Method for producing functionalized polyesters

Abstract

The present application is directed to a method for preparing an amino-functional polyester, said method comprising: providing a mixture comprising at least one lactone monomer, a catalyst and a polyamine having at least one primary and at least one secondary amine group; and, subjecting said mixture to ring-opening polymerization conditions.

Claims

1. A method for preparing an amino-functional polyester, said method comprising: providing a mixture comprising at least one lactone monomer, a catalyst and a polyamine having at least one primary and at least one secondary amine group; and, subjecting said mixture to ring-opening polymerization conditions, wherein the catalyst is 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU) or both.

2. The method according to claim 1, wherein said mixture comprises at least one lactone monomer conforming to Formula (1): ##STR00007## wherein: n1; each R is independently selected from the group consisting of hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkoxy and C6 aryl with the proviso that at least n R's are hydrogen.

3. The method according to claim 2, wherein said mixture comprises at least one lactone monomer conforming to Formula (1a): ##STR00008## wherein: n is an integer of from 1 to 4; and, each R is independently selected from the group consisting of hydrogen and C1-C6 alkyl, with the proviso that at least n+2 R's are hydrogen.

4. The method according to claim 1, wherein said mixture comprises at least one lactone monomer selected from the group consisting of: p-propiolactone; -butyrolactone; -valerolactone; -butyrolactone; -valerolactone; -valerolactone; monomethyl--valerolactone; monoethyl--valerolactone; monohexyl--valerolactone; -caprolactone; monomethyl--caprolactone; monoethyl--caprolactone; monohexyl--caprolactone; dimethyl--caprolactone; di-n-propyl--caprolactone; di-n-hexyl--caprolactone; trimethyl--caprolactone; triethyl--caprolactone; pivalolactone; and, 5-methyloxepan-2-one.

5. The method according to claim 1, wherein said mixture comprises, based on the total weight of monomers: from 80 to 100 wt. % of said at least one lactone monomer; and, from 0 to 20 wt. % of at least one co-monomer selected from the group consisting of: epoxide compounds; cyclic carbonates; glycolide; and lactide.

6. The method according to claim 1, wherein said polyamine is aliphatic or cycloaliphatic.

7. The method according to claim 1, wherein said polyamine has at least two primary amine groups and at least one secondary amine group.

8. The method according to claim 1, wherein a molar ratio of lactone monomer to polyamine is in the range from 1:1 to 500:1.

9. The method according to claim 1, wherein said catalyst comprises 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU).

10. The method according to claim 1, wherein said catalyst is provided in an amount of from 0.1 to 5 wt. %, based on the total weight of monomers.

11. The method according to claim 1, wherein said mixture subjected to ring-opening polymerization conditions is essentially free of solvent.

12. The method according to claim 1, wherein said ring-opening polymerization conditions comprise a temperature of from 50 to 200 C.

13. An amino-functional polyester obtained by the method of claim 1 having at least one terminal hydroxy group.

14. An amino-functional polyester obtained by the method of claim 1, said polyester having at least one of: i) a weight average molecular weight (Mw) of from 300 to 5000 g/mol; ii) a polydispersity index of less than 2.5; iii) an amine value (NHv) of from 20 to 350 mg KOH/g; iv) a total hydroxyl and amine value (OHv+NHv) of from 40 to 500 mg KOH/g.

15. A curable coating, adhesive or sealant composition comprising: an amino functional polyester as defined in claim 14; and, at least one multifunctional compound (H) having at least two functional groups (F) selected from the group consisting of: epoxy groups; isocyanate groups; and cyclic carbonate groups.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 appended hereto is a chromatogram obtained from the Gel Permeation Chromatographic (GPC) analysis of polyesters prepared in accordance with an embodiment of the present invention.

(2) FIG. 2 appended hereto is a comparative chromatogram obtained from the Gel Permeation Chromatographic (GPC) analysis of polyesters prepared in accordance with the disclosure of US 20100179282A1 (Evonik Degussa).

DETAILED DESCRIPTION OF THE INVENTION

(3) As described herein before, the present invention provides a method for preparing an amino-functional polyester, said method comprising: providing a mixture comprising at least one lactone monomer, a catalyst and a polyamine having at least one primary and at least one secondary amine group; and, subjecting said mixture to ring-opening polymerization conditions.

(4) There is no specific intention to limit the lactone compounds which may be used in the present invention as monomers, provided the compounds can undergo ring-opening polymerization in the presence of a catalyst. Generally, however, suitable lactone monomers will conform to the general Formula (1) herein below:

(5) ##STR00003## wherein: n1; i. each R is independently selected from the group consisting of hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkoxy and C6 aryl with the proviso that at least n R's are hydrogen.

(6) Preferred lactone monomers conforming to Formula (1) are characterized by the limitations: n is an integer of from 1 to 4; and, each R is independently selected from the group consisting of hydrogen and C1-C6 alkyl, with the proviso that at least n+2 R's are hydrogen.

(7) As exemplary lactone monomers, which may be used alone or in combination, may be mentioned: -propiolactone; -butyrolactone; -valerolactone; -butyrolactone; -valerolactone; -valerolactone; monomethyl--valerolactone; monoethyl--valerolactone; monohexyl--valerolactone; -caprolactone; monomethyl--caprolactone; monoethyl--caprolactone; monohexyl--caprolactone; dimethyl--caprolactone; di-n-propyl--caprolactone; di-n-hexyl--caprolactone; trimethyl--caprolactone; triethyl--caprolactone; pivalolactone; and, 5-methyloxepan-2-one.

(8) In addition to the aforementioned lactones, further co-monomers may be included in the polymerization mixture in an amount up to 20 wt. %, based on the total weight of monomers. When present said co-monomers should desirably be selected from the group consisting of: epoxide compounds, such as glycidyl ethers, monoepoxides of dienes and polyenes, glycidyl esters and alkylene oxides; cyclic carbonates; glycolide; lactide; and, combinations thereof.

(9) Non-limiting examples of suitable epoxide compounds which may be used as co-monomers include: ethylene oxide; propylene oxide; butylene oxide; 3,4-epoxy-1-pentene; styrene oxide; vinyl glycidyl ether; isopropenyl glycidyl ether; butadiene monoxide; and, phenyl glycidyl ether. A preference for ethylene oxide and/or propylene oxide might be mentioned.

(10) Non-limiting examples of suitable cyclic carbonates include those represented by:

(11) ##STR00004## wherein: f and g are integers of from 1 to 3; i. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected for each carbon unit (i.e., for each (C).sub.f and (C).sub.g unit) from hydrogen, C1-C6 alkyl, C6-aryl or OC.sub.6H.sub.5; ii. h is 0 or 1; and, iii. E is O.

(12) As specific examples of suitable cyclic carbonate co-monomers may be mentioned: trimethylene carbonate (TMC); tetramethylene carbonate (TEMC); pentamethylene carbonate (PMC); and, 1,2-propanediol carbonate.

(13) The ring opening polymerization of the present invention involves the use, as an initiator, of a polyamine having: at least one and preferably at least two primary amine groups; and, at least one secondary amine group. In principle, all polyamines which meet this condition of possessing such amine groups of different reactivity are suitable. The polyamine initiator may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic. A preference for aliphatic and/or cycloaliphatic polyamines might be mentioned, however.

(14) Without intention to limit the present invention, exemplary polyamines containing at least one primary and at least one secondary amino group include: N-methylethylenediamine; N-ethylethylenediamine; N-propylethylenediamine; N-butylethylenediamine; N-benzylethylenediamine; N-phenylethylenediamine; N-methylpropylenediamine; N-ethylpropylenediamine; N-propylpropylenediamine; N-butylpropylenediamine; N-benzylpropylenediamine; N-phenylpropylenediamine; N-hydroxyethylethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; pentaethylenehexamine; bishexamethylenetriamine; N-cyclohexylpropylenediamine; and, N-[3-(tridecyloxy)propyl]-1,3-propanediamine (Adogen 583).

(15) It is here mentioned that a preference exists for aliphatic and/or cycloaliphatic polyamines, both in general and with regard to the above-mentioned list of exemplary polyamines.

(16) The proportion of lactone monomer to initiator in the process may vary widely depending upon the particular properties desired in the polyester or in the products to be derived there from. Obviously where the polyester is to have substantially the properties of a product having a succession of lactone residues, the proportion of initiator to lactone may be very small, in as much as theoretically one molecule of initiator is sufficient to initiate the polymerization of an infinite number of lactone molecules. Conversely, and particularly where the initiator used is at least trifunctional and/or where it is desired that the polyester product be of a conjugated structure having a more or less alternating distribution of lactone residues, the relative proportions may be approximately equal.

(17) The above acknowledged, the molar ratio of lactone monomers to said polyamine initiator will generally be in the range from 1:1 to 500:1, will preferably be in the range from 2:1 to 50:1 and will more preferably be in the range from 2:1 to 20:1.

(18) As noted hereinbefore, the ring polymerization process of the present invention is performed in the presence of a suitable catalyst. An instructive reference on appropriate ionic or nonionic catalysts for the ring opening polymerization is Ring Opening Polymerization, Vol. I, pages 461-521, K. J. Ivin and T. Saegusa (1984). Known catalysts, which may be used alone or in combination, include but are not limited to: amine compounds or salts thereof with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamines, monoethanolamines, diethanolamines, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamines, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU); tin 2-ethylhexanoate (tin octanoate); tin dichloride (SnCl.sub.2); porphyrin aluminum complexes; (n-C.sub.4H.sub.9O).sub.4Al.sub.2O.sub.2Zn; composite metal cyanide; aqueous diethylzinc or diethylcadmium; aluminum triisopropoxide; titanium tetrabutoxide; zirconium tetrapropoxide; tributyltin methoxide; tetraphenyltin; lead oxide; zinc stearate; bismuth 2-ethylhexanoate; potassium alcoholate; antimony fluoride; and yttrium or lanthanide series rare earth metal based catalysts (coordination catalysts), such as described in U.S. Pat. No. 5,028,667.

(19) It is preferred herein that the catalyst is metal free. In particular, but without intention to limit the present invention, good results have been obtained where 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and/or 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU) have been employed as the polymerization catalyst.

(20) Whilst the determination of an appropriate catalytic amount of a compound is facile to a person of ordinary skill in the art, it is preferred that the polymerization catalyst be used in an amount of from 0.1 to 5 wt. %, for instance from 0.1 to 2.0 wt. %, based on the total weight of monomers.

(21) The ring-opening polymerization reaction can be initiated at room temperature. The exothermic nature of reaction will naturally elevate the temperature of the reactants. That said, the reaction temperature should be maintained in the range from 50 to 200 C., or from 60 to 150 C. If the maintained temperature is lower than 50 C., the reaction rate may be unfavorably low. On the other hand, if the maintained temperature is higher than 200 C., the polymer degradation rate is increased and low-molecular weight components can form and even vaporize.

(22) As is known in the art, the polymerization vessel may be dried and purged with an inert gassuch as nitrogen or argonbefore initiating the ring-opening polymerization reaction. Moreover, to obviate the formation of a discolored polyester product, either a partial vacuum or an inert atmosphere may be maintained in the reaction vessel during the polymerization: by effecting such a partial vacuum or by passing nitrogen or argon through the reaction mixture, the presence of oxygen in the reaction vessel can be precluded or minimized.

(23) The polymerization may be performed either in solution or in the melt without a solvent but in either case the vessel should be equipped with an effective stirrer, such as a mechanical stirrer: it has been observed that good stirring can drive the polymerization reaction to completion.

(24) It is preferred herein for the polymerization mixture to be essentially free of solvents: for completeness, this statement of preference includes the polymerization mixture being essentially free of water. However, if one elects to perform the polymerization in solution, suitable solvents should be non-reactive, essentially anhydrous, organic liquids capable of dissolving at least 1 wt. % and preferably over 10 wt. % of the amino functional polyester products at 25 C. And as suitable organic solvents there can be mentioned: aromatic hydrocarbons, such as toluene and xylene; aliphatic hydrocarbons, such as heptane and decane; alicyclic hydrocarbons, such as cyclohexane and Decalin; chlorinated hydrocarbons such as chloroform and trichloroethylene; esters, such as ethyl acetate and methyl butyrate; and, ethers, such as tetrahydrofuran (THF) and dioxane.

(25) The progress of the polymerization reaction can be monitored by Nuclear Magnetic Resonance (NMR) spectroscopy, with reaction completion being deemed to occur when signals associated with the initial lactones disappear completely. Depending upon the lactone monomer, it is considered that the reaction progress might also be monitored by: refractive index measurements, wherein the reaction may be regarded as complete as soon as the refractive index becomes constant; and, thermal analysis given that the reaction of the lactones promotes an exotherm such that the complete consumption of said lactones corresponds with the cooling down of the mixture. In any event, the polymerization reaction time will typically be from 0.1 to 10 hours, for example from 0.5 to 5 hours. If applicable and desired, a vacuum can be applied at an elevated temperaturesuch as from 120 to 160 C.to remove any unreacted monomer.

(26) Whilst this is not critical to its later application, the reaction product (hereinafter denoted as AF-PES) may be separated and purified using methods known in the art: mention in this regard may be made of extraction, evaporation, distillation and chromatography. Where it is intended that the (optionally purified) reaction product (AF-PES) be stored upon production, the polyesters should be disposed in a vessel with an airtight and moisture-tight seal.

(27) The polyesters obtained in accordance with this process are characterized by having at least one terminal hydroxyl group. The initiator is incorporated into the polyester structure, which polyester is thus further characterized by having secondary amine groups.

(28) In accordance with the preferred embodiments of the invention, the derived amino-functional polyester (AF-PES) is characterized by at least one of: a weight average molecular weight of from 300 to 5000 g/mol, preferably from 500 to 4000 g/mol; a polydispersity index of less than 2.5, preferably less than 2.3; an amine value (NHv) of from 20 to 350 mg KOH/g, preferably from 25 to 250 mg KOH/g; and, a total hydroxyl and amine value (or alkaline value, OHv+NHv) of from 40 to 500 mg KOH/g, preferably from 50 to 400 mg KOH/g.

(29) For completeness, it is noted that these limitations are not mutually exclusive and one, two, three or four of these characterizations may thus be applicable.

(30) Coating, Sealant and Adhesive Compositions

(31) The amino-functional polyesters (AF-PES) obtained using the process of the present invention can be employed as a reactive component of a curable coating, adhesive or sealant composition. The further reactant(s) of such compositions will generally be one or more multifunctional compounds (H) having at least two functional groups (F) selected from the group consisting of: (i) activated unsaturated groups, such as (meth)acryloyl groups; (ii) activated methylene groups, such as acetoacetate and malonate groups; (iii) epoxy groups; (iv) isocyanate groups; (v) aromatic activated aldehyde groups; (vi) cyclic carbonate groups; and, (vii) acid, anhydride and ester groups, including oxalate esters. Latent compounds, in which the functional groups (F) are blocked but which are activatable under specific physicochemical conditions, are also envisaged as suitable further reactants for the coating, adhesive or sealant compositions.

(32) No particular limitation is imposed on the number of functional groups (F) possessed by the (activated) compound (H): compounds having 2, 3, 4, 5, 6, 7, 8, 9 or 10 functional groups may be used, for instance. Moreover, the reactant compound (H) can be a low-molecular-weight substancethat is its molecular weight is less than 500 g/molor an oligomeric or polymeric substance that has a number average molecular weight (Mn) above 500 g/mol. And, of course, mixtures of compounds (H) may be used.

(33) In an embodiment of the coating, adhesive or sealant composition, the reactant compound (H) having at least two functional groups is selected from the group consisting of: polyepoxide compounds; cyclic carbonates; and, polyisocyanates. More particularly, the reactant compound (H) having at least two functional groups is selected from the group consisting of: polyepoxide compounds; and, cyclic carbonates.

(34) Suitable polyepoxide compounds may be liquid, solid or in solution in solvent. Further, such polyepoxide compounds should have an epoxy equivalent weight of from 100 to 700 g/eq, for example from 120 to 320 g/eq. And generally, diepoxide compounds having epoxy equivalent weights of less than 500 or even less than 400 are preferred.

(35) Suitable diglycidyl ether compounds may be aromatic, aliphatic or cycloaliphatic in nature and, as such, can be derivable from dihydric phenols and dihydric alcohols. And useful classes of such diglycidyl ethers are: diglycidyl ethers of aliphatic and cycloaliphatic diols, such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentane diol and cyclohexane diol; bisphenol A based diglycidylethers; bisphenol F diglycidyl ethers; diglycidyl o-phthalate, diglycidyl isophthalate and diglycidyl terephthalate; polyalkyleneglycol based diglycidyl ethers, in particular polypropyleneglycol diglycidyl ethers; and, polycarbonatediol based glycidyl ethers. Other suitable diepoxides which might also be mentioned include: diepoxides of double unsaturated fatty acid C1-C18 alkyl esters; butadiene diepoxide; polybutadiene diglycidyl ether; vinylcyclohexene diepoxide; and, limonene diepoxide.

(36) Illustrative polyepoxide compounds include but are not limited to: glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; and, sorbitol polyglycidyl ether.

(37) Without intention to limit the present invention, examples of highly preferred polyepoxide compounds for use as compound (H) include: bisphenol-A epoxy resins, such as DER 331, and DER 383; bisphenol-F epoxy resins, such as DER 354; bisphenol-A/F epoxy resin blends, such as DER 353; aliphatic glycidyl ethers, such as DER 736; polypropylene glycol diglycidyl ethers, such as DER 732; solid bisphenol-A epoxy resins, such as DER 661 and DER 664 UE; solutions of bisphenol-A solid epoxy resins, such as DER 671-X75; epoxy novolac resins, such as DEN 438; brominated epoxy resins such as DER 542; castor oil triglycidyl ether, such as ERISYS GE-35H; polyglycerol-3-polyglycidyl ether, such as ERISYS GE-38; and, sorbitol glycidyl ether, such as ERISYS GE-60.

(38) As examples of suitable cyclic carbonate group-containing monomeric and oligomeric compounds may be mentioned: compounds produced by reacting hydroxyl-functional cyclocarbonates with a polyisocyanate; and, compounds produced by the addition of CO.sub.2 to an epoxy group-containing monomer or oligomer. The disclosures of the following citations may be instructive in disclosing suitable cyclic carbonate functional compounds: U.S. Pat. Nos. 3,535,342; 4,835,289; 4,892,954; UK Patent No. GB-A-1,485,925; and, EP-A-0 119 840.

(39) The total amount of compounds (H) present in the curable composition is preferably selected so that the molar ratio of amine groups of said functional polyesters (AF-PES) to the functional groups (F) is in the range of from 1:10 to 10:1, for example from 5:1 to 1:5, and is preferably in the range of from 1:2 to 2:1. For example, the molar ratio of amine groups of said functional polyesters (AF-PES) to either epoxy groups or cyclic carbonate groups in the hardening compound (H) may be from 1:2 to 3:2 or from 2:3 to 4:3.

(40) In an alternative expression of the composition, the total amount of compounds (H) is suitably from 0.1-50 wt. %, preferably from 0.5 to 40 wt. % and more preferably 1 to 30 wt. %, based on the combined total amount of the amino-functional polyesters (AF-PES) and the compounds (H).

(41) As is standard in the art, the curable composition may comprise additives and adjunct ingredients. Suitable additives and adjunct ingredients include: catalysts; antioxidants; UV absorbers/light stabilizers; metal deactivators; antistatic agents; reinforcers; fillers; antifogging agents; propellants; biocides; plasticizers; lubricants; emulsifiers; dyes; pigments; rheological agents; impact modifiers; adhesion regulators; optical brighteners; flame retardants; anti-drip agents; nucleating agents; wetting agents; thickeners; protective colloids; defoamers; tackifiers; solvents; reactive diluents; and, mixtures thereof. The selection of suitable conventional additives for the composition depends on the specific intended use thereof and can be determined in the individual case by the skilled artisan.

(42) In certain embodiments of the invention, no catalysts will be required to catalyze the reaction of the cyclic amine groups with the functional groups (F) of the compound (H): this may typically be the case where cyclic carbonate groups or epoxy groups are present as the functional groups (F). However, in other cases and preferably where the compound (H) has reactive groups F that are different from said cyclic carbonate or epoxy groups, a catalyst may be required: suitable catalysts for the hardening will then be determined in a known manner dependent upon the type of the reactive functional groups (F). The catalysts, when desired, are used in an amount of from 0.01 to 10 wt. %, preferably from 0.01 to 5 wt. %, based on the total weight of the curable composition.

(43) The curable coating, adhesive or sealant composition should comprise less than 5 wt. % of water, based on the weight of the composition, and is most preferably an anhydrous composition that is essentially free of water. These embodiments do not preclude the composition from either comprising organic solvent or being essentially free of organic solvent.

(44) Broadly, all organic solvents known to the person skilled in the art can be used as a solvent but it is preferred that said organic solvents are selected from the group consisting of: esters; ketones; halogenated hydrocarbons; alkanes; alkenes; and, aromatic hydrocarbons. Exemplary solvents are methylene chloride, trichloroethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate, cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, di-isobutyl ketone, dioxane, ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl acetate, 2-ethylhexyl acetate, glycol diacetate, heptane, hexane, isobutyl acetate, isooctane, isopropyl acetate, methyl ethyl ketone, tetrahydrofuran or tetrachloroethylene or mixtures of two or more of the recited solvents.

(45) Methods and Applications

(46) To form a coating, sealant or adhesive composition, the reactive compounds are brought together and mixed in such a manner as to induce the hardening of the binder. More particularly, the amino-functional polyesters (AF-PES) and the compounds (H) may be mixed in pre-determined amounts by hand, by machine, by (co-)extrusion or by any other means which can ensure fine and highly homogeneous mixing thereof.

(47) The hardening of the binder compositions of the invention typically occurs at temperatures in the range of from 10 C. to 150 C., preferably from 0 C. to 100 C., and in particular from 10 C. to 70 C. The temperature that is suitable depends on the specific compounds (H) and the desired hardening rate and can be determined in the individual case by the skilled artisan, using simple preliminary tests if necessary. Of course, hardening at temperatures of from 5 C. to 35 C. or from 20 C. to 30 C. is especially advantageous as it obviates the requirement to substantially heat or cool the mixture from the usually prevailing ambient temperature. Where applicable, however, the temperature of the mixture of the amino-functional polyesters (AF-PES) and the compounds (H) may be raised above the mixing temperature using conventional means, including microwave induction.

(48) The compositions according to the invention may find utility inter alia in: varnishes; inks; elastomers; foams; binding agents for fibers and/or particles; the coating of glass; the coating of mineral building materials, such as lime- and/or cement-bonded plasters, gypsum-containing surfaces, fiber cement building materials and concrete; the coating and sealing of wood and wooden materials, such as chipboard, fiber board and paper; the coating of metallic surfaces; the coating of asphalt- and bitumen-containing pavements; the coating and sealing of various plastic surfaces; and, the coating of leather and textiles.

(49) It is also considered that the compositions of the present invention are suitable as pourable sealing compounds for electrical building components such as cables, fiber optics, cover strips or plugs. The sealants may serve to protect those components against the ingress of water and other contaminants, against heat exposure, temperature fluctuation and thermal shock, and against mechanical damage.

(50) By virtue of the fact that the compositions of the present invention are capable of creating a high binding strength in a short time, often at room temperatureparticularly where epoxy or cyclic carbonate hardeners (H) are employedthe compositions are optimally used for forming composite structures by surface-to-surface bonding of the same or different materials to one another. The binding together of wood and wooden materials and the binding together of metallic materials, such as mild steel, may be mentioned as exemplary adhesive applications of the present compositions.

(51) In a particularly preferred embodiment of the invention, the curable compositions are used as solvent-free or solvent-containing lamination adhesives for gluing plastic and polymeric films, such as polyolefin films, poly(methylmethacrylate) films, polycarbonate films and Acrylonitrile Butadiene Styrene (ABS) films.

(52) In each of the above described applications, the compositions may applied by conventional application methods such as: brushing; roll coating using, for example, a 4-application roll equipment where the composition is solvent-free or a 2-application roll equipment for solvent-containing compositions; doctor-blade application; printing methods; and, spraying methods, including but not limited to air-atomized spray, air-assisted spray, airless spray and high-volume low-pressure spray. For coating and adhesive applications, it is recommended that the compositions be applied to a wet film thickness of from 10 to 500 m. The application of thinner layers within this range is more economical and provides for a reduced likelihood of thick cured regions that mayfor coating applicationsrequire sanding. However, great control must be exercised in applying thinner coatings or layers so as to avoid the formation of discontinuous cured films.

(53) Various features and embodiments of the disclosure are described in the following examples, which are intended to be representative and not limiting.

EXAMPLES

(54) The following materials and abbreviations are employed in the Examples: TBD: Triazabicyclodecene Bax: N-Cyclohexyl-1,3-propanediamine, available from TCI America. CL: -Caprolactone. VL: -Valerolactone. TEPA: Tetraethylenepentamine, available from Sigma-Aldrich. DETA: Diethylenetriamine. BADGE: Bisphenol A diglycidyl ether, available from Tocris Bioscience. CC-BADGE: Carbonated (CO.sub.2) bisphenol A diglycidyl ether. Erisys GE60: Sorbitol glycidyl ether, available from CVC Thermoset Specialties. PEI: Polyethylenimine having a weight average molecular weight (Mw) of 800 g/mol, available from Sigma-Aldrich. ARMS: As-received Mild Steel.

Example 1: Synthesis of Amino-functionalized Polyesters (NH-PES)

(55) ##STR00005##

(56) Amino-functionalized polyesters were formed using the following general procedure:

(57) The amine was mixed with TBD (1 wt. % based on the total amount of lactone monomers) in an open beaker and mechanically stirred for 5 minutes. The lactones were weighed and mixed in a different container before they were added to the mixture of amine-TBD.

(58) For the stoichiometry of the reaction, the functionality of diamines is considered as f=1 and the functionality of polyamines is considered as f=2.

(59) The addition of the lactones promoted an exotherm that warmed up the reaction mixture (60 C.); under good stirring, the reaction was brought to completion, leading to the desired amino-polyester. The reaction was monitored by NMR until the signals associated with the initial lactones disappeared completelyafter approximately 2 hourswhich corresponded with the cooling down of the mixture.

Example 1A: NH-PES 2A Using a Diamine

(60) N-Cyclohexyl-1,3-propanediamine (1.56 g) and TBD (114 mg) were mixed for 5 minutes in a 50 mL flask with mechanical stirring. -caprolactone (11.4 g) was added to the amine-TBD mixture and was further stirred for 2 hourswith concomitant monitoring by 1H-NMRto obtain an NH-PES with an amino value of 39 mg KOH/g.

Example 1B: NH-PES 2F Using a Polyamine

(61) TEPA (18 g) and TBD (823 mg, 1 wt. % based on the total amount of lactone monomers) are mixed for 5 minutes in a 250 mL flask with mechanical stirring. A mixture of -caprolactone (43.8 g) and -valerolactone (38.5 g) are added to the amino-TBD mixture and stirred for 2 hoursunder 1H-NMR monitoringto obtain an NH-PES with amino value of 130 mg KOH/g.

(62) Further examples, prepared using the same procedure, are detailed in Table 1 below.

(63) TABLE-US-00001 TABLE 1 NH-PES Lactones Amine Amine Value NH- (g) (g) TBD Ratio State of (NHv, mg PES CL VL Bax TEPA DETA (mg) Lactone:Amine NH-PES KOH/g) 2A 11.4 1.56 114 10:1 Solid 39 2B 24.0 10.0 240 4:1 Fluid 210 2C 20.0 12.6 200 3:1 Fluid 228 2D 20.0 9.47 200 4:1 Fluid 206 2E 18.3 15.9 15.0 341 2:2:1 Fluid 274 2F 43.8 38.5 18.0 823 4:4:1 Fluid 130 2G 43.8 38.5 9.0 823 8:8:1 Fluid 72 2H 100.0 22.6 1000 4:1 Viscous paste 136

Example 2

(64) The molecular weight of four of the above mentioned amino functionalized polyesters (Table 1: 2B, 2D, 2F, 2G) was analyzed by gel permeation chromatography (GPC). Aliquots of each polyester were dissolved in tetrahydrofuran (THF) and the GPC analysis was performed, using THF as the solvent and poly(methylmethacrylate) (PMMA) as the analytical standard for calibration. The results of this analysis are shown in Table 2.

(65) TABLE-US-00002 TABLE 2 GPC Analysis Weight Average Molecular Polydispersity NH-PES Weight (Mw, g/mol) Index 2B 627 1.77 2D 336 1.04 2F 1709 1.80 2G 3125 2.16

(66) FIG. 1 appended hereto graphically represents the results of the chromatographic analysis of three of the amino-functional polyesters (2B, 2F, 2G) obtained in this Example, said graph depicting Refractive Index (RI) signal intensity versus elution time (minutes).

(67) These tabulated and graphical results demonstrate that the ring-opening polymerization of the present invention provides a selective and controlled method for preparing amino-polyesters with a homogeneous distribution of molecular weights: no significant amounts of low molecular weight species are generated as a side product of the reaction mechanism.

Comparative Example 1

(68) Polyesters were obtained by poly-condensing one or more dicarboxylic acids with one or more polyols: the acids and polyols are identified in Table 3 below. The respective condensations were conducted in an inert gas atmosphere at temperatures between 130 C. and 220 C. The obtained polyesters were then reacted with the identified polyaminesin the absence of solvent and under a nitrogen atmosphereat temperatures between 90 C. and 130 C. over a duration of 1 to 8 hours. The products of the aminolysis reaction may be depicted as follows:

(69) ##STR00006##

(70) TABLE-US-00003 TABLE 3 Composition of Comparative Polyesters Comparative Example Acid 1 Acid 2 Polyol Amine C1 Sebacic acid Isophthalic Dipropylene glycol TEPA Acid C2 Adipic acid Isophthalic Tripropylene glycol TEPA Acid C3 Adipic acid Neopentyl glycol TEPA C4 Adipic acid Dipropylene glycol TEPA

(71) FIG. 2 appended hereto graphically represents the results of the Gel Permeation Chromatographic (GPC) analysis of these aminolysis products, providing Refractive Index (RI) signal intensity versus elution time (minutes). It can be seen that all products obtained by aminolysis showed a heterogeneous molecular weight distribution with separated populations of molecules of different molecular weight. More particularly, one large and well-distinguished peakof approximately 10% by areais detected in all comparative examples and corresponds to monomeric glycols and/or oligoesters released as side products of the reaction.

(72) It is submitted that these results indicate aminolysis of polyesters to be a non-selective and uncontrolled method for preparing amino-polyesters, which method leads to heterogeneous molecular weight distributions of products with significant amounts of low molecular weight species as a side product of the reaction mechanism. These observations would represent a drawback to the use of such amino-functional polyesters in those applications that require strict control on migration limits of non-reacted low-molecular weight species and of non-intentionally added substances (NIAS).

Example 3: Adhesion Performance of Adhesive Formulations

(73) As shown in Table 4a herein below, four (4) adhesive formulations (AF1-AF4) were prepared by independently mixing two of the above defined amino functionalized polyesters (Table 1: NH2B, NH2F) with 40 mol. % polyethylenimine (MW 800) and then with an epoxy resin curing partner (BADGE; Erisys GE60). The mixtures were prepared at a ratio of [Epoxy groups]:[Primary and Secondary Amino groups] of 1:1 and were cured at either 100 C. or 80 C. for 2 hours.

(74) TABLE-US-00004 TABLE 4a Adhesive Formulations Adhesive Identity NH-PES with PEI BADGE Erisys GE 60 Formulation of NH-PES (g) (g) (g) AF-1 2B 1.245 1.255 AF-2 2B 1.285 1.215 AF-3 2F 1.603 0.897 AF-4 2F 1.639 0.861

(75) Utilizing these adhesive formulations, lap shear tests were performed according to DIN EN 1465 and using the following substrates: ARMS-ARMS; Polycarbonate, PC-PC; ABS-ABS; and, Beech Wood-Beech Wood. The results of the tests performed at room temperature are shown in Table 4b herein below, wherein: SF means substrate failure; AF means adhesive failure; and, CF means cohesive failure.

(76) TABLE-US-00005 TABLE 4b Lap Shear Strength Adhesive Poly- Beech Formu- Curing ARMS carbonate ABS Wood lation Conditions (MPa) (MPa) (MPa) (MPa) AF-1 100 C., 2 hours 14.49 1.42 1.42 13.85 for ARMS, AF CF AF SF AF-2 polycarbonate 3.87 4.67 1.05 6.22 and beech wood AF SF AF CF AF-3 substrates. 7.12 3.36 0.90 4.46 80 C., 2 hours AF AF AF CF AF-4 for ABS. 3.40 1.69 0.85 1.92 AF CF AF CF

Example 4: Adhesion Performance of Adhesive Formulations

(77) As shown in Table 5a herein below, two (2) adhesive formulations (AF5-AF6) were prepared by independently mixing two of the above defined amino functionalized polyesters (Table 1: NH2B, NH2F) with 40 mol. % polyethylenimine (MW 800) and then with a cyclic carbonate functional curing partner (CC-BADGE): said curing partner was obtained by the addition of CO.sub.2 to the epoxide compound. The mixtures were prepared at a ratio of [Cyclic Carbonate groups]:[Primary and Secondary Amino groups] of 1:1 and were cured at 130 C. for 20 hours.

(78) TABLE-US-00006 TABLE 5a Adhesive Formulations Adhesive NH-PES with PEI CC-BADGE Formulation Identity of NH-PES (g) (g) AF-5 2B 1.114 1.386 AF-6 2F 1.478 1.022

(79) Utilizing these adhesive formulations, lap shear tests were performed according to DIN EN 1465 and using the following substrates: ARMS-ARMS; and, Beech Wood-Beech Wood. The results of the tests performed at room temperature are shown in Table 5b herein below, wherein: SF means substrate failure; AF means adhesive failure; CF means cohesive failure; and, NM means not measured.

(80) TABLE-US-00007 TABLE 5b Lap Shear Strength Beech Adhesive Curing ARMS Wood Formulation Conditions (MPa) (MPa) AF-5 130 C., 20 1.36 2.56 hours AF CF AF-6 2.75 NM AF