Vulcanicola rubber compound

(57) Abstract:

The invention relates to the production of vulkanizetas rubber compound, the vulcanizates on the basis of which have high resistance to thermal-oxidative aging. The invention can be used in tire and rubber industry to obtain vulcanizates with long-term resistance to thermal-oxidative aging. Prepare a rubber compound based on unsaturated rubber with a vulcanizing agent, accelerators, vulcanization activators. Can be entered plasticizers, fillers and other additives. In the rubber mixture is injected antioxidant 0.5 to 5.0 wt.h. on 100 wt.h. rubber consisting of a liquid alloy of antioxidants obtained at a temperature of 70-90°C in the following ratio, wt. h: N-isopropyl-N-phenyl-n-phenylenediamine - 35,00-40,00; N,N'-diphenyl-n-phenylenediamine - a 10,00 24,00; 2-mercaptobenzothiazol - 6,00-10,00; -caprolactam - 35,00-40,00 and powdery media, and the ratio of the alloy of antioxidants and powdery media of wt.h.: alloy antioxidants - 15,00-50,00; powdered media - 50,00-85,00. The technical result is to increase thermal-oxidative resistance of rubbers. 6 table.

Known vulcanizate rubber compound based on unsaturated rubbers, stable N-isopropyl-N-phenyl-n-phenylenediamine (Koshelev F. F. and other General rubber technology, ed. “Chemistry”, M., 1968, S. 174).

The lack of rubber compounds using as the stabilizer of N-isopropyl-N-phenyl-n-phenylenediamine is short protection of vulcanizates based on them from thermo-oxidative aging, as the stabilizer is inherent in unproductive consumption due to the high diffusion activity, leading to evaporation and leaching from the surface of the vulcanizates (Rubber and rubber No. 2, 2001, S. 26-31).

Also known rubber compound, in which as an additive to rubber for inhibition of ozone injected comprehensive antioxidant, a mixture smetanovo clay with a mixture of Quaternary amine, a polar solvent and antiozonant. Get expanded organic derivative of a clay and a Quaternary amine, with which antiozonant associated in the complex compound (U.S. Patent No. 4532285, MKI 08 To 00 is no technological scheme of production of complex antioxidant, as required purification of the obtained product from the solvent and recovery of the latter. All this leads to additional economic cost and environmentally unsafe.

Known rubber mixture containing powdered stabilizer (Rubber and rubber No. 2, 1985, S. 7-8), a mixture of liquid and retinoid stabilizers phenolic type (Agidol 20, Agidol 123) with a solid-phase carrier (colloidal silicic acid, kaolin, chalk).

The drawback of such rubber mixtures is low stabilizing activity of the powdery stabilizer in protecting rubber from thermo-oxidative aging. This is a consequence of the fact that the antioxidants of phenol type on the effectiveness of protective actions yield the amine antioxidants type.

Closest to the claimed vulkanizetas rubber compound may be a rubber compound containing liquid antioxidants amine type, such as N-alkyl-N-phenylenediamine-1,4 (deafen FA) (“Chemical additives to the polymer Handbook edited by Maslova, I. P., “Chemistry”, 1981, S. 26-27).

However, in this case, the rubber may not provide effective protection to their vulcanizates, as their stabilizers castleattraction (no preventive protection mechanism).

Getting vulkanizetas rubber mixtures containing antioxidant provides high thermal-oxidative resistance of vulcanizates is the problem to which this invention is directed.

The technical result is to increase thermal-oxidative resistance of the vulcanizates.

The technical result is achieved using a composition vulkanizetas rubber compound based on unsaturated rubber composition of the antioxidant in the amount of 0.5-5 wt.h. on 100 wt.h. rubber consisting of a liquid alloy of antioxidants obtained at a temperature of 70-90 ° C in the following ratio, wt.h.:

N-isopropyl-N-phenyl-N-phenylenediamine 35,00 - 40,00

N,N’-diphenyl-N-phenylenediamine a 10,00 24,00

2-mercaptobenzthiazole 6,00 - 10,00

-caprolactam 35,00 - 40,00

and powdered media, and the ratio of the alloy of antioxidants and powdery media of wt.h.:

Alloy antioxidants 15,00 - 50,00

Powdered media 50,00 - 85,00

As the carrier can be used with mineral, synthetic fillers, for example, colloidal silicic acid (BS-100, BS-120), kaolin, chalk.

The vulcanizates on the OIT alloy antioxidants, the current mechanisms of chain termination and preventing the growth of chain oxidation, as well as a carrier, on which surface adsorbed alloy of antioxidants, a long time is not subjected to thermal-oxidative aging. The vulcanizates on the basis of the proposed rubber mixtures containing composite antioxidant, effectively protected against thermal-oxidative aging, not only because of the synergistic action of antioxidants, but also have long-term protection due to adsorption on the surface of the carrier alloys of antioxidants, reducing their diffusion to the surface of the vulcanizates, which reduces wasteful consumption of antioxidants.

When selected, the contents of the ingredients of composite antioxidant alloys under normal conditions represent a viscous liquid (viscosity Brookfield at 25 ° C not more than 3000 SDR), which allows the deposition of alloys on the media in the absence of solvents.

Application of the proposed method the dosage of N-isopropyl-N-phenyl-n-phenylenediamine (deafen AF) in a ratio of less than 35.00 wt.h. the product is less efficient in protecting against thermal-oxidative aging. When the content of diafine OP more than 40,00 wt is the exercise of these alloys by deposition on the media, which leads to the increase in the cost of the product without increasing its effectiveness.

Increased dosages of N,N’-diphenyl-n-phenylenediamine (diafana FF) in the alloy more 24,00 wt.h. reduces the content of diafine AF and/or captax, which reduces the effectiveness of the protective action of composite antioxidant; or a decrease in the content-caprolactam, which leads to the formation of solid alloys. The content of diafine FF 10.00 wt.h. in the composition of the alloy of antioxidants increases the cost of the product by increasing the dosage of more expensive products in the composition of the alloy.

2-mercaptobenzthiazole (captax) is the stabilizer preventive type and derivative of n-phenylendiamine forms a synergistic system. The use of captax at a dosage greater than 10.00 wt.h., changes the ratio of components of the alloy, resulting alloys are solid. Application 2-mercaptobenzthiazole at a dosage of less than 6.00 wt.h. alloy antioxidants will have a synergistic effect due to too low a dosage of the antioxidant preventive type.

Content-caprolactam in the range of dosages 35,00-40,00 wt.h. ensure caresource different adsorption ability, therefore, for each media type to define the optimal dosage of the composition of the antioxidant. Thus, when used as a carrier of colloidal silicic acid (BS-100, BS-120) is optimal content 50,00-60,00 wt.h. in the composition of the antioxidant. This is justified by the fact that the higher the dosage of filler there is the dusting of the obtained product, as well as reducing the protective effect of composite antioxidant. When smaller amounts of colloidal silicic acid, the resulting substance is a viscous paste-like product.

When used as a carrier kaolin optimum content in the composition of the antioxidant is 70,00 wt.h. Increased dosages of the medium leads to a decrease of the protective action. Lowering the dosage of the carrier results in a paste-like compositions.

When used as a carrier chalk effective is the content 85,00 wt.h. Increased dosages of the carrier reduces the efficiency of composite antioxidant in General, the use of media in fewer yields a viscous paste-like products.

Composite prot is emom reactor, equipped with a mechanical stirrer anchor type. Charged to the reactor, the alloy ingredients of antioxidants, melt them at a temperature of 70-90 ° C and stirred to obtain a homogeneous mixture.

- in the mixer (clemesha) download the alloy of antioxidants, powdered media and stirred at a temperature of 20 to 90 ° C until a homogeneous powder mass for 30-40 minutes Unloading of product produced in the receiving tank.

Rubber mixture according to the invention contains an unsaturated rubber, vulcanizes substances, composite antioxidant and other additives.

As rubbers can be applied unsaturated rubbers: natural, branch, Rubezhnoe, Ukraine, butadiene-nitrile, etc., and combinations thereof. Vulcanizing agents, accelerators and vulcanization activators are selected from the group of sulfur, tirami, polysulfide accelerators, dithiocarbamate, thiazole, sulfenamide, guanidine, and organic peroxides.

In addition, the rubber mixture can be introduced plasticizers, fillers, pore-forming substances, dyes and other additives.

Example 1. In the mill in the usual method of preparing a rubber mixture, whose composition is given in table.1, 2, 3 (the blowing follows: to a reactor with a stirrer at a temperature of 70-90 ° C load 17,50 g of N-isopropyl-N-phenyl-n-phenylenediamine; 12.00 g of N,N’-diphenyl-n-phenylenediamine; 17,50 g-caprolactam; 3.00 g of 2-mercaptobenzthiazole, conducting the mixture to obtain a homogeneous mixture. Then gradually, for example for 3 min, add 50,00 g of colloidal silicic acid (BS 100 or BS-120), stirring constantly. The ratio of the alloy of antioxidants - powdered media is 50%-50%. After the download of colloidal silicic acid composition of the mixture in the reactor continue to stir for 30-40 minutes the Obtained composite antioxidant discharged into the receiving tank, and then injected into the rubber compound in the dosage specified in the recipe rubber compound.

According to the proposed example, get a rubber mixture containing powdered composite antioxidant.

Example 2. Analogously to example 1, with the difference charged to the reactor of 10.50 g of N-isopropyl-N-phenyl-n-phenylenediamine; 7.20 g of N,N’-diphenyl-n-phenylenediamine; 10,50 g-caprolactam; of 1.80 g of 2-mercaptobenzthiazole, and as a carrier load 70,00 g of kaolin. The ratio of the alloy of antioxidants - powdered media is 30%-70%. The rubber compound is shown in table.1, 2, 3 (part 4).

Example 3. Analogously to example 1, with the difference that in the reactor searchproperties, and as a media download 85,00 g of chalk. The ratio of the alloy of antioxidants - powdered media is 15%-85%. The rubber compound is shown in table.1, 2, 3 (part 5).

Example 4. Analogously to example 1, with the difference that in the reactor load of 20.00 g of N-isopropyl-N-phenyl-n-phenylenediamine; 5,00 g N,N’-diphenyl-n-phenylenediamine; 20,00 g-caprolactam; 5,00 g 2-mercaptobenzthiazole. The ratio of the alloy of antioxidants - powdered media is 50%-50%. The rubber compound is shown in table.1, 2, 3 (composition 6).

Example 5. Analogously to example 2, with the difference that was charged to the reactor 12.00 g of N-isopropyl-N-phenyl-n-phenylenediamine, 3.00 g of N,N’-diphenyl-N-phenylenediamine; 12.00 g-caprolactam, 3.00 g of 2-mercaptobenzthiazole. The ratio of the alloy of antioxidants powdered media is 30%-70%. The rubber compound is shown in table.1, 2, 3 (part 7).

Example 6. Analogously to example 3, with the difference that in the reactor load of 6.00 g of N-isopropyl-N-phenyl-n-phenylenediamine; 1.50 g of N,N’-diphenyl-n-phenylenediamine; 6,00 g-caprolactam; 1.50 g of 2-mercaptobenzthiazole. The ratio of the alloy of antioxidants powdered media is 30%-70%. The rubber compound is shown in table.1, 2, 3 (part 8).

For sravnenie is 2, 3), and deafen FA (prototype), deposited on the carrier (white carbon BS-100), the deposition was carried out according to known technique deposition (Rubber and rubber No. 2, 1985, S. 7-8) (composition in table 2.1, 2, 3).

Known and offer rubber compound is prepared according to the standard mode, vulcanized in a press heated at a temperature IS in the optimum.

From the above table.4 results of physico-mechanical test should be that the rubber mixtures containing composite antioxidant to a lesser extent lose their mechanical properties during thermal-oxidative aging than rubber mixtures containing deafen OP or deafen FA (prototype) deposited on the media.

So in the vulcanizates containing composite antioxidants (example 1-6), not observed falling relative strength in the early stages of thermal-oxidative aging (48 h), i.e., the change of measure in this case is 0%, while in the vulcanizates containing as an antioxidant deafen FA (prototype), deposited on the carrier, falling relative strength in the same conditions, thermal-oxidative aging is 4%. In subsequent phases, thermal-oxidative aging (76-92 h) also observed lower rate of parasystem, containing deafen FA deposited on the carrier (the prototype), the indicator of relative strength is reduced from 15 to 25%.

The vulcanizates based on isoprene rubber containing composite antioxidant, is also less prone to thermal-oxidative aging than the vulcanizates containing antioxidant prototype or traditionally used deafen OP, this is evidenced by the data presented in the table.5

The vulcanizates based on butadiene-nitrile rubber in the process of thermal-oxidative aging are structuring their ineffective protection leads to a fall in the relative elongation. The proposed composite antioxidants largely protects nitrile rubber from oxidation factors that, as follows from the data presented in table.6, expressed on a longer preservation of the relative elongation.

Use as part of vulkanizetas rubber composite antioxidant provides vulcanizates long-term protection against thermal-oxidative aging.

Vulcanicola rubber mixture comprising an unsaturated rubber, and the antioxidant is 0.5 to 5 wt.h. on 100 wt.h. rubber consisting of a liquid alloy of antioxidants obtained at a temperature of 70-90°C, in the following ratio, wt.h.:

N-Isopropyl-N-phenyl-n-phenylenediamine 35,00-40,00

N,N'-Diphenyl-n-phenylenediamine a 10,00 24,00

2-Mercaptobenzthiazole 6,00-10,00

-Caprolactam 35,00-40,00

and powdered media, and the ratio of the alloy of antioxidants and powdery media of wt.h.:

Alloy antioxidants 15,00-50,00

Powdered media 50,00-85,00