DE1719094C3 - Process for the production of an adhesive for bonding rubber to metal - Google Patents

Description

There is already a method of making will. The most diverse volcanic

Dichlorobutadiene copolymers are used by copolymers 30 cation accelerators; good results

The ation of 2,3-dichlorobutadiene- (1,3) with acrylonis were with parachinone dioxime, 1,3-di- (2-benzo-

monomers in the presence of free radical-forming thiazolylmercaptomethyl) urea, benzothiazolyl

Known catalysts, according to which a mixture of disulfide, 4,4'-dithiodimorpholine, dinitrosobenzene u.

10 to 90 percent by weight 2,3-dichlorobutadiene (1,3) like. Achieved.

and 90 to 10 percent by weight α-chlorine or α-bromine 35 The invention relates to a process for acrylonitrile at temperatures between about 0 and the production of an adhesive for connecting 100 ⁰ C in solution, suspension or emulsion poly-rubber with metal Is based on a copolymer of merized. 2,3-dichlorobutadiene (l, 3) with an unsaturated compound has now been found that rubber-metal adhesives can be produced with such a bond of a film former and optionally customary copolymers, additives in an organic solvent, which, have excellent adhesive strength. With indicated by the fact that 20 to 90 weight such adhesives can be achieved good bonds even under unfavorable percent of a copolymer from 30 to 90 weight conditions. In addition, percent 2,3-dichlorobutadiene (1,3) and 70 to 10 are on a larger number of types of rubber weight percent «chlorine or a-bromo-acrylonitrile, vulcanizable with than the known rubber-metal 45 80 to 10 Percentage by weight of a film former adhesive. All customary natural and synthetic mixes, the mix a stabilizer and given types of rubbers can, when using adhesives, an accelerator and fillers incorporated materials that contain such a copolymer, with and this mixture in an organic solution of various metals such as aluminum, brass bronze, nickel, steel etc. 50 dissolves or disperses therein.

In addition to the prior art, according to a preferred embodiment of the

GB-PS 7 09 033 to point out, in the rubber-metal invention, a copolymer of 70 weight

Adhesive mixtures are described, the copoly percent 2,3-dichlorobutadiene (1, 3) and 30 weight

merizates of 2,3-dichlorobutadiene (l, 3) and a percentage of α-chloro- or a-bromoacrylonitrile are used,

contain saturated compounds. In contrast to 55 the mixture are made in a manner known per se

a stabilizer and optionally an accelerator prepared according to the present invention

Adhesives in which the 2,3-dichlorobutadiene (l, 3) / and fillers are incorporated. As with rubber-to-metal

“Chlorine or bromo acrylonitrile usually stick at room temperature if an acidic stabilizer is used

Remains in solution and no tendency to gel like z. B. dibasic lead phosphite or tribasic

Education shows, the adhesives of GB-PS 7 09 033 60 have lead sulfate.

the disadvantage that the copoly- In general, the adhesive mixture is called

merisat tends at room temperature for Gclbildung, 5- used to 50 ° / ₀ solution. As a solvent

which can also be achieved by vigorous stirring during cooling - aromatic hydrocarbons are particularly suitable

lens cannot be prevented. ! Such adhesives, such as benzene, toluene, xylene etc., ketones, esters

After prolonged standing, substances form as a result of the crystalline and chlorinated hydrocarbons, such as monochlorine

sation of the polymer from gel-like structures; they benzene, dichlorobenzene, perchlorethylene etc. It can

Therefore, to use them, they must first, however, also use other organic solvents

60 ⁰ C are heated. or solvent mixtures are used, if

the adhesive mixture is soluble in them. The choice of the solvent to be used in each case is directed depending on the desired viscosity of the solution and the application device. The solvent should also be relatively volatile so that long drying times are not necessary.

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

The adhesives that are produced according to the invention using the copolymers of 2,3-dichlorobutadiene (l, 3) are made with -halo-acrylonitrile, have an extraordinarily high bond strength; one The rubber-metal bond obtained in this way can practically no longer be solved without the attempt Rubber part tears or tears.

The following rubber compounds are used in the examples given below.

25th

Butadiene-styrene-rubber mixture

Parts

Styrene-butadiene rubber 100

Ν, Ν-diphenylethylenediamine 0.52

Zinc oxide 7.04

Sewer soot that is easy to process ... 60.13 Asphaltic resin plasticizer .... 4.05 Coal tar saturated hydrocarbon plasticizer 1.60

2-benzothiazolyl disulfide 0.25

Tetramethylthiuram disulfide 0.25

Sulfur 2.02

Butyl rubber mixture

Parts

Isobutylene isoprene rubber 100

Stearic acid 1

Zinc oxide 5

Sewer soot that is easy to process ... 10

Semi-reinforced furnace soot 45

Dibenzoyl-p-quinone dioxime 6

Lead red 10

Nitrile rubber mixture

Parts

Butadiene-acrylonitrile rubber 100

Zinc oxide 5

Stearic acid 0.5

Sewer soot that is easy to process ... 50.0

Tricresyl phosphate 7.5

Dibutyl phthalate 7.5

Sulfur 1.5

2-benzothiazolyl disulfide 1,5

2-chlorobutaJien-1,3-rubber mixture

Parts

2-chlorobutadiene-1,3-rubber 100

Phenyl-0-naphthylamine 2

Magnesia 4

Semi-reinforced furnace soot 50

Zinc oxide 7

Sulfur 1

Piperidinium pcntamethylene dithiocarbonate 0.25

Natural rubber mixture

Parts

Smoked Sheets 100

Stearic acid 3

Zinc oxide 8

Phenyl-0-naphthylamine 1.20

Sewer soot that is easy to process ... 46

Semi-reinforced furnace soot 8

Pine tar 2

2-benzothiazolyl disulfide 1

Sulfur 3

In each example, the bond strength was determined according to ASTM Standards, Strip Test D-429-58, Method B, definitely.

B e i s ρ i e 1 1

An adhesive mixture was made using 3 g of dichlorobutadiene / λ-BrGmacrylonitrile copolymer (70/30) and 7.0 g of chlorinated natural rubber

scheduled. The copolymer and the chlorinated natural rubber were dissolved in 30.9 g of xylene. the Adhesive mixture was applied to a strip of cold rolled steel in the form of a thin film and leave to dry. A styrene

The butadiene rubber mixture was brought into contact with the adhesive film and ^{vulcanized in a press at 188 °} 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 / cm ^{2 was destroyed} to 100%.

Example 2

The adhesive mixture of Example 1 was applied to a strip of cold rolled steel and leave to dry. A second strip of natural rubber compound was attached to the adhesive film brought into contact. The whole thing was in one

Press vulcanized at 188 ° 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 / cm ^2.

B e i s ρ i e 1 3

It was an adhesive mixture using 3.5 g of dichlorobutadiene / a-bromoacrylonitrile copoly-

5 ^{T 6}

merisat (70/30), 6.5 g chlorinated natural rubber, dispersed. The adhesive mix was considered thinner

0.6 g tribasic lead sulfate, 1.0 g furnace soot and film on strips of cold-rolled steel.

1.0 g of quinone dioxime are made up. All substances were brought in and then dried. .

dissolved or dispersed in 32.0 g of xylene. One strip Following the same procedure as in Examples 1, cold rolled steel was cleaned and then with the 5 2 and 7 styrene-butadiene, natural and butyl

Adhesive coated in the form of a thin film, bonded to the steel strips and rubber

which was then left to dry. Tested according to ASTM For styrene-butadiene rubber

A butadiene styrene rubber mixture was found to be 90%, with natural rubber to 90% and

brought together the adhesive film and in a 100 / _o destruction in the case of butyl rubber. The adhesive press vulcanized at 153 ° C for about 25 minutes. io strength was almost the same as that

The adhesive strength was determined according to ASTM. If the rubber itself is firm,

an average tensile stress of about 10.3 kg / cm ² . .

100% of the rubber was destroyed. Example 9

B ei s Di el 4 ¹ S An adhesive mixture of 5.0 g of dichloro

butadiene / λ-bromoacrylonitrile copolymer (70/30), 5.0 g

The adhesive mixture from Example 3 was made up of vinyl chloride-vinylidene chloride copolymer, 0.6 g of a strip of cold-rolled steel in the form of a thin tribasic lead sulfate and 1.0 g of carbon black. Film applied and exposed to drying. All components were dissolved in 25.0 g of xylene. A natural rubber mixture was dispersed with the adhesive 20 or. The adhesive mixture was brought into contact as stoffilm and the whole as a thin film on strips of kaltgewaltzem Suhl 20 minutes cured at 153 ⁰ C for. The adhesive applied and then dried. Styrene-butadiene strength was determined according to ASTM. Natural rubber and butyl rubber mixture were placed on these strips at an average tensile stress of about 11.2 kg / cm ² . The strip with the SBR Kaueine 100 detected ° / ₀ sodium destruction of the gum. 25 chuk mix was pressurized for 25 minutes

at 153 ° C, the sample with the natural rubber mixture

Example 5 ^{for about 20} minutes at 153 ⁰ C and the sample with

the butyl rubber mixture for about 20 minutes

The adhesive composition of Example 3 was cured at about 160 C ^c. All three rubber-to-metal bodies a strip of cold rolled steel in the shape of a 30 were tested according to ASTM. Applied to the styrene-butadiene thin film and then dried. Rubber resulted at a medium tensile stress. A 2-chlorobutadiene-1,3 rubber mixture was destroyed from 9.45 kg / cm ² to 95%. The natural was brought into contact with the adhesive film and the rubber was vulcanized at a medium tensile stress whole for about 25 minutes at 155 ° C. of 8.1 kg / cm ^{2 destroyed} by 90%. The butyl rubber The adhesive strength was tested according to ASTM. At 35, at an average tensile stress of 5.0 kg / cm ^{2 and} an average tensile stress of about 8.6 kg / cm ² 100 ° / ₀ ig was destroyed, the rubber tore 100 ° / ₀ ig.

Example 10 Example 6

40 An adhesive mixture of 3.0 g of dichloro was

The adhesive mixture from Example 3 was applied as a butadiene /-chloroacrylonitrile copolymer (75/25), 7.0 g thin film to a strip of cold-rolled chlorinated natural rubber, 0.7 g dibasic steel and left to dry. Lead phosphite, 0.9 g dinitrosobenzene prepared. All nitrile rubber mixture was mixed with the adhesive components were dissolved in 32.0 g of xylene or film added? Combined and the whole dispersed in a press 45. This adhesive mixture was vulcanized ^{at 160 °} C. for about 20 minutes as a thinner one. The film applied to strips of cold rolled steel adhesive strength was tested according to ASTM. At one and dried. Styrene-butadiene, natural and butyl tensile stress of 8.6 kg / cm ² , the rubber-rubber compounds were 100% torn as in Example 9. _au f these strips applied and vulcanized. Ls showed

50 to 100 ° / ₀ destruction strength tested at all three

Example 7 Rubbers. It follows that the detention

strength above the tensile strength of the rubber The adhesive mixture from Example 3 was found to be thin film on a strip of cold rolled steel

applied and dried. Butyl rubber mixture 55 B e i s ρ i e 1 11

was brought together with the adhesive film and

the whole thing in a press for about 20 minutes at An adhesive mixture of 3.5 g of dichloro

160 C vulcanized. The adhesive strength was 6.5 g according to butadiene / α-chloroacrylonitrile copolymer (70/30) ASTM tested. With a tensile stress of about chlorinated natural rubber, 0.6 g dinitrosobenzene, At 5.4 kg / cm, the rubber was 100% broken. 60 0.3 g quinone dioxime, 0.6 g benzothiazyl sulfide, 2.0 g

Carbon black and 1.0 g of dibasic lead phosphite are made up.

Example 8 All components were dissolved in 48.0 g of xylene or

dispersed. The glue came as a thin film

A glue mix was applied to strips of cold rolled steel using and of 5.0 g of dichlorobutadiene / tt-bromoacrylonitrile (70/30) 65 dried. According to that described in Example 7 and 5.0 g of chlorinated polypropylene resin, 0.6 g of three-process were styrene-butadiene, natural and basic lead sulfate, 1.0 g furnace soot. All butyl rubber compounds are placed on the strips and Components were dissolved or vulcanized in 25.0 g of xylene. In all cases the Priifum?

100% of the rubber is destroyed. From this it can be seen that the bond strength between the three Rubber types and the steel is above the tensile strength of the rubber.

In the examples given above, some adhesive mixtures were prepared without an accelerator. In these examples, the rubbers 100 ° / ₀ were ig destroyed. This shows that the adhesive mixtures can be prepared without accelerators. Although the mixture additives can be varied over a very wide range, the copolymer should not usually exceed 60 or 70% of the adhesive formulation. However, as stated above, the copolymer can also contain more than 90% and less than 20% of the adhesive composition.

Example 12

To compare the adhesive behavior of an adhesive mixture prepared according to the invention with a The adhesive of GB-PS 7 09 033 was introduced by means of solution polymerization and a peroxide catalyst 70/30 - dichlorobutadiene acrylonitrile - Copoly merisat according to GB-PS 7 09 033 and a corresponding dichlorobuladiene / a-bromoacrylonitrile copolymer manufactured. While the last-mentioned solution had a low viscosity at room temperature, the acrylonitrile copolymer solution had it a stiff consistency.

The following adhesive mixtures were then produced from the copolymers:

Dichlorobutadiene / oc-bromoacrylonitrile copolymer

Dichlorobutadiene / acrylonitrile copolymer .,.

Chlorinated natural rubber

Metal salt stabilizer ....

soot

Quinone oxime

Soluble dye

Xylene

Butyl acetate

6.4

11.8

1.7

1.9

1.2

0.1

11.4

65.5

6.4

11.8

1.7

1.9

1.2

0.1

11.4

65.5

The adhesive mixture B was obtained hot in order to keep the polymer ^{in solution at 60 °} C. Both adhesive mixtures were painted onto metal plates, dried to form a film and | vulcanized at 153 ° C for 25 minutes in contact with natural rubber. The adhesion was tested by means of 90 "adhesion tests.

Adhesive Mix A was average

love tensile strength of 9.5 kg / cm ² at 100% cerium

disturbance. The adhesive mixture B could be used with de;

Hand peeled off, which is common to both hot al

cold application was also the case.

Claims (1)

ι η ² A / In contrast, the inventively produced Claim · Adhesives are already used at room temperature will. This results in essential Method of making an adhesive for turning advantages such as more convenient handling, quick-joining of rubber with metal on the basis of a 5 lere application, etc. Although in GB-PS 7 09 033 Copolymer of 2,3-dichlorobutadiene (l, 3) is mentioned that by certain solvents Mixing unsaturated compound of a film former inhibits gel formation under certain circumstances and optionally customary additives can be in one, it is naturally more desirable organic solvents, characterized by using polymers that are characterized as the invention, that one 20 to 90 Ge io prepared in accordance with. Usual organic weight percent of a copolymer from 30 to solvents are soluble. 90 percent by weight 2,3-dichlorobutadiene (l, 3) and In addition, the 70 to 10 percent by weight α-chlorine or α-bromine adhesives produced according to the invention show a significantly better adhesive acrylonitrile with 80 to 10 percent by weight of a hold in With regard to rubber-metal bonds mixed as the film former, the mixture contains a stabilizer from GB-PS 7 09 033, as can be seen from the post-filler and optionally an accelerator and example 12 below.
Incorporates fillers and this mixture in one. In adhesive mixtures it is generally necessary to dissolve a component as a viscosity regulator and a weight percent solution or to provide a dispersed film-forming agent in the case of adhesive mixtures. Adhesive mixtures that crave. 20 using the above-mentioned polymers can be built up, for. B. chlorinated natural rubber, chlorinated polypropylene, vinyl chloride-vinylidene chloride copolymers, Phenolic resins and the like included, but they can also be used with other macro- 25 molecular substances can be produced as film formers. These adhesive mixtures can also Fillers, extenders and dyes are incorporated without affecting the bond strength