Adhesive composition

FIELD: chemistry.

SUBSTANCE: invention relates to an adhesive composition for attaching fluorinated rubber to metal. The adhesive composition contains 3-aminopropyl triethoxy silane, paraformaldehyde-based resin in monoethanolamine, ethyl alcohol, deionised water and additionally glycerine. The adhesive composition is meant for spray-treating fittings and then drying the fittings at temperature 140-150°C with adhesive consumption of 60-80 ml/m2.

EFFECT: adhesive composition is capable of providing sufficient adhesive strength with low content of dry residue.

2 tbl, 3 ex

 

The invention relates to the development of the adhesive composition for attaching rubber to metal during vulcanization and can be used in the manufacture of rubber products for the automotive industry.

Know the use of carbofunctional organosilicon derivatives, in particular 3-aminopropyltriethoxysilane (AGM-9), for the preparation of adhesives and surface treatment (Lazarev GV, Sobolevsky MV, Rosenberg V.R. Carbofunctional organosilane and organosiloxane. M.: Chemistry, 1990. - p.124; Novitskaya S. p., Nudelman Z.N., Dontsov AA Forecaster. M: Chemistry, 1988, s). Such adhesives, such as Hemosil 512, etc. may contain resin (rezol, phenolic), IM-9, a solvent (methyl ethyl ketone). The water content of the organic solvent is methylethylketone (TU 6-09-782-76) limited regulatory document and does not exceed 0.8 wt.%. An organic solvent such adhesives is the main water - secondary. Upon dilution with methyl ethyl ketone water in such Klee significantly decreases the adhesive strength of the rubber to the metal.

Famous water company Henkel adhesive XW 7484 and XW7856, which is an aqueous dispersion, cholesteremia on the surface of the heated metal in a solid film (Y. Morozov, Reznichenko S. Recent advances in the chemistry and technology of elastomers - international conference is on rubber and rubber IRC'98, Rubber & rubber, 1, 1999, p.46). Such adhesives comparable to systems containing the solvent, although somewhat inferior to them in strength of attachment of the rubber to the metal. However, for mounting rubbers on the basis of any of the elastomers and what their composition is, no data (Beiersdorf D. Mount rubbers to metal with the help of middleware systems "Henkel". Rubber & rubber, 6, 1996, p.3 7...).

Known adhesives and adhesives for fastening rubber products based on acrylate rubbers to metal surfaces during vulcanization: Hemosil 350 and 360 (dry residue 38-42 and 42-45 wt.%, respectively) of the firm Henkel, water-based glue VA-1 (TU 2294-330-12654617-95, dry residue of not less than 12%).

The composition of the adhesives Hemosil 350 and 360 (by analogy with Chemosil 211) includes soluble organic polymers and dispersed solids in organic solvents (ethanol/ethyl acetate). This product is included in the group flammable substances (Henkel K GaA, SPK 04/90).

The main disadvantages are presented adhesives and glues are a necessity when used to apply different solvents, thinners (organic liquid) and high dry matter content, which is a set of various soluble polymers, dispersed solids.

The composition of water-based glue VA-1 is a water-soluble phenolic resin, polymers (p is libetarian) and dispersed solids. The concrete structure is not given.

Also known aqueous Composition as an adhesive substrate for mounting rubber to metal during vulcanization or adhesive for hot mounting rubbers on the basis of ftorkauchukov and acrylate rubbers containing 3-aminopropyltriethoxysilane, paraformaldehyde, monoethanolamine, glycerol, ethanol, dimethyl ether of triethylene glycol (TGM-3), patent RU No. 2315796. The presence of TGM-3 complicates the composition as TGM-3 water-insoluble and floats on the surface of the solution.

Closest to the claimed method is adhesive composition (Golfarb VI, Lapaeva N.A., Gorban VI, Pichhadze SJ Patent No. 2180675. Adhesive composition, prototype), which is an aqueous adhesive for fluoride rubbers, suitable for attaching the rubber to the metal surface of the valve cuff. The main disadvantage of the adhesive is not sufficiently high adhesive strength.

The technical result of the invention is to achieve a high adhesive strength fluoride rubber to the metal surface of the valve seals by application of aqueous adhesive composition with a low content of dry residue.

This technical result is achieved by the use in the aqueous adhesive composition of the 3-aminopropyltriethoxysilane, resin-based paraf is maldehyde in monoethanolamine, ethyl alcohol, addition of glycerin.

The invention consists in the use of aqueous adhesive composition, capable of providing sufficient adhesive strength for fastening fluoric rubber 420 (base rubber SCF-26 and SCF-26 OHM) to the metal reinforcement cuffs. Increase adhesion is within 13...17% Rel.

We offer adhesive composition for attaching fluorine rubber 420 (base rubber SCF-26) to metal surfaces of valves designed to handle the valve by spraying, followed by drying of the valve at a temperature of 140-150°C at a flow rate of adhesive 60-80 ml/m2. The basic composition of the fluorinated rubbers 420, similar to the composition in A.S. No. 2199560, 27.02.2003, bull. No. 6, comprises parts by weight of: a copolymer of vinylidenefluoride with HEXAFLUOROPROPYLENE SCF-26 - 66, a copolymer of vinylidenefluoride with HEXAFLUOROPROPYLENE low-molecular SCF-26 OHM - 34, magnesium oxide - 5, calcium hydroxide - 6, carbon T-900 - 30, bisphenol - diphenylolpropane - 1,6, the catalyst TABAH - triethylmethylammonium - 0.6, dispersant - low-molecular-weight polyethylene - 1.

Example 1. Technology of preparation of the adhesive composition

To 20 kg of water with stirring, poured the mixture 659,4 g AGM-9 (d=0,942 g/cm3), 20 g of glycerin (d=1,260 g/cm3nD20=l,4740) and 1134 g of ethyl alcohol. After that add 117,2 g of the solution (d=1,172 g/cm3nD0 =1,4735) of paraformaldehyde in monoethanolamine. Monoethanolamine (or 2-hydroxyethylamine), d=1,022 g/cm3nD22=1,4539. The mixture is stirred for 15 minutes and leave at room temperature for one day. The adhesive composition of this example corresponds to sample No. 1, table 1.

In the end you get a viscous opalescense liquid, which is used as an adhesive composition. Applying adhesive to the valve is carried out by spray, brush or dipping, followed by drying at a temperature of 140...150°C.

Example 2. Technology of preparation of a solution of paraformaldehyde in monoethanolamine

A solution of paraformaldehyde in monoethanolamine prepared separately by mixing 1000 g (33,33 mol) of paraformaldehyde in 1022 g (16,67 mol) of monoethanolamine. Dissolving paraformaldehyde in monoethanolamine comes with heat. So paraformaldehyde are added to monoethanolamine portions with stirring, not allowing the temperature rises above 60...80°C. the dissolution Process takes 6...7 hours.

In addition to dissolving paraformaldehyde in monoethanolamine, apparently, the formation of the following compounds:

CH2=O, HO-CH2CH2-N-((CH2-O)nH)2, HO-CH2CH2-NH-(CH2-O)nH, as evidenced by the data of IR spectroscopy, (cm-1):3400 3420..., ν(OH) - concave hydroxyethylene group; 2960, 2890, ν(C-H); 1640 1690..., ν(C=O) - amide I; 1600 - δ(C-H); 1030 1070..., ν(NC3) - tertiary amino groups:

CH2=O, HO-CH2CH2-N-((CH2-O)nH)2, HO-CH2CH2-NH-(CH2-O)nH.

Example 3. Performance evaluation of adhesive composition

The bond strength of rubber fluoric rubber with standard metal samples were evaluated according to THE 38.105-823-88 Details rubber for car Gas, KAMAZ and other plants". The norm THAT is not less than 25 kgf/cm2for seals.

The adhesive composition is applied to the valve, a spray adhesive, drying at 140-150°C, flow rate of the adhesive is 60-80 ml/m2. Samples of the adhesive compositions shown in table 1, the strength characteristics in table 2.

Table 1
Samples tested adhesive compositions (% weight)
ComponentsThe placeholderSample
123456789 10
3-aminopropyltriethoxysilane3,503,013,004,003,502,005,003,05is 3.083,204,50
A solution of paraformaldehyde in monoethanolamine0,400,530,200,600,401,000,700,600,200,600,20
Ethanol6,005,175,007,006,004,008,007,005,007,005,00
Glycerin-0,090,08 0,120,100,060,140,120,080,140,06
Deionized water90,1091,2091,7288,2890,0092,9486,1689,2391,6489,0690,24
The density of the solution, g/cm30.9900,9910.9910.9930.9910.9920.9940,9930,9910,9940,992

Table 2
Physical-mechanical testing of adhesive formulations (average of 5 samples)
SampleThe placeholder 12345678910
Adhesive strength (kgf/cm240,245,846,4of 45.7to 47.241,842,645,946,241,041,2

The analysis of the presented results shows that the optimum concentration of glycerol is in the range of 0.08...to 0.12 wt.%. Deviations from the optimum in the smaller and larger side lead to deterioration of adhesion. Testing the adhesive composition for attaching the rubber to the metal surface of the valve was carried out on fungi and directly on the engine oil seals VAZ with satisfactory results of experiments.

Adhesive composition for attaching a fluoride rubber to metal comprising 3-aminopropyltriethoxysilane, resin-based paraformaldehyde in monoethanolamine, ethyl alcohol and deionized water,characterized in that he further comprises glycerin in the following ratio, wt.%:

3-aminopropyltriethoxysilane3 - 4
a solution of paraformaldehyde in monoethanolamine0,2 - 0,6
glycerin0,08 - 0,12
ethanol5 - 7
deionized waterrest



 

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