IL166744A - Polyurethane/urea compositions - Google Patents

Description

Polyurethane/urea compositions Kenneth I.Sawyer C. 158447 Divisional application of IL 129583/99 Polyurethane/urea Compositions FIELD OF THE INVENTION The present invention relates to water activated single component polyurethane/urea compositions which are storage stable. Cured composition gives polyurethane/urea resin haying excellent properties.

Further, the present invention relates to the use of the compositions of the present invention for the production of anticorrosive paints, floor repairing materials, water proof materials, adhesives, wall covering materials and caulking materials.

BACKGROUND OF THE INVENTION' Polyurethane/urea resins have excellent properties -such as rubber elasticity, abrasion resistance and service life, and hence has been particularly used in recent years for acticorrosive paints, floor repairing materials, water proof materials, adhesives, wall covering materials, and caulking materials.

Methods , for the preparation of polyurethane/urea resins are essentially divided into two groups: two-component method and one component method.

In the two-component method an organic polyisocyanate or modified or blocked polyisocyanate and polyamine and/or polyol are mixed at the time of application on site to cause cure. In the two .component type composition curing speed can be easily controlled, but it is required to measure each component exactly in site, to mix the two components until a uniform mixture is obtained and to use up the mixture within. the pot life. A disadvantage of this process is that often under difficult conditions on construction sites one must work with complicated and expensive mixing units. 01584473X25-01 In the one component method, a polyurethane/urea composition may be cured by atmospheric moisture after application in site. One component type polyurethane/urea is easier to use and this method has recently attracted much attention. The one component type polyurethane/urea composition is referred to as a moisture curable polyurethane/urea and the following compositions have been known in the art: (1) Moisture curable polyurethane compositions by using a reaction of polyisocyanate with moisture (water). In this process a part of isocyanate is converted to amine by the decarboxylation of isocyanate water adduct and the resultant amine reacts with another polyisocyanate molecule to progress curing.

Although, composition of type (1), has a relatively good storage stability in a sealed vessel, they have a markedly poor curing ability and a disadvantage of foaming. Amine or tin catalysts may be incorporated in order to improve curing ability. The additives, however, lower storage stability of the compositions, accelerates foaming and cause problems in actual use. (2) British Patent 1064841 and US Patent 4720535 describe moisture curable polyurethane compositions composed of sterically hindered polyaldimine or polyketimine and polyisocyanate or blocked polyisocyanate. These systems, however, have a disadvantage for practical use, because the curing process may be too long to establish a balance of performance between curability and storage stability.

In view of the prior art, it is strongly desired to develop a moisture curable polyurethane composition which is excellent in storage stability in sealed containers, i.e., capable of being stored under constant viscosity for a long period, rapidly curable without bubble formation in the presence of moisture, and outstanding mechanical strength after curing.

SUMMARY OF THE INVENTION An object of the present invention is to provide a moisture curable polyurethane composition which is excellent in storage stability, has good curing properties, and can be used for various applications. Another object of the invention is to provide a water proof material, flooring material, sealing material, wall covering material and paint comprising the composition.

As a result of an intensive investigation in order to solve the above problems, the present inventors have found a method for hydrolysing a polyaldimine which is derived from an aromatic aldehyde compound and the like with atmospheric moisture to obtain a readily reactive polyamine. By this method curing ability, mechanical strength, and storage stability of the moisture curable polyurethane/urea compositions are improved. Thus, various polyurethane/urea compositions can be'developed.

Thus, the present invention provides a moisture curable, storage stable, single component polyuretane/urea composition comprising: (i) oligomeric polyaminobenzoates or polyaminobenzamides wherein at least one of its aromatic amino groups is blocked by reaction with an aldehyde; and (ii) organic polyisocyanate or blocked organic polyisocyanate, and optionally (iii) a catalyst for accelerating curing, auxiliary agents and/or additives The moisture curable polyurethane/urea composition wherein the said storage stability in hermetically closed package exceeds 6 months at room temperature.

The oligomeric polyaminobenzoates or polyaminobenzamides used in the composition of the invention are selected from a group consisting of compounds of formula [1] : [1] wherein n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -O- or -N(R)-; 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 200 to about 6,000; R is hydrogen, CpC2o alkyl, [(Ci-C20 Alkoxy)aryl]methyl, or [(Ci-C20 Alkyl)aryl]methyl; More preferably, the ' oligomeric polyaminobenzoates used in the present invention are selected from polytetramethyleneglycol-di-p-aminobenzoates, polyethyleneglycol-di-p-aminobenzoates and polypropyleneglycol-di-p-aminobenzoates.

The aldehydes used to block at least one of the aromatic amino groups of the oligomeric polyaminobenzoates or polyamino-benzamides preferably have a boiling point higher than 180 °C and is selected from the group consisting of aromatic, heterocyclic, sterically hindered and long chain aldehydes.

Examples of aromatic aldehydes are those represented by the formula [2] : wherein R1, R2 and R3 are selected from hydrogen, halogen, Ci-C20 alkyl, Ci-C20 alkoxy, acyloxy, acylamino, and C1-C20 alkylthio; Examples of sterically hindered aldehydes are those represented by the formula [3] [3] wherein R4 is aryl, substituted aryl, C1-C20 alkyl, aralkyl, hydrogen; R5, R6 are C,-C6 alkyl; X is a covalent bond or selected from the group consisting of-O-, -CH2- -S-, -NHCOO-, -NHCONH-, -CO H-, -CONR5- -COO-; More specific examples of aldehydes used in the present invention are benzaldehyde, furfural, anisaldehyde, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde and dimethylbenzaldehyde.

Examples of polyisocyanates used in the compositions of the present invention are carbodiimide modified polyisocyanate, biuret modified polyisocyanate, isocyanurate, modified polyisocyanate or urethane modified polyisocyanate. The polyisocyanates may be derived from sterically hindered isocyanates and isocyanate-ended polyurethane/urea prepolymer.

More preferably, the polyisocyanates are represented by the formula [4] [4] wherein R7 and R8 are hydrogen, Ci-C6 alkyl or haloalkyl; R9, R10 R1 1, R12 are hydrogen, halogen, C|-C6 alkyl or Ci-C6 alkoxy.

The compositions of the invention may optionally comprise a catalyst for accelerating curing, such as for example protic acids or salts thereof or phosphate esters.

Protic acids are those selected from the group consisting of carboxylic acids, preferably aromatic carboxylic acids, sulfonic acids and phosphoric acids.

The present invention further provides a moisture curable polyurethane/urea caulking, sealing, wall covering material or paint, adhesive, water proof or flooring material, comprising the above composition.

According to another aspect, the present invention provides novel oligomeric polyaminobenzoates or polyaminobenzamides of formula [1] : [1] wherein at least one of its aromatic amino groups is blocked by reaction with aldehyde; n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -0- or -NR-; 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 200 to about 6,000; R is hydrogen, Ci-C2o alkyl, [(Ci-C2o Alkoxy)aryl]methyl, or [(Ci-C20 Alkyl)aryl]methyl.

DETAILED DESCRIPTION OF THE INVENTION The moisture curable polyurethane/urea composition of the present invention comprises polyaldimine/amine and organic polyisocyanate or blocked organic polyisocyanate.

Polyaldimine/amines for use in the invention are oligomeric polyaminobenzoates or polyaminobenzamides wherein at least one of its aromatic amino groups is blocked by reaction with an aldehyde.

Preferably, the polyaminobenzoates or polyaminobenzamides are compounds represented by the formula [1] n is an integer from 2 to 4, preferably is selected from 2 or 3, more preferably 2; . each k is one or two, preferably one; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted, preferably para-aminosubstituted; each Z is -O- or -NR-, preferably -0-; G is an n-valent radical, obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine. Preferably the divalent G group is a group derived from polyoxyalkylene glycols obtained by addition polymerization of tetrahydrofuran, propylene oxide and/or ethylene oxide to water, 1,4-butanediol, ethylene glycol or propylene glycol. A trivalent G group is a group derived from polyoxyalkylene triols obtained by addition polymerisation of tetrahydrofuran, propylene oxide and/or ethylene oxide to glycerol or trimethylolpropane and is selected from the group of polytetramethyleneglycols, polyethyleneglycols or polypropyleneglycols.

Preferably, a divalent or trivalent polyoxyalkylene group has a molecular weight of from about 200 to about 6,000, more preferably from 250 to 4,000. R is hydrogen, Ci-C20 alkyl, [(C1-C20 Alkoxy)aq]methyl or [(Q-C20 Alky l)aryl] methyl .

Preferably, said polyaldimine/amine of formula [1] is selected from the group of polyaldimines of polytetramethyleneglycol-di-p-aminobenzoates, polyethyleneglycol-di-p-aminobenzoates, polypropyleneglycol-di-p-aminobenzoates.

The polyaldimine can be prepared by reacting polyaminobenzoates or polyaminobenzamides with aldehydes.

The aldehydes which react with said polyaminobenzoates or polyaminobenzamides are preferably selected from the group consisting of aromatic, heterocyclic, sterically hindered and long chain aldehydes.

Preferably, the said aromatic aldehydes are represented by the formula [2] : [2] wherein R1, R2 and R3 are hydrogen , halogen, Cj-C2o alkyl, C1-C20 alkoxy, acyloxy, acylamino, or C1-C20 alkylthio.

Preferably,, the said sterically hindered aldehydes are represented by the formula [3] [3] wherein R4 is hydrogen or selected from the group consisting of aryl, substituted aryl, Ci-C20 alkyl or aralkyl; R5 and R6 are C C6 alkyl; X is a covalent bond or selected from -0-, -CH2-, -S-, -NHCOO-, -NHCONH-, -CONH-, -CONR5- or -C00-.

More preferably the aldehydes are selected from the group consisting of benzaldehyde, anisaldehyde, furfural, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, dimethylbenzaldehyde.

The blocked polyaminobenzoates or polyaminobenzamides of the present invention may be prepared by the following procedure: The above described polyaminobenzoate or polyaminobenzamide is heated with an aldehyde to allow dehydration reaction and water generated by the reaction is distilled out azeotropically or absorbed by molecular sieves or reacted with water sponger. These reactions could be carried out with or without solvent. After completion of the reaction the solvent is distilled off from the reaction mixture to obtain the desired aldimine.

The said water sponger could be organic mono- or polyisocyanate.

The composition of the present invention consists of the mixing of the above aldimine with organic polyisocyanate or blocked organic isocyanate.

Preferably the said polyisocyanate . is carbodiimide modified polyisocyanate, biuret modified polyisocyanate, isocyanurate modified polyisocyanate or urethane modified polyisocyanate.

Preferably the said polyisocyanate is derived from a sterically hindered isocyanate.

More preferably the said polyisocyanate is represented by the formula [4] wherein R7 and R8 are hydrogen, Ci-C6 alkyl or haloalkyl; R9, R10 R11, R12 are hydrogen, halogen, Ci-C6 alkyl or d-C6 alkoxy.

Most preferably the said polyisocyanate is an isocyanate-ended polyurethane/urea prepolymer. These prepolymer which has a plurality of isocyanate groups and can be used for the invention is prepared by reacting the above organic polyisocyanate compound with a known polyol, known polyamine and other known compounds having two or more active hydrogens in a molecule. Free isocyanate groups are remained in the polyurethane prepolymer.

The moisture curable polyurethane composition of the invention can be prepared by mixing the polyaldimine with the polyisocyanate and/or the polyurethane prepolymer containing the isocyanate groups.

The ratio of the number of amino groups in the polyamine formed by the hydrolysis of polyaldimine to the number of isocyanate groups contained in the above described polyisocyanate and/or the polyurethane prepolymer having the isocyanate groups is from 0.5 to 2.0, preferably from 0.7 to 1.5.

The moisture^ curable polyurethane composition of the present invention which is prepared by the above described process can be employed intact for various uses such as sealing materials, wall covering materials, paints and adhesives.

Further, in order to control viscosity, resin properties and service life depending upon the uses, fillers, thixotropic agents, plasticizers, adhesion improvers, colorants, stabilizers and catalysts for curing acceleration can be incorporated into the moisture curable polyurethane composition of the invention.

In the preparation of water proof materials and flooring materials, fillers are preferably added to the moisture curable polyurethane composition consisting of the above polyaldimine and the above polyisocyanate and/or the polyurethane prepolymer having isocyanate groups.

Useful fillers include, for example, calcium carbonate, talc, kaolin, aluminum sulfate, ziolite, diatomaceous earth, polyvinyl, chloride paste resin, glass balloon and polyvinylidene chloride resin balloon. The fillers are used in the range of 60 % by weight or less, preferably from 20 to 60 % by weight of the composition. In the case of preparing the sealing materials and wall covering materials, thixotropic agents are preferably added to the moisture curable polyurethane composition consisting of the above polyaldimine and the above polyisocyanate and/or the polyurethane prepolymer having isocyanate groups.

Exemplary thixotropic agents which can be used for the invention include colloidal silica, fatty acid amide wax, aluminum stearate, surface treated bentonite, polyethylene short fiber, and phenol resin short fiber. The thixotropic agents are blended in the range of from 0.2 to 15 % by weight, preferably from 0.5 to 10 % by weight of the composition.

Representative plasticizers for use in the invention include, for example, dioctyl phthalate, dibutyl phthalate, dilauryl phthalate, butyl benzyl phthalate, dioctyl adipate, diisodecyl adipate, diisodecyl phthalate and trioctyl phosphate. The plasticizers can be blended in the range of 50 % by weight or less, preferably from 0 to 40% by weight of the composition.

Suitable solvents for use in the invention include, for example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; petroleum base solvents from gasoline to kerosene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and ether esters such as cellosolve acetate and buy cellosolve acetate and butiryl cellosolve acetate.

The solvents can be used in the range of 50 % by weight or less, preferably from 0 to 40% by weight of the composition.

Exemplary adhesion improvers which can be preferably used in the invention include known silane coupling agents. The adhesion improvers can be used in the range of 5% by weight or less, preferably from 0.05 % to 2 % by weight of the composition.

Carbon black, titanium white, chromium oxide, iron oxide red and other colorants can be blended in the range of preferably from 0.1 % to 5 % by weight of the composition. Sterically hindered phenol compounds, triazol compounds and other stabilizers can be added in the range of from 0.1 to 2% by weight of the composition.

Further, catalysts for curing acceleration can also be blended in the polyurethane composition of this invention. Preferred curing acceleration catalysts include protic acids and phosphate esters. Preferably, the said protic acids are carboxylic, sulfonic or phosphonic acids. The amount of these catalysts is in the range of preferably from 0.05 to 5% by weight of the composition.

No particular restriction is imposed on the method of blending these components. Simple mixing or mixing by other known methods can be arbitrarily carried out. For example, the filler, plasticizers, thixo tropic agent and other necessary additives are blended in a mixer such as a planetary mixer or a dissolver. Then the organic polyisocyanate and/or the prepolymer having isocyanate groups and polyaldimine are added into the mixer and thoroughly mixed.

When the additives have high moisture content, these additives must previously be dehydrated or addition of a dehydrating agent such as zeolite is required.

The moisture curable polyurethane composition thus obtained can be used immediately, or can also be stored by packing in a sealed container under a nitrogen atmosphere. In such a case, the composition has very good storage stability and has high retention of physical properties and good stability of viscosity even it stored at increased temperatures. On the other hand, when the seal is broken, the composition is rapidly cured by exposing to the atmospheric moisture. Poreless solid polyurethane/urea products having excellent mechanical strengths can thus be obtained, which property is quite different from conventional, moisture curable polyurethane.

The moisture curable polyurethane/urea composition of the invention is excellent in curing ability and also in storage stability for a long period. The composition provides sealing materials, wall covering materials, water proof materials, flooring materials, paints and adhesives depending upon the object for use. These materials have also excellent storage stability and workability, and can be rapidly cured by atmospheric moisture on application in site.

Further, the cured products have high modulus and excellent strength.

The invention will be further described with the aid of the following non-limiting examples.

Example 1 Preparation of polyaminobenzoates and polyaminobenzamides blocked by reaction with aldehyde.

Polyaminobenzoate or polyaminobenzamide and aldehyde were condensed in an inert solvent until expected amount of water had separated in a water collecting device. Following this the mixture was evaporated under vacuum.

For determining the aldimine content the obtained residue was dissolved in. acetic acid then titrated with 0.1 N perchloric acid in dioxane. In addition, the samples were characterized using Ή NMR and IR spectra.

The initial materials used and the resulting aldimines are summarized in Table 1.

Table 1 - ratio (mol/mol) between Aldehyde and Polyamine quantity ** P-2000 is Polyamine 2000 P- 1000 is Polyamine 1000 P-650 is Polyamine 650 P-400 is Polyamine 400 P-250 is Polyamine 250 Polyamine is a synonym of a-(4-aminobenzoyl)-u)-[(4- aminobenzoyl)oxy]poly(oxy-l,4-butanediyl).

Example 2 Preparation of polyaminobenzoates and polyaminobenzamides blocked by reaction with aldehyde in the presence of molecular sieves.

Mixture of polyaminobenzoate or polyaminobenzamide, aldehyde, molecular sieves and inert solvent was stirred under argon for from 1 to 3 days at room temperature. The obtained mixture was filtered and evaporated under reduced pressure.

The initial materials used and the resulting aldimines are summarized in Table 2 below: Table 2 Example Polyaminobenzoate or Aldehyde mol*/ Aldimine Polyaminobenzamide mol 2a P-2000** 4-Tolualdehyde 3.0 ALD-9 2b P-1000 4-Anisaldehyde 2.5 ALD-10 2c P-650 3,4-Dimethoxybenzaldehyde 2.5 ALD-11 2d P-400 4-Dodecycloxybenzaldehyde 2.5 ALD-12 2e P-250 4-Isopropylbenzaldehyde 2.5 ALD-13 Example 3 Preparation of a single component polyurethane/urea system Polyisocyanate or blocked polyisocyanate was mixed together with such a quantity of aldimine prepared according to Example 1 or 2 while stirring at room temperature, so that the ratio of -NCO/ to amino and aldimino groups was 1.2. Following this flask was filed with nitrogen and curing catalyst was added to the mixture.

The mixture was applied to a glass plate with a thickness of 0.5 mm and allowed to stand at 25 °C under relative humidity of 50 % for 12 hours and a coated film was tested by pencil hardness, After storage for 14 days at 50 °C it was found that the properties of the mixture had undergone little change.

The polyisocyanates alone was treated by the same procedures as above. No surface curing was observed after 24 hours.

Table 3 Composition of the single component polyurethane/urea system and properties of cured films.

* Isonate® 2143 (obtained from Dow Chemical Co.) is modified MDI with 29.2% NCO content by weight.

Example 4 - Comparative example Preparation of a single component polyurethane/urea system.

Polyaminobenzoate or polyaminobenzamide, aldehyde, curing catalyst (0.2 ÷ 1.0 w/w %) and plasticizer (10 ÷ 20 w/w %) were mixed in an inert solvent and the obtained mixture was kept 2 hours at room temperature, Polyisocyanate was added to the mixture while stirring at room temperature, so the ratio of NCO to amino groups was 2.0. The obtained mixture was evaporated under reduced pressure.

After storage for 14 days at 50 °C it was found that the mixture was gelated.

Claims (28)

1. A moisture curable, storage stable, single component polyurethane/urea composition comprising (i) polyaminobenzoates or polyaminobenzamides of formula [1] : wherein at least one of the aromatic amino groups is blocked by reaction with aldehyde; n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -0- or -N -; G is a 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 200 to about 6,000; and R is hydrogen or selected from the group consisting of Ci-C20 alkyl, [(Ci-C20 Alkoxy)aryl]methyl and [(Ci-C20 Alkyl)aryl]methyl; (ii) organic polyisocyanate or blocked organic polyisocyanate; and optionally (iii) a catalyst for accelerating curing, auxiliary agents and/or additives.

2. A composition according to claim 1 wherein said storage stability in a hermetically sealed package exceeds 6 months at room temperature.

3. A composition according to claim 1 wherein said polyaminobenzoate is selected from the group consisting of polytetramethyleneglycol-di-p-aminobenzoates, polyethyleneglycol-di-p-aminobenzoates and polypropyleneglycol-di-p-aminobenzoates. 01584473V23-01 IL 166744/2 18

4. A composition according to claim 1 wherein said aldehyde is selected from the group consisting of aromatic, heterocyclic, sterically hindered and long chain aldehydes.

5. A composition according to claim 1 wherein said aldehyde has a boiling point higher than 180°C.

6. A composition according to claim 5 wherein said aromatic aldehyde is represented by the formula [2]: wherein R1, R2 and R3 are hydrogen, halogen, Ci-C20 alkyl, Ci-C20 alkoxy, acyloxy, acylamino, or C|-C2o alkylthio.

7. A composition according to claim 5 wherein said sterically hindered aldehyde is represented by the formula [3] wherein R4 is aryl, substituted aryl, Ci-C20 alkyl, aralkyl, or hydrogen; R5 and R6 are Ci-C6 alkyl; and X is a covalent bond or is selected from the group consisting of -0-, -CH2- -S-, -NHCOO- -NHCONH-, -CONH-, -CONR5- and -COO-.

8. A composition according to claim 1 wherein said aldehyde is selected from the group consisting of benzaldehyde, anisaldehyde, furfural, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde and dimethylbenzaldehyde. 01584473\23-01 IL 166744/2 19

9. A composition according to claim 1 wherein said polyisocyanate is carbodiimide modified polyisocyanate, biuret modified polyisocyanate, isocyanurate modified polyisocyanate or urethane modified polyisocyanate.

10. A composition according to claim 1 wherein said polyisocyanate is derived from a sterically hindered isocyanate.

11. 1 1. A composition according to claim 1 wherein said polyisocyanate is represented by the formula [4] wherein R7 and R8 are hydrogen, Ci-C6 alkyl, or haloalkyl; and R9, R10, Ru, and R12 are hydrogen, halogen, Ci-C6 alkyl, or Ci-C6 alkoxy.

12. A composition according to claim 1 wherein said polyisocyanate is an isocyanate-ended polyurethane/urea prepolymer.

13. A composition according to claim 1 wherein said catalyst for curing acceleration is selected from the group consisting of protic acids or salts thereof or phosphate esters.

14. A composition according to claim 14 wherein said protic acid is selected from the group consisting of carboxylic, sulfonic or phosphoric acids.

15. A composition according to claim 15 wherein said carboxylic acid is an aromatic carboxylic acid. 01584473X23-01 IL 166744/2 20

16. A composition according to claim 1 wherein said auxiliary agents and/or additives are selected from the group consisting of fillers, thixotropic agents, plasticizers, adhesion improvers, colorants, stabilizers, and solvents.

17. A moisture curable polyurethane/urea caulking, sealing, wall covering material or paint, adhesive, water proof or flooring material, comprising the composition of claim 1 .

18. Polyaminobenzoates or polyaminobenzamides of formula [1] : wherein at least one of the aromatic amino groups is blocked by reaction with aldehyde; n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -O- or -NR-; 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 200 to about 6,000; and R is hydrogen or is selected from the group consisting of Ci-C20 alkyl, [(Ci-C20 Alkoxy)aryl]methyl and [(Ci-C20 Alkyl)aryl]methyl.

19. Polyaminobenzoates or polyaminobenzamides according to claim 1 8, wherein said aldehyde is selected from the group consisting of benzaldehyde, anisaldehyde, furfural, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, and dimethylbenzaldehyde. 01 584473X23-01 1L 166744/2 21

20. A method for preparing a moisture curable, storage stable, single component polyurethane/urea composition comprising mixing (i) polyaminobenzoates or polyaminobenzamides of formula [1]: wherein at least one of the aromatic amino groups is blocked by reaction with aldehyde; n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -O- or -NR-; G is a 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 200 to about 6,000; and R is hydrogen or selected from the group consisting of C1-C20 alkyl, [(Ci-C20 Alkoxy)aryl] methyl and [(C1-C20 Alkyl)aryl]methyl; (ii) organic polyisocyanate or blocked organic polyisocyanate; and optionally (iii) a catalyst for accelerating curing, auxiliary agents and/or additives.

21. The method of claim 20, wherein said polyisocyanate is an aromatic polyisocyanate and/or a polyurethane/urea prepolymer having terminal aromatic isocyanate groups.

22. The method of claim 20, wherein said aldehyde is selected from the group consisting of benzaldehyde, anisaldehyde, furfural, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, and dimethylbenzaldehyde. 01584473X23-01 IL 166744/2 22

23. The method of claim 20, wherein said catalyst for curing acceleration is selected from the group consisting of protic acids or salts thereof or phosphate esters.

24. The method of claim 20, wherein said auxiliary agents and/or additives are selected from the group consisting of fillers, thixotropic agents, plasticizers, adhesion improvers, colorants, stabilizers, and solvents.

25. A method of preparing a polyaldimine comprising: reacting polyaminobenzoates or polyaminobenzamides of having the formula [1] with an aldehyde; wherein in formula [1], n is an integer from 2 to 4; each k is one or two; each benzoyl nucleus is para, meta, or di-meta-aminosubstituted; each Z is -O- or -NR-; 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 200 to about 6,000; and R is hydrogen or is selected from the group consisting of C-|C20 alkyl, [(Ci-C20 Alkoxy)aryl]methyl and [(Ci-C20 Alkyl)aryl]methyl.

26. The method of claim 25, wherein said aldehyde is selected from the group consisting of aromatic, heterocyclic, sterically hindered and long chain aldehydes.

27. The method of claim 26, wherein said aldehyde is selected from the group consisting of benzaldehyde, anisaldehyde, furfural, ethoxybenzaldehyde, butoxybenzaldehyde, hexyloxybenzaldehyde, octyloxybenzaldehyde, decyloxybenzaldehyde, dodecyloxybenzaldehyde, hexadecyloxybenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, and dimethylbenzaldehyde.

28. An article of manufacture comprising a metal or non-metal substrate having the composition of any one of claims 1 -16 applied thereto. 01584473\23-01 For the Applicants REINHOLD CO H.N AND PARTNERS