Process for the Hydrolysis of Latent Amine Curing

Europaisches Patentamt (19) European Patent Office Office europeenpeen des brevets EP 0 586 615 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) intci.6: C08G 59/68, C08G 18/24, of the grant of the patent: C08G 59/70 09.07.1997 Bulletin 1997/28 (86) International application number: (21) Application number: 92917421.7 PCT/US92/03018 Date of 15.04.1992 (22) filing: (87) International publication number: WO 92/18551 (29.10.1992 Gazette 1992/27)

(54) PROCESS FOR THE HYDROLYSIS OF LATENT AMINE CURING AGENTS BY TIN CATALYSTS VERFAHREN FUR DIE HYDROLYSE VON LATENTEN AMINHARTUNGSMITTELN MITTELS Zl N N KATALYS ATO REN PROCEDE D'HYDROLYSE D'AGENTS DURCISSANTS AMINIQUES LATENTS A L'AIDE DE CATALYSEURS A L'ETAIN

(84) Designated Contracting States: • CARNEY, Eugene Edward DE ES FR GB Sykesville, MD 21784 (US)

(30) Priority: 22.04.1991 US 689385 (74) Representative: UEXKULL & STOLBERG Patentanwalte (43) Date of publication of application: Beselerstrasse 4 16.03.1994 Bulletin 1994/11 22607 Hamburg (DE)

(73) Proprietor: Henkel Teroson GmbH (56) References cited: 69123 Heidelberg (DE) DE-A- 1 745 944 GB-A- 1 379 985 US-A- 3 789 045 US-A- 4 016 113 (72) Inventors: • BUSH, Richard, Wayne Columbia, MD 21045 (US)

DO lO CO CD 00 LO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice the Patent Office of the Notice of shall be filed in o to European opposition to European patent granted. opposition a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. a. 99(1) European Patent Convention). LU

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Description

This invention relates to the curing of a wide variety of amine curable monomers and prepolymers useful as ad- hesives, sealants and coatings by the activation of latent amine curing agents by catalyzing the moisture-induced 5 hydrolysis of said latent amine curing agents by amine modified tin compounds. Many monomers and prepolymers can be cured or cross-linked by amines. Examples of such amine-curable materials include the various acrylates, epoxides, urethanes, anhydrides and the like. Formulations of these curable materials are often made up as one component systems in which the monomer or prepolymer is admixed with the amine curing agent. To provide for adequate shelf life, the curing agent must be in a deactivated or latent form until the 10 formulation is ready for use. The curing agent is then activated via exposure to moisture which causes a hydrolysis reaction to take place to thereby regenerate the amine. A representative example of this process is the moisture induced hydrolysis of a ketimine to form the corresponding amine and ketone (R1 , R2 and R3 representing well known substituent groups):

15 R1R2C=NR3 + H20 ^ R1R2C=0 + H2NR3

The regeneration of the amine by hydrolysis is not instantaneous, however, and since the rate of cure is a function of available amine curing agent, the cure time is dependent on the rate of hydrolysis. 20 For many applications, it is highly desirable to have a rapid initial or partial moisture cure to provide "green strength". Green strength results from polymerization occurring at ambient temperatures, and an adhesive or sealant with high green strength has high initial adhesion or tack. Furthermore, sufficient green strength will hold an adhesive bond in place during subsequent processing and final curing stages. The prior art discloses generally the use of tin compounds in polymerizations employing amine-based curing 25 agents, but does not teach the use of such compounds to catalyze hydrolysis reactions. U.S. Patent No. 4,616,066 discloses in Col. 8, line 5, the use of dibutyltin dilaurate (DBTDL) in a polymer system which includes an epoxy resin and a ketimine made into an aqueous emulsion for electrodeposition. However, the DBTDL serves not as a hydrolysis catalyst for the ketimine, but rather as a curing agent in the later baking step. U.S. Patent No. 4,713,481 discloses in Col. 7, line 29, the use of DBTDL in a polymerization process which includes the reaction of a ketone-blocked ethyl- 30 enediamine and an isocyanate-terminated polyurethane. The DBTDL is used to catalyze formation of the polyurethane. U.S. Patent No. 4,711 ,944 relates to humidity resistant coatings of copolymers of t-butyl acrylateand polyepoxides. In Col. 5, line 50, there is disclosed the use of stannous octoate or DBTDL as a catalyst for the reaction of epoxy groups to crosslink hydroxyl, carboxyl or amide functions on the polyacrylate. The stannous octoate and DBTDL are not used as hydrolysis catalysts for latent amines. 35 The prior art has disclosed non-tin based compounds for accelerating moisture cure. In U.S. Patent No. 4,861 ,832, amines are listed in Col. 5, lines 20-30 as co-curing agents in a reaction involving epoxy resin and a ketimine. Acids are also known as hydrolysis catalysts for latent amines as taught by U.S. Patent No. 4,816,542 at Col. 3, lines 53-55, where they catalyze the cure of polyurethane prepolymers. Thus, while the prior art recognizes the need for catalysis of various reactions involving the moisture curing of 40 monomers and prepolymers, there has heretofore been no use of a tin catalyst for such application.

SUMMARY OF THE INVENTION

It is accordingly an object of the invention to provide a method for increasing the rate of cure of monomers and 45 prepolymers which are cured via a latent amine curing agent. It is another object of the invention to provide a method as above by using a catalyst which increases the rate of cure by increasing the rate of hydrolysis of the latent amine. A further object of the invention is to provide a polymeric composition which includes an amine-curable polymer, a latent amine curing agent and a catalyst to increase the rate of hydrolysis of the latent amine. 50 These objects are achieved by a method for moisture-induced hydrolysis of a latent amine curing agent in an amine-curable polymeric composition, wherein the latent curing agent is a ketimine, aldimine, an enamine or oxazolidine comprising combining the latent curing agent with a catalytically effective amount of an organotin compound. The organotin compound is formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms and an amine-containing compound. The curing agent is hydrolyzed in the presence of the organotin compound. Optionally, 55 the organotin compound is in the form of a water adduct. The objects of the invention are also achieved by a method for curing an amine-curable polymer. In the latter method, the polymer is combined with a latent amine curing agent and a catalytically effective amount of the organotin compound. The polymer is then cured by cross-linking with the curing agent after the latter has been subjected to a

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moisture-induced hydrolysis which liberates the amine. The presence of the organotin compound increases the rate of hydrolysis of the latent amine. The objects of the invention are also achieved by a polymeric composition which includes an amine-curable polymer, a latent amine curing agent and the organotin compound used in the practice of the invention. 5 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The organotin compounds used in the practice of the invention are amine modified salts of stannous alkanoates. In general, the stannous salts are salts of carboxylic acids having from 2 to 20 carbon atoms, preferably from 6 to 10 10 carbon atoms, with stannous octoate being highly preferred. In general, the amine reacted with the stannous alkanoate is a mono- or polyfunctional amine which optionally includes ether groups. Illustrative of mono- and polyfunctional amines useful in preparing the hydrolysis-catalyst include ethylenediamine, triethylenetetraamine, diethylenetriamine, epoxy adducts of triethylenetetraamine, epoxy adducts of ethylenediamine, epoxy adducts of diethylenetriamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, hexanediamine, 4,9-dioxadodecane- 15 1 ,12-diamine, 4,4'-diaminodicyclohexylmethane, 9-aminomethylstearylamine, polybutadiene diamine, m-phenylenediamine, tris(aminoethyl)amine, 2-methylpentamethylenediamine, bis-aminopropylpiperazine, diethylenetriamine, 3- (diethylamino)propylamine, piperazine, butylamine, dimethylaminoethanol, dodecylamine, triethylamine, and amine- terminated polybutadiene. The amine-terminated polybutadiene preferably has a molecular weight of from 500 to 5000, most preferably be- 20 tween 1000 and 3000. A preferred example of this catalyst is the reaction product of stannous octoate and ethylenediamine. The ratio of stannous alkanoate to amine in the catalyst can vary. In general, the ratio of moles of stannous alkanoate to equivalents of amino groups varies from 1 :8 to 8:1 . The catalyst can also be prepared as an adduct of a stannous alkanoate, an amine and water. Use of the water-containing adduct further increases the rate of hydrolysis. 25 The latent curing agents the hydrolysis of which is catalyzed by the above tin catalysts include the various ketimines prepared by the reaction of ketones and primary mono- and polyfunctional amines with the withdrawal of water formed by, for example, azeotropic distillation. Illustrative of suitable amines for preparing said ketimines are triethylenetetraamine, diethylenetriamine, ethylenediamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, 1 ,6-diaminohexane, 1 ,3-diaminopropane, 1 ,4-diaminobutane, 30 1 ,6-diaminohexane, 4, 9-dioxadodecane-1 ,12-diamine, and 4,4'-diaminodicyclohexylmethane. A particularly preferred group of amines are tris(aminoalkyl) amines and dialkylenetriamines, which are reacted with diisopropyl ketone as explained hereinbelow. Other suitable amines for preparing the ketimines include the polymeric polyamines having molecular weights ranging up to 5000. Examples of such polyamines are diamines which can be prepared by reductive cyanoethylation 35 of polyols, such as polytetrahydrofuran. Products of this type contain terminal primary amino groups in the form of aminopropoxy groups. Other polyamines include polyoxypropylene diamine and amine-terminated polybutadiene and poly(butadiene/acrylonitrile). Ketones reactable with the above amines to provide the ketimines are those which, apart from the keto group, contain no groups which react with a primary amino group. Illustrative of suitable ketones are acetone, methyl ethyl 40 ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diethyl ketone, dipropyl ketone and cyclohexanone. Particularly preferred is diisopropyl ketone. Other latent curing agents which can be catalyzed by the tin compounds in the practice of the invention include aldimines, enamines (prepared by the reaction of primary and secondary alkanolamines with aldehydes or ketones) and oxazolidines. 45 The preparation of ketimines is done by reacting compounds having primary amino groups with aliphatic or cyclic ketones. The reaction may optionally be catalyzed with acid. Typically the mixture is heated at reflux and the water of reaction and the excess carbonyl compound are removed by azeotropic distillation. In a preferred embodiment, the latent amine curing agent is a tri- or tetraketimine formed using diisopropyl ketone (DIPK). The use of these specific higher functional ketimines results in a cure that proceeds more rapidly compared so to formulations with diketimines. In addition, these specific tri- and tetrafunctional ketimines are more stable than other ketimines not based on DIPK. The preferred triketimines are the reaction product of a tris(aminoalkyl)amine with diisopropyl ketone (DIPK) in a 1:3 (stoichiometric) molar ratio. In general, the tris(aminoalkyl)amine contains between 3 and 15 carbon atoms. A specific example of atris(aminoalkyl)amine is tris(aminoethyl) amine (TREN) . The reaction product using TREN 55 is designated TREN(DIPK)3. Tetraketimines are formed in a two-step reaction, the first step being the reaction of a dialkylenetriamine with DIPK in a 1 :2 (stoichiometric) molar ratio. Two of the molecules formed in this first step are then coupled by reaction of the secondary NH groups with a diacrylate, a diepoxide or a diisocyanate to form the tetraketimine. In general, the di-

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alkylenetriamine contains between 2 and 10 carbon atoms. A detailed discussion of the above triketimines and tetraketimines is given in concurrently filed U.S. Patent No. 5 1 98 524. The monomers and prepolymers used in conjunction with the tin catalyst in the practice of the invention include 5 any monomer or prepolymer curable by a latent amine curing agent. Such materials include inter alia the various well known polyurethanes, anhydrides, acrylates and epoxy compounds, the latter composed of one or more curable resins containing more than one 1 ,2-epoxy group per molecule. The epoxy compounds suitable for use in the invention can be any monomeric or polymeric compound or mixture of compounds having an epoxy equivalent greater than one, that is, wherein the average number of epoxy groups per 10 molecule is greater than one. Useful epoxy compounds include the polyglycidyl ethers of polyhydric polyols, such as ethylene glycol, triethylene glycol, 1 ,2-propylene glycol, 1 ,5-pentanediol, 1 ,2,6-hexanetriol, glycerol, 2,2-bis(4-hydroxy cyclohexyl)propane and polyalkylene glycols such as polypropylene glycol; the polyglycidyl esters of aliphatic or aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid and dimerized is linoleic acid; the polyglycidyl ethers of polyphenols, such as bisphenol A, 1 , 1 -bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4-hydroxyphenyl)isobutane, 1 ,5-dihydroxynaphthalene, and novolak resins. Preferred epoxy compounds include higher molecular weight resins such as the chain-extended diglycidyl ether of bisphenol A, dimerized linoleic acid-extended bisphenol A diglycidyl ether, and polyether polyurethanes terminated with bisphenol A diglycidyl ether. Suitable polyurethane prepolymers include isocyanate-functional urethanes prepared by reacting a polyol, poly- 20 ether, hydroxyl-terminated polyester, polyester amide, polyamine, or other polyfunctional active hydrogen-containing compound with a diisocyanate or other polyisocyanate having up to eight functional isocyanate groups. Such reactants include polyhydroxy polyesters, polyhydroxy polyethers and polyisocyanates having two or three reactive isocyanate groups. Generally, any isocyanate-functional urethane known in the art can be employed in the practice of this invention, with such urethanes having a molecular weight of at least 500, particularly in the range of 1,000 to 10,000 being 25 preferred. Any of the polyisocyanates having at least two reactive isocyanate groups can be employed in forming isocyanate- functional urethanes suitable for use in conjunction with the tin catalyst of the invention. Such polyisocyanates include, without limitation, aliphatic polyisocyanates such as 1 ,6-hexamethylene diisocyanate, 1 ,8-octamethylene diisocyanate, 1 , 1 2-dodecamethylene diisocyanate; 2,2,4-trimethyl-hexamethylene diisocyanate; and the like; 3,3'-diisocyanatodipro- 30 py| ether; 3-isocyanatomethyl-3,5,5'-trimethylcyclohexyl isocyanate; cyclopentalene-1 ,3-diisocyanate; cyclohexylene- 1 ,4-diisocyanate; methyl 2,6-diisocyanatocaprolate; bis-(2-isocyanatoethyl)fumarate; 4-methyl-1 ,3-diisocyanatocy- clohexane; transvinylene diisocyanate and similar unsaturated polyisocyanates; 4,4'-methylene-bis-(cyclohexylisocy- anate) and related polyisocyanates; methane diisocyanates; bis-(2-isocyanatoethyl) carbonate and similar carbonate polyisocyanates; N,N',N"-tris-(6-isocyanatohexamethylene) biuret and related polyisocyanates; as well as other known 35 polyisocyanates derived from aliphatic polyamines; aromatic polyisocyanates such as toluene diisocyanates; xylene diisocyanates; dianisidine diisocyanate; 4,4'-diphenylmethane diisocyanate; 1-ethoxy-2,4-diisocyanatobenzene; 1-chlor-2,4-diisocyanatobenzene; tris(4-isocyanatophenyl) methane; naphthalene diisocyanates; 4,4'-diphenyl diisocyanate; phenylene diisocyanates; 3,3'-dimethyl-4,4'-biphenyl diisocyanate; p-isocyanatobenzoyl isocyanates, and tet- rachloro-1 ,3-phenylene diisocyanate. 40 Acrylates useful as amine curable materials include ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, trimethylene glycol diacrylate, neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1 ,6-hexamethylene glycol diacrylate, 1 ,10-decamethylene glycol diacrylate, trimethyl- olpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and mixtures thereof. Other well known amine curable monomers and prepolymers include the well known anhydride-functional com- 45 pounds. In a preferred embodiment, an epoxy is combined with an acrylate and the above-described tri- or tetraketimines to form an adhesive composition. The epoxy and acrylate can be separate prepolymers or both epoxy and acrylate functionalities can be formed on the same molecule. Such compounds are described in the aforementioned U.S. Patent No. 5 198 524. so The amount of tin catalyst used can vary from 0.1% to 5% by weight, desirably from 0.5% to 4% and preferably from 1% to 3% by weight of the total weight of latent amine and monomer and/or prepolymer in the formulation. The following examples illustrate the invention. All percentages in the examples, and elsewhere in the specification, are by weight unless otherwise specified. The stannous octoate used was obtained from Air Products under the "T-9" trademark. The acronym EDA refers to ethylenediamine. 55 In the examples, an inclined groove device was used to measure the degree of cure. This device consists of a Teflon® block machined to contain four grooves, each 10 cm long, 1 cm wide, and varying uniformly in depth from 0 to 10 mm. The moisture-curable adhesive is flowed into the groove, levelled, and the device placed in a cabinet of desired humidity for the desired time. The device is removed and the cured adhesive is peeled from the thin end until

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uncured adhesive is observed. The horizontal distance is divided by 10 to obtain the depth of cure.

EXAMPLE 1

5 Stannous octoate (1.684 g or 4.16 mmoles) was mixed with ethylenediamine (0.125 g or 2.08 mmoles) to give a viscous yellow-orange mixture. This mixture (0.2 g) was stirred at 70°C into 9.8 g of a moisture-curable epoxy formulation (consisting of epoxy-terminated polyether urethane resin, epoxy resins, calcium silicate, fumed silica, and 6% of the bis-ketimine of hexanediamine and diisopropyl ketone. A portion of the resulting mixture was placed in a plastic beaker and exposed to the atmosphere (70-80% RH), and within one hour after formulation there was noticeable odor 10 of diisopropyl ketone evolved. After 3 hours the surface of the sample had only slight surface tack. After 4 hours the sample could be peeled from the walls of the beaker without sticking, indicating a through-cure. A similarly prepared sample stored in dry desiccator for 8 hours showed only slight cure, proving that moisture is necessary.

EXAMPLE 2 15 Use of Stannous Octoate (with and without amine) as Catalyst, and Comparison Run Containing No Catalyst

Three mixtures were prepared using the same epoxy formulation as in Example 1 but varying the catalyst, and exposed to atmospheric moisture (70-80% RH): 20 Sample No. (1) (Comparison) (2) (3) Epoxy formulation, grams 10.0 9.8 9.8 Stannous octoate, grams - 0.2 Stannous octoate/EDA, grams (2/1 mole ratio) - - 0.2

After 1 hour, Sample 1 had only faint ketone odor, while Samples (2) and (3) had significant ketone odor. After 3 hours, Sample (1) was still sticky, but Samples (2) and (3) had only slight surface tack. After 4 hours, Sample (1) was just beginning to cure, while Samples (2) and (3) exhibited through-cure in thicknesses up to about 2 mm. After 24 30 hours, Sample (1) was still sticky, while Samples (2) and (3) were tackfree and cured through, with Sample (3) appearing to be more completely cured.

EXAMPLE 3

35 Effect of Amine Content; Demonstration of Adhesive Strength

Stannous octoate and ethylenediamine were mixed as in Example 1 but at mole ratios of 1:1 and 8:1 (instead of 2:1). These catalyst mixtures were used at 2% in the epoxy formulation of Example 1 , applied as a 2.54x2.54x0.05 cm (1x1x0. 020-inch) bond line between the ends of cleaned 10.16x2.54x8.13 cm (4x1x0. 032-inch) cold rolled steel strips 40 configured as a lap specimen. The bonds were exposed to 1 00% RH for 1 6 hours, then a 500 g weight was suspended from one end and the specimen hung in a 180°C oven for 30 minutes. The bonds survived this test, indicating that they had moisture cured to provide green strength sufficient to hold during the heat cycle of a subsequent elevated temperature cure. Similar bonds containing 2% stannous octoate (without amine) failed this test after 16 hours, but passed after 24 hours at 100% RH. Bonds containing no catalyst failed after 45 24 hours, but passed after 32 hours at 100% RH.

EXAMPLE 4

Use of Alternative Epoxy Prepolymer 50 An epoxy resin was prepared by reacting 7 parts of a polyoxypropylene triamine (Jeffamine 403 available from Texaco Co.) with 50 parts of the diglycidyl ether of bisphenol A ("EPON" 828). To 9.18 parts of this resin was added 1 .24 parts of the hexanediamine diisopropyl ketimine (used in Example 1 ), and 0.20 g of catalyst consisting of an 8/1 mole ratio of stannous octoate/ ethylenediamine (used in Example 3). The mixture was placed in an inclined groove 55 device varying in depth from 0-10 mm. After 17.5 hours at 100% RH, the cure had penetrated 2.4 millimeters.

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EXAMPLE 5

Curing of an acrylate system with a triketimine.

5 Atriketimine (designated TREN(DIPK)3) was prepared by reaction of tris(aminoethyl)amine (TREN) with diisopropyl ketone. Apolyether urethane triacrylate of equivalent weight 1660 (ANCAREZ 300Afrom Pacific Anchor Company) was formulated with pentaerythritol tetraacrylate (PETA), calcium carbonate, 8% TREN(DIPK)3 and 2% stannous octoate/EDA (8/1 mole ratio) and placed in the inclined groove as in Example 4. After 9 hours at 100% RH the cure had penetrated 2.9 mm. 10 EXAMPLE 6

Curing of a Mixed Acrylate/Epoxy System is A mixture of 6.10 g polyether urethane triacrylate (ANCAREZ 300A), 0.06 g PETA, 1 .38 g epoxy-functional amine (as prepared in Example 4), 1 .22 g stearate-coated calcium carbonate, 0.32 g of 33% dicyandiamide. in "EPON" 828, 0.92 g TREN(DIPK)3 (Example 5) and 0.2 g of stannous octoate/EDA (1/1 mole ratio) was placed in the inclined groove as in Example 4, alongside a control recipe containing no tin catalyst. Cure penetrations in millimeters at various times at 100% RH were as follows: 20 2hr 4hr 6 hr 10 hr 2% Stannous octoate/EDA 0.8 1.3 2.0 2.5 Control 0.0 0.0 0.5 1.2 25 EXAMPLE 7

Alternative Catalysts

30 The epoxy resin of Example 1 was formulated with 6% HDA(DIPK)2 and 2% of the following catalysts:

Mole Ratio Stannous octoate/hexanediamine 8/1 Stannous diamine 8/1 35 octoate/polybutadiene

In inclined groove tests at 100% RH, the compositions cured significantly faster than a control containing no catalyst.

EXAMPLE 8

Amine/Stannous Octoate Adducts Containing Various Amines

The following amines were combined in a similar manner with stannous octoate, tested as hydrolysis catalysts, and found to be effective: m-phenylenediamine; tris(aminoethyl)amine; and piperazine.

EXAMPLE 9

Faster Catalyst Based on Amine/Water/Stannous Octoate Adduct

To a solution of 0.0457g (2.54 mmoles) water, plus 0.382 g (6.37 mmoles) ethylenediamine was added 2.53 g (6.25 mmoles) of stannous octoate (designated T-9) to give an exothermic reaction and a viscous yellow suspension, which was then heated at 80°C for 8 hours. A mixture of 7.62 g of Ancarez 300A plus 0.08 g of pentaerythritol tetraacrylate plus 0.80 g of TREN(DIPK)3 ketimine plus 1 .50 g of stearate coated calcium carbonate plus 0.20 g of the EDA/ H20/T-9 catalyst was prepared under dry conditions and placed in an inclined groove, along with two similar formulations that contained as catalyst 2% EDA/T-9 (1/8 mole ratio) or H20/T-9 (1/2 mole ratio). Upon exposure to 1 00% RH, depth of cure results (in mm) were as follows:

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mole ratio 2 hrs 4 hrs 10.5 hrs 15.5 hrs EDA/H20/T-9 1/0.4/1 1.7 3.2 7.0 10.0 5 EDA/T-9 1/8 1.5 2.9 4.0 5.0 H20/T-9 1/1 1.4 2.8 3.8 4.9

EXAMPLE 10

10 Amine/Water/Stannous Octoate Adducts Containing Various Amines

Adducts with H20 and stannous octoate were prepared with the following amines and shown to have activity as hydrolysis catalysts: ethylenediamine; m-phenylenediamine; 2-methylpentamethylenediamine; bis-aminopropylpiperazine; diethylenetriamine; 3-(diethylamino)propylamine; piperazine; butylamine; dimethylaminoethanol; hexanedi- 15 amine; dodecylamine; and triethylamine.

EXAMPLE 11

EDA/Water/Stannous Octoate Compositions and Concentrations 20 Catalysts with various ratios of EDA/H20/stannous octoate were prepared and tested, including the following mole ratios:

EDA/H20/stannous octoate 25 0.5/0.5/1.0 0.7/0.3/1.0 0.8/0.2/1.0 1.0/0.4/1.0 1.0/1.0/1.0 30 1.0/3.0/1.0 2.0/2.0/1.0 3.0/1.0/1.0

35 The catalysts with EDA and H20 contents of 1 .0 or greater were the most effective. Catalyst concentrations of 2% by weight in the total formulation were typically used, but concentrations as low as 0.3% were still effective.

Claims

Claims for the following Contracting States : DE, FR, GB

1. A method for moisture-induced hydrolysis of a latent amine curing agent in an amine-curable polymeric composi- 45 tion, wherein the latent amine curing agent is a ketimine, aldimine, an enamine, or oxazolidine, comprising combining the curing agent with a catalytically effective amount of an organotin compound formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms and an amine-containing compound, and hydrolyzing the curing agent. so 2. A method according to claim 1 , wherein the ratio of moles of stannous alkanoate to equivalents of amino groups in the amine-containing compound is from 1 :8 to 8: 1 .

3. A method according to claim 1 , wherein the stannous alkanoate is stannous octoate.

55 4. A method according to claim 1 , wherein the amine-containing compound is a mono- or polyfunctional amine selected from the group consisting of ethylenediamine, triethylenetetraamine, diethylenetriamine, epoxy adducts of triethylenetetraamine, epoxy adducts of ethylenediamine, epoxy adducts of diethylenetriamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, hexanediamine, 4, 9-dioxadodecane-1 ,12-diamine, 4,4'-diaminodicyclohexylmethane,

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9-aminomethylstearylamine, polybutadiene diamine, m-phenylenediamine, tris(aminoethyl)amine, 2-methylpentamethylenediamine, bis-aminopropylpiperazine, diethylenetriamine, 3-(diethylamino)propylamine, piperazine, butylamine, dimethylaminoethanol, dodecylamine, triethylamine, amine-terminated polybutadiene, and mixtures thereof. 5 5. A method according to claim 4, wherein the amine-containing compound is ethylenediamine.

6. A method according to claim 1 , wherein the amine-curable polymeric composition comprises a monomer or prepolymer selected from the group consisting of an epoxy compound, an acrylate compound, an isocyanate com- 10 pound, an anhydride compound, and one or more ketimine curing agents.

7. A method according to claim 6, wherein the amount of the organotin compound is from 0. 1 to 5% by weight of the polymeric composition. is 8. A method according to claim 1, wherein the amine-curable polymeric composition is an adhesive composition comprising a mixture of a polyfunctional acrylate, a polyfunctional epoxy and a ketimine prepared from a polyamine and diisopropyl ketone, the ketimine selected from the group consisting of a triketimine, a tetraketimine, and mixtures thereof.

20 9. A method according to claim 1, wherein the amine-curable polymeric composition is an adhesive composition comprising a mixture of the reaction product of an acrylate and an epoxy, and a ketimine prepared from a polyamine and diisopropyl ketone, the ketimine selected from the group consisting of a triketimine, a tetraketimine and mixtures thereof.

25 10. A method according to claim 1 , wherein the reaction forming the organotin compound further includes reacting the stannous alkanoate and amine-containing compound with water.

11. A polymeric composition comprising a mixture of an amine-curable polymer, a latent amine curing agent selected from the group consisting of a ketimine, aldimine, an enamine, or oxazolidine and a catalytically effective amount 30 of an organotin compound formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms and an amine-containing compound.

12. A polymeric composition according to claim 11 characterized in that the organotin compound is formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms, an amine-containing compound and water. 35 13. A polymeric composition according to claim 11 or 12, wherein the amine-containing compound is a mono- or polyfunctional amine selected from the group consisting of ethylenediamine, triethylenetetraamine, diethylenetriamine, epoxy adducts of triethylenetetramine, epoxy adducts of ethylenediamine, epoxy adducts of diethylenetriamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, hexanediamine, 4,9-dioxadodecane-1,12-diamine, 4,4'-diaminodicy- 40 clohexylmethane, 9-aminomethylstearylamine, polybutadiene diamine, m-phenylenediamine, tris(aminoethyl) amine, 2-methylpentamethylenediamine, bis-aminopropylpiperazine, diethylenetriamine, 3-(diethylamino)propylamine, piperazine, butylamine, dimethylaminoethanol, dodecylamine, triethylamine, amine-terminated polybutadiene, and mixtures thereof.

45 14. A method for curing a composition according to at least one of the claims 11 to 13 by moisture-induced hydrolysis of the latent amine curing agent in the presence of the organotin compound, the polymer being cross-linked with the amine liberated by the hydrolysis.

15. A cured polymeric composition comprising the reaction product of the polymeric composition according to claim so 11 or 12.

Claims for the following Contracting State : ES

55 1. A method for moisture-induced hydrolysis of a latent amine curing agent in an amine-curable polymeric composition, wherein the latent amine curing agent is a ketimine, aldimine, an enamine, or oxazolidine, comprising combining the curing agent with a catalytically effective amount of an organotin compound formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms and an amine-containing compound, and hydrolyzing

8 EP0 586 615B1

the curing agent.

2. A method according to claim 1 , wherein the ratio of moles of stannous alkanoate to equivalents of amino groups in the amine-containing compound is from 1 :8 to 8: 1 . 5 3. A method according to claim 1 , wherein the stannous alkanoate is stannous octoate.

4. A method according to claim 1 , wherein the amine-containing compound is a mono- or polyfunctional amine selected from the group consisting of ethylenediamine, triethylenetetraamine, diethylenetriamine, epoxy adducts of 10 triethylenetetraamine, epoxy adducts of ethylenediamine, epoxy adducts of diethylenetriamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, hexanediamine, 4, 9-dioxadodecane-1 ,12-diamine, 4,4'-diaminodicyclohexylmethane, 9-aminomethylstearylamine, polybutadiene diamine, m-phenylenediamine, tri(aminoethyl)amine, 2-methylpentamethylenediamine, bis-aminopropylpiperazine, diethylenetriamine, 3-(diethylamino)propylamine, piperazine, butylamine, dimethylaminoethanol, dodecylamine, triethylamine, amine-terminated polybutadiene, and mixtures is thereof.

5. A method according to claim 4, wherein the amine-containing compound is ethylenediamine.

6. A method according to claim 1 , wherein the amine-curable polymeric composition comprises a monomer or pre- 20 polymer selected from the group consisting of an epoxy compound, an acrylate compound, an isocyanate compound, an anhydride compound, and one or more ketimine curing agents.

7. A method according to claim 6, wherein the amount of the organotin compound is from 0.1 to 5 % by weight of the polymeric composition.

8. A method according to claim 1, wherein the amine-curable polymeric composition is an adhesive composition comprising a mixture of a polyfunctional acrylate, a polyfunctional epoxy and a ketimine prepared from a polyamine and diisopropyl ketone, the ketimine selected from the group consisting of a triketimine, a tetraketimine, and mixtures thereof.

9. A method according to claim 1, wherein the amine-curable polymeric composition is an adhesive composition comprising a mixture of the reaction product of an acrylate and an epoxy, and a ketimine prepared from a polyamine and diisopropyl ketone, the ketimine selected from the group consisting of a triketimine, a tetraketimine and mixtures thereof.

10. A method according to claim 1 , wherein the reaction forming the organotin compound further includes reacting the stannous alkanoate and amine-containing compound with water.

11. A polymeric composition comprising a mixture of an amine-curable polymer, a latent amine curing agent selected 40 from the group consisting of a ketimine, aldimine, an enamine, or oxazolidine and a catalytically effective amount of an organotin compound formed from the reaction of a stannous alkanoate having from 2 to 20 carbon atoms and an amine-containing compound.

12. A polymeric composition according to claim 11 characterized in that the organotin compound is formed from the 45 reaction of a stannous alkanoate having from 2 to 20 carbon atoms, an amine-containing compound and water.

13. A polymeric composition according to claim 11 or 12, wherein the amine-containing compound is a mono- or polyfunctional amine selected from the group consisting of ethlylenediamine, triethylenetetraamine, diethylenetriamine, epoxy adducts of triethylenetetramine, epoxy adducts of ethylenediamine, epoxy adducts of diethylenetriamine, so 1 ,3-diaminopropane, 1 ,4-diaminobutane, hexanediamine, 4,9-dioxadodecane-1,12-diamine, 4,4'-diaminodicyclohexylmethane, 9-aminomethylstearylamine, polybutadiene diamine, m-phenylenediamine, tris(aminoethyl) amine, 2-methylpentamethylenediamine, bis-aminopropylpiperazine, diethylenetriamine, 3-(diethylamino)propylamine, piperazine, butylamine, dimethylaminoethanol, dodecylamine, triethylamine, amine-terminated polybutadiene and mixtures thereof. 55 14. A method for curing a composition according to at least one of the claims 11 to 13 by moisture-induced hydrolysis of the latent amine curing agent in the presence of the organotin compound, the polymer being cross-linked with the amine liberated by the hydrolysis.

9 EP0 586 615B1

15. A method for preparing a cured polymeric composition comprising curing of the polymeric composition according to claim 11 or 12.

Patentanspriiche

Patentanspriiche fur folgende Vertragsstaaten : DE, FR, GB

1. Verfahren zur Feuchtigkeits-induzierten Hydrolyse eines latenten Aminhartungsmittels in einer Amin-hartbaren polymeren Zusammensetzung, worin das latente Aminhartungsmittel ein Ketimin, Aldimin, Enamin oderOxazolidin ist, das das Kombinieren des Hartungsmittels mit einer katalytisch wirksamen Menge einer zinnhaltigen organischen Verbindung, die durch die Reaktion eines Zinnalkanoats mit 2 bis 20 Kohlenstoffatomen und einer aminhaltigen Verbindung gebildet ist, und die Hydrolyse des Hartungsmittels umfaBt.

2. Verfahren gemaB Anspruch 1, worin das Molverhaltnis an Zinnalkanoat zu den Aquivalenten der Aminogruppen in der aminhaltigen Verbindung 1 : 8 bis 8 : 1 ist.

3. Verfahren gemaB Anspruch 1 , worin das Zinnalkanoat Zinnoctoat ist.

4. Verfahren gemaB Anspruch 1, worin die aminhaltige Verbindung ein aus der Gruppe ausgewahltes mono- oder polyfunktionelles Amin ist, die aus Ethylendiamin, Triethylentetraamin, Diethylentriamin, Epoxyaddukten von Triethylentetraamin, Epoxyaddukten von Ethylendiamin, Epoxyaddukten von Diethylentriamin, 1 ,3-Diaminopro- pan, 1 ,4-Diaminobutan, Hexandiamin, 4,9-Dioxadodecan-1 ,12-diamin, 4,4'-Diaminodicyclohexylmethan, 9-Ami- nomethylstearylamin, Polybutadiendiamin, m-Phenylendiamin, Tris(aminoethyl)amin, 2-Methylpentamethylendia- min, Bisaminopropylpiperazin, Diethylentriamin, 3-(Diethylamino)propylamin, Piperazin, Butylamin, Dimethylami- noethanol, Dodecylamin, Triethylamin, Amin-terminiertes Polybutadien and Mischungen daraus besteht.

5. Verfahren gemaB Anspruch 4, worin die aminhaltige Verbindung Ethylendiamin ist.

6. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung ein aus der Gruppe ausgewahltes Monomer oder Prapolymer enthalt, die aus einer Epoxyverbindung, einer Acrylatverbindung, einer Iso- cyanatverbindung, einer Anhydridverbindung und einem oder mehreren Ketiminhartungsmitteln besteht.

7. Verfahren gemaB Anspruch 6, worin die Menge der zinnhaltigen organischen Verbindung 0,1 bis 5 Gew.-% der polymeren Zusammensetzung betragt.

8. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung eine Klebstoffzusammen- setzung ist, die eine Mischung aus einem polyfunktionellen Acrylat, einem polyfunktionellen Epoxyd und einem Ketimin enthalt, das aus einem Polyamin und Diisopropylketon hergestellt ist, wobei das Ketimin aus der Gruppe ausgewahlt ist, die aus einem Triketimin, einem Tetraketimin und Mischungen daraus besteht.

9. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung eine Klebstoffzusammen- setzung ist, die eine Mischung aus dem Reaktionsprodukt eines Acrylats und eines Epoxyds und einem Ketimin enthalt, das aus einem Polyamin und Diisopropylketon hergestellt ist, wobei das Ketimin aus der Gruppe ausgewahlt ist, die aus einem Triketimin, einem Tetraketimin und Mischungen daraus besteht.

10. Verfahren gemaB Anspruch 1, wobei die die zinnhaltige organische Verbindung bildende Reaktion weiterhin das Reagieren des Zinnalkanoats und der aminhaltigen Verbindung mit Wasser umfaBt.

11. Polymere Zusammensetzung enthaltend eine Mischung aus einem Amin-hartbaren Polymer, einem latenten Amin- hartungsmittel, das aus der Gruppe ausgewahlt ist, die aus einem Ketimin, Aldimin, einem Enamin oderOxazolidin besteht, und einer katalytisch wirksamen Menge einer zinnhaltigen organischen Verbindung, die durch die Reak- tion eines Zinnalkanoats mit 2 bis 20 Kohlenstoffatomen und einer aminhaltigen Verbindung gebildet ist.

12. Polymere Zusammensetzung gemaB Anspruch 11 , dadurch gekennzeichnet, dal3 die zinnhaltige organische Ver- bindung durch Reaktion eines Zinnalkanoats mit 2 bis 20 Kohlenstoffatomen, einer aminhaltigen Verbindung und Wasser gebildet ist.

10 EP0 586 615B1

13. Polymere Zusammensetzung gemaB Anspruch 11 oder 12, worin die aminhaltige Verbindung ein mono- oder polyfunktionelles Amin ist, das aus der Gruppe ausgewahlt ist, die aus Ethylendiamin, Triethylentetraamin, Diethy- lentriamin, Epoxyaddukten von Triethylentetraamin, Epoxyaddukten von Ethylendiamin, Epoxyaddukten von Diethylentriamin, 1 ,3-Diaminopropan, 1 ,4-Diaminobutan, Hexandiamin, 4,9-Dioxadodecan-1 ,12-diamin, 4,4'-Dia- 5 minodicyclohexylmethan, 9-Aminomethylstearylamin, Polybutadiendiamin, m-Phenylendiamin, Tris(aminoethyl) amin, 2-Methylpentamethylendiamin, Bisaminopropylpiperazin, Diethylentriamin, 3-(Diethylamino)propylamin, Piperazin, Butylamin, Dimethylaminoethanol, Dodecylamin, Triethylamin, Amin-terminiertes Polybutadien und Mi- schungen daraus besteht.

10 14. Verfahren zur Hartung einer Zusammensetzung gemaB mindestens einem der Anspruche 11 bis 13 durch Feuch- tigkeits-induzierte Hydrolyse des latenten Aminhartungsmittels in Anwesenheit der zinnhaltigen organischen Ver- bindung, wobei das Polymer durch das bei der Hydrolyse freigesetzte Amin vernetzt ist.

15. Gehartete polymere Zusammensetzung enthaltend das Reaktionsprodukt der polymeren Zusammensetzung ge- 15 ma!3 Anspruch 11 oder 12.

Patentanspriiche fur folgenden Vertragsstaat : ES

20 1. Verfahren zur Feuchtigkeits-induzierten Hydrolyse eines latenten Aminhartungsmittels in einer Amin-hartbaren polymeren Zusammensetzung, worin das latente Aminhartungsmittel ein Ketimin, Aldimin, Enamin oderOxazolidin ist, das das Kombinieren des Hartungsmittels mit einer katalytisch wirksamen Menge einer zinnhaltigen organischen Verbindung, die durch die Reaktion eines Zinnalkanoats mit 2 bis 20 Kohlenstoffatomen und einer aminhaltigen Verbindung gebildet ist, und die Hydrolyse des Hartungsmittels umfaBt. 25 2. Verfahren gemaB Anspruch 1, worin das Molverhaltnis an Zinnalkanoat zu den Aquivalenten der Aminogruppen in der aminhaltigen Verbindung 1 : 8 bis 8 : 1 ist.

3. Verfahren gemaB Anspruch 1 , worin das Zinnalkanoat Zinnoctoat ist. 30 4. Verfahren gemaB Anspruch 1, worin die aminhaltige Verbindung ein aus der Gruppe ausgewahltes mono- oder polyfunktionelles Amin ist, die aus Ethylendiamin, Triethylentetraamin, Diethylentriamin, Epoxyaddukten von Triethylentetraamin, Epoxyaddukten von Ethylendiamin, Epoxyaddukten von Diethylentriamin, 1 ,3-Diaminopro- pan, 1 ,4-Diaminobutan, Hexandiamin, 4, 9-Dioxadodecan-1 ,12-diamin, 4,4'-Diaminodicyclohexylmethan, 9-Ami- 35 nomethylstearylamin, Polybutadiendiamin, m-Phenylendiamin, Tris(aminoethyl)amin, 2-Methylpentamethylendia- min, Bisaminopropylpiperazin, Diethylentriamin, 3-(Diethylamino)propylamin, Piperazin, Butylamin, Dimethylami- noethanol, Dodecylamin, Triethylamin, Amin-terminiertes Polybutadien and Mischungen daraus besteht.

5. Verfahren gemaB Anspruch 4, worin die aminhaltige Verbindung Ethylendiamin ist. 40 6. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung ein aus der Gruppe ausgewahltes Monomer oder Prapolymer enthalt, die aus einer Epoxyverbindung, einer Acrylatverbindung, einer Iso- cyanatverbindung, einer Anhydridverbindung und einem oder mehreren Ketiminhartungsmitteln besteht.

45 7. Verfahren gemaB Anspruch 6, worin die Menge der zinnhaltigen organischen Verbindung 0,1 bis 5 Gew.-% der polymeren Zusammensetzung betragt.

8. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung eine Klebstoffzusammen- setzung ist, die eine Mischung aus einem polyfunktionellen Acrylat, einem polyfunktionellen Epoxyd und einem so Ketimin enthalt, das aus einem Polyamin und Diisopropylketon hergestellt ist, wobei das Ketimin aus der Gruppe ausgewahlt ist, die aus einem Triketimin, einem Tetraketimin und Mischungen daraus besteht.

9. Verfahren gemaB Anspruch 1 , worin die Amin-hartbare polymere Zusammensetzung eine Klebstoffzusammen- setzung ist, die eine Mischung aus dem Reaktionsprodukt eines Acrylats und eines Epoxyds und einem Ketimin 55 enthalt, das aus einem Polyamin und Diisopropylketon hergestellt ist, wobei das Ketimin aus der Gruppe ausgewahlt ist, die aus einem Triketimin, einem Tetraketimin und Mischungen daraus besteht.

10. Verfahren gemaB Anspruch 1, wobei die die zinnhaltige organische Verbindung bildende Reaktion weiterhin das

11 EP0 586 615B1

Reagieren des Zinnalkanoats und der aminhaltigen Verbindung mit Wasser umfaBt.

11. Polymere Zusammensetzung enthaltend eine Mischung aus einem Amin-hartbaren Polymer, einem latenten Amin- hartungsmittel, das aus der Gruppe ausgewahlt ist, die aus einem Ketimin, Aldimin, einem Enamin oderOxazolidin 5 besteht, und einer katalytisch wirksamen Menge einer zinnhaltigen organischen Verbindung, die durch die Reak- tion eines Zinnalkanoats mit 2 bis 20 Kohlenstoffatomen und einer aminhaltigen Verbindung gebildet ist.

13. Polymere Zusammensetzung gemaB Anspruch 11 oder 12, worin die aminhaltige Verbindung ein mono- oder polyfunktionelles Amin ist, das aus der Gruppe ausgewahlt ist, die aus Ethylendiamin, Triethylentetraamin, Diethy- lentriamin, Epoxyaddukten von Triethylentetraamin, Epoxyaddukten von Ethylendiamin, Epoxyaddukten von is Diethylentriamin, 1 ,3-Diaminopropan, 1 ,4-Diaminobutan, Hexandiamin, 4, 9-Dioxadodecan-1 ,12-diamin, 4,4'-Dia- minodicyclohexylmethan, 9-Aminomethylstearylamin, Polybutadiendiamin, m-Phenylendiamin, Tris(aminoethyl) amin, 2-Methylpentamethylendiamin, Bisaminopropylpiperazin, Diethylentriamin, 3-(Diethylamino)propylamin, Piperazin, Butylamin, Dimethylaminoethanol, Dodecylamin, Triethylamin, Amin-terminiertes Polybutadien und Mi- schungen daraus besteht. 20 14. Verfahren zur Hartung einer Zusammensetzung gemaB mindestens einem der Anspruche 11 bis 13 durch Feuch- tigkeits-induzierte Hydrolyse des latenten Aminhartungsmittels in Anwesenheit der zinnhaltigen organischen Ver- bindung, wobei das Polymer durch das bei der Hydrolyse freigesetzte Amin vernetzt ist.

25 15. Verfahren zur Herstellung einer geharteten polymeren Zusammensetzung umfassend das Harten der polymeren Zusammensetzung gemaB Anspruch 11 oder 12.

Revendications 30

Revendications pour les Etats contractants suivants : DE, FR, GB

1. Procede d'hydrolyse induite par I'humidite d'un agent durcissant contenant une amine latente, dans une compo- 35 sition polymere durcissable par une amine, caracterise en ce que I'agent durcissant contenant une amine latente est une cetimine, une aldimine, une enamine, ou une oxazolidine, qui comprend la combinaison de I'agent de durcissement avec une quantite catalytiquement efficace d'un compose organostannique forme a partir de la reaction d'un alcanoate stanneux ayant de 2 a 20 atomes de carbone et d'un 40 compose contenant une amine, et I'hydrolyse de I'agent de durcissement.

2. Procede selon la revendication 1 , caracterise en ce que le rapport de moles d'alcanoate stanneux aux equivalents de groupes amino dans le compose contenant une 45 amine, va de 1 :8 a 8:1 .

3. Procede selon la revendication 1 , caracterise en ce que I'alcanoate stanneux est I'octoate stanneux. 50 4. Procede selon la revendication 1 , caracterise en ce que le compose contenant une amine est une amine mono- ou polyfonctionnelle choisie dans le groupe qui consiste en I'ethylenediamine, la triethylenetetraamine, la diethylenetriamine, les adduits epoxydede triethylenetetraamine, 55 les adduits epoxy d'ethylenediamine, les adduits epoxy d'ethylenetriamine, la 1 ,3-diaminopropane, le 1,4-diaminobutane, I'hexanediamine, la4,9-dioxadodecane-1,12-diamine, le 4,4'-diaminodicyclohexylmethane, le 9-amino- methylstearyl-amine, la polybutadiene diamine, la m-phenylenediamine, la tris-(aminoethyl)amine, 2-methylpentamethylenediamine, la bis-aminopropylpiperazine, la diethylenetriamine, la 3-(diethylamino)propylamine, lapipe-

12 EP0 586 615B1

razine, la butylamine, le dimethylaminoethanol, la dodecylamine, la triethylamine, le polybutadiene termine par une amine, et les melanges de ceux-ci.

5. Procede selon la revendication 4, 5 caracterise en ce que le compose contenant une amine est I'ethylenediamine.

6. Procede selon la revendication 1 , caracterise en ce que 10 la composition polymere durcissable par une amine comprend un monomere ou prepolymere choisi dans le groupe qui consiste en un compose epoxy, un compose acrylate, un compose isocyanate, un compose anhydride et un ou plusieurs agents de durcissement cetimines.

7. Procede selon la revendication 6, is caracterise en ce que la quantite de derive organostannique varie de 0,1 a 5 % en poids de la composition polymere.

8. Procede selon la revendication 1 , caracterise en ce que 20 la composition polymere durcissable par une amine, est une composition adhesive qui comprend un melange d'acrylate polyfonctionnel, un epoxy polyfonctionnel, et une cetimine preparee a partir d'une polyamine et de dii- sopropylcetone, la cetimine etant choisie dans le groupe consistant en une tricetimine, une tetracetimine et les melanges de celles-ci.

25 9. Procede selon la revendication 1 , caracterise en ce que la composition polymere durcissable par une amine est une composition adhesive comprenant un melange de produits de reaction d'un acrylate et d'un epoxy et d'une cetimine preparee a partir d'une polyamine et de diiso- propylcetone, la cetimine etant choisie dans le groupe consistant en un tricetimine, une tetracetimine et les me- 30 langes de celles-ci.

10. Procede selon la revendication 1, caracterise en ce que la reaction formant le derive organostannique inclut en outre la reaction de I'alcanoate stanneux et du compose 35 contenant une amine, avec de I'eau.

1 1 . Composition polymere comprenant un melange de polymere durcissable par une amine, un agent de durcissement contenant une amine latente, choisi dans le groupe consistant en une cetimine, une aldimine, une enamine, ou une oxazolidine et une quantite catalytiquement efficace d'un derive organostannique forme a partir de la reaction 40 d'un alcanoate stanneux ayant de 2 a 20 atomes de carbone et d'un compose contenant une amine.

12. Composition polymere selon la revendication 11, caracterisee en ce que le derive organostannique est forme a partir de la reaction d'un alcanoate stanneux ayant de 2 a 20 atomes de 45 carbone, d'un compose contenant une amine et de I'eau.

13. Composition polymere selon la revendication 11 ou 12, caracterisee en ce que le compose contenant une amine est un polyamine mono- ou polyfonctionnelle choisie dans le groupe qui consiste so en I'ethylenediamique, la triethylenetetraamine, la diethylenetriamine, les adduits epoxy de triethylenetetramine, les adduits epoxy d'ethylene diamine, les adduits epoxy de thylenetriamine, le 1 ,3-diaminopropane, le 1 ,4-diaminobutane, I'hexane diamine, la 4, 9-dioxadodecane-1 ,12-diamine, le 4,4'-diaminodicyclohexylmethane, la 9-aminomethylstearylamine, la polybutadiene diamine, la m-phenylenediamine, latris(aminomethyl)amine, Ia2-methylpentamethylenediamine, la bis-aminopropylpiperazine, la diethylenetriamine, la 3-(diethylamino)propylamine, la 55 piperazine, la butylamine, le dimethylaminoethanol, la dodecylamine, la triethylamine, le polybutadiene termine par une amine, et les melanges de ceux-ci.

14. Procede de durcissement d'une composition selon au moins I'une des revendications 11 a 1 3 par hydrolyse induite

13 EP0 586 615B1

par I'humidite d'un agent de durcissement contenant une amine latente en presence d'un derive organostannique, le polymere etant reticule par I'amine liberee par I'hydrolyse.

15. Composition polymere durcie comprenant le produit de reaction de la composition polymere selon les revendica- 5 tions 11 ou 12.

Revendications pour I'Etat contractant suivant : ES

10 1. Procede d'hydrolyse induite par I'humidite d'un agent durcissant contenant une amine latente, dans une composition polymere durcissable par une amine, caracterise en ce que I'agent durcissant contenant une amine latente est une cetimine, une aldimine, une enamine, ou une oxazolidine, qui comprend la combinaison de I'agent de durcissement avec une quantite catalytiquement efficace d'un compose is organostannique forme a partir de la reaction d'un alcanoate stanneux ayant de 2 a 20 atomes de carbone et d'un compose contenant une amine, et I'hydrolyse de I'agent de durcissement.

2. Procede selon la revendication 1 , caracterise en ce que 20 le rapport de moles d'alcanoate stanneux aux equivalents de groupes amino dans le compose contenant une amine va de 1 :8 a 8:1 .

3. Procede selon la revendication 1 , caracterise en ce que 25 I'alcanoate stanneux est I'octoate stanneux.

4. Procede selon la revendication 1 , caracterise en ce que le compose contenant une amine est une amine mono- ou polyfonctionnelle choisie dans le groupe qui consiste 30 en I'ethylenediamine, la triethylenetetraamine, la diethylenetriamine, les adduits epoxydede triethylenetetraamine, les adduits epoxy d'ethylenediamine, les adduits epoxy d'ethylenetriamine, le 1 ,3-diaminopropane, le 1,4-diaminobutane, I'hexanediamine, la4,9-dioxadodecane-1,12-diamine, le 4,4'-diaminodicyclohexylmethane, la 9-aminomethylstearylamine, la polybutadiene diamine, la m-phenylenediamine la tris(aminoethyl)amine, la 2-methylpentamethylenediamine, la bis-aminopropylpiperazine, la diethylenetriamine, la 3-(diethylamino)propylamine, lapipe- 35 razine, la butylamine, le dimethylaminoethanol, la dodecylamine, la triethylamine, le polybutadiene termine par une amine, et les melanges de ceux-ci.

5. Procede selon la revendication 4, caracterise en ce que 40 le compose contenant une amine est I'ethylenediamine.

6. Procede selon la revendication 1 , caracterise en ce que la composition polymere durcissable par une amine comprend un monomere ou prepolymere choisi dans le groupe 45 qui consiste en un compose epoxy, un compose acrylate, un compose isocyanate, un compose anhydride et un ou plusieurs agents de durcissement cetimines.

7. Procede selon la revendication 6, caracterise en ce que so la quantite de derive organostannique varie de 0,1 a 5 % en poids de la composition polymere.

8. Procede selon la revendication 1 , caracterise en ce que la composition polymere durcissable par une amine, est une composition adhesive qui comprend un melange 55 d'acrylate polyfonctionnel, un epoxy polyfonctionnel, et une cetimine preparee a partir d'une polyamine et de dii- sopropylcetone, la cetimine etant choisie dans le groupe consistant en une tricetimine, une tetracetimine et les melanges de celles-ci.

14 EP0 586 615B1

Procede selon la revendication 1 , caracterise en ce que la composition polymere durcissable par une amine est une composition adhesive comprenant un melange de produits de reaction d'un acrylate et d'un epoxy et d'une cetimine preparee a partir d'une polyamine et de diiso- propylcetone, la cetimine etant choisie dans le groupe consistant en un tricetimine, une tetracetimine et les melanges de celles-ci.

Procede selon la revendication 1 , caracterise en ce que la reaction formant le derive organostannique inclut en outre la reaction de I'alcanoate stanneux et du compose contenant une amine, avec de I'eau.

Composition polymere comprenant un melange de polymere durcissable par une amine, un agent de durcissement contenant une amine latente, choisi dans le groupe consistant en une cetimine, une aldimine, une enamine, ou une oxazolidine et une quantite catalytiquement efficace d'un derive organostannique forme a partir de la reaction d'un alcanoate stanneux ayant de 2 a 20 atomes de carbone et d'un compose contenant une amine.

Composition polymere selon la revendication 11, caracterisee en ce que le derive organostannique est forme a partir de la reaction d'un alcanoate stanneux ayant de 2 a 20 atomes de carbone, d'un compose contenant une amine et de I'eau.

Composition polymere selon la revendication 11 ou 12, caracterisee en ce que le compose contenant une amine est un polyamine mono- ou polyfonctionnelle choisie dans le groupe qui consiste en I'ethylenediamine, la triethylenetetraamine, la diethylenetriamine, les adduits epoxy de triethylenetetramine, les adduits epoxy d'ethylene diamine, les adduits epoxy de diethylenetriamine, le 1 ,3-diaminopropane, le 1 ,4-diaminobutane, I'hexane diamine, la 4, 9-dioxadodecane-1 ,12-diamine, le4,4'-diaminodicyclohexylmethane, la 9-aminomethylstearylamine, la polybutadiene diamine, la m-phenylenediamine, latris(aminomethyl)amine, Ia2-methylpentamethylenediamine, la bis-aminopropylpiperazine, la diethylenetriamine, la 3-(diethylamino)propylamine, la piperazine, la butylamine, le dimethylaminoethanol, la dodecylamine, la triethylamine, le polybutadiene termine par une amine, et les melanges de ceux-ci.

Procede de durcissement d'une composition selon au moins une des revendications 11 a 13 par hydrolyse induite par I'humidite, d'un agent de durcissement contenant une amine latente en presence d'un derive organostannique, le polymere etant reticule par I'amine liberee par I'hydrolyse.

Procede de preparation d'une composition polymere durcie qui comprend le durcissement de la composition polymere selon la revendication 11 ou la revendication 12.