RU2101304C1 - Method of rubber modifying agent producing - Google Patents

Abstract

FIELD: rubber industry. SUBSTANCE: method involves dispersing a nitrogen-containing polymer an and oxygen-containing compound in water at mass ratio of a nitrogen-containing polymer, water and an oxygen-containing compound = 1:(0.1-10.0):(0.05-0.5) followed by treatment with reaction mass of carrier - silicon dioxide or kaolin, or zeolite, or lignin at mass ratio of nitrogen-containing compound, an oxygen-containing compound and carrier = 1: (0.05-0.5): (1-30) and the obtained product is isolated. Nitrogen-containing compound: polyethyleneimine, or polyhexamethyleneguanidine, or polyethylenepolyamine at polymerization degree 2-10, 2-90 and 2-10, respectively. Oxygen-containing compound: polyethylene glycol or polypropylene glycol or derivative of hydroxybenzene. EFFECT: improved method of producing. 2 tbl

Description

 The invention relates to organic chemistry, in particular to the production of rubber modifiers that enhance the bond strength of rubbers with reinforcing materials in the tire and rubber industry.

A known method of producing a rubber modifier - hexamethylenetetraminresorcinol by the interaction of resorcinol and hexamethylenetetramine with the addition of a dust-free agent of a solution in aliphatic alcohols C ₁ -C ₅ mineral oil or phthalic and sebacic acid ester [1]
The disadvantage of this method is that the target product is of poor quality: a low level of bond strength of rubbers with brass-plated steel cord and low adhesion bond resistance to various types of aging. In the manufacturing process, a large amount of effluent is formed containing resorcinol and hexamethylenetetramine.

The closest in technical essence and the achieved result to the claimed is a method of producing a rubber modifier by dispersing hexamethylenetetramine with resorcinol in an aqueous medium, followed by filtration and drying, the process is carried out in suspension at a particle size of the starting products of 20-250 microns and t = 0-15 ^o C [ 2]
The disadvantages of this method of producing a rubber modifier include the fact that the obtained modifier gives rubbers low bond strength with steel cord under dynamic and static conditions, especially when exposed to water vapor, and elevated temperatures. In addition, the product has great caking during storage, high consumption of expensive raw materials and the use of substances purchased from imports, resorcinol. In the production process, effluents are formed containing resorcinol and its oxidation products, which are difficult to clean.

 The basis of the invention is the task of improving the method of producing a rubber modifier with a higher technical result, namely, improving the quality of the modifier, i.e. increasing the adhesion of rubbers to brass-plated steel cord under dynamic conditions and to textile cords under static conditions, increasing the adhesion bond resistance to steam and thermal aging, reducing the consumption of expensive reactive components while expanding their range and replacing imported raw materials (resorcinol) with relatively cheap raw materials in Ukraine and Russia with a good final form of the final product, convenient for automatic dosing, as well as changes in the technology for modif ikator towards a safer process by eliminating production waste.

где n=2-90; A^- = H₂PO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ ; NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; C₁₇H₃₅COO^-; HCO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$
а в качестве кислородсодержащего соединения используют полигликоли (полиэтиленгликоль или полипропиленгликоль) общей формулы:

где R₁=-ОН; С₄H₉; R₂=R₃= -H
или R₂=R₃= -CH₃ или R₂= -H или R₃= -CH₃
n + m 2-120
или производное гидроксибензола общей формулы:

диспергирование осуществляют при массовом соотношении азотсодержащего полимера, воды и кислородсодержащего соединения, равном 1: (0,1-10,0): (0,05-0,5), с последующей обработкой реакционной массой носителя-диоксида кремния или каолина, или цеолита, или лигнина при массовом соотношении азотсодержащего полимера, кислородсодержащего соединения и носителя, равном 1:(0,05-0,5):(1,0-30,0), и выделяют полученный продукт.The problem is solved in that in the method for producing a rubber modifier by dispersing nitrogen-containing and oxygen-containing compounds in water, polyethyleneimine with n = 2-90 or polyethylenepolyamine with n = 2-IO or polyhexamethylene guanidine with n = 2-90 or its salt of the general formula are used as the nitrogen-containing compound :

where n = 2-90; A ^- = H ₂ PO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ ; NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; C ₁₇ H ₃₅ COO ^- ; Hco $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$
and as an oxygen-containing compound, polyglycols (polyethylene glycol or polypropylene glycol) of the general formula are used:

where R ₁ = —OH; C ₄ H ₉ ; R ₂ = R ₃ = -H
or R ₂ = R ₃ = —CH ₃ or R ₂ = —H or R ₃ = —CH ₃
n + m 2-120
or a hydroxybenzene derivative of the general formula:

dispersion is carried out at a mass ratio of a nitrogen-containing polymer, water and an oxygen-containing compound equal to 1: (0.1-10.0): (0.05-0.5), followed by treatment with a reaction mass of a silica or kaolin or zeolite carrier or lignin at a mass ratio of a nitrogen-containing polymer, an oxygen-containing compound and a carrier equal to 1: (0.05-0.5) :( 1.0-30.0), and the resulting product is isolated.

 Essentially, a method is proposed for producing an adhesive rubber modifier by applying an aqueous solution of polyethyleneimine or polyethylene polyamine or polyhexamethylene guanidine or its salts together with polyethylene glycol or polypropylene glycol or a hydroxybenzene derivative on a support silica or kaolin or zeolite or lignin and drying the resulting product to 2% allows the moisture content to dry to 2% increase the specific surface of the modifier and thereby increase its effectiveness, i.e. improve its quality, reduce the content of expensive components while replacing imported raw materials with raw materials from Ukraine and Russia. At the same time, there is no waste water in the modifier production technology, and the final product has a powdery outlet form suitable for automatic weighing.

 To obtain a high-quality modifier, the following ratio of the claimed components should be observed: polyethyleneimine, or polyethylene polyamine, or polyhexamethylene guanidine, or its salt: polyethylene glycol or polypropylene glycol or a derivative of hydroxybenzene: silicon dioxide or kaolin, or zeolite, or lignin, on a dry residue of 1: (0.05-0 5) :( 1.0-30.0). With an increase in the content in the modifier of polyethylene glycol or polypropylene glycol or a hydroxybenzene derivative or carrier above the specified limits, the adhesive properties of the inventive modifier deteriorate, since then the concentration of the most active component of the nitrogen-containing polymer decreases in it. If these components are used in ratios below the declared limits, a final product with a poor outlet shape (caked, components sweat to the surface) is obtained that is heterogeneous in composition, which also leads to a deterioration in its quality.

 For the treatment of the support, aqueous solutions of the reaction mixture should be used in the following weight ratio of the components polyethyleneimine, or polyethylene polyamine, or polyhexamethylene guanidine, or its salt: water, polyethylene glycol or polypropylene glycol or a hydroxybenzene derivative equal to 1: (0.1-10.0) :( 0, 05-0.5). With solutions containing the components of the following limits, the surface of the carrier is non-uniformly wetted, which leads to an unstable quality modifier, and large quantities of water are added with solutions containing components above the specified limit, which must be removed when the modifier is isolated.

 According to reports, the claimed combination of essential features characterizing the essence of the invention is unknown from the prior art. Therefore, the invention meets the criterion of "novelty."

 As a result of the analysis, it was found that the properties of the features of the proposed method do not coincide with the properties of the identified analogues, an additional classification of the claimed features cannot be performed. Therefore, the claimed features meet the definition of "distinctive features."

 The invention does not follow for a specialist explicitly from the prior art.

 The set of features characterizing the known solutions (inventions) do not ensure the achievement of new properties and only the presence of distinctive features allows you to get new higher properties, a new technical result. Therefore, the present invention meets the criterion of "inventive step".

 The invention is illustrated by the following examples.

A 30% aqueous solution of polyhexamethylene guanidine hydrochloride (TU 10-09-481-87) or polyethyleneimine (MRTU 6-02-422-67), or polyethylene polyamine (TU 6-02-594-75), or polyhexamethylene guanidine or its salts is prepared in advance general formula (1), specifically - ^* polyhexamethylene guanidine hydrophosphate or poligeksametilenguanidinnitrata ^* or ^* poligeksametilenguanidinstearata or poligeksametilenguanidingidrokarbonata ^{* (*} obtained from aqueous solutions of polyhexamethylene guanidine hydrochloride followed by leaching of the appropriate acid ) in the presence of polyethylene glycols or polypropylene glycols of the general formula (2), specifically polyethylene glycol (TU 6-36-6205603-12-89, TU 6-14-719-82, TU 6-14-826-86) or propinol B-400 ( TU 6-14-300-80), or a hydroxybenzene derivative of the general formula (3), specifically 5-methylresorcinol or 2,5-dimethylresorcinol or resorcinol or 5-ethylresorcinol or * 4,5-dimethylresorcinol.

80 g of silica or kaolin, or zeolite, or lignin carrier are introduced into a mixer with Z-shaped blades and a steam jacket. The prepared 30% aqueous solution in the amount of 66 ml is treated with the carrier with mixing. Introduction components are mixed until a homogeneous product is obtained, and then dried at a temperature of 90-120 ^o C to a moisture content of not more than 2%. To obtain a modifier, silicon dioxide is used as a carrier - white carbon black BS-120 or BS-100 or BS-50 (GOST 18307 -78) or kaolin (GOST 19608-84), or zeolite (TU 113-23-91-05-90), or lignin (TU op. 64-11-123-89).

 In the manufacture of aqueous solutions, a nitrogen-containing polymer, water and an oxygen-containing compound are taken in a mass ratio of 1: (0.1-10.0) :( 0.05-0.5). Solutions containing components below the specified limits, i.e. with a small amount of water, the carrier is non-uniformly wetted - an inhomogeneous product of poor quality is obtained. When processing the carrier with solutions with a ratio of components above the specified limits, an unjustifiably large amount of water is introduced into the modifier, which must be removed when the modifier is isolated, which requires unjustified additional energy consumption.

 The obtained modifier is used in rubber compositions for lining metal cord (composition 1, table. 1) and in rubber compositions for lining textile cords (composition 2, table. 1).

 The compositions of the obtained modifiers are given in table.2.

 By the method claimed in and.with. USSR N1049492, C 07 D 487/22 publ. in B.I. 1983, a modifier is prepared that is used as a prototype and is also used in the compositions of these rubbers.

Rubber compounds are prepared in a rubber mixer with a mixing chamber volume of 2 l in two stages. The rotation speed of the rotors in the first stage is 40 rpm, the mixing temperature is 140 ^o C, the mixing time is 4 minutes The rotation speed of the rotors in the second stage is 30 rpm, the mixing temperature is 100 ^o , the mixing time is 2 minutes. The modifier is administered together with bulk ingredients in the 2nd stage. Samples for testing are vulcanized in an electric press for 25 minutes at a temperature of 153 ± 1 ^o C.

Tests of the bond strength of rubbers with steel cord under dynamic conditions are carried out in the mode of pulsed cyclic loads according to the methodology of the Research Institute of KGSh (the numerator in Table 2) and GOST 17443-80 (the Khromov dynamic method, the denominator in Table 2) both at 25 ^o C and after holding the samples in an air thermostat at 100 ^o C for 72 hours (IR-10 method, Art. 81), in a water vapor environment at 90 ^o C for 72 hours (IR-12 method Art. 81), under static conditions СЭВ 1763-79 or GOST 14311-77 (Н-method) standard - after exposure in an air thermostat at 100 ^o C for 72 hours (IR-10 method, Art. 81), water vapor at 90 ^o C for 72 hours (method IR-12, article 81). Determination of the bond strength of rubber with textile cord is carried out according to GOST 23785.7-89 at 25 and 130 ^o C.

 Belt rubber (part 1, table 1) is attached to brass metal cord 9l 15/27 or 28l 22/15, and frame rubber (part 2, table 1) to impregnated textile cords 232 BP and 23 KNTS.

 The results of determining the adhesive characteristics of the modified rubbers are presented in table. 2.

As can be seen from the data presented in table. 2, example 2, the inventive modifier causes, compared with the prototype, an increase in the adhesion of rubbers to brass-plated cords 9l 15/27, 28l 22/15 during repeated deformations (in dynamic conditions) at a temperature of 2530 1.7-2.2 times, after heat aging 2.0-2.5 times, after steam aging 2.0-2.8 times, in static conditions after heat aging and steam-air aging 70-80% Increase adhesion to textile cords at 25 ^o C for cord 232 BP is 25% and for cord 23 KNTS -15% at 130 ^o C, respectively 20 and 15%
The optimal mass ratio of the concentrations of polyhexamethylene guanidine hydrochloride, polyethylene glycol and silicon dioxide on a dry residue is 1: 0.25: 7.0. When using these components in a mass ratio below 1: 0.05: 1.0, a product with an inhomogeneous composition with a poor final shape (caking powder) is obtained, which leads to a deterioration in the adhesion properties of rubbers. When using these components in a mass ratio above 1: 0.5: 30.0, the quality of the modifier also deteriorates and the adhesion properties of the rubbers decrease. Use in the release of the inventive modifier of polyhexamethylene guanidine hydrochloride, polyethylene glycol and silicon dioxide in a mass ratio of from 1.0: 0.05: 1.0 to 1.0: 0.5: 30.0 leads to a final product with high quality, providing the benefits of modified adhesion rubber in comparison with the prototype and with a good final form of loose powder. At the same time, in the production process of the modifier, compared to the prototype, there are no production drains.

 Reactive expensive components that are primarily responsible for increasing the bond strength of rubbers with reinforcing materials, the prototype is resorcinol and hexamethylenetetramine, the content of which is 99.9% and polyhexamethylene guanidine hydrochloride and polyethylene glycol in the inventive modifier, the content of which is 51-4.7% Thus when implementing the proposed method, the concentration of expensive reactive components in the modifier is reduced in 1.9-21 times due to the application of their n and the highly developed surface of silicon dioxide and, as a result, increased activity. At the same time, resorcinol, which is an imported product, is excluded from the modifier.

 From the data of example 3 it is seen that instead of polyhexamethylene guanidine hydrochloride in the inventive modifier, polyethyleneimine or polyethylene polyamine, or polyhexamethylene guanidine, or polyhexamethylene guanidine phosphate, or polyhexamethylene guanidine nitrate, or polyhexamethylene guanidine stearate, or polyhexamethylene carbonate. Moreover, the quality of the modifier, i.e. bond strength of rubbers with metal cord and textile cords under various test conditions does not change.

 The degree of polymerization of these components is claimed within n 2-90. When n is less than 2, the claimed compounds are monomers and are not included in the scope of the claims on the application. When n is greater than 90, the adhesion properties of rubbers do not improve.

 The results shown in example 4 show that polyhexamethylene guanidine hydrochloride or its analogues can be applied to the surface of the carrier together with polyethylene glycol or polypropylene glycol, or derivatives of hydroxybenzene of the formula (3). Moreover, the adhesion characteristics of rubbers in dynamic and static conditions and the stability of the adhesive bond to various types of aging practically does not change. Polyethylene glycol and polypropylene glycol are declared as part of a modifier with a degree of polymerization of 2-120. When the degree of polymerization is less than 2, the claimed compounds are monomers and do not fall within the scope of the claims on the application; when the degree of polymerization is greater than 120, improvements in the bond strength of rubbers with reinforcing materials do not occur.

 From the results of example 5 it follows that as a carrier in the composition of the inventive modifier can be used not only silicon dioxide, but also kaolin or zeolite, or lignin. The adhesive characteristics of the modified rubbers practically do not depend on the type of carrier used in various test conditions.

 An experimental batch of modifier was manufactured at the Dnepropetrovsk plant of chemical products and was aimed at production tests at AL Dneproshina and PO Belotserkovshina. Tests showed a high technical result of the proposed method for producing a rubber modifier.

 Based on the foregoing, it follows that the inventive method for producing a rubber modifier meets the criterion of "industrial applicability".

Claims (1)

A method of producing a rubber modifier by dispersing nitrogen and oxygen-containing compounds in water, characterized in that polyethyleneimine with a degree of polymerization of n 2 90, or polyethylene polyamine with a degree of polymerization of n 2 10, or polyhexamethylene guanidine with a degree of polymerization of n 2 90, or its used as a nitrogen-containing compound salts of the general formula

where n 2 90;
A ^- H ₂ PO ₄ ^- , NO ₃ ^- , C _{1 7} H _{3 5} COO ^- , HCO ₃ ^- ,
and as the oxygen-containing compounds use polyglycols (polyethylene glycol or polypropylene glycol) of the General formula

where R ₁ -OH, -C ₄ H ₉ ;
R ₂ R ₃ —H, or R ₂ R ₃ —CH ₃ , or R ₂ —H, R ₃ —CH ₃ ;
n + m 2 120,
or a hydroxybenzene derivative of the general formula

where R ₁ -CH ₃ , -H;
R ₂ —CH ₃ , —H;
R ₃ —CH ₃ , —C ₂ H ₅ , H,
dispersion is carried out at a mass ratio of the nitrogen-containing compound, water and oxygen-containing compound 1 0.1 10.0 0.05 0.5, followed by treatment with the reaction mass of the carrier of silicon dioxide, or kaolin, or zeolite, or lignin, at a mass ratio of the nitrogen-containing compound, oxygen-containing compound and carrier 1 0.05 0.5 1 30 and the resulting product is isolated.

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