Curable composition

Abstract

A composition including at least one polymer containing silane groups, at least one epoxy resin, and at least one amine of the formula (I). The composition is low in odor, low in toxicity, and highly workable. It enables low-emission products which cure rapidly at ambient temperature to form macroscopically homogeneous films or bodies having good mechanical properties, high thermal stability and good adhesion properties, the mechanical properties being able to be adjusted from very elastic through to tough elastic. The composition is especially suitable as adhesive and/or sealant or coating.

Claims

1. A composition comprising at least one polymer containing silane groups, at least one epoxy resin, and at least one amine of the formula (I) ##STR00004## where A is selected from the group consisting of 1,2-ethylene, 1,2-propylene, and 1,3-propylene, R each independently is a hydrogen or methyl or phenyl radical, Q is a five-, six- or seven-membered cycloalkyl, or an aryl radical having 4 to 7 carbon atoms, or an aryl radical having an oxygen, sulfur or nitrogen atom in the ring and having 4 to 7 carbon atoms, Y represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino, each having 1 to 18 carbon atoms, m is 1 or 2, and n is 0 or 1 or 2 or 3.

2. The composition as claimed in claim 1, wherein the polymer containing silane groups is a polyether containing silane groups.

3. The composition as claimed in claim 1, wherein it has a content of polymer containing silane groups in the range from 5 to 80 weight %.

4. The composition as claimed in claim 1, wherein the epoxy resin is a liquid resin based on a diglycidyl ether of bisphenol A, of bisphenol F or of bisphenol A/F.

5. The composition as claimed in claim 1, wherein it has an epoxy resin content in the range from 15 to 70 weight %.

6. The composition as claimed in claim 1, wherein A is 1,2-propylene, R is a hydrogen radical, Q is a phenyl radical, m is 1 and n is 0.

7. The composition as claimed in claim 1, wherein R is a hydrogen radical, Q is a phenyl radical, m is 1 and n is 0.

8. The composition as claimed in claim 1, wherein it has a content of amine of the formula (I) in the range from 1 to 35 weight %.

9. The composition as claimed in claim 1, wherein it additionally comprises at least one aminosilane.

10. The composition as claimed in claim 1, wherein it is a two-component composition consisting of a first component and a second component, which are produced, packed and stored separately from one another, the amine of the formula (I) not being present in the same component as the epoxy resin.

11. The composition as claimed in claim 1, wherein it additionally comprises at least one further amine, which does not conform to the formula (I), and/or at least one accelerator.

12. A cured composition obtained from the composition as claimed in claim 1 by mixing all of the ingredients and/or components of the composition, applying the mixed composition and curing the applied composition.

13. A method comprising applying the composition as claimed in claim 1 to a substrate, wherein the composition is applied to the substrate as adhesive and/or sealant or as coating.

14. A bonded and/or sealed or coated article obtained from the method as claimed in claim 13, the article comprising an at least partly cured form of the composition.

15. The composition as claimed in claim 1, wherein A is 1,2-ethylene.

16. The composition as claimed in claim 1, wherein A is 1,2-propylene.

17. A composition comprising: at least one polymer containing silane groups, at least one epoxy resin, and at least one amine of the formula (I) ##STR00005## where A is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 2-methyl-1,5-pentylene, 1,6-hexylene, 2,2(4),4-trimethyl-1,6-hexylene, 1,3-cyclohexylenebis(methylene), (1,5,5-trimethylcyclohexan-1-yl)methane-1,3, 3-aza-1,5-pentylene, 3,6-diaza-1,8-octylene, 3,6,9-triaza-1,11-undecylene, 4-aza-1,7-heptylene, 3-aza-1,6-hexylene, 4,7-diaza-1,10-decylene, and 7-aza-1,13-tridecylene, R in each case is a hydrogen radical, Q is a phenyl radical, m is 2, n is 0, and Y represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino, each having 1 to 18 carbon atoms.

18. A composition comprising: at least one polymer containing silane groups, at least one epoxy resin, and at least one amine of the formula (I) ##STR00006## where A is selected from the group consisting of 3,6-diaza-1,8-octylene, 3,6,9-triaza-1,11-undecylene, 4,7 diaza-1,10-decylene, and 7-aza-1,13-tridecylene, R each independently is a hydrogen or methyl or phenyl radical, Q is a five-, six- or seven-membered cycloalkyl, or an aryl radical having 4 to 7 carbon atoms, or an aryl radical having an oxygen, sulfur or nitrogen atom in the ring and having 4 to 7 carbon atoms, Y represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino, each having 1 to 18 carbon atoms, m is 1 or 2, and n is 0 or 1 or 2 or 3.

Description

EXAMPLES

(1) Adduced hereinafter are working examples which are intended to elucidate the invention described in detail. It will be appreciated that the invention is not restricted to these described working examples.

(2) ANEW stands for amine hydrogen equivalent weight.

(3) EEW stands for epoxy equivalent weight.

(4) Standard conditions refer to a temperature of 231 C. and a relative air humidity of 505%. SC stands for standard conditions.

(5) Description of Measuring Methods:

(6) Viscosity was measured on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1, cone tip-plate distance 0.05 mm, shear rate 10 rpm).

(7) Amine value was determined by means of titration (with 0.1N HClO.sub.4 in acetic acid versus crystal violet).

(8) Polymer Containing Silane Groups Used:

(9) STP Polymer-1:

(10) In the absence of moisture, 1000 g of Acclaim 12200 polyol (from Bayer; low monol polyoxypropylenediol, OH number 11.0 mg KOH/g, water content around 0.02 wt %), 43.6 g of isophorone diisocyanate (Vestanat IPDI from Evonik Industries), 126.4 g of diisodecyl phthalate and 0.12 g of dibutyltin dilaurate were heated to 90 C. with continuous stirring and left at this temperature until the free isocyanate group content as determined by titrimetry had reached a value of 0.63 wt %. Subsequently, 62.3 g of diethyl N-(3-trimethoxysilylpropyl)aminosuccinate were mixed in and the mixture was stirred at 90 C. until it was no longer possible to detect any free isocyanate by means of FT-IR spectroscopy. The silane-functional polymer was cooled to room temperature and stored in the absence of moisture. It was liquid at room temperature and had a viscosity at 20 C. of 99 Pa.Math.s.

(11) STP Polymer-1 contains 10 weight % of plasticizer (diisodecyl phthalate).

(12) Epoxy Resin Used:

(13) Araldite GY 250:

(14) bisphenol A diglycidyl ether, EEW 187.5 g/eq (from Huntsman)

(15) Amines of the Formula (I) Used:

(16) N-Benzylpropane-1,2-diamine:

(17) A round-bottom flask was initially charged with 444.8 g (6 mol) of propane-1,2-diamine under a nitrogen atmosphere at room temperature. With good stirring, a solution of 212.2 g (2 mol) of benzaldehyde in 1500 mL of isopropanol was slowly added dropwise, and the mixture was stirred for 2 hours. The reaction mixture was then hydrogenated in a continuous hydrogenation apparatus with a Pd/C fixed bed catalyst at a hydrogen pressure of 90 bar, a temperature of 85 C. and a flow rate of 5 mL/min. To monitor the reaction, IR spectroscopy was used to check whether the imine band at about 1665 cm.sup.1 had disappeared. Thereafter, the hydrogenated solution was concentrated on a rotary evaporator at 65 C., removing unreacted propane-1,2-diamine and isopropanol. A clear, pale yellowish liquid was obtained. 300 g of this were distilled at 80 C. under reduced pressure, with collection of 237.5 g of distillate at a vapor temperature of 60 to 63 C. and 0.08 to 0.09 bar. A colorless liquid having an amine value of 682 mg KOH/g was obtained, which, by .sup.1H NMR, was a mixture of N.sup.1-benzylpropane-1,2-diamine and N.sup.2-benzylpropane-1,2-diamine in a ratio of about 2/1 and had a GC purity of >97%.

(18) Gaskamine 240:

(19) styrenized 1,3-bis(aminomethyl)benzene, AHEW 103 g/eq (from Mitsubishi Gas Chemical)

(20) Further Substances Used:

(21) DBTDL 10%: dibutyltin(IV) dilaurate, 10% by weight in diisodecyl phthalate Silquest A-1120: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, AHEW 74.1 g/eq (from Momentive) Ancamine K54: 2,4,6-tris(dimethylaminomethyl)phenol (from Air Products) Jeffamine D-230: polyetherdiamine with average molecular weight of 230 g/mol, AHEW 60 g/eq (from Huntsman) Jeffamine D-400: polyetherdiamine with average molecular weight of 430 g/mol, AHEW 115 g/eq (from Huntsman) Vestamin TMD: 2,2(4),4-trimethylhexamethylenediamine, AHEW 39.6 g/eq (from Evonik) Vestamin IPD: 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g/eq (from Evonik) EP adduct 1: reaction product of 1,5-diamino-2-methylpentane and Araldite DY-K, prepared as described hereinafter; AHEW 106.5 g/eq

(22) EP adduct 1 was prepared by heating an initial charge of 4.65 kg of 1,5-diamino-2-methylpentane (Dytek A from Invista) under a nitrogen atmosphere to 70 C. and then, with good stirring, slowly adding 1.83 kg of Araldite DY-K, in the course of which the temperature of the reaction mixture was 70 to 80 C. After 1 hour at 80 C., the reaction mixture was cooled down and 1,5-diamino-2-methylpentane and further volatile constituents were removed by distillation by means of a thin-film evaporator (0.5-1 mbar, jacket temperature 160 C.).

(23) Production of Two-Component Compositions:

(24) For each example, the ingredients specified in tables 1 to 3 were mixed in the specified amounts (in parts by weight) of component-1 by means of a centrifugal mixer (SpeedMixer DAC 150, FlackTek Inc.) and stored with exclusion of moisture.

(25) Similarly, the ingredients of component-2 specified in tables 1 to 3 were processed and stored.

(26) Subsequently, the two components of each composition were processed by means of the centrifugal mixer to give a homogeneous liquid and this was tested immediately as follows:

(27) 1 minute after mixing, the viscosity was determined at 20 C.

(28) To measure the time until the composition became free from tack, abbreviated to TFT, a small portion of the mixed composition at room temperature was applied in a layer thickness of around 3 mm to cardboard and, under standard conditions, a determination was made of the time which elapsed until an LDPE pipette used to gently touch the surface of the composition for the first time no longer had any residues left on it.

(29) The tensile strength, the elongation at break and the elasticity modulus at 0.5 to 5.0% elongation (modulus of elasticity 5%) were determined according to DIN EN 53504 on flat specimens with a length of 75 mm, with a gage length of 30 mm and a gage width of 4 mm, produced by punching from films with a thickness of around 2 mm of the composition cured under the respective reported conditions. The values designated by 10d SC and 14d SC in the tables were determined after storage times of 10 and 14 days, respectively, under standard conditions. The values designated +2d 80 C. were determined on flat specimens which had been stored for 10 days under standard conditions and subsequently for 2 days in a forced air oven at 80 C. For examples Z-1 to Z-7 and Ref-1 to Ref-4, these values were determined with a pulling speed of 200 mm/min. For examples Z-8 to Z-10 and Ref-5 to Ref-8, they were determined with a pulling speed of 10 mm/min.

(30) Shore A hardness was determined according to DIN 53505 on test specimens cured under standard conditions for 14 days. The value in this case was determined in each case on the top, on the side of the test specimen facing the air. Additionally, the test specimen was turned over and a determination was likewise made on the bottom, on the side not exposed to the air. The two values are reported as top/bottom in table 2. Here, values for top and bottom that are very similar are a sign of complete and undisrupted curing.

(31) After 14 days under SC, the appearance of all the films was rated visually. After curing, all of the films were absolutely nontacky, free from blisters, and either nontransparently white, or opaque to semitransparent (referred to as opaque-transparent), or almost transparent, or transparent, in each case with a glossy to silk-matt surface. Example Ref-4 showed streaking on the surface. The results are reported in tables 1 to 3.

(32) Examples Z-1 to Z-10 are inventive compositions. Examples Ref-1 to Ref-8 are comparative examples.

(33) TABLE-US-00001 TABLE 1 Composition and properties of examples Z-1 to Z-3 and of comparative examples Ref-1 to Ref-2. Example Z-1 Z-2 Z-3 Ref-1 Ref-2 Component-1: STP Polymer-1 53.0 53.0 53.0 53.0 53.0 Araldite GY 250 38.0 38.0 38.0 38.0 38.0 DBTDL 10% 2.0 2.0 2.0 2.0 2.0 Dioctyl adipate 7.0 7.0 7.0 7.0 7.0 Component-2: Silquest A-1120 2.5 2.5 2.5 2.5 2.5 N-Benzylpropane- 10.4 7.0 1,2-diamine Gaskamine 240 19.5 Jeffamine D-230 11.4 Jeffamine D-400 7.0 21.8 Ancamine K54 1.2 1.2 1.2 1.2 1.2 Viscosity [Pa .Math. s] 11.7 10.8 13.8 12.1 7.1 TFT [min.] 35 30 35 40 35 Appearance almost opaque- trans- almost trans- trans- trans- parent trans- parent parent parent parent 10 d SC: Tensile strength 8.7 9.8 7.4 6.9 6.0 [MPa] Elongation at break 140% 139% 93% 103% 71% Modulus of elasticity 48.4 26.0 66.5 39.1 40.8 5% [MPa] Tear resist. [N/mm] 20.2 14.1 21.2 13.5 14.3 Tear resist. stands for tear resistance

(34) TABLE-US-00002 TABLE 2 Composition and properties of examples Z-4 to Z-7 and of comparative examples Ref-3 to Ref-4. Example Z-4 Z-5 Ref-3 Z-6 Z-7 Ref-4 Component-1: STP Polymer-1 50.0 50.0 50.0 40.0 40.0 40.0 Araldite GY 250 48.0 48.0 48.0 48.0 48.0 48.0 DBTDL 10% 2.0 2.0 2.0 2.0 2.0 2.0 Dioctyl adipate 5.0 5.0 5.0 Vinyltrimethoxysilane 5.0 5.0 5.0 Component-2: Silquest A-1120 0.3 0.6 0.6 0.3 0.6 0.6 N-Benzylpropane-1,2-diamine 15.3 15.3 Gaskamine 240 28.7 28.7 Jeffamine D-400 23.9 23.9 Vestamin TMD 2.8 2.8 Ancamine K54 0.4 0.8 0.7 0.4 0.8 0.7 Viscosity [Pa .Math. s] 34.4 37.7 24.4 7.9 9.5 6.4 TFT [min.] 40 110 40 85 100 40 Appearance opaque- opaque- opaque- opaque- opaque- opaque- transp. transp. transp. transp. transp. transp., streaking 14 d SC: Tensile strength [MPa] 4.9 7.4 6.7 4.2 6.6 6.1 Elongation at break 120% 81% 80% 80% 67% 61% Modulus of elasticity 5% [MPa] 5.6 7.9 13.2 8.3 11.7 10.3 Tear resist. [N/mm] 5.0 5.2 6.5 6.2 6.0 8.3 Shore A top/bottom 78/75 80/79 88/78 75/74 82/80 81/74 Tear resist. stands for tear resistance; transp. stands for transparent

(35) TABLE-US-00003 TABLE 3 Composition and properties of examples Z-8 to Z-10 and of comparative examples Ref-5 to Ref-8. Example Z-8 Z-9 Z-10 Ref-5 Ref-6 Ref-7 Ref-8 Component-1: STP Polymer-1 32.8 32.8 32.8 32.8 32.8 32.8 32.8 Araldite GY 250 66.5 66.5 66.5 66.5 66.5 66.5 66.5 DBTDL 10% 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Component-2: Silquest A-1120 5.0 5.0 5.0 5.0 5.0 5.0 5.0 N-Benzylpropane- 17.0 8.5 1,2-diamine Gaskamine 240 33.0 Jeffamine D-230 9.5 19.0 Vestamin TMD 13.0 Vestamin IPD 14.0 EP adduct 1 34.0 Viscosity [Pa .Math. s] 6.6 6.3 8.7 5.6 7.4 11.3 21.4 TFT [min.] 140 120 105 120 91 100 90 Appearance nontransp. opaque- opaque- opaque- nontransp. nontransp. nontransp. white transp. transp. transp. white white white 10 d SC Tensile strength 10.3 11.7 14.0 11.3 3.6 4.8 4.9 [MPa] Elongation at 8% 10% 12% 9% 8% 9% 66% break Modulus of 188 186 149 183 47 58 21 elasticity 5% [MPa] +2 d 80 Tensile strength 11.6 15.2 18.2 14.2 3.6 4.9 4.0 [MPa] Elongation at 6% 8% 10% 14% 6% 5% 16% break Modulus of 206 243 231 209 59 86 46 elasticity 5% [MPa] nontransp. stands for nontransparent transp. stands for transparent