RU2464291C1 - Resin for increasing adhesive capacity of rubber mixtures - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: composition of the resin includes colophony, eutectic melt of ε-caprolactam with N-isopropyl-N-phenyl-n-phenylenediamine, polymeric petroleum resin and protective wax in defined proportions.

EFFECT: high adhesive power of rubber mixtures.

2 tbl

Description

The invention relates to the production of resins to increase the stickiness of rubber compounds (rubber blanks) and can be used in the tire and rubber industry.

Known resins for these purposes relate to products of synthetic and natural origin [Makhlis F.A., Fedyukin D.L. Rubber Terminology Guide: Ref. ed. - M. Chemistry, 1989. - 400 p.].

Synthetic resins, which are mainly represented by alkyl-formaldehyde, alkyl-phenol-formaldehyde sulfide, xylene and terpene oligomeric products [ibid., P. 405], have a common drawback - when used in rubber compounds, they have a significant effect on the vulcanization of rubbers. For example, increasing or decreasing the start time of scorch due to inconsistent molecular weight, they require a fairly frequent adjustment of the vulcanizing group, which, of course, negatively affects the stability of the technological process for the production of tires and rubber products.

Natural resins include petroleum refining products - petroleum polymer resins (for example, Pyroplast resin according to TU 220-00 / 505 18328-05). But they do not provide the necessary stickiness to rubber compounds.

Closest to the claimed technological solution is rosin [Directory of rubber. Rubber production materials. M., Chemistry, 1971, 608 S.].

However, rosin does not provide adhesion to rubber mixtures under conditions of prolonged storage at temperatures below room temperature.

An example of this is the deterioration in the stickiness of the rubberized layers of the cord and other profiled blanks (tread, breaker) when the temperature in the production room is 15-20 ° C. Rosin migrating to the surface of the rubber billet, under these conditions, quickly enough passes into a glassy state, which, of course, reduces the initial stickiness.

This goal is achieved through the use of ε-caprolactam-N-isopropyl-N'-phenyl-n-phenylenediamine eutectic melt in a composition with rosin and other technological additives specified in the claims (mass ratio of components in a 1: 1 eutectic melt). A resin for increasing the stickiness of rubber compounds is obtained by fusing rosin, a petroleum resin and a protective wax with a eutectic melt in the following ratio, wt.%:

Rosin 30.00-40.00 Eutectic melt ε-caprolactam-N-isopropyl-N'-phenyl-n-phenylenediamine 5.00-10.00 Petroleum Resin 30.00-40.00 Protective wax 15.00-25.00

Increasing the stickiness of rubber compounds (rubber billets) is achieved by a triple eutectic alloy (TES), which is obtained by fusion of a double eugectic alloy (DEL) ε-caprolactam-N-isopropyl-N'-phenyl-n-phenylenediamine with rosin in a mass ratio of 1: one.

DES is also formed when the mass ratio of ε-caprolactam with N-isopropyl-N'-phenyl-n-phenylenediamine 1: 1. This alloy does not crystallize and remains liquid according to Brookfield 450-700 cps at temperatures above minus 18 ° C.

TPP also does not crystallize, does not go into a glassy state and remains a very viscous liquid at temperatures above plus 5 ° C.

When the rosin content in the thermal power plant is 89 wt.% (In the claimed material it is the maximum rosin content in the resin of 40 wt.%), The alloy turns into a plastic mass, but does not undergo vitrification to a temperature of + 10 ° C.

It is possible to further increase the rosin content in the ternary alloy, but at the same time its technological properties deteriorate - in the reactor, at a resin preparation temperature (95 ± 5 ° C) rosin with a large excess of it is difficult to melt. In general, this makes the process lengthy and energy intensive. At the same time, preparation of the resin at temperatures above 100 ° C leads to a large outgassing.

Without special technological additives, a triple alloy is practically unsuitable. In the claimed range of ratios, the ternary alloy is difficult to grind, since the particles of the crushed product are able to stick together and remain sticky under normal conditions. This disadvantage, depriving the alloy of consumer properties, is eliminated by introducing into it a composition of petroleum resin and protective wax. Moreover, protective wax, eliminating the stickiness of the particles of the ternary alloy, cannot be used in the alloy separately from the oil polymer resin, since its compositions with the ternary alloy are able to delaminate and significantly reduce the stickiness of rubber blanks. At the same time, the composition of the ternary alloy and the oil-polymer resin, introduced into the alloy separately from the protective wax, has the same negative property as the ternary alloy - its particles are no less sticky. Finally, the resin as a whole, consisting of the claimed components, has the properties of a marketable product, and when introduced into the rubber compound, it provides the latter with stickiness even when working in a relatively cool production room (15-20 ° C).

The stickiness and preservation of its rubber blanks at relatively low temperatures is achieved by using the inventive resin in the same quantities as rosin. Usually it is 3-5 parts by weight. per 100 parts by weight rubber compound.

The resin preparation process is carried out as follows: an equilibrium mass amount of ε-caprolactam with N-isopropyl-N'-phenyl-n-phenylenediamine is loaded into a stirred reactor at a temperature of 90 ± 5 ° C to obtain a DES. Rosin is added to the double melt in an amount corresponding to TPP. After the obtained homogeneous TPP, the rest of the rosin is charged. Homogenization of the melt is achieved, after which oil-polymer resin and protective wax are successively loaded in small portions. Homogeneous melt is poured onto a conveyor belt, during which the melt turns into a hard alloy and is removed from the conveyor belt in the form of flakes.

Rosin is used according to TU 2494-006-98528460-10

ε-caprolactam - GOST 7580-86

N-isopropyl-N-phenyl-n-phenylenediamine - IPPD - product of the Chinese or Slovak production of Duslo firm

Petroleum resin-pyroplast according to TU 220-001-50518328-05 or according to TU 38.402213-93

Protective wax (ЗВ-П) - according to TU 381011290-90 or according to TU 38.301-25-11-93.

Table 1 shows the composition of the resins that meet the requirements of the proposed application, and compositions that do not meet the requirements.

Table 1 Resin Compounds Ingredients The compositions of the resins, wt.% one 2 3 four 5 6 7 Rosin 25.00 40.00 30.00 35.00 40.00 35.00 30.00 Eutectic alloy of ε-caprolactam with N-isopropyl-N'-phenyl-paraphenylenediamine 10.00 15.00 10.00 5.00 5.00 7.50 10.00 Petroleum Resin 40.00 30.00 30.00 45.00 35.00 30.00 35.00 Protective wax 25.00 15.00 30.00 15.00 20.00 17.50 25.00

Note. Compounds 5 and 7 are prepared with pyroplast according to TU 220-001-50518328-05 and protective wax according to TU 38-1011290. Composition 6 - with pyroplast according to TU 38.402213-93 and protective wax according to TU 38.301-25-11-93.

Examples with compositions 1, 2, 3, and 4 do not meet the stated requirements or do not provide manufacturability to the product:

Composition 1 - the relatively low rosin content does not provide the necessary stickiness to the rubber compounds;

Compositions 2 and 4 are not technologically advanced due to excessive stickiness of the product particles;

Composition 3 - not technologically advanced due to the separation of the resin melt during its cooling.

A distinctive feature of the inventive resins in the examples with compositions 5, 6 and 7 is to provide the initial stickiness of the rubber compounds at the level of rosin mixtures and the tendency to stickiness during storage of rubber billets in a production room at a temperature of 10-20 ° C.

Table 2 presents the test results of the tread rubber compound and its vulcanizates based on rubber SKI-3 - 35 parts by weight, rubber SKD - 30 parts by weight, rubber SKMS30 ARKM15 - 25 parts by weight, Dutch regenerate RNR5OB11 - 10 parts by weight; containing carbon black N339 - 61 parts by weight The serial mixture also contains 3 parts by weight. rosin per 100 parts by weight rubber. In the experimental mixtures, an equilibrium mass rosin was replaced by resin according to the proposed compositions 5, 6 and 7.

The property of rubber compounds - stickiness was evaluated according to the method proposed by Monsanto, on the device "Tel-Tak". The property of vulcanizates according to GOST 270-75.

From the data of table 2, it can be seen that the use of the proposed resins practically does not affect the elastic strength properties of the vulcanizates, nor does it affect the initial stickiness of the rubber compounds.

table 2 Properties of rubber compounds and vulcanizates The properties Rubber Code Serial (prototype) Experienced 5 Experienced 6 Experienced 7 Conditional strength at 30% elongation, MPa 7.8 8.8 8.6 8.2 Conditional tensile strength, MPa 15.4 15,5 15.4 15,5 Relative extension, % 535 540 535 540 The stickiness of the tread rubber compounds on the device "Tel-Tak", kPa:
- immediately after preparation of the mixtures 109 110 111 109 The stickiness of the tread rubber compounds on the device "Tel-Tak", kPa: - after cooling mixtures at 5 ° C: tests after 1 day 77 80 82 79 tests after 2 days 59 66 70 65

Claims (1)

The resin for increasing the tackiness of rubber compounds contains rosin, eutectic melt of ε-caprolactam with N-isopropyl-N'-phenyl-n-phenylenediamine, an oil-polymer resin and a protective wax in the following ratio, wt.%:
Rosin 30.00-40.00 Eutectic melt ε-caprolactam-N-isopropyl-N'-phenyl-n-phenylenediamine 5.00-10.00 Petroleum Resin 30.00-40.00 Protective wax 15.00-25.00