Low-emission liquid film for sealing buildings

Abstract

A composition, including at least one silane group-containing polymer that is liquid at room temperature, at least one epoxide liquid resin, and at least one aliphatic polyamine having a molecular weight of at least 115 g/mol and having at least three amine hydrogens reactive toward epoxide groups. The composition is a liquid that is configured to form a sealing membrane after curing. The sealing film applied in liquid form is isocyanate-free, low-odor, and easy to process because of the low viscosity and the long open time. The sealing film cures quickly and forms a high-quality elastic material having good mechanical properties and good weather resistance.

Claims

1. A composition comprising: at least one polymer which is liquid at room temperature and contains silane groups, at least one liquid epoxy resin, at least one aliphatic polyamine having a molecular weight of at least 115 g/mol and containing at least three amine hydrogens that are reactive toward epoxide groups, wherein: the at least one aliphatic polyamine includes a combination of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and at least one amine selected from the group consisting of triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and N,N′-bis(3-aminopropyl)ethylenediamine, and the composition is a liquid that is configured to form a sealing membrane after curing, and the composition in the cured state at room temperature has an elongation at break of at least 70%.

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 2, wherein the polyether containing silane groups further contains urethane groups and/or urea groups.

4. The composition as claimed in claim 1, wherein a weight ratio between the polymer containing silane groups and the liquid epoxy resin is in the range from 70/30 to 40/60.

5. The composition as claimed in claim 1, wherein the at least one aliphatic polyamine further includes a polyoxyalkylenediamine or -triamine having an average molecular weight in the range from 200 to 500 g/mol.

6. The composition as claimed in claim 1, wherein the at least one aliphatic polyamine further includes an amine represented by formula (I), ##STR00003## where A is an alkylene radical having 2 to 15 carbon atoms which optionally contains one or more nitrogen atoms, R each independently is a hydrogen or methyl or phenyl radical, Q is a five-, six- or seven-membered cycloalkyl or aryl radical optionally 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 having 1 to 18 carbon atoms, m is 1 or 2, and n is 0 or 1 or 2 or 3.

7. The composition as claimed in claim 1, further comprising at least one aromatic diluent having a boiling point of at least 180° C.

8. The composition as claimed in claim 1, further comprising at least one reactive diluent which contains at least one epoxide group.

9. The composition as claimed in claim 1, wherein the composition 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 aliphatic polyamine not being present in the same component as the liquid epoxy resin.

10. The composition as claimed in claim 1, wherein the composition is a three-component composition consisting of a first component, a second component, and a third component, which are produced, packed and stored separately from one another, the liquid epoxy resin, the aliphatic polyamine and the polymer containing silane groups each being present in a separate component.

11. The composition as claimed in claim 1, further comprising at least one constituent selected from the group consisting of driers, accelerators, and plasticizers.

12. A sealing membrane for sealing a roof, the sealing membrane comprising the composition as claimed in claim 1.

13. 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.

14. A roof sealing system comprising: optionally a primer and/or a base coat and/or a repair or leveling compound, at least one layer of the composition as claimed in claim 1 in a layer thickness of 0.5 to 3 mm, optionally in combination with a mechanical reinforcement, and optionally a topcoat and/or seal coat.

15. The composition as claimed in claim 7, wherein the aromatic diluent is at least one selected from the group consisting of 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, and diphenylmethanol.

16. The composition as claimed in claim 15, wherein the aromatic diluent is benzyl alcohol.

17. The composition as claimed in claim 1, wherein the composition in the cured state at room temperature has an elongation at break of at least 80%.

18. The composition as claimed in claim 1, wherein the weight ratio between 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and the at least one amine selected from the group consisting of triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and N,N′-bis(3-aminopropyl)ethylenediamine is in a range of from 10/90 to 90/10.

19. The composition as claimed in claim 1, wherein the composition in the cured state at room temperature has an elongation at break of at least 150%.

20. The composition as claimed in claim 1, wherein the at least one aliphatic polyamine includes the combination of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and at least one of triethylenetetramine and tetraethylenepentamine.

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) “AHEW” stands for amine hydrogen equivalent weight.

(3) “EEW” stands for epoxy equivalent weight.

(4) “Standard climatic conditions” refer to a temperature of 23±1° C. and a relative air humidity of 50±5%. “SCC” stands for “standard climatic conditions”.

(5) Description of Measuring Methods:

(6) Viscosity was determined on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 25 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 0.1 N HClO.sub.4 in acetic acid versus crystal violet).

(8) Silane Group-Containing Polymers Used:

(9) STP Polymer-1:

(10) In the absence of moisture, 1000 g of Acclaim® 12200 polyol (from Covestro; 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% by weight of plasticizer (diisodecyl phthalate).

(12) MS Polymer™ S303H:

(13) Polymer containing silane groups, from the reaction of polyethers containing allyl groups with hydrosilanes (hydrosilylation), being free from urethane groups and/or urea groups (from Kaneka Corp.).

(14) Further Substances Used:

(15) Araldite® GY 250: bisphenol A diglycidyl ether, EEW 187.5 g/eq (from Huntsman) Araldite® PY 302-2: bisphenol A/F diglycidyl ether, EEW 173.5 g/eq (from Huntsman) Araldite® DY E: monoglycidyl ether of C.sub.12 to C.sub.14 alcohols, EEW around 290 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) N-Benzylpropane-1,2-diamine: prepared as described below, AHEW 54.8 g/eq Gaskamine® 240: styrenized 1,3-bis(aminomethyl)benzene, AHEW 103 g/eq (from Mitsubishi Gas Chemical) Dytek® A: 1,5-diamino-2-methylpentane, AHEW 29.0 g/eq (from Invista) Vestamin® IPD: 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g/eq (from Evonik) MXDA: 1,3-bis(aminomethyl)benzene, AHEW 34.0 g/eq (from Mitsubishi Gas Chemical) 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane, AHEW 35.5 g/eq (from Mitsubishi Gas Chemical) TEPA: tetraethylenepentamine (TEPA), AHEW around 30 g/eq (technical, from Huntsman) CeTePox® 0214 H: reaction product of 2,2(4),4-trimethylhexamethylenediamine and acrylonitrile, AHEW 70 g/eq (from CTP) Silquest® A-1120: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, AHEW 74.1 g/eq (from Momentive) DBTDL 10%: dibutyltin(IV) dilaurate, 10% by weight in diisodecyl phthalate Ancamine® K54: 2,4,6-tris(dimethylaminomethyl)phenol (from Air Products) Cardanol: Cardolite® NX-2026 from Cardolite Corp. Rütasolv DI: diisopropylnaphthalene, isomer mixture (from Rütgers)

N-benzylpropane-1,2-diamine

(16) 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%.

(17) Production of Sealing Membranes:

(18) For each sealing membrane, the ingredients specified in tables 1 to 4 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.

(19) Similarly, the ingredients of component-2 specified in tables 1 to 4 were processed and stored.

(20) 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:

(21) 1 minute after mixing, the viscosity was determined at 20° C.

(22) The potlife was determined by using a spatula to agitate 20 grams of the mixed composition at regular intervals. When the mixed composition was felt for the first time to have thickened to too great an extent for reasonable working, the potlife was read off.

(23) 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.

(24) To determine the mechanical properties, the liquid-applied membrane was poured onto a PTFE-coated film to give a film of thickness 2 mm and stored under standard climatic conditions for 14 days, and a few dumbbells having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and these were tested in accordance with DIN EN 53504 at a strain rate of 200 mm/minute for tensile strength (breaking force), elongation at break, and modulus of elasticity at 0.5 to 5.0% elongation (modulus of elasticity 5%). Furthermore, a number of test specimens were punched out for determination of the tear resistance and were tested in accordance with DIN ISO 34 at a strain rate of 500 mm/min.

(25) 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 tables 1 to 4. Here, values for top and bottom that are very similar are a sign of complete and undisrupted curing. After 14 days under SCC, the appearance of all the films was rated visually. After curing, all of the films were absolutely nontacky, free from bubbles, and white to pale yellowish, opaque to semitransparent (referred to as “opaque—transparent”), with a glossy to silk-matt surface. Certain films showed streaking on the surface, and this is reported in each case.

(26) The results are reported in tables 1 to 4.

(27) Examples Z-1 to Z-17 are inventive liquid-applied sealing membranes.

(28) TABLE-US-00001 TABLE 1 Composition and properties of examples Z-1 to Z-6. Example Z-1 Z-2 Z-3 Z-4 Z-5 Z-6 Component-1: STP Polymer-1 47.5 45.0 45.0 45.0 48.0 48.0 Araldite ® GY 250 38.0 38.0 38.0 38.0 38.0 38.0 Vinyltrimethoxysilane 2.5 5.0 5.0 5.0 5.0 5.0 Dioctyl adipate 7.0 7.0 7.0 7.0 7.0 7.0 DBTDL 10% 5.0 5.0 5.0 5.0 2.0 2.0 Component-2: Silquest ® A-1120 0.5 0.5 0.3 0.4 0.4 0.7 Jeffamine ® D-400 19.9 19.9 — 10.6 10.4 10.4 Vestamin ® TMD 2.4 2.4 — — — — N-Benzylpropane- — — 13.0 8.0 7.2 6.8 1,2-diamine Ancamine ® K54 1.2 1.2 0.7 1.0 — — Viscosity [Pa .Math. s] 6.1 3.9 5.1 4.4 4.7 4.5 TFT [min.] 60 65 50 50 95 90 Appearance opaque - opaque - opaque - opaque - opaque - opaque - transp. transp. transp. transp. transp. transp. Tensile strength 5.3 5.0 4.2 6.3 5.8 5.3 [MPa] Elongation at break 133% 125% 122% 128% 128% 101% Modulus of elasticity 5.1 6.7 3.5 5.8 3.4 4.4 5% [MPa] Tear resist. [N/mm] 5.1 6.0 4.4 5.4 3.7 4.0 Shore A top/bottom 68/68 67/59 65/63 69/63 n.d. 68/59 “Tear resist.” stands for “tear resistance”; “transp.” stands for “transparent”; “n.d.” stands for “not determined”.

(29) TABLE-US-00002 TABLE 2 Composition and properties of examples Z-7 to Z-13. Example Z-7 Z-8 Z-9 Z-10 Z-11 Z-12 Z-13 Component-1: STP Polymer-1 53.0 53.0 53.0 53.0 53.0 53.0 53.0 Araldite ® GY 250 38.0 38.0 38.0 38.0 38.0 38.0 38.0 Dioctyl adipate 7.0 7.0 7.0 7.0 7.0 7.0 7.0 DBTDL 10% 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Component-2: Silquest ® A-1120 0.6 0.5 0.5 0.5 0.5 0.4 0.5 Jeffamine ® D-400 26.0 20.8 22.4 19.1 19.9 18.3 19.1 N-Benzylpropane- — 2.5 — — — — — 1,2-diamine Gaskamine ® 240 — — 2.7 — — — — Dytek ® A — — — 2.3 — — — Vestamin ® IPD — — — — 2.4 — — MXDA — — — — — 2.2 — 1,3-BAC — — — — — — 2.3 Ancamine ® K54 1.4 1.3 1.4 1.2 1.2 1.1 1.2 Viscosity [Pa .Math. s] 8.8 9.8 11.2 9.9 10.7 11.5 11.3 TFT [min.] 70 60 70 70 65 65 55 Appearance opaque - opaque - opaque - opaque - opaque - opaque - opaque - transp. transp. transp. transp., transp. transp. transp., streaking streaking Tensile strength 5.6 5.6 5.1 5.8 4.1 3.5 2.7 [MPa] Elongation at break 123% 118% 108% 138% 97% 102% 86% Modulus of 11.4 8.8 9.6 4.3 9.5 3.4 5.4 elasticity 5% [MPa] Tear resist. [N/mm] 7.6 6.5 6.7 3.6 5.5 3.4 3.9 Shore A top/bottom 72/65 77/64 74/65 68/66 75/65 66/65 68/64 “Tear resist” stands for “tear resistance”; “transp.” stands for “transparent”

(30) TABLE-US-00003 TABLE 3 Composition and properties of examples Z-4, Z14 and Z-15. Example Z-4 Z-14 Z-15 Component-1: STP Polymer-1 45.0 45.0 45.0 Araldite ® GY 250 38.0 38.0 38.0 Vinyltrimethoxysilane 5.0 5.0 5.0 Dioctyl adipate 7.0 7.0 7.0 DBTDL 10% 5.0 5.0 5.0 Component-2: Silquest ® A-1120 0.4 0.4 0.4 Jeffamine ® D-400 10.6 10.6 10.6 N-Benzylpropane-1,2-diamine 8.0 8.0 8.0 Ancamine ® K54 1.0 1.0 1.0 Benzyl alcohol — 5.0 — Cardanol — — 5.0 Viscosity [Pa .Math. s] 4.4 2.9 3.2 TFT [min.] 50 80 65 Appearance opaque-transparent opaque-transparent opaque-transparent Tensile strength [MPa] 6.3 5.6 7.0 Elongation at break [%] 128 114 138 Modulus of elasticity 5% [MPa] 5.8 5.0 5.7 Tear resistance [N/mm] 5.4 4.9 4.8 Shore A top/bottom 69/63 66/56 69/58

(31) TABLE-US-00004 TABLE 4 Composition and properties of examples Z-16 and Z-17. Example Z-16 Z-17 Component-1: STP Polymer-1 44.0 — MS Polymer ™ S303H — 44.0  Araldite ® GY 250 25.6 25.6  Araldite ® PY 302-2 6.4 6.4 Araldite ® DY-E 2.0 2.0 Rütasolv DI 5.0 5.0 Vinyltrimethoxysilane 5.0 5.0 Dioctyl adipate 10.0 10.0  DBTDL 10% 2.0 2.0 Component-2: Vestamin ® IPD 2.1 2.1 MXDA 2.0 2.0 TEPA 1.2 1.2 CeTePox ® 0214 H 0.7 0.7 Ancamine ® K54 0.8 0.8 Benzyl alcohol 6.2 6.2 Viscosity [Pa .Math. s] 3.0 1.5 TFT [min.] 75 around 2 days Appearance opaque-transparent inhomogeneous, uneven, nontransparent, sticky at the bottom Tensile strength [MPa] 3.0 0.9* Elongation at break [%] 352 210*    Modulus of elasticity 5% 0.9 0.7* [MPa] Tear resistance [N/mm] 5.4 3.6* Shore A top/bottom 32/35 n.d. *measured after 21 rather than 14 days under SCC “n.d.” stands for “not determined”