RU2261885C2 - Gluing composition - Google Patents

Abstract

FIELD: glues.

SUBSTANCE: invention relates to high-strength glues of cold hardening able to harden in the range of temperatures 10-15°C under conditions of enhanced moisture and on wetted surfaces. Invention proposes a glue composition comprising the following components, mas. p. p.: epoxydiane resin, 100; polyamide resin (product of condensation of polyethylene polyamine with higher unsaturated synthetic dicarboxylic acid methyl esters), 14-16; organosilicon amine, 1.15-1.30, and, additionally, chlorine-containing resin, 14-30; amine hardening agent, 8-22, and catalyst, 0.5-1.6. For improving the technological effectiveness the composition can comprise additionally mineral filling agent (titanium dioxide, asbestos or synthetic corundum) in the amount 5-20 mas. p. p. Prepared gluing composition can be used for repair work of glued constructions, articles and aviation technique aggregates in field conditions, and for gluing metallic and nonmetallic materials and aviation and other branches of machine engineering. Invention provides enhancing strength in shift, exfoliation and break off, enhanced water proofing, in tropic climate, possibility for hardening and retaining strength properties after hardening in the range of temperature 10-15°C under conditions of enhanced moisture and on wetted surfaces.

EFFECT: improved properties of gluing composition.

8 cl, 4 tbl, 1 ex

Description

The present invention relates to the field of high-strength cold-curing adhesives, capable of curing in the temperature range of 10-15 ° C in conditions of high humidity and on wet surfaces, designed primarily for field repair of glued structures, including cellular, parts and components of aircraft , as well as for use as a structural adhesive composition for bonding metal and non-metallic materials in aviation and other engineering industries.

Known adhesive composition containing an epoxy diane resin, triglycidyl chloropolyol resin, polyethylene polyamine and a 50% solution in diethylene glycol of complexes of boron trifluoride with aniline or n-toluidine (RF patent No. 1806158).

A disadvantage of the known composition is that it cures at a temperature of 25 ± 5 ° C, which does not allow its use for repair of glued structures in the field.

The closest analogue adopted for the prototype is the adhesive composition of the following composition, parts by weight;

epoxy resin brand ED-5  60 polyamide resin is a condensation product fractions of polyethylene polyamine containing diethylene triamine and triethylenetetramine, and dimerized fatty acids soybean oil  40 a mixture of aminoethoxysilanes (about 98% diethylaminomethylene triethoxysilane and about 2% aminohexamethylene-6-aminomethylenetriethoxyaminosilane)  0.6 filler  5

(A.S. USSR No. 590976).

The disadvantages of the adhesive composition of the prototype are low adhesive strengths under shear and separation, water and tropic resistance, low elasticity (peeling strength) and the inability to cure it at temperatures below 18 ° C, which does not allow it to be used for repairs in the field (in temperature range 10 ° -15 ° C and with high humidity) parts and assemblies of aircraft.

The technical task of the invention is to increase the shear strength, peeling (elasticity) and separation, water and tropic resistance, the possibility of curing and maintaining strength properties after curing in the temperature range 10-15 ° C in conditions of high humidity and on wet surfaces.

The solution of the technical problem is achieved by the fact that the proposed adhesive composition comprising an epoxy diane resin, polyamide resin and organosilicon amine, characterized in that as a polyamide resin it contains a condensation product of polyethylene polyamine with methyl esters of higher synthetic unsaturated dicarboxylic acids and additionally it contains a chlorine-containing resin , amine hardener and catalyst in the following ratio, wt.h .:

epoxy diane resin  100 polyamide resin  14-36 organosilicon amine  1.15-1.30 chlorine resin  14-30 amine hardener  8-22 catalyst  0.5-1.6

As the organosilicon amine, the composition contains bisparaaminophenyleneaminomethylene tetramethyldisiloxane,

γ-aminopropyltriethoxysilane, 1-aminohexamethylene-6-aminomethylenetriethoxyaminosilane, diethylaminomethylene triethoxysilane or mixtures thereof.

As a chlorine-containing resin, the composition contains N, N, N ', N'-tetraglycidyl derivative of 3,3-dichloro-4,4-diaminodiphenylmethane, the product of the interaction of epichlorohydrin with water and a reactive chlorine-containing resin.

As an amine hardener, the composition contains the condensation products of phenol, formaldehyde and dimethylamine or a polyester with amine groups.

As a catalyst, the composition comprises polyethylene polyamine, dicyanoethylethylenediamine or N, N, N ', N'-tetramethylhexamethylene diamine.

To impart thixotropy and improve manufacturability, the proposed composition may additionally contain a mineral filler in an amount of 5-20 m.h.

As a mineral filler, it may contain titanium dioxide, asbestos or electrocorundum.

The composition is capable of curing in the temperature range of 10-15 ° C in conditions of high humidity and on wet surfaces,

The proposed adhesive composition has the ability to cure in the temperature range of 10-15 ° C in conditions of high humidity and on wet surfaces, while the composition of the prototype under these conditions remains in a highly viscous state, which makes it impossible to apply it to glued surfaces.

The qualitative and quantitative ratio of the components in the present invention allows to obtain an adhesive composition with the possibility of curing in the temperature range of 10-15 ° at high humidity and on wet surfaces while maintaining strength properties after curing in these conditions.

As a polyamide resin, condensation products of polyethylene polyamine with methyl esters of both dimerized fatty acids of vegetable oils and higher synthetic dicarboxylic acids can be used, but it is preferable to use condensation products of polyethylene polyamine with methyl esters of higher unsaturated dicarboxylic acids of electrochemical synthesis (TU 6-10-11- 569-22-87) with an amine number of 460-490 mg KOH / g.

As an organosilicon amine, various representatives of this class can be used, but it is preferable to use bisparaaminophenyleneaminomethylene tetramethyldisiloxane (TU 6-02-7-187-85), γ-aminopropyltriethoxysilane (TU 6-10-724-77), 1-aminohexamethylene-6-aminomethylenetriethoxyaminos (TU 6-02-586-86), diethylaminomethylenetriethoxysilane (TU 6-02-573-86) or mixtures thereof.

To achieve a technical result, various chlorine-containing resins can be used in the present invention, but it is most preferable to use N, N, N ', N'-tetraglycidyl derivative of 3,3-dichloro-4,4-diaminodiphenylmethane with a mass fraction of chlorine of 13-15% (TU 6-05-1725-75), the product of the interaction of epichlorohydrin with water in the presence of an acid catalyst (TU P-206-70) with a mass fraction of chlorine of 15-20% and a liquid butadiene nitrile reactive chlorine-containing resin with a mass fraction of chlorine of 2.5-3, 5% (TU 2294-004-23112977-2002).

Any similar hardeners can be used as the amine hardener, but the best technical result is achieved using condensation products of phenol, formaldehyde and dimethylamine - such as 2,4,6-tris (dimethylaminomethyl) phenol (TU 6-09-4136-75) and 2- (dimethylaminomethyl) phenol (TU 6-05-241-295-81) or a polyester with amine groups (TU2492-003-23112977-2000) with a mass fraction of amine groups of 2.8-9.8% and a dynamic viscosity of 15 Pa · s at 25 C.

Both aliphatic and aromatic amines can be used as a catalyst, but the best technical result is achieved using aliphatic amines - dicyanoethylethylenediamine (TU 6-05-1863-78), N, N, N, N-tetramethylhexamethylenediamine (TU 6-09 -14-1723-79) and polyethylene polyamine (TU 6-02-594-80).

Various fillers can be used as a mineral filler, but it is preferable to use titanium dioxide (GOST 9808-75), asbestos (TU 6-05-1379-86) and electrocorundum (TU 6-02-05-68).

The compositions of the proposed adhesive composition of cold curing and adhesive composition of the prototype are presented in table 1.

Table 1.
The compositions of the proposed adhesive composition and composition of the prototype Name of components Composition, parts by weight by examples 1 2 3 4 5 6 7 Prototype Epoxy Diane resin (GOST 10587-84) ED-16 - 100 - - - 100 - ED-20 100 - - 100 100 - - ED-22 - - 100 - - - 100 ED-5 60 Polyamide resin - - - - - - - 40 The condensation product of polyethylene polyamine with methyl esters of higher unsaturated synthetic dicarboxylic acids 14.0 22.6 18.8 25.5 29.5 36.0 16.5 - 1-aminohexamethylene-6-aminomethylene triethoxysilane - 1,0 - - 1,2 - - Diethylaminomethylene triethoxysilane - 0.3 - - - - 1.3 0.6 Bisparaaminophenyleneaminomethylene tetramethyldisiloxane 1.15 - - 1.15 - 0.2 - γ-aminopropyltriethoxysilane - - 1.18 0.15 - 1,1 - N, N, N, N'-tetraglycidyl derivative of 3,3-dichloro-4,4-diaminodiphenylmethane 14 - - twenty - - - - The product of the interaction of epichlorohydrin with water - - thirty - - - 25 - Reactive liquid chlorine butadiene nitrile resin - eighteen - - 22 - twenty Amine Polyester - - - eighteen fifteen - 22 - 2,4,6-tris- (dimethylaminomethyl) phenol 10 - nine - - - - - 2 (dimethylaminomethyl)) enol - 12 - - - 8 - - Dicyanoethyl diethylenetriamine - - - 1,0 - - 1.4 - Polyethylene polyamine - 0.9 - - - 1,1 - -

N¹-тетраметилгексаметилендиаминN ₁ N ₁ N

N ¹ -tetramethylhexamethylenediamine 0.5 - 1,6 - 1.3 - - - Titanium dioxide - - thirty - - - 25 - Asbestos 5 - - - - - - 5 Electrocorundum - 10 - fifteen - - - -

Examples of implementation

Example 1

The adhesive composition of example 1 is prepared by sequentially mixing the components in the ratios shown in table 1 of example 1. The composition is thoroughly mixed after the introduction of each subsequent component.

The technology for preparing the adhesive composition in examples 2-7 is similar to the preparation of the adhesive composition in example 1.

The adhesive compositions are applied to surfaces prepared for gluing (anodized in chromic acid or sanded and degreased) with a spatula in an even layer on both surfaces to be glued. Bonding is carried out at a temperature of 18-20 ° C for 72 hours.

The shear strength of adhesive joints is evaluated according to GOST 14759-69, peeling - RTM 1.2.015-81, peeling - GOST 14760-69.

The properties of the proposed structural adhesive composition are presented in table 2.

Table 2.
Properties of the proposed adhesive composition and the composition of the prototype Properties The proposed adhesive composition according to examples Prototype 1 2 3 4 5 6 7 Shear strength, kgf / cm ² , adhesive joints at test temperature, ° C: twenty 260 255 270 295 280 275 268 150 80 165 160 170 206 180 170 155 90 125 90 89 95 132 125 105 95 fifty Peeling strength (elasticity), kgf / cm, adhesive joints at test temperature, ° С: twenty 3,7 4.4 4.2 5,6 4.7 4,5 5.2 0.3 80 3.0 4.0 3.8 4.0 3,5 3.0 3.8 0.2 125 1.8 2.0 1.9 2.0 2.2 1.8 1.9 0.1 Strength with uniform separation, kgf / cm ² , at test temperature, ° C: twenty 380 400 370 400 420 405 390 204 80 190 205 195 210 220 215 190 100 Shear strength, kgf / cm ² , adhesive joints after exposure to various factors: - water for 3 months at a test temperature, ° C: twenty 255 252 263 283 265 260 263 90 80 160 155 158 198 170 163 152 75 - tropical climate chambers for 3 months at the test temperature, ° С: twenty 250 250 268 287 273 253 263 110 80 158 155 165 200 175 163 150 70 - elevated temperatures: 80 ° C - 1000 h, at test temperature, ° C: twenty 275 268 283 305 295 285 275 155 80 170 173 178 210 195 180 160 85 125 100 98 105 135 130 110 105 125 ° C - 1000 h, at test temperature, ° C: twenty 268 260 268 280 265 273 260 160 80 165 158 165 200 165 158 145 - 125 85 90 92 125 115 98 90 45 The tensile strength of the honeycomb samples, kg / cm ² , at the test temperature, ° C: twenty 60 57 56 60 58 57 55 45 80 32 38 40 46 42 43 42 thirty

The tests were carried out on samples of aluminum alloy D16AT, anodized in chromic acid.

Table 3 presents the properties of the adhesive joints when shearing samples of aluminum alloy D16AT anodized in chromic acid, and when tearing off samples of a honeycomb structure (honeycomb - Amg2N foil, sheathing - fungus D16 with shot peening) and the proposed adhesive composition according to example 5, cured in temperature range 10-13 ° C in conditions of high humidity.

Table 3. Cure mode Surface preparation Shear strength, kg / cm, at test temperature, C Strength at separation from cells, kg / cm, at test temperature, C twenty 80 twenty 80 20-22 ° C, 24 hours source 280 180 57 * fifty* 10-13 ° C, 24 source 255 160 48 * 45 * h wet 225 138 35 ** 20** moisturized 248 158 45 * 42 * * destruction of 100% by honeycomb ** destruction of 30% by honeycomb, 70% by glue

Table 4 presents the properties of the proposed adhesive composition according to example 5, cured in the temperature range 10-14 ° C, on various bonded materials.

Table 4. Bonding material Shear strength (kgf / cm ² ) at test temperature, ° C Strength at uniform separation (kgf / cm ² ) at test temperature, ° С twenty 80 twenty 80 Steel 30HSA 284 153 - - Titanium alloy OT-4 295 170 - - Carbon fiber KMU-4 228 * 185 * 62 ** 51 ** Fiberglass EDT-10 215 * 138 * 48 *** 34 ***

* destruction of the material to be bonded - delamination; ** stratification of the skin; *** separation of honeycombs from glue.

The proposed adhesive composition in comparison with the prototype provides an increase in the strength of adhesive joints at a shear at 20 ° C - by an average of 80%, at 80 ° C - by an average of 90%, with peeling - an average of 20 times, when separated from cells - an average of 10-25%.

The proposed adhesive composition for repair in comparison with the prototype has the ability to cure in the temperature range 10-15 ° C at high humidity and on wet surfaces and maintain high strength properties after curing in these conditions, which allows you to quickly and accurately perform repairs of aircraft in the field . In addition, high strength indicators, increased water and tropic resistance, resistance to high temperatures make it possible to use the proposed composition as a structural adhesive composition for bonding metal and nonmetallic materials in the automotive industry, shipbuilding and other engineering industries.

Using the proposed adhesive composition for repair will increase the reliability and resource of aircraft products.

Claims (8)

1. An adhesive composition comprising an epoxy diane resin, a polyamide resin and an organosilicon amine, characterized in that as the polyamide resin it contains a condensation product of polyethylene polyamine with methyl esters of higher unsaturated synthetic dicarboxylic acids and additionally it contains a chlorine resin, an amine hardener and a catalyst in the following the ratio of components, parts by weight: Epoxy Dianova Resin 100 Polyamide resin 14-36 Organosilicon amine 1.15-1.30 Chlorine Resin 14-30 Amine hardener 8-22 Catalyst 0.5-1.6 2. The adhesive composition according to claim 1, characterized in that as an organosilicon amine it contains bisparaaminophenyleneaminomethylene tetramethyldisiloxane, γ-aminopropyltriethoxysilane, 1-aminohexamethylene-6-aminomethylenetriethoxyaminosilane, diethylaminomethylene triethoxysilane or mixtures thereof. 3. The adhesive composition according to any one of claims 1 and 2, characterized in that as the chlorine-containing resin it contains N, N, N ', N'-tetraglycidyl derivative of 3,3-dichloro-4,4-diaminodiphenylmethane, the product of the interaction of epichlorohydrin with water and reactive chlorine-containing resin. 4. The adhesive composition according to any one of claims 1 to 3, characterized in that as an amine hardener it contains phenol, formaldehyde and dimethylamine condensation products or a polyester with amine groups. 5. The adhesive composition according to any one of claims 1 to 4, characterized in that it contains polyethylene polyamine, dicyanethylethylenediamine and N, N, N, N-tetramethylhexamethylene diamine as a catalyst. 6. The adhesive composition according to any one of claims 1 to 5, characterized in that it further comprises a mineral filler in an amount of 5-20 wt.h. 7. The adhesive composition according to claim 6, characterized in that it contains asbestos, titanium dioxide or electrocorundum as a mineral filler. 8. The adhesive composition according to any one of claims 1 to 7, characterized in that it is capable of curing in the temperature range of 10-15 ° C under conditions of high humidity and on wet surfaces.