This ionic shielding action is only a hypothesis and is not to be a limiting factor of the subject invention. The in situ ionic shielding action is hypothesized to be obtained by the reaction of the stabilizing solvent, e.g., acetone, and the polyol, e.g., a mixture of ethylene giycol and propylene giycol. This in situ reaction and its continued maintenance while in a sealed and lidded container is believed to be the electrochemical basis for being able to provide a single pot, polyurea based, elastomer polymer composition having long term shelf life, with constant clarity, fluidity and drying time factors. It is hypothesized that the reaction between the stabilizing solvent, e.g. acetone, and the polyol, e.g., a mixture of ethylene giycol and propylene giycol, produces an excess of hydrogen ions which interact with the primary amine groups of the oligomeric amino benzoic acid ester or amide or aromatic diamine derivative, thereby preventing reaction thereof with the polyisocyanate until a portion of the stabilizing carrier is removed, e.g., by evaporation.

The invention is further described and illustrated by the following examples which are not intended to be limiting. In these examples, all parts and percentages are defined in liquid volume units of milliliters (ml) such as to comprise a total examples base reference volume of 40 ml, unless otherwise specified. In these examples, the specified ingredients of the formulations were added in the sequence set forth with moderate stirring of 24-45 seconds after each new ingredient addition at a temperature of 25°C at 1 atmosphere of pressure.

EXAMPLE 1 - COATINGS The following ingredients were mixed at 25°C to obtain a reaction solution:

INGREDIENTS PARTS BY VOLUME (ml)

acetone 32.10

VERSALINK® P- 1000 4.00

TINUVIN® 1130 0J0 ethylene giycol 0.50 propylene giycol 0.50

decanoic acid oxiranyl methyl ester (GLYDEXX® N-10, available from Exxon Chemical Co., Houston, TX) 1.00 ISONATE® 2143L ("2143L") 1.80

A total of thirty-six samples of the resultant reaction solution was prepared and coated on a wood substrate surface at room temperature and assigned to shelf-life status evaluation pursuant to the following parameters (two samples per parameter): a) long-term stability and coating effectiveness; b) long-term effectiveness in compliance with ASTM C267-96 (compression strength) and ASTM D4541 (pull-off strength); and c) long-term reapplication coating "dry-time" changes.

This parameter is used to evaluate the effectivity of the 1 -pint mix in Cesmo of coating "day-time", where, at specific time intervals, coatings were applied to cord rolled substrates from shelf-life samples ranging progressively from one week to nine months.

The results of each of these performance tests are set forth in Table 1 below where each group consisted of twelve units.

TABLE 1

In Table 1, above, the grading term "PASS" means:

1 ) under "Clarity Stability" - no change in clarity;

2) under "ASTM C267-96" - no more than 5% variation in test values over the entire time period of the tests; 4 of 6 samples showed increase in test values;

3) under "ASTM D4541" - all samples continued to exhibit test values above specification values; and

4) under "Reapplication Dry-Time" - 9 months Dry Time showed no greater than 15-18 minutes increase over initial preparation dry time; The term "N/A" means "not applicable", i.e., no further testing is required.

The compositions of the formulations of Group 1 through Group 3 all met or surpassed the objectives of rapid dry-rate and a 6 to 9 month long term stability as a single package polyurea coating composition. These groups also exhibited a constant clarity and no appreciable change in tack-free drying time.

EXAMPLE 2 - COATINGS

The procedure of Example 1 was repeated, except the formulation included:

INGREDIENTS PARTS BY VOLUME (ml) acetone 31.85

VERSALINK® P- 1000 4.00

TINUVIN® 1130 0.15 propylene giycol 1.20

GLYDEXX® N-10 1.00

2143L 1.80

The testing results obtained were as follows:

(a) all three groups passed the clarity stability and effectiveness tests; (b) all groups (1-3) passed the ASTM C267-96 test;

(c) all groups (1-3) passed the ASTM D4541 test. With respect to the reapplication drying time test, the following results were obtained:

(1) at one hour and 45 minutes, a matte finish was obtained and remained for one week; (2) at two hours, a matte finish was obtained and remained for three months;

(3) at two hours and 30 minutes, a matte finish was obtained and remained for nine months.

All coatings produced a matte finish with no sign of "fish eye" or "orange peel" blemishes. The shelf life stability obtained was 6 to 8 months.

EXAMPLE 3 - COATINGS

A reaction solution was prepared from the following ingredients:

INGREDIENTS PARTS BY VOLUME (ml) acetone 31.00

VERSALINK® P- 1000 4.00

ethylene giycol 1.00 propylene giycol 0.50

GLYDEXX® N-10 2.00

2143L 1.50

The resultant reaction solution after a 9-month shelf life was applied to a treated wood substrate surface at 25°C and atmosphere pressure. The resultant solution had excellent clarity and coating effectiveness requiring a drying time ranging from 2 hours to 24 hours as compared to an optimum time of 1.5 to 2 hours. EXAMPLE 4 - COATINGS

The procedure of Example 1 was repeated with the following formulation: INGREDIENTS PARTS BY VOLUME (ml) acetone 31.00

VERSALINK® P- 1000 5.00 ethylene giycol 0.5

propylene giycol 0.5

GLYDEXX® N-10 1.00 2143L 2.00

Sixteen samples were prepared and identified by two groups of 8 units each. The two groups were subject to the protocol of Example 1. All units passed the parameters described over a 6 to 9 month shelf life sampling period. Tack-free drying times of an average of 45 minutes at 25°C were observed for all samples when coated on stainless steel test place surfaces. Al coatings produced a very high gloss finish with no signs of "fish eye" or "orange peel" blemishes. All drying times for reapplication after a 4-month test interval were on average 1.5 to 1.75 hours.

EXAMPLE 5 - COATINGS

The procedure of Example 1 was repeated with the following formulation:

INGREDIENTS PARTS BY VOLUME (ml)

acetone 29.65

VERSALINK® P- 1000 4.00 ethylene giycol 0.50

propylene giycol 0.50

GLYDEXX® N- 10 ("N- 10") 1.00

ME-080 (a polytetramethylene based prepolymer of 4J'-diphenylmethan diisocyanate, available from Bayer Corp., Pittsburgh, Pennsylvania, having a nominal NCO percentage of 8.4) 4.35

The resultant reaction solution passed the test protocols specified in TABLE 1. Additionally, after one week of aging at 25°C, sample films cast at 25°C at standard atmospheric pressure exhibited the following properties set forth in TABLE 2, below:

TABLE 2

The coatings resulting form the reaction solution obtained by removal of at least a portion of the stabilizing carrier (acetone) were tested with a James Static Friction machine. The coatings exhibited a significantly high value of coefficient of friction as shown in TABLE 3 which presents the results of six sets of measurements for comparing the coefficient of friction between coated and uncoated surfaces of concrete and wood substrates.

TABLE 3

EXAMPLE 6 - COATINGS

The procedure of Example 1 was repeated except that VERSALINK® P-650 was used instead of VERSALINK® P- 1000. VERSALINK® P-650 is an oligomeric diamine of the formula:

where X is about 4 to 40. having an average moleculer weight of 830. The formulation employed was the following:

INGREDIENTS PARTS BY VOLUME (ml) acetone 22.17

VERSALINK® P-650 8.33 ethylene giycol 1.00

propylene giycol 1.00

N-10 2.00 methyl methacr ate 2.50

2143L 3.00

The resultant reaction solution was accelerated to remove at least a portion of the stabilizing carrier to cast film on glass substrates. The films were then subjected to the testing protocols of Example 1 and all the films passed. Additionally, after one week of aging at 25°C sample films exhibited the following properties set forth in Table 4, below:

TABLE 4

EXAMPLE 7 - CAULKING, GROUT, APPLICATIONS

A reaction solution was prepared from the following:

INGREDIENTS PARTS BY VOLUME (ml) acetone 27.5

VERSALINK® P- 1000 6.67 ethylene giycol 0.84 propylene giycol 0.84

N-10 1.68

2143L 2.50

The resultant reaction solution had a viscosity of about 8500 centipoise at 25°C. A portion of the resultant solution was mixed with 12%> by weight of gypsum or cement or glass fibers and was easily trowlable on cracked surfaces of wood, brick, concrete and asphalt base roofing to form a coat thereon. After drying, about 1.5 hours, the resultant coat was cured at 70-80°F for 12 hours whereby a total water barrier was obtained.

EXAMPLE 8 - CAULKING, GROUT APPLICATIONS INGREDIENTS PARTS BY VOLUME (ml) acetone 33.5

VERSALINK® P- 1000 4.00

ethylene giycol 0.25 propylene giycol 0.25

HELOXY® - 68 (a neopentyl giycol diglycidy ether available from Shell Chemical Company,

Houston, Texas) 0.50

ISONATE® 2143L 1.50 The resultant reaction solution had a viscosity of about 10,000 to 16,000 centipoise at 25 °C and it was applied by a trowel to porous brick masonry having numerous pits and depressions (ranging from

inch to ! inch in depth and Vi inch to 2 inches in irregular length). The resultant coating was maintained at 25°C for 1.5 to 2 hours to obtain a tack- free coating. After 24 hours at 25°C a matte finish transparent coating was obtained with excellent skid resistance and abrasions toughness.

In Table 5 below is given some of the properties of the resultant coating which was applied in a 1-inch diameter by a Vi inch in height cylinder after 30 days at 25°C.

TABLE 5

EXAMPLE 9 - CAULKING APPLICATION

A reaction solution was prepared from the following:

INGREDIENTS PARTS BY VOLUME (ml) acetone 5.00

VERSALINK® P- 1000 16.67

Poly (oxy alkylene) giycol (available as MULTRANOL 9165 from Bayer Corp., Pittsburgh, Pennsylvania) 13.33

2143L 5.00

The resultant reaction solution passed a one year sealed container shelf-life test conducted by an analytical laboratory contractor. EXAMPLE 10 - INTERNAL SURFACE COATING APPLICATION

A reaction solution was prepared from the following:

INGREDIENTS PARTS BY VOLUME (ml) acetone 22.5 γ-butyrolactone 9.7

VERSALINK® P- 1000 4.0

ethylene giycol 0.5 propylene giycol 0.5

GLYDEXX® N-10 1.0

ISONATE® 21431 1.8

The resultant reaction solution had a viscosity of about 900 to 1000 centipoise at 25°C.

The solution was applied by brush to a 6 inch by 4 inch cold-rolled steel coupon substrate to form a first coat thereon having a tack-free dry time of 2 to 2.5 hours at 25°C. A second coat was applied having a tack-free dry time of 1.5 to 1.75 hours at 25°C. After 15 hours at 25 °C a coating was obtained which had a matte finish and a SHORE D hardness of 90-92 (ASTM785-93).

EXAMPLE 11

A reaction solution was prepared in which the carrier solvent was a mixture of α-butyrolactone and propylene giycol methyl ether acetate in a volume ratio of 70 to 30. The formulation included the following:

INGREDIENTS PARTS BY VOLUME (ml)

α-butyrolactone 18.00

propylene giycol methyl ether acetate (ARCOSOLVE® PM Acetate, available from ARCO Chemicals, Newton Square Pennsylvania) 14.10 VERSALINK® P- 1000 4.00

TINUVIN® 1130 0J0 propylene giycol 0.50 ethylene giycol 0.50

GLYDEXX® N-10 1.00

ISONATE® 2143 1.80

The resultant reaction solution had a viscosity of about 1.6 centipoise at 25°C and possessed excellent flow and rapid leveling coating characteristics. A stability test conducted by an analytical lab indicated no gelation or loss of clarity at 9 months. The solution was applied to surfaces of concrete, wood, glass, metal, leather, fabric, vinyl and lucite and a tack-free dry time at 25 °C ranged from 3 to 6 hours depending upon the substrate. The resultant coatings were extremely scuff and abrasion resistant per ASTM 785-93 tests and exhibited a skid resistance per the standard James Static Friction Machine of 3.62 (dry) and 6.14 (wet) for a three layer coating on a metal substrate surface.

EXAMPLE 12

The acetone component of Examples 1 through 10 were totally replaced by solvent mixture comprising γ-butyrolactone (43.15% by volume) and propylene giycol methyl ether acetate (56.25%) by volume) to obtain excellent application results.

BEST MODE

The Best Mode of practicing the present invention is to provide a polyurea composition for use in coating or molding, said polyurea composition comprising: a) a first component selected from an oligomeric aminobenzoic acid ester or amide having the formula

wherein n is an integer from 2 to 4. x is one or two; each benzoyl nucleus is para-, meta-, or di-metaamino -substituted; each Z is -O- or -N-; G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000; and a suitable aromatic diamine or a mixture of the foregoing;

(b) a second component comprising a polyisocyanate; and

(c) a polyol having the formula

R₈ Rg

H ( OCH I CH I) pOH where p is an integer of 1 to 3 and R₈ and R are independently of each other H and lower

alkyland a stabilizing solvent selected from the group consisting of: (a') an aldehyde or ketone of the formula,

O

R₅ — C — R₄ where R4 and R5 are independently of each other hydrogen and lower alkyl or R₄ and R5 are joined to form a five or six-membered ring; (b¹) an ester having the formula, 0

CH₂ — C — OR₆

I

R7

where R₆ and R₇ are independently of each other lower alkyl and R₇ is additionally H and lower alkoxy; (c') ortho-, meta-, or para- dimethyl benzene;

(d') N-methyl pyrrolidone; (e¹) Solvesso solvent; (f ) a petroleum hydrocarbon; (g') a lactone of the formula,

0 C=0

\ /

(lower alkylene) and (h') a mixture of any of the foregoing.

INDUSTRIAL APPLICABILITY

The present invention provides a novel and versatile composition adapted for coating, molding, casting, and similar operations. The composition is formed of a polyurea base in a stabilizing solvent to achieve a long storage life without degradation of the properties of the composition. The resultant coated or cast material achieves significant value in weather resistance and substrate protection. In addition to the manufacture of the composition, application is found in coating substrates or producing products from the composition, and those products coated or made are of generally improved quality over those previously known.

Claims

1. CLAIM

1. A polyurea composition comprising: b) a first component selected from an oligomeric aminobenzoic acid ester or amide having the formula

wherein n is an integer from 2 to 4. x is one or two; each benzoyl nucleus is

para-, meta-, or di-metaamino -substituted; each Z is -O- or -N-; G is an

n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000; and a suitable aromatic diamine or a mixture of the foregoing;

(b) a second component comprising a polyisocyanate; and

(c) a stabilizing carrier.

2. The composition as defined in claim 1 wherein said stabilizing carrier comprises a

stabilizing solvent and a polyol.

3. The composition as defined in claim 2 wherein said stabilizing solvent is selected from the group consisting of:

(a') an aldehyde or ketone of the formula,

O

I I

Rs— C— R₄ where R4 and R5 are independently of each other hydrogen and lower alkyl or Rj and R₅ are joined to form a five or six-membered ring; (b¹) an ester having the formula,

O

I I

CH —C— OR₆

I

R7 where R₆ and R7 are independently of each other lower alkyl and R7 is additionally H and lower alkoxy;

(c') ortho-, meta-, or para- dimethyl benzene;

(d') N-methyl pyrrolidone;

(e¹) Solvesso solvent;

(f ) a petroleum hydrocarbon;

(g') a lactone of the formula,

O C=O

\ /

(lower alkylene)

(h') a mixture of any of the foregoing.

4. The composition as defined in claim 3 wherein said stabilizing solvent is acetone.

5. The composition as defined in claim 3 wherein said ester (b') comprises an acetate

selected from the group consisting of methylacetate, ethylacetate, butylacetate,

methoxypropyl acetate or a mixture of any of the foregoing acetates.

6. The composition as defined in claim 2 wherein said polyol is one having the formula

Rs R₉

I I H(OCHCH)pOH

where p is an integer of 1 to 14 and R and R₉ are independently of each other H and lower alkyl.

7. The composition as defined in claim 6 wherein said polyol is one where p is equal to 1 to 3.

8. The composition as defined in claim 7 wherein said polyol is one selected from the

group consisting of ethylene giycol, propylene giycol, 1-3-butylene giycol, 1-4-butylene

giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

9. The composition as defined in claim 8 wherein said stabilizing solvent comprises acetone and said polyol comprises a mixture of ethylene giycol and propylene giycol.

pOH

10. The composition as defined in claim 9 wherein said oligomeric amino benzoic acid amide has the formula,

H₂

with a molecular weight of 1238 and where m is an integer of 13 to 14.

11. A method of stabilizing a polyurea composition, comprising combining a first

component selected from an oligomeric aminobenzoic acid ester or amide of the formula,

wherein n is an integer from 2 to 4, x is one or two, each benzoyl nucleus is para-, meta-,

or di-metaamino-substituted; each Z is -O- or -N-; and G is an n- valent radical obtained

by removal of hydroxy groups or amino groups from an n- valent polyol or polyamine having a molecular weight of from about 400 to about 6,000: a suitable aromatic diamine

or a mixture of the foregoing; and a second component comprising a polyisocyanate in a stabilizing carrier to form a reaction solution.

12. The method as defined in claim 1 1 wherein said stabilizing carrier comprises a stabilizing solvent and a polyol.

13. The method as defined in claim 12 wherein said stabilizing solvent is selected from the group consisting of

(a') an aldehyde or ketone of the formula, O

I I

R₅-C-R₄ where R and R₅ are independently of each other hydrogen and lower alkyl or R and R₅ are joined to form a five or six-membered ring; (b') an ester having the formula,

O

CH₂— C— OR₆

I R₇ where R₆ and R7 are independently lower alkyl and R7 is additionally H and lower

alkoxy;

(c') ortho-, meta- or para- dimethyl benzene;

(d¹) N-methyl pyrrolidone;

(e¹) Solvesso solvent;

(f ) a petroleum hydrocarbon;

(g') a lactone of the formula; and

(h¹) a mixture of any of the foregoing.

14. The method as defined in claim 13 wherein said stabilizing solvent is acetone.

15. The method as defined in claim 13 wherein said ester (b') comprises an acetate

selected from the group consisting of methylacetate, ethylacetate. butylacetate, methoxypropyl acetate or a mixture of any of the foregoing acetates.

16. The method as defined in claim 12 wherein said polyol is one having the formula,

R₈ R₉

I I H(OCHCH)pOH where p is an integer of 1 to 14 and R8 and R9 are independentlv of each other H and lower alkyl.

17. The method as defined in claim 16 wherein said polyol is one where p equals 1 to 3.

18. The method as defined in claim 17 wherein said polyol is one selected from the group consisting of ethylene giycol. propylene giycol, 1-3-butylene giycol. 1-4-butylene giycol, 2-2-butylene giycol and a mixture of any of the foregoing glycols.

19. The method as defined in claim 18 wherein said stabilizing solvent comprises acetone

and said polyol comprises a mixture of ethylene giycol and propylene giycol.

20. The method as defined in claim 19 wherein said oligomeric amino benzoic acid amide

has the formula

with a molecular weight of 1238 and where m is an integer of 13 to 14.

21. A method of preparing a polyurea composition, which comprises, combining a first component selected from the group consisting of an oligomeric benzoic acid ester or amide of the formula

wherein n is an integer from 2 to 4, x is one or two; each benzoyl nucleus is para-, meta-, or di-metaamino-substituted, each Z is -O- or -N-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000; a suitable aromatic diamine

or a mixture of the foregoing, with a second component comprising a polyisocyanate in a stabilizing carrier.

22. The method as defined in claim 21 wherein said stabilizing carrier comprises a stabilizing solvent and a polyol.

23. The method as defined in claim 22 wherein said stabilizing solvent is selected from

the group consisting of:

(a') an aldehyde or ketone of the formula

O

I I

Rs- where R₄ and R₅ are independently of each other hydrogen and lower alkyl or R₄ and R₅ are joined to form a five or six-membered ring; (b') an ester having the formula:

I R₇

where R₆ and R7 are independently of each other lower alkyl and R7 is additionally H and lower alkoxy;

(c') ortho-, meta-, or para- dimethyl benzene; (d') N-methyl pyrrolidone;

(e') Solvesso solvent; (f) a petroleum hydrocarbon; (g') a lactone of the formula,

O C=O

\ /

(lower alkylene) and (h') a mixture of any of the foregoing.

24. The method as defined as defined in claim 23 wherein said stabilizing solvent is acetone.

25. The method as defined in claim 23 wherein said ester (b¹) comprises an acetate

selected from the group consisting of methylacetate, ethylacetate, butylacetate,

methoxypropyl acetate or a mixture of any of the foregoing acetates.

26. The method as defined in claim 23 wherein said polyol is one having the formula

R₈ R₉

I I

H(OCHCH)pOH where p is an integer of 1 to 14 and R₈ and R are independently of each other H and lower alkyl.

27. The method as defined in claim 26 wherein said polyol is one where p equals 1 to 3.

28. The method as defined in claim 27 wherein said polyol is one selected from the group

consisting of ethylene giycol, propylene giycol. 1-3-butylene giycol, 1-4-butylene giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

29. The method as defined in claim 28 wherein said stabilizing solvent comprises acetone

and said polyol comprises a mixture of ethylene giycol and propylene giycol.

30. The method as defined in claim 29 wherein said oligomeric amino benzoic acid amide has the formula

O O

1 )

H₂N— ' -C-0"(CH₂CH₂CH₂CH₂CH₂-0)_m— C~NH₂

with a molecular weight of 1238 and where m is an integer of 13 to 14.

31. A method of coating a surface of a substrate, which comprises:

(a) applying to the surface a reaction solution, comprising a first reactant selected

from an oligomeric aminobenzoic acid ester or amide of the formula

wherein n is an integer from 2 to 4, x is one or two; each benzoyl nucleus is para-, meta-, or di-metaamino- substituted; each z is -O- or -N-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000; a suitable aromatic diamine or a mixture of the foregoing; a second reactant comprising a polyisocyanate and a stabilizing carrier, to coat the surface to form a reaction solution coated surface, and

(b) treating said reaction solution coated surface to remove at least a portion of said stabilizing carrier therefrom and to form a reaction product coating thereon resulting from first and second reactants.

32. The method as defined in claim 31 wherein said stabilizing carrier comprises a

stabilizing solvent and a polyol.

33. The method as defined in claim 32 wherein said stabilizing solvent is selected from the group consisting of

(a¹) an aldehyde or ketone of the formula,

O

I I

R₅__ C— R₄ where R and R5 are independently of each other hydrogen and lower alkyl or R and R₅ are joined to form a five or six-membered ring, (b') an ester having the formula,

O 1 1

CH₂— C— OR₆

I

R7 where R₆ and R7 are independently of each other lower alkyl and R7 is additionally H and lower alkoxy;

(c¹) ortho-, meta-, or para- dimethyl benzene; (d') N-methyl pyrrolidone; (e^τ) Solvesso solvent;

(f) a petroleum hydrocarbon;

(g') a lactone of the formula;

O C=O

\ /

(lower alkylene) and (h¹) a mixture of any of the foregoing.

34. The method as defined in claim 33 wherein said stabilizing solvent is acetone.

35. The method as defined in claim 33 wherein said ester (b¹) comprises an acetate selected from the group consisting of methylacetate. ethylacetate. butylacetate,

methoxypropyl acetate or a mixture of any of the for going acetates.

36. The method as defined in claim 32 wherein said polyol is one having the formula

Rs R₉

I I

H(OCHCH)pOH

where p is an integer of 1 to 14 and R₈ and R are independently of each other H and lower alkyl.

37. The method as defined in claim 32 wherein said polvol is one where p equals 1 to 3.

38. The method as defined in claim 37 wherein said polyol is one selected from the group consisting of ethylene giycol, propylene giycol, 1-3-butylene giycol, 1-4-butylene giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

39. The method as defined in claim 38 wherein said stabilizing solvent comprises acetone and said polyol comprises a mixture of ethylene giycol and propylene giycol.

40. The method as defined in claim 39 wherein said oligomeric amino benzoic acid amide has the formula

O O

H₂N— < V-C^~0^~(CH₂CH₂CH₂CH₂CH₂-0)_m-C-NH₂

with a molecular weight of 1238, and where m is an integer of 13 to 14.

41. A method of preparing a solid polyurea which comprises: (a) combining a first component comprising an oligomeric aminobenzoic acid ester or amide of the formula

wherein n is an interger from 2 to 4, each x is one or two: each benzoyl nucleus is para-. meta or di-metaamino-substituted; each z is -O- or -N-, and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or

polyamine having a molecular weight of from about 400 to about 6,000; a suitable

aromatic diamine or a mixture of the foregoing; with a second component comprising a polyisocyanate in a stabilizing carrier to form a reaction solution; and (c) removing at least a portion of said stabilizing carrier from said reaction solution to precipitate the solid polyurea.

42. The method as defined in claim 41 wherein said stabilizing carrier comprises a

stabilizing solvent and a polyol.

43. The method as defined in claim 42 wherein said stabilizing solvent is selected from the group consisting of:

(a¹) an aldehyde or ketone of the formula

O

I I

R₅_ — R₄

where R and R₅ are independently of each other hydrogen and lower alkyl or F-4 and R~ are joined to form a five or six-membered ring; (b') an ester having the formula,

O

I I CH₂_C— OR₆

I

R7 where R₆ and R7 are each independent of the other lower alkyl and R7 is additionally H and lower alkoxy,

(c') ortho-, meta- or para- dimethyl benzene;

(d') N-methyl pyrrolidone;

(e') Solvesso solvent;

(f ) a petroleum hydrocarbon;

(g') a lactone of the formula;

O C=O

\ /

(lower alkylene) and (h) a mixture of any of the foregoing.

44. The method as defined in claim 43 wherein said stabilizing solvent is acetone.

45. The method as defined in claim 43 wherein said ester (b¹) comprises an acetate selected from the group consisting of methylacetate, ethylacetate, butylacetate,

methoxypropyl acetate or a mixture of any of the foregoing acetates.

46. The method as defined in claim 43 wherein said polyol is one having the formula R₈ R₉ H(OCHCH)pOH

where p is an integer of 1 to 14 and R₈ and R are independently of each other H and lower alkyl.

47. The method as defined in claim 46 wherein said polyol is one where p equals 1 to 3.

48. The method as defined in claim 47 wherein said polyol is one selected from the group consisting of ethylene giycol, propylene giycol. 1-3-butylene giycol, 1-4-butylene giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

49. The method as defined in claim 48 wherein said stabilizing solvent comprises acetone

and said polyol comprises a mixture of ethylene giycol and propylene giycol.

50. The method as defined in claim 49 wherein said oligomeric amino benzoic acid amide has the formula.

with a molecular weight of 1238, and where m is an integer of 1 to 14.

51. An article obtained from the composition of claim 1.

52. An article obtained from the composition of claim 10.

53. A composition comprising a storage stable reaction solution obtained by the method of step (a) of claim 41.

54. A composition comprising a solid polyurea which is obtained by the method of claim

41.

55. The composition as defined in claim 53 wherein said stabilizing carrier comprises a stabilizing solvent and a polyol.

56. The method as defined in claim 55 wherein said stabilizing solvent is selected from the group consisting of (a') an aldehyde or ketone of the formula,

O

I I

R₅— C— R₄

where R and R₅ are independently of each other hydrogen and lower alkyl or R₄ and R₅ are joined to form a five or six-membered ring, (b') an ester having the formula,

O

I I CH₂— C— OR₆

I

R7 where R₆ and R7 are independently of each other lower alkyl and R₇ is additionally H and lower alkoxy;

(c') ortho-, meta-, or para- dimethyl benzene; (d¹) N-methyl pyrrolidone;

(e') Solvesso solvent;

(f) a petroleum hydrocarbon;

(g') a lactone of the formula;

O C=O \ /

(lower alkylene) and

(h¹) a mixture of any of the foregoing.

57. The composition as defined in claim 56 wherein said stabilizing solvent is acetone.

58. The composition as defined in claim 56 wherein said ester (b') comprises an acetate selected from the group consisting of methylacetate, ethylacetate, butylacetate, methoxypropyl acetate, or a mixture of any of the foregoing acetates.

59. The method as defined in claim 56 wherein said polyol is one having the formula

H(OCHCH)pOH where p is an integer of 1 to 14 and R₈ and R₉ are independently of each other H and lower alkyl.

60. The composition as defined in claim 59 wherein said polyol is one where p is equal to 1 to 3.

61. The method as defined in claim 60 wherein said polyol is one selected from the group consisting of ethylene giycol, propylene giycol. 1-3-butylene giycol, 1-4-butylene giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

62. The method as defined in claim 61 wherein said stabilizing solvent comprises acetone

and said polyol comprises a mixture of ethylene giycol and propylene giycol.

63. The method as defined in claim 62 wherein said oligomeric amino benzoic acid amide has the formula.

o o

// i l

H₉N- C- 0-(CH₂CH₂CH₂CH₂CH O)_rr— C-NH₂

with a molecular weight of 1238, and where m is an integer of 1 to 14.

64. The composition as defined in claim 54 wherein said stabilizing carrier comprises a stabilizing solvent and a polyol.

65. The method as defined in claim 64 wherein said stabilizing solvent is selected from the group consisting of

(a') an aldehyde or ketone of the formula,

O

I I R₅— C— ₄

where R and R₅ are independently of each other hydrogen and lower alkyl or R and R₅ are joined to form a five or six-membered ring, (b^!) an ester having the formula, O

CH₂— C— OR₆

I

R₇

where R₆ and R7 are independently of each other lower alkyl and R7 is additionally H and lower alkoxy;

(c¹) ortho-, meta-, or para- dimethyl benzene;

(d') N-methyl pyrrolidone; (e') Solvesso solvent;

(f) a petroleum hydrocarbon; (g') a lactone of the formula;

0 C=O

\ / (lower alkylene) and

(h¹) a mixture of any of the foregoing.

66. The composition as defined in claim 64 wherein said stabilizing solvent is acetone.

67. The composition as defined in claim 64 wherein said ester (b') comprises an acetate selected from the group consisting of methylacetate, ethylacetate, butylacetate, methoxypropyl acetate, or a mixture of any of the foregoing acetates.

68. The method as defined in claim 64 wherein said polyol is one having the formula

R₈ R₉

I I

H(OCHCH)pOH

where p is an integer of 1 to 14 and R₈ and R₉ are independently of each other H and lower alkyl.

69. The composition as defined in claim 68 wherein said polyol is one where p is equal

to 1 to 3.

70. The method as defined in claim 69 wherein said polyol is one selected from the group consisting of ethylene giycol, propylene giycol. 1-3-butylene giycol, 1-4-butylene giycol, 2-3-butylene giycol and a mixture of any of the foregoing glycols.

71. The method as defined in claim 70 wherein said stabilizing solvent comprises acetone and said polyol comprises a mixture of ethylene giycol and propylene giycol.

72. The method as defined in claim 71 wherein said oligomeric amino benzoic acid amide has the formula. o o

//

H₉N- C-0-(CH₂CH₂CH₂CH₂CH₂-0)_rr— C-NH₂

with a molecular weight of 1238, and where m is an integer of 1 to 14.