DE1719094A1 - Use of a copolymer of 2,3-dichlorobutadiene (1,3) and alpha-halo-acrylonitrile in rubber / metal adhesives - Google Patents

Description

Use of a copolymer of 2,3-dichlorobutadiene (1,3) and α-Halo-Acrylonitrile in Rubber / Metal Adhesives The invention relates to the use of a copolymer of 2,3-dichlorobutadiene (1,3) and α-haloacrylonitrile in a glue for rubber / metal.

It is already a process for the production of dichlorobutadiene copolymers by copolymerization of 2,3-dichlorobutadiene- (1,3) with horyl monomers in the presence known of free radical forming catalysts, according to which a mixture of 10 up to 90% by weight of 2,3-dichlorobutadiene (1,3) and 90 to 10% by weight of α-chlorine or α-Bromoacrylonitrile at temperatures between about 0 and 100 ° C in solution, suspension or emulsion polymerized. will.

It has now been found that such copolymers, the 30 to 90% by weight, preferably 70% by weight, 2,3-dichlorobutadiene (1,3) and 70 to 10% by weight, preferably 30% by weight, α-chloro- or α-bromo-acrylonitrile contained in Adhesives for rubber / metal incorporated, give them excellent adhesive strength.

Such adhesives can be used even under the most unfavorable conditions achieve good bonds. They are also available on a greater number of types of rubber Can be vulcanized on as the well-known rubber / metal adhesive. All common natural and synthetic rubbers can be used when using adhesives that contain such a copolymer contain, with a wide variety of metals, such as aluminum, brass, bronze, nickel, Steel, etc. are glued.

In the case of adhesive mixtures, it is generally necessary to have one component to be provided as a viscosity regulator and film former.

Adhesive mixtures made using the above-mentioned copolymers can be built up, for. B. chlorinated rubber, chlorinated polypropylene, Contain vinyl chloride-vinylidene chloride copolymers, phenolic resins and the like, however, they can also be produced with other macromolecular substances as film formers will. These element mixtures can also contain fillers, extenders and dyes can be incorporated without affecting the bond strength. Bs can a wide variety of vulcanization accelerators are used; good results were with parachinondioxime, 1,3-di- (2-benzothiazolyl-mercaptomethyl-) urea, Benzenethiazolyl disulfide, 4,4'-dithiodimorpholine, dinitrosobenzene and the like achieved.

The invention thus relates to the use of a from 30 to 90 wt., preferably 70% by weight, 2,3-I) chlorobutadiene- (i, 3) and 70 to 10% by weight, preferably 30 wt .-%, α-chloro- or α-bromoacrylonitrile produced copolymer in an adhesive for rubber steel, with 20 to 90% by weight of the copolymer with 80 to 10 wt .-% of a pilming agent are mixed and the mixture itself In a known manner, stabilizers, accelerators and possibly fillers can be incorporated.

In general, the. Adhesive mixture as a 5 to 50% solution used. Particularly suitable solvents are aromatic hydrocarbons, such as benzene, toluene, xylene etc., ketones, esters and chlorinated hydrocarbons, such as menochlorobenzene, dichlorobenzene, perchlorethylene, etc. However, others can also be used organic solvents or solvent mixtures are used, provided that the Adhesive mixture is soluble in them. The choice of the particular solvent to be used depends on the desired viscosity of the solution and the application device, The solvent should also be relatively volatile so that there are no long ones Drying. times are necessary.

The adhesive solution is applied in a manner known per se to a metal or applied a rubber surface. After evaporation of the solvent, the metal and rubber surfaces to be connected are brought together and heated under pressure, 90 that vulcanization can take place. Vulcanization time and temperature depend on the type of materials to be bonded and the components of the adhesive mixture away.

The adhesives according to the invention using the copolymers of 2,3-dichlorobutadiene- (1,3) are made with α-halo-acrylonitrile, have an extremely high bond strength; a rubber / metal bond made with it can practically no longer be solved without the rubber part tearing during the attempt or tear.

The following rubber compounds are then added to the Examples used to illustrate the rubber / metal adhesive according to the invention to be brought.

BUTADIENE-STYRENE rubber mixture SER 1500 rubber 100 parts N, N-diphenylethylenediamine 0.52 parts of zinc oxide 7.04 parts of easy-to-process sewer black (EPC carbon black) 60.13 Parts Asrhaltischer Marzweichmacher 4.05 parts coal tar-saturated hydrocarbon plasticizer 1.60 parts of 2-benzothiazolyl disulfide 0.25 parts tetramethylthiuram disulfide 0.25 Parts sulfur 2.02 parts BUTYL rubber compound isobutylene-isoprene rubber 100 parts Stearic acid 1 part zinc oxide 5 ropes Easy to process sewer carbon black (EPC carbon black) 10 parts of semi-reinforced furnace black (SRF carbon black) 45 parts of dibenzoyl-p-quinone dioxime 6 Parts red lead 10 parts NATURAL RUBBER MIXING @ Smoked Sheets 100 parts Stearic acid parts zinc oxide 8 parts phenyl-ß-naphthylamine 1.20 parts easy to process Sewer soot (EPC soot) 46 parts semi-reinforced furnace soot (SRF soot) 8 parts pine tar 2 parts of 2-benzothiazolyl disulfide 1 part of sulfur 3 parts of NITRIL rubber mixture Butadiene-AcrylniCril-Kautschuk 100 parts zinc oxide 5 parts stearic acid 0.5 parts Easy to process sewer black (EPC black) 50.0 parts Tricresyl phosphate 7.5 parts Dibutyl phthalate 7.5 parts sulfur 1.5 parts 2-benzothiazolyl disulfide 1.5 parts 2-CHLOROBUTADIEN-1, K3 rubber mixture 2-chlorobutadiene-1,3 rubber 100 parts phenyl -ß-naphthylamine 2 parts magnesium oxide 4 parts semi-reinforced furnace black (SRF carbon black) 50 parts Zinc oxide 7 parts sulfur 1 part piperidinium petamethylene dithiocarbonate 0.25 parts The following examples demonstrate the use of adhesive blends from copolymers of 2,3-dichlorobutadiene - (1,3) v. -Halogenacrylonitrile for connection of rubber and a film former with cold rolled steel.

In each example, the adhesive strength according to AST @ standards, strip test D-429-58, Procedure.

EXAMPLE 1 An adhesive mixture was made / using full 3 g Dichlorobutadiene / α-bromoacrylonitrile copolymer (70/30) and 7.0 g chlorinated Natural rubber applied. The mixed polymer and the chlorinated natural rubber were dissolved in 30.9 g of xylene. The adhesive mixture was cold rolled onto a strip Steel applied in the form of a thin film and left to dry. isine Styrene-butadiene rubber mixture was brought into contact with the adhesive film and vulcanized in a press at 1880 C for about 25 minutes. The adhesive strength was determined according to ASTM. It was found that the rubber at a medium Tensile stress of about 9.1 kg / cm2 was 100% destroyed.

BEIS @ IEL 2 The adhesive mixture according to Example 1 was applied to a Strips of cold rolled steel applied and left to dry. I'm second Strips of natural rubber compound were brought into contact with the adhesive film. That The whole thing was vulcanized in a press at 1880 C for about 20 minutes. the adhesive strength was tested and determined according to ASTM.

The rubber was 100% destroyed at about 9.5 kg: cm2.

EXAMPLE 3 An adhesive mix was made using 3.5 g dichlorobutadiene / α-bromoacrylonitrile copolymer (70/30), 6.5 g chlorinated Natural rubber, 0.6 g tribasic lead sulfate, 1.0 g furnace black and 1.0 g quinone dioxime scheduled. All substances were dissolved or dispersed in 32.0 g of @ylene.

A strip of cold rolled steel was cleaned and then with the Adhesive coated in the form of a thin film, which is then left to dry became. an @utadiene styrene rubber compound was combined with the adhesive film and vulcanized in a press for about 25 minutes at 153 ° C. The stability was determined according to ASTM. At an average tensile stress of about 10.3 kg / cm2 100% of the rubber is destroyed.

EXAMPLE 4 The adhesive mixture from Example 3 was applied to a strip cold-rolled steel applied in the form of a thin film and exposed to drying. my natural chewing school mix was brought into contact with the adhesive film and. the whole thing vulcanized at 1530 C for about 20 minutes. She was adhesive strength determined according to AST @.

It became one at an average tension of about 11.2 kg / cm2 100 70% destruction of the rubber detected.

EXAMPLE 5 The adhesive mixture from Example 3 was applied to an otripe cold rolled steel applied in the form of a thin film and then dried. A 2-chlorobutadiene-1,3 rubber compound was combined with the adhesive film and vulcanized the whole thing at 1550 C for about 25 minutes. The adhesive strength was tested according to ASTL. The rubber tore at an average tensile stress of approximately 8.6 kg / cm2 100 o-ig.

Example 6 The material mixture from Example 3 was found to be thinner Film applied to a strip of cold rolled steel and allowed to dry. Nitrile rubber compound was brought together with the adhesive film and the whole thing vulcanized in a press for about 20 minutes at 160 ° C. the Adhesion Strength was tested according to ASTM. At a tensile stress of 8.6 kg / cm2 the rubber closed 100 @ torn.

EXAMPLE 7 The adhesive mixture from Example 3 was produced as a thin film applied to a strip of cold rolled steel and dried. . Butyl rubber mixture was collapsed with the adhesive film and the whole thing in a press about 20 Vulcanized for minutes at 1600 C. The adhesive strength was tested according to ASTM. At a tensile stress of about 5.4 kg / cm2, the rubber was 100% torn.

EXAMPLE 8 An adhesive blend was made using 5.0 g dichlorobutadiene / α-bromacrylonitrile (70/3) and 5.0 g chlorinated polypropylene resin, 0.6 g tribasic lead sulphate, 1.0 g furnace soot made up. All components were dissolved or dispersed in 25.0 g of xylene. The adhesive mix was considered thinner Film applied to strips of cold rolled steel and then dried.

Using the same procedure as in games 1, 2 and 7, SBR rubber, natural rubber and butyl rubber were brought together with the steel strips and tested according to A @ TM. With SBR rubber the result was 90%, with natural rubber 90%; and 100% destruction in the case of butyl rubber. So the adhesive strength was approximately that same as the strength of the rubber sibs.

EXAMPLE 9 An adhesive mixture of 5.0 g dichlorobutadiene / α-bromoacrylonitrile copolymer (70/30), 5.0 g vinyl chloride-vinylidene chloride copolymer, 0.6 g tribasic lead sulphate and 1.0 g carbon black (fast extrusion carbon black) are used. all components were dissolved or dispersed in 25.0 g of xylene. The mixture of substances never applied as a thin film to strips of cold-rolled steel and then dried. SBR rubber, natural rubber and butyl rubber compound were applied to these strips hung up. The strip with the SBR rubber compound was under pressure for 25 minutes at 153 ° @, the sample with the natural rubber mixture for about 20 minutes at 153 ° and vulcanized the sample with the butyl rubber compound at about 1600 for about 20 minutes. All three rubber-to-metal bodies were tested according to ASTM. in the SBR rubber resulted 95% destruction at an average tensile stress of 9.45 kg / cm2. The natural rubber was destroyed by 90% at an average tensile stress of 8.1 kg / cm2. The butyl rubber was 100% destroyed at an average tensile stress of 5.0 kg / cm2.

EXAMPLE 10 An adhesive mixture of 3.0 g dichlorobutadiene / α -Chloroacrylonitrile copolymer (75/25), 7.0 g chlorinated natural rubber, 0.7 g dibasic lead phosphite, 0.9 g dinitrosobenzene. All components were dissolved or dispersed in 32.0 g of xylene. This glue mix was considered thinner Film applied to strips of cold rolled steel and dried. SBR-ummi, natural rubber and butyl rubber compounds were made as well as in Example 9 placed on these strips. There was 100% destruction in all three examined rubber types. It follows that the adhesive strength over the tensile strength of the rubber itself.

EXAMPLE 11 An adhesive mixture of 3.5 g of Vichlorobutadiene / α-chloroacrylonitrile copolymer (70/30), 6.5 g chlorinated natural rubber, 0.6 g dinitrosobenzene, 0.3 g quinone dioxime, 0.6 g benzothiazyl sulfide, 2.0 g iß and 1.0 g dibasic lead phosphite made up. All components were in 48.0 g of xylene dissolved or dispersed. The adhesive was made as a thin film on strips of cold rolled Steel applied and dried. Following the procedure described in Example 7 SBR rubber, natural rubber and butyl rubber compounds were placed on the strips. In all cases the rubber was 100% destroyed during the test. It was closed see that the adhesive strength between the three types of rubber and the steel is about the tensile strength of the tested rubber.

In the examples given above, some adhesive mixtures were used scheduled without an accelerator. In these examples the gums were 100% destroyed. This shows that the adhesive mixtures set up without an accelerator can be. Although the mixture additives are reduced over a very rough range can be, the copolymer should usually not 60 or Exceed 70% of the adhesive build-up. However, as stated above, can the copolymer also contain more than 90% and less than 20% of the adhesive.

Claims (1)

Claim using one of 30 to 90% by weight, preferably 70% by weight, 2,3-dichlorobutadiene (1,3) and 70 to 10% by weight, preferably 30% by weight, α-chloro- or α-bromo-acrylonitrile produced copolymer in one Glue for rubber / metal, where 20 to 90 wt .-% of the copolymer with 80 to 10 % By weight of a pilm-forming agent are mixed, the mixture a stabilizer, accelerator and possibly fillers and the adhesive mixture before use to a 5 to 50% strength by weight solution in an inert organic solvent is resolved.