RU2229491C1 - Colophony resin and a method for preparation thereof - Google Patents

Abstract

FIELD: rubber industry. SUBSTANCE: invention relates to manufacture of process additive for use in tire and general mechanical rubber industries in order to increase adhesiveness of rubber compounds based on natural and synthetic rubbers. Colophony resin is obtained by modifying colophony, in particular mixture of tallow colophony and tallow pitch in weight proportion (10-90): (90-10), by formalin or paraform, or fumaric acid, or maleic acid, or maleic anhydride as modifying agent taken in amounts 0.5 to 10 wt parts per 100 wt parts of colophony in presence of 1.0 to 10.0 wt parts of calcium oxide. Preparation procedure consists in mixing tallow colophony with tallow pitch, heating mixture to 140-150^(r)', stirring resulting melt and heating it 195-200^(r)', adding CaO and ageing mixture for 3-5 h followed by adding modifying agent and conducting polymerization process for 5-6 h in vacuum with some amount of inert gas, after which final product is granulated. Thus obtained colophony resin increases adhesiveness of rubber compounds more than by 20%. Possibility of preparing product in granulated state allows automating its use. EFFECT: improved environmental conditions of operation and reduced cost price of produce. 4 cl, 10 ex

Description

The invention relates to the production of technological additives intended for use in the tire and rubber industry in order to increase the stickiness of rubber compounds based on natural and synthetic rubbers.

It is known to use pine gum rosin as a technological additive that increases the stickiness of rubber compounds. However, pine rosin does not always provide the necessary level of stickiness of rubber compounds. The high acid number of rosin limits its use in rubber compounds based on saturated halogenated rubbers (HKB, LBC), reducing the effectiveness of the use of such rubbers. The use of rosin has another significant drawback. Its final form - monolith - does not meet the modern requirements of tire production. The release of rosin in granular form encounters difficulties due to the high chemical activity of the rosin surface and its tendency to oxidize, which, when stored in a warehouse, leads to sticking of its granules and spontaneous combustion. The use of rosin in the form of a monolith increases the complexity of preparatory operations before putting rosin into production, does not allow the use of automatic dosing, reduces productivity and worsens sanitary and hygienic working conditions.

In addition, the volume of extraction of raw materials for obtaining rosin - pine resin - depends on the time of year. In this regard, the production and delivery of the product to the consumer is irregular, which also creates additional difficulties when using the product.

Also known is the technological additive obtained on the basis of the product of distillation of tall oil - tall pitch, as well as tall pitch modified with HMTA (Tall products and the possibility of their use in the formulation of rubber compounds, "Forest chemistry and tapping", issue 1, M., 1987) .

However, this additive does not provide a sufficiently high level of stickiness and the necessary viscosity of rubber compounds. In addition, the high content of volatile components with a strong unpleasant odor in it sharply affects the consumer properties of the product and negatively affects the environmental conditions of production and the environment.

Closest to the claimed invention is a method for producing rosin resin by modifying tall oil rosin with maleic anhydride and formaldehyde by heating using dimethyl polysiloxanes (RF patent No. 2130042, C 09 F 1/04, publ. 05/10/1999).

The disadvantages of the method include the fact that the resulting product does not provide the necessary level of stickiness of the rubber compounds and is available in the form of a monolith. Moreover, the production method involves the use of dimethyl polysiloxanes in the form of 50% solutions based on aromatic hydrocarbons (xylene, toluene), which leads to a deterioration in the environmental parameters of the product production process.

The proposed technical solution is aimed at creating a technological additive obtained in an environmentally friendly way and ensuring its effective use for increasing the stickiness of rubber compounds, including mixtures based on halogenated rubbers, as well as improving the consumer properties of the product itself, including the absence of an unpleasant odor, as well as a convenient outlet a form allowing the product to be used in automatic dosing systems at consumer enterprises.

The claimed technical result is achieved in that the rosin resin obtained by modifying the rosin with a modifying agent contains a mixture of tall oil rosin and tall pitch, taken in a mass ratio (10-90) :( 90-10), and formalin as a modifying agent or paraform, or fumaric acid, or maleic acid, or maleic anhydride, the resin obtained in the presence of calcium oxide in the following ratio of starting components, in parts by weight:

A mixture of tall oil rosin and tall pitch 100

Calcium oxide 1.0-10.0

Modifying agent selected from the series:

formalin or paraform, or fumaric

acid, or maleic acid, or

maleic anhydride 0.5-10

These signs are interconnected with the formation of a stable set of essential features sufficient to obtain the claimed technical result.

Tall pitch is the bottom residue obtained in the process of distillation of tall oil formed during the processing of sulphate oil produced by the sulphate method of producing wood pulp.

Tall oil rosin is a product obtained by boiling resin acids formed during distillation of tall oil.

Rosin resin can be obtained with the additional use of a stabilizer in an amount of 0.05-1.0 wt. including the compounds of the alkyl phenolamine type, mainly N-alkyl-N-phenylparaphenylenediamine or diafen FP, or the alkyl phenol type, mainly 2.6 ditretbutyl-4-methylphenol. Stabilizers of this type are widely known in the manufacture of tires and rubbers.

To obtain the claimed technical result, specially selected technological modes of its production are necessary, according to which, in the method for producing rosin resin, including polymerizing tall oil rosin with a modifying agent when heated, it is necessary to pre-mix tall oil rosin with tall pitch in a weight ratio taken within (10-90) :( 90-10), the mixture is heated to a temperature of 140-150 ° C, ensuring its melting, the resulting melt is mixed and heated to a temperature of 185-200 ° C, after which CaO is introduced into it, the mixture is incubated for 3-5 hours and a modifying agent is introduced, which is used as formalin or paraform, or fumaric acid, or maleic acid, or maleic anhydride, then it is carried out for 5-6 hours the polymerization process, which is carried out under vacuum with an inert gas additive, followed by granulation of the finished product, with every 100 wt. including a mixture of tall oil rosin and tall pitch contribute 1.0-10.0 wt. including CaO and 0.5-10 wt. including a modifying agent.

The use of a mixture of tall oil rosin and tall pitch in the stated ratio provides a product with the desired physico-chemical properties and the final form. An increase in the content of tall pitch in the mixture leads to low values of the softening temperature of the product and in connection with the impossibility of granulation. On the contrary, a decrease leads to an increase in the tendency of the product to oxidize and self-ignite, which creates problems when storing its granular form.

The introduction of calcium oxide into the melt of a mixture of taly pitch and tall oil rosin, followed by the introduction of the declared modifying agents into the melt, allows to increase the degree of polymerization and the softening temperature of the final product. Moreover, the claimed quantitative ratio of the above components of the mixture is optimal and provides the achieved technical result.

To ensure uniformity of the polymerization process and increase the degree of homogeneity of the finished product, including during its storage by the method, additional introduction of a stabilizer into the mixture after the modifying agent in an amount of 0.05-1.0 wt. hours

The stabilizer is an alkylphenolamine-type compound, preferably N-alkyl-N-phenylparaphenylenediamine or diafen FP, or an alkylphenol type, predominantly 2.6 ditretbutyl-4-methylphenol.

The method is as follows.

100 mass parts of the mixture, which is tall oil rosin and tall pitch, taken in the mass ratio (10-90) :( 90-10) are introduced into the reaction vessel. The mixture is heated to a temperature of 140-150 ° C, ensuring its melting. The resulting melt is stirred and heated to a temperature of 185-200 ° C. After that, CaO is added to it in an amount of 1.0-10 parts by weight, the mixture is kept for 3-5 hours and a modifying agent is introduced, which is used as formalin or paraform, or fumaric acid, or maleic acid, or maleic anhydride in an amount of 0.5-10 wt.h. Then, for 5-6 hours, a polymerization process is carried out, which is carried out under vacuum with an inert gas additive, followed by granulation.

The claimed rosin resin and its production method is illustrated by the following examples:

Example 1. Tall oil rosin and tall pitch taken in a mass ratio (10:90) in an amount of 100 kg are introduced into the reaction vessel. The mixture is heated to a temperature of 145 ° C. Then the obtained melt is stirred and heated to a temperature of 195 ° C. After that, CaO in the amount of 3 kg is introduced into the melt, the mixture is incubated for 3 hours, and formalin in the amount of 0.5 kg is introduced. Then, for 5.5 hours, a polymerization process is carried out, which is carried out under vacuum with an inert gas additive, followed by granulation. The resulting resin has a softening temperature of 80 ° C, an acid number of 82 mg / KOH.

Example 2. The process is conducted in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 20:80, the amount of CaO is 1.0 kg, and formalin is 2.5 kg. The resulting resin has a softening temperature of 85 ° C, an acid number of 73 mg / KOH.

Example 3. The process is carried out in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 30:70, the amount of CaO is 5 kg, and formalin is 10 kg. The resulting resin has a softening temperature of 95 ° C, an acid number of 43 mg / KOH.

Example 4. The process is carried out in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 40:60, the amount of CaO is 3.0 kg, and formalin is 5 kg. The resulting resin has a softening temperature of 95 ° C, an acid value of 30 mg / KOH.

Example 5. The process is carried out in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 40:60, the amount of CaO is 5 kg, and formalin is 3 kg. In this case, after the introduction of formalin, a stabilizer is additionally introduced into the mixture, which is N-alkyl-N-phenylparaphenylenediamine in an amount of 0.2 kg. The resulting resin has a softening point of 98 ° C, an acid value of 28 mg / KOH.

Example 6. The process is conducted in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 80:20, the amount of CaO is 10 kg, and formalin is 3 kg. In this case, after the introduction of formalin, a stabilizer is additionally introduced into the mixture, which is 2.6 ditretbutyl-4-methylphenol in an amount of 1 kg. The resulting resin has a softening temperature of 95 ° C, an acid number of 43 mg / KOH.

Example 7. The process is carried out in accordance with example 1, except that the mass ratio of tall pitch and tall rosin is 90:10, the amount of CaO is 5 kg, and formalin is 3 kg. In this case, after the introduction of formalin, a stabilizer is additionally introduced into the mixture, which is an AF diaphen in an amount of 0.5 kg. The resulting resin has a softening point of 98 ° C, an acid number of 22 mg / KOH.

Example 8. The process is carried out in accordance with example 5, except that the ratio of tall pitch and tall rosin is 90:10, the amount of CaO is 5 kg, and maleic anhydride is used as a modifying agent.

The resulting resin has a softening temperature of 105 ° C, an acid number of 24 mg / KOH.

Example 9. The process is carried out in accordance with example 3, except that paraform is used as a modifying agent. The resulting resin has a softening temperature of 110 ° C, an acid value of 23 mg / KOH.

Example 10. The process is carried out in accordance with example 7, except that fumaric acid is used as a modifying agent. The resulting resin has a softening temperature of 102 ° C, an acid number of 21 mg / KOH.

The rosin resin obtained in accordance with the claimed method is intended to be used as a technological additive for increasing the stickiness of rubber mixtures based on natural and synthetic rubbers. The dosage of additives in the rubber is from 0.5 to 10 wt. hours per 100 wt. including rubber. The most optimal dosage is 1-5 wt. hours per 100 wt. including rubber. Lining rubber mixtures are prepared in a rubber mixer in 2 stages at a rotor speed of 80 rpm (1 stage) and 60 rpm (2 stage). At the first stage, rubber, filler, stearin, zinc oxide, the technological additive obtained by the claimed method are introduced into the rubber mixer. In the second stage, a vulcanizing group. The duration of mixing with the upper shutter lowered in the first and second stages, respectively, is 5 minutes and 3 minutes. Vulcanization is carried out in an electric press at 155 ° C for 45 minutes

Determination of the technological properties of rubber compounds and indicators of vulcanizers are determined by standard methods in accordance with GOST.

As follows from the above data, the use of a technological additive - rosin resin - provides an increase in the stickiness of rubber compounds by more than 20%. The possibility of producing the finished product in granular form allows you to automate the process of its use, to ensure the improvement of environmental working conditions and reduce labor costs.

Claims (4)

1. A rosin resin obtained by modifying rosin with a modifying agent, characterized in that it contains a mixture of tall oil rosin and tall pitch taken in a mass ratio (10-90) :( 90-10), and formalin or paraform or fumaric acid, or maleic acid, or maleic anhydride, the resin obtained in the presence of calcium oxide, in the following ratio of starting components, in parts by weight: A mixture of tall oil rosin and tall pitch 100 Calcium oxide 1.0 - 10.0 Modifying agent selected from the series: formalin or paraform, or fumaric acid, or maleic acid, or maleic anhydride 0.5 - 10 2. The rosin resin according to claim 1, characterized in that it can be obtained with the additional use of a stabilizer in an amount of 0.05-1.0 parts by weight, which is an alkyl phenolamine type compound, mainly N-alkyl-N'-phenyl paraphenylene diamine or diafen FP, or an alkyl phenol type, preferably 2.6 ditretbutyl-4-methylphenol. 3. A method of producing a rosin resin, comprising polymerizing tall oil rosin with a modifying agent when heated, characterized in that the tall oil rosin is pre-mixed with tall oil pitch in a weight ratio taken in the range (10-90) :( 90-10), the mixture is heated to a temperature 140-150 ° C, ensuring its melting, the obtained melt is mixed and heated to a temperature of 185-200 ° C, after which CaO is introduced into it, the mixture is kept for 3-5 hours and a modifying agent, which is used as formalin, is introduced, or paraform, or fumaric acid, or maleic acid, or maleic anhydride, then for 5-6 hours carry out the polymerization process, which is carried out under vacuum with an inert gas additive, followed by granulation of the finished product, with each 100 wt.h. a mixture of tall oil rosin and tall pitch contribute 1.0-10.0 wt.h. CaO and 0.5-10 parts by weight modifying agent. 4. The method according to claim 3, characterized in that after adding the modifying agent to the mixture, a stabilizer is additionally added in an amount of 0.05-1.0 parts by weight, which is an alkyl phenolamine type compound, mainly N-alkyl-N'-phenyl paraphenylene diamine or diafen FP, or an alkyl phenol type, preferably 2.6 ditretbutyl-4-methylphenol.