RU2443743C1 - Adhesive composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: adhesive composition contains the following in pts.wt: polychloroprene rubber nairit NT - 100, butylphenolformaldehyde resin 101K - 90, zinc oxide - 5, magnesium oxide - 12, thiuram - 2, organic solvent - mixture of ethylacetate and nefras - 800, modifier which is a mixture of aliphatic amine-triethanolamine or polyethylene amine - 0.1-0.3 with Rosil R-175 silica filler - 10. The mixture of alphatic amine and filler is obtained beforehand as a result of a reaction at room temperature.

EFFECT: invention increases strength when gluing together vulcanised rubber.

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Description

The invention relates to adhesive compositions based on chloroprene rubber and can be used in the rubber industry for bonding vulcanized rubbers based on various rubbers to each other.

Known adhesive composition comprising chloroprene rubber, thiuram, zinc oxide, as a resin, the product of the joint condensation of phenol of acetaldehyde and acetanaphthene and a solvent (USSR Author's Certificate No. 1579920, class C09J 111/00; Publ. 23.07.90). As a solvent, a mixture of ethyl acetate and gasoline is used.

However, this adhesive composition does not provide a sufficiently high strength when bonding products from vulcanized rubber.

Known adhesive composition comprising polychloroprene rubber, epoxy resin, low molecular weight butadiene rubber, tertiary amine, solvent (Copyright certificate. USSR No. 685673, class C08L 11/00; Publ. 15.09.79).

However, this adhesive composition has low strength when bonding rubber products based on various rubbers.

Known adhesive composition comprising polychloroprene rubber, butylphenol formaldehyde resin, a copolymer of styrene and piperylene, rosin esterified with glycerol; pine rosin, diphenylguanidine, 2,2-dibenzothiazole disulfide, zinc oxide, magnesium oxide, organic solvent (Pat. 2028358 Russia, MKI ⁶ C09J 111/00; Publish. 09.02.95).

However, the specified adhesive composition, although it has a similar composition, is intended for bonding products from ferrites.

Closest to the invention in technical essence is an adhesive composition comprising 88HT nairite glue, 101K butylphenol formaldehyde resin, zinc oxide, magnesium oxide, thiuram, an organic solvent that is a mixture of ethyl acetate and nefras, the modifier is methacrylic acid glycide ester and bottoms from aniline production ( Pat. 2261883 Russia, IPC ⁷ C09J 111/00; Publ. 10.10.05).

However, the specified adhesive composition does not provide a sufficiently high strength when bonding vulcanized rubber.

Objective: the development of the composition of the adhesive composition having increased strength when bonding vulcanized rubber to each other.

The technical result is to increase the strength when bonding vulcanized rubber to each other.

The technical result is achieved in that the adhesive composition comprising polychloroprene rubber Nairit NT, butylphenol-formaldehyde resin 101K, thiuram, zinc oxide, magnesium oxide, an organic solvent, which is a mixture of ethyl acetate and nefras, and it contains a modifier, which is a mixture of aliphatic, as a modifier amine - triethanolamine or polyethylene polyamine with a silica filler Rosil grade R-175, previously obtained at room temperature, at the following components, wt.h .: polychloroprene rubber Nairit NT - 100.0, butylphenol formaldehyde resin 101K - 90.0, thiuram - 2.0, zinc oxide - 5.0, magnesium oxide - 12.0, the specified organic solvent - 800 , 0, aliphatic amine - 0.1-0.3, silica filler Rosil grade R-175 - 10.0.

Polychloroprene rubber nairit NT (TU-601781-73) is the main film-forming in adhesive adhesives.

Butylphenol formaldehyde resin 101K (TU-60004691277193-97).

Vulcanizing group: zinc oxide (zinc white), magnesium oxide (burnt magnesia GOST 844-79) were previously used in adhesive compositions (Kardashov D.A., Petrova A.V. Polymer adhesives. M .: Chemistry, 1983).

Organic solvent: a mixture of ethyl acetate (GOST 8981-78) and nefras (GOST 443-76).

Triethanolamine (TU 2423-061-05807977-2002) is used for gas purification in the production of pure carbon dioxide, in the textile and cement industries, in the production of cutting fluids, cosmetics, household chemical goods, as raw materials in organic synthesis.

Polyethylene polyamine (TU 2413-214-00203312-2002) is used as a raw material for the production of an active base for corrosion inhibitors, epoxy compounds, amine resins, as a hardener for epoxy resins, varnishes and paints, detergents and additives.

Silica filler Rosil grade R-175 (Rosil-175) (TU 2168-038-00204872-2001) is a fine precipitated silicon dioxide. It is used for the production of tires, rubber products, artificial leather, in the paint and varnish, oil industry.

The modifier is obtained by direct interaction of an aliphatic amine and a silica filler Rosil grade R-175, at room temperature for 1 hour. The modifier is a viscous mass of white.

When using the specified modifier, the adhesive properties of the adhesive composition are significantly increased. This is due to an increase in the content of functional groups in the adhesive composition. The interaction with the macromolecule of chloroprene rubber leads to an increase in the concentration of polar groups and the formation of additional chemical bonds, which contributes to an increase in the mobility of the macromolecule and deeper diffusion of its sections deep into the surface of the vulcanizate. This explains the increase in strength when bonding vulcanized rubber to each other.

The adhesive composition is prepared as follows.

First, a rubber mixture is prepared (a mixture of Nairite NT, magnesium oxide, zinc oxide, thiuram) in a rubber mixer for 10 minutes, while the temperature of the mixer gradually rises (as the components of the mixture are introduced) from 50 ° C to 85 ° C. After unloading the mixture at a temperature of 105 ° C, it is paged for 5 minutes. Then the heated rubber mixture with a part of the solvent (about 0.1 part of the total amount of solvent) is loaded into the glue mixer. The remaining amount of solvent along with other ingredients of the adhesive composition with butylphenol formaldehyde resin indicated by the modifier is loaded in portions into the mixer as the rubber mixture swells. The total adhesive mixing time is 4.5-5 hours, while the introduction of the modifier can be carried out after preparation of the adhesive composition based on the remaining components.

An example of the preparation of the adhesive composition. Into a glue mixer containing 88HT nairite glue prepared in a known manner (TU-2252-033-45539771-2000), including polychloroprene rubber Nairit NT, 101K butylphenol formaldehyde resin, thiuram, zinc oxide, magnesium oxide and an organic solvent, the calculated amount is added, the calculated amount and mix the contents of 5-10 minutes until a homogeneous mass.

Get the adhesive composition 1-6, the compositions of which are shown in table 1.

The glue is a light beige color. The glue is technological, it is well applied to the surface of rubber.

Various contents of the specified modifier were investigated (Table 2). The declared amounts of the components of the modifier aliphatic amine - 0.1-0.3 and silica filler Rosil grade R-175 - 10.0 due to the fact that with an increase or decrease in these dosages, the adhesive strength during bonding decreases.

Comparative tests of the strength properties of adhesive compositions for all variants of the claimed composition and prototype when bonding vulcanized rubber based on polyisoprene rubber (SKI-3), ethylene propylene rubber (SKEPT-40), butadiene nitrile rubber (SKN-18M) and chloroprene rubber (Neoprene AC) in table 2. For comparative tests, 6 variants of compositions were prepared (by the method described in the example) and a composition without a modifier (control example), the formulations of which are presented in Table 1.

The proposed compositions were tested for adhesive shear strength, achieved when kept under a load of 2 kg, at room temperature (20 ° C) for 24 hours. The data are presented in table 2, which shows that the best results were obtained using the composition of compositions 2 and 5. Adhesive shear strength was determined on an MPC-250 tensile testing machine (RTM 1.2.126-88). The technology for bonding samples is as follows. One-time application of the prepared adhesive on the prepared surface, drying of the adhesive film at room temperature (20 ° C) for 1-2 minutes, after which the adhesive surfaces were pressed tightly.

The proposed adhesive composition provides a significant increase in the strength properties of adhesive joints in comparison with the adhesive composition without a modifier. So, the shear strength of the adhesive joint when bonding vulcanized rubber based on SKI-3 without a modifier is 0.47 MPa, and using the proposed modifier 1.24 MPa (composition 5).

Thus, when used in the proposed adhesive composition, the specified strength increases when bonding vulcanized rubber products based on various rubbers, which is due to the participation of this modifier in improving the adhesive properties of the adhesive.

Table 1 Component The content of components, parts by weight, in the composition one 2 3 four 5 6 Test case Polychloroprene rubber Nairit NT one hundred one hundred one hundred one hundred one hundred one hundred one hundred Butylphenol formaldehyde resin 101K 90 90 90 90 90 90 90 Tiuram 2 2 2 2 2 2 2 Zinc oxide 5 5 5 5 5 5 5 Magnesium oxide 12 12 12 12 12 12 12 Organic solvent (a mixture of ethyl acetate and nefras in a percentage of 50:50) 800 800 800 800 800 800 800 Triethanolamine 0.1 0.2 0.3 - - - - Polyethylene polyamine - - - 0.1 0.2 0.3 - Rosil brand R-175 10.0 10.0 10.0 10.0 10.0 10.0 -

table 2 Substrate Type Shear Strength, MPa Metric for composition Test case one 2 3 four 5 6 SKI-3 1.06 1.13 0.83 0.91 1.24 0.87 0.47 SKEPT-40 1,07 1.20 0.85 1.24 1.47 1,03 0.75 SKN-18M - 0.98 0.94 0.95 1.13 - 0.77 Neoprene speaker 1,67 1.70 1.40 1.35 1.44 1.26 0.75

We found that the reason for the increase in the adhesive characteristics of the adhesive composition is not only an increase in the concentration of polar groups when a modifier is introduced into the composition, but also the formation of additional chemical bonds during the interaction of this modifier with mobile allylic chlorine atoms in the polychloroprene rubber macromolecules, which leads to an increase in the density of the spatial network and, apparently, to hardening the adhesive film.

The technical and economic effect obtained from the use of the adhesive composition lies in the fact that its application can significantly improve the quality of fastening of vulcanized rubber products based on various rubbers, and improve the technological parameters of the bonding process.

Claims (1)

Adhesive composition including polychloroprene rubber Nairit NT, butylphenol formaldehyde resin 101K, thiuram, zinc oxide, magnesium oxide, modifier, organic solvent, which is a mixture of ethyl acetate and nefras, characterized in that it contains a modifier, which is a mixture of alumin triethanolamine or polyethylene polyamine and silica filler Rosil grade R-175, previously obtained at room temperature, in the following ratio, wt.h .:
polychloroprene rubber nairit NT one hundred 101K butylphenol formaldehyde resin 90 tiuram 2 zinc oxide 5 magnesium oxide 12 specified organic solvent 800 aliphatic amine 0.1-0.3 silica filler Rosil brand R-175 10