KR100291873B1 - Ozone deterioration inhibitor with high molecular weight amine - Google Patents

Abstract

[Ozone Cracking Inhibitor Containing High Molecular Weight Amine]

The present invention

(1) an aldehyde selected from the group consisting of formaldehyde, acetaldehyde and mixtures thereof, and general formula N, N'-disubstituted, wherein R ¹ and R ² are independently selected from the group of radicals consisting of C ₃ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl and C ₇ -C ₁₂ aralkyl a reaction material comprising an amine-containing compound selected from the group consisting of -p-phenylene diamine, (i) conditions for the presence of an acid catalyst, And (iii) reacting under condensation conditions comprising dissolving the amine containing compound in an organic solvent to form a condensation product;

(2) removing the reaction water from the condensation product;

(3) adjusting the pH of the condensation reaction product to at least 7 to form a basic reaction mixture;

(4) filtering off the neutralized catalyst to form a solvent reaction mixture;

(5) heating the solvent reaction mixture to a temperature in the range of about 110 to 250 ° C. in vacuo; And

(6) a reaction of a multistage process comprising isolating a reaction product derived solely from the aldehyde and the amine, the reaction product exhibiting ozone cracking prevention activity in a diene containing rubber from a heated solvent reaction mixture. A composition which exhibits ozone cracking prevention activity in a diene-containing rubber, characterized by a product.

Description

[Name of invention]

Ozone deterioration inhibitor containing high molecular weight amine

Detailed description of the invention

The present invention relates to a composition comprising a high molecular weight amine-containing ozone deterioration inhibitor prepared in a multi-step process.

In order to prevent the breakdown of the diene rubber by ozone decomposition and oxidation, an amine-containing ozone deterioration inhibitor is usually used for the diene rubber. A common example of such an amine containing compound is an antiozonant such as N, N'-disubstituted-p-phenylene diamine. Manufacturers of rubber products, such as tires, have made significant developments in rubber chemistry that extend the life of rubber products. In order to prolong this life, the demand for ozone deterioration inhibitors is increasing. Therefore, there is a need to develop better ozone deterioration inhibitors and to further extend the life of these rubber products.

The present invention relates to a compound comprising a high molecular weight amine-containing ozone deterioration inhibitor prepared in a multi-step process.

Compositions showing ozone deterioration activity in diene-containing rubber

(1) an aldehyde selected from the group consisting of formaldehyde, acetaldehyde or mixtures thereof, and a general formula N, N'-disubstituted-, wherein R ¹ and R ² are independently selected from the group of radicals consisting of C ₃ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl and C ₇ -C ₁₂ aralkyl A reaction material comprising an amine-containing compound selected from the group consisting of p-phenylene diamine is selected from (i) the presence conditions of the acid catalyst, and (ii) the molar ratio condition of the aldehyde: amine-containing compound in the range of about 1.01: 2 to 2: 1. And (iii) reacting under condensation conditions comprising dissolving the amine containing compound in an organic solvent to form a condensation product;

(2) removing water from the condensation product;

(3) adjusting the pH of the condensation reaction product to at least 7 to form a basic reaction mixture;

(4) filtering off the neutralized catalyst to form a solvent reaction mixture;

(5) heating the solvent reaction mixture to a temperature in the range of about 110 to 250 ° C. in vacuo; And

(6) a reaction product of a multistage process prepared by isolating a reaction product derived solely from the aldehyde and the amine, the reaction product exhibiting anti-ozonation activity in a diene-containing rubber, from a solvent reaction mixture. It includes.

The present invention also provides a rubber selected from the group consisting of natural rubbers, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers, and mixtures thereof, with high molecular weight amine-containing ozone deterioration inhibitors of the present invention. A method for reducing deterioration of diene containing rubber, including mixing together.

In addition, the present invention

(1) a rubber selected from the group consisting of natural rubbers, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers, and mixtures thereof; And

(2) aldehydes selected from the group consisting of formaldehyde, acetaldehyde and mixtures thereof, and general formula N, N'-disubstituted, wherein R ¹ and R ² are independently selected from the group of radicals consisting of C ₃ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl and C ₇ -C ₁₂ aralkyl a reactant comprising an amine containing compound selected from the group consisting of -p-phenylene diamine, (i) conditions of presence of an acid catalyst, And (iii) reacting under condensation conditions, including dissolving the amine-containing compound in an organic solvent to form a condensation product;

2) removing water from the condensation product;

3) adjusting the pH of the condensation reaction product to at least 7 to form a basic reaction mixture;

4) filtering off the neutralized catalyst to form a solvent reaction mixture;

5) heating the solvent reaction mixture to a temperature in the range of about 110 to 250 ° C. in vacuo; And

6) A rubber comprising a reaction product of a multistage process comprising isolating a reaction product derived solely from the aldehyde and the amine, the reaction product exhibiting anti-ozonation activity in a diene containing rubber, from a solvent reaction mixture. To a composition.

Compounds of the present invention are prepared by reacting an aldehyde selected from the group consisting of formaldehyde, acetaldehyde or mixtures thereof with the amine containing compounds described above. Formaldehyde may be free formaldehyde, for example paraformaldehyde. The source of formaldehyde may also be an aqueous solution, such as a 37% by weight aqueous solution known as formalin.

Specific amines that can be used to react with aldehydes include N, N'-diphenyl-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-di-β-naphthyl- p-phenylenediamine, No-tolyl-N'-phenyl-p-phenylenediamine, N, N-di-p-tolyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl -p-phenylenediamine, N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-1-methylpropyl- N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine and N, N'-bis (1-methylpropyl) -p-phenylenediamine are mentioned.

Aldehydes react with amine containing compounds under conditions suitable for condensation reactions. The reaction product consists of a number of amine containing compounds, all of which have varying molecular weights. The molecular weights of the components in the reaction product vary depending on the specific amine containing compound, the particular aldehyde, the proportion of the reactant, the catalyst, the amount of the catalyst, the reaction temperature and the reaction time clearly selected. The molecular weight of the compositions of the present invention may range from about 378 to about 20,000, preferably from about 2,000 to about 10,000.

The molar ratio of aldehyde; amine containing compound may range from about 1.01: 2 to 2: 1, preferably about 1.25: 2 to 1.75: 1.

The condensation reaction is carried out in the presence of a catalyst to accelerate the reaction. Examples of catalysts that can be used include acid catalysts such as sulfuric acid, methane sulfonic acid, hydrochloric acid, xylene sulfonic acid and toluene sulfonic acid. The amount of catalyst that can be used varies depending on the particular catalyst selected. For example, the acid catalyst should range from about 0.01 to about 100 g, preferably from about 1 to about 10 g, per mole of amine.

The condensation reaction can be carried out over a wide range of temperatures. The condensation reaction is exothermic and can be carried out at temperatures ranging from room temperature to elevated temperatures. In general, the condensation reaction may be carried out at a temperature of about 5 to about 150 ° C, preferably at a temperature of about 20 to about 125 ° C.

Organic solvents should be used to dissolve the amine containing compound for continued reaction with the aldehyde. The solvent is preferably inert to the condensation reaction. Examples of suitable solvents for use in the present invention include saturated and aromatic hydrocarbons such as hexane, octane, dodecane, naphtha, decalin, tetrahydronaphthalene, kerosene, mineral oil, cyclohexane, cycloheptane, alkyl cycloalkanes , Benzene, toluene, xylene, alkyl-naphthalene and the like; Tetra hydrofuran, diethyl ether, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, or mono of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol or oxyethyleneoxypropylene glycol Ethers such as dialkyl ether and the like; And alkyl alcohols such as perfluoroethane, monofluorobenzene, or methanol or ethanol, which are inert under the reaction conditions. Another class of solvents are sulfones such as dimethylsulfone, diethylsulfone, diphenolsulfone, sulfolane and the like. As long as the mixtures of the solvents mentioned are compatible with each other under the reaction conditions and do not properly dissolve the amine containing compound and interfere with the condensation reaction, these mixtures can also be used.

The condensation reaction can be carried out under various pressures and the preferred pressure is atmospheric pressure.

The condensation reaction is carried out for a time sufficient to produce the desired condensation product, on which subsequent high heating and isolation anti molecular weight ozone deterioration agent is produced. In general, the condensation reaction time may vary from minutes to hours. When choosing slower reaction conditions, the reaction time will have to be extended until the desired product is produced. The residence time of the reactants will be influenced by the reaction temperature, the concentration and type of reactants, the concentration and type of catalyst, the solvent and other factors. Preferably, the condensation reaction is carried out until a theoretical water of reaction is produced.

As soon as the condensation reaction is complete, the condensation product is heated to remove the reaction water. The condensation product may be heated by conventional methods as known to those skilled in the art. As can be seen, the temperature should exceed 100 ° C.

As soon as the reaction water is removed, the pH of the residual condensation reaction product is adjusted to basic pH. Therefore, the pH rises to a range of 7 or more. The pH of the residual condensation reaction product is preferably in the range of about 9 to about 11. Suitable regulators that can be used to adjust the pH include aqueous solutions of sodium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, sodium carbonate, potassium carbonate and the like. Preference is given to using potassium carbonate.

After the reaction mixture is made basic, the aqueous layer is removed from the pH adjuster which makes the mixture basic, the organic layer is heated to remove all remaining traces of water and hot filtered to remove all traces of neutralizing catalyst.

After removing the catalyst, the organic layer or solvent containing reactant is heated in vacuo to a temperature in the range of about 110 to 250 ° C. Preferably, the solvent reaction mixture is heated to a temperature in the range of about 150 to about 200 ° C. The purpose of the heating step is to strip off the organic solvent in vacuo and rearrange the condensation reaction product as much as possible to form the compounds of the invention.

Heating of the solvent reaction mixture can be carried out at various pressures, that is, in the range of about 0 to 100 psig.

The heating step is carried out for a time sufficient to strip off the unnecessary organic solvent. In general, the heating time varies from a few minutes to several hours. To choose slower reaction conditions, the reaction time will have to be extended until the desired product mixture is obtained. The residence time of the reaction mixture will be influenced by the heating temperature, reaction pressure and solvent selection. Preferably, the heating step is performed for about 15 minutes to about 2 hours.

Upon completion of the heating step, the desired mixture of high molecular weight ozone deterioration agent is isolated. Isolation methods are commonly well known to those skilled in the art and may consist of simply pouring the heated and stripped basic reaction mixture into a crystallization dish and cooling the reaction mixture for later use. The reaction product isolated in the multistage process contains a mixture of high molecular weight amine ozone inhibitors. This molecular weight distribution contributes to the advantages of the present invention, and in fact having a high molecular weight is believed to contribute to lowering the viscosity of the amine ozone deterioration inhibitor.

Various polymers can be stabilized by the method of the present invention. In particular, the ozone deterioration inhibitor of the present invention may be used together with a vulcanizable elastomer. By "vulcanizable elastomer or rubber" is meant herein to encompass not only various synthetic rubbers, but also natural rubber forms and all of their lower and regenerated forms. Representative synthetic polymers include homopolymers of butadiene and its analogs and derivatives such as methylbutadiene, dimethylbutadiene and pentadiene, as well as copolymers of butadiene, or analogs formed from analogs or derivatives thereof, with other unsaturated organic compounds. Can be. Examples of the former compound include acetylene such as vinyl acetylene; Isobutylene, which copolymerizes with olefins such as isoprene to form butyl rubber; Vinyl compounds such as vinyl chloride, acrylic acid, acrylonitrile (which polymerize with butadiene to form NBR), methacrylic acid and styrene; the former compounds polymerize with butadiene to form vinyl esters and various unsaturated aldehydes, Ketones and ethers such as acrolein, methyl isopropenylketone and vinyl ethyl and ether, as well as SBR. These also include various synthetic rubbers prepared by homopolymerization of isoprene and copolymerization of isoprene with other diolefins and various unsaturated organic compounds, in addition to 1,4-cis polybutadiene and 1,4-cispolyisoprene. Synthetic rubbers such as, and similar synthetic rubbers such as EPDM. Preferred rubbers for use with high molecular weight amine containing ozone deterioration agents are polybutadiene, butyl rubber, EPDM, butadiene-styrene copolymers and 1,4-cis-polyisoprene.

The high molecular weight ozone deterioration inhibitor of the present invention may be blended into a productive raw material (containing a cured package containing sulfur) or a non-productive raw material. The blending of the ester into the polymer can be carried out by the use of conventional mixing means, such as a Banbury mixer, a Brabender mixer.

The amine containing ozone deterioration inhibitor of this invention can be used for the said polymer in a wide variety of ratios. Such amine containing anti-ozone deterioration agents may be used in whole or in part in place of conventional anti-ozone deterioration agents. In general, the amount of amine-containing ozone deterioration agent that can be added to the polymer composition is in the range of about 0.25 to about 10.0 parts per 100 parts of polymer, preferably in the range of about 0.5 to about 8.0 parts.

Rubber compositions containing amine-containing ozone deterioration inhibitors include, for example, tires, motor devices, rubber bushings, powder belts, printing rolls, rubber shoe heel and soles, floor rubber tiles, leg wheels, elastomeric seals and Gaskets, conveyor belt covers, weaving machines, hard rubber battery cases, automotive floor mats, truck fenders, ball mill liners, and the like. Preferably, rubber compositions containing amine ozone depleting agents are used in tire applications, including treads, sidewalls, apex and chafers of tires.

In addition to the amine ozone deterioration inhibitor of the present invention, other rubber additives can also be blended into the rubber. Additives commonly used in vulcanized rubbers are, for example, carbon black, thickener resins, processing aids, ozone deterioration inhibitors, fatty acids, activators, waxes, oils and disintegrating agents.

Representative examples of conventional antioxidants and antiozonants (commonly classified together as antidegradants) that can be used include monophenols, bisphenols, thiobisphenols, thioalkylphenols, polyphenols, hydroquinone derivatives, phosphates, thioesters, Naphthylamine, diphenylamine and other diarylamine derivatives, para-phenylene diamine and quinoline.

As is known to those skilled in the art, depending on the desired use of the vulcanizable rubber material, any of the additives mentioned above are commonly used in conventional amounts. Typical addition amounts of carbon black are about 20 to 100 parts by weight in diene rubber (phr) (typically about 40 to 70 phr in many tire applications).

Typical amounts of thickener resins are from about 2 to 10 phr, typical amounts of processing aids are from about 1 to 8 phr, typical amounts of antioxidants are from 1 to about 5 phr, typical amounts of ozone deterioration agents are from 1 to about 5 phr, stearic acid and oleic acid and the like. Typical amounts of such fatty acids are from about 1 to about 2 phr, typical amounts of zinc oxide are from 3 to 5 phr, typical amounts of waxes are from 1 to about 5 phr, typical amounts of processed oil are from 5 to about 50 phr, and typical amounts of disintegrants from 0.1 to 1 phr to be.

The vulcanization of rubber containing a mixture of high molecular weight ozone deterioration agents is carried out in the presence of a rubber vulcanizing agent. Examples of suitable vulcanizing agents include sulfur elements (free sulfur) or sulfur donor vulcanizing agents such as amine disulfides, polymerizable polysulfides or sulfur olefin adducts. The vulcanizing agent is preferably a sulfur element. As is known to those skilled in the art, vulcanizing agents are used in amounts ranging from about 0.5 to 8 phr, preferably 1.0 to 3.0 phr.

Accelerators are generally used in rubber compositions to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized rubber. In some cases a single promoter system, ie a primary promoter, is used. Typically, primary promoters are used in amounts ranging from about 0.5 to 2.0 phr. In many other cases, 2 may consist of a primary promoter generally used in large quantities (0.5 to 2.0 phr) and a secondary promoter used in small amounts (0.05 to 0.50 phr) to activate the vulcanized rubber and improve its properties. Use at least two promoter combinations. Blends of these promoters are known to cause synergistic effects on the final properties, and are somewhat superior in physical properties compared to using only one promoter. In addition, it is also possible to use delayed functional promoters which give satisfactory curing at normal vulcanization temperatures without being affected by standard processing temperatures. Suitable types of such promoters that may be used include amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. The primary promoter is sulfenamide. When using a secondary accelerator, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound.

The following examples are intended to illustrate the invention but are not intended to limit the invention.

Example 1

67 g (0.25 M) of N in a 1 L three-necked flask equipped with a Claissen adapter with a thermometer mounted on a Dean Stark trap connected to a heating mantle, mechanical stirrer, dropping funnel and water condenser Charge-(1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 1.0 g xylene sulfonic acid and 125 g toluene. The mixture is heated to 44 ° C. with stirring to form a solution, to which 26 g of 37% formalin (1.25 M formaldehyde) is added and stirred at 44 ° C. to 38 ° C. for 1 hour 30 minutes. Formaldehyde; The molar ratio of amine is 1.25: 1. The mixture is heated slowly at 38-83 ° C. over 2 hours with stirring. The reaction mixture is then stirred for an additional 45 minutes at a pot temperature of 83 to 110 ° C. to remove the reaction water by evaporation (all reaction water is evaporated). The reaction mixture is then cooled to 95 ° C. and 2.0 g of Na ₂ CO ₃ (as a solution) in 20 g of water are added and stirred at 95-75 ° C. for 1 h and a half. The aqueous layer is removed by sedimentation, the toluene reaction product solution is heated to remove the last traces of water, which is hot filtered through a polypropylene mat filler at about 90-100 ° C., at a pot temperature of 196 ° C. and a pressure of 27 mm. Strip in vacuo. 71 g of very dark and hard resin was obtained. GPC analysis with polystyrene standards in tetrahydrofuran using an index of refraction detector showed THF in the following apparent molecular weight range:

Molecular weight area (%)

13128 35.0

3861 40.1

722 14.9

365 9.9

Example 2

The conditions and treatment of Example 1 were repeated except that 13 g of 37% formalin (formula 0.625M based on amine 1.0M) was added. The product was stripped in vacuo at a pot temperature of 172 ° C. and a pressure of 27 mm. 67 g of very dark product was obtained. GPC analysis showed the apparent molecular weight range of THF as follows:

Molecular weight area (%)

2253 59.2

645 20.2

360 20.6

Example 3

Example 1, except that 56.5 g (0.25 M) of N- (2-methylethyl) -N'-phenyl-p-phenylenediamine, 1.0 g of xylene sulfonic acid and 125 g of toluene were heated to 45 ° C. with stirring. Conditions and treatments were repeated. 26.0 g 37% formalin (1.25 moles of formaldehyde based on 1.0 mole of amine) are added and the mixture is heated at 45-83 ° C. over 2 h with stirring. The reaction mixture is allowed to react at 84 to 110 ° C. for ¾ hours until all reaction water is stopped. The product was run as in Example 1 and stripped in vacuo at a pot temperature of 176 ° C. and a pressure of 22 mm. 60.5 g of a very dark and hard resin were obtained. GPC analysis showed the apparent molecular weight range of THF as follows;

Molecular weight area (%)

2033 2.5

1040 67.4

621 30.0

Example 4

Example, except that 56.5 g (0.25 mol) of N- (2-methylethyl) -N'-phenylene-p-phenylenediamine, 1.0 g of xylene sulfonic acid and 125 g of toluene were heated to 60 ° C. to prepare a solution. The conditions and treatment of 1 were repeated. 11.3 g 37% formalin (0.55 mole formaldehyde based on 1.0 mole amine) is added and the mixture is slowly heated to 84 ° C. over 30 minutes. The reaction mixture is stirred at 84 ° C. for 3 hours, and then the reaction mixture is reacted at a pot temperature of 85 to 112 ° C. for ¾ hour until all of the reaction water generation stops. The reaction mixture was carried out as in Example 1 and stripped under vacuum at a pot temperature of 184 ° C. and a pressure of 25 mm. 59 g of reaction product was obtained. GPC analysis showed the apparent molecular weight range of THF as follows:

Molecular weight area (%)

1067 36.7

799 15.9

503 22.1

299 25.3

Example 5

The conditions and treatment procedure of Example 1 were repeated except that the toluene solution made into a solution by heating to 55 ° C. was cooled to 8 ° C., and 14 g of 99% acetaldehyde (1.25 M based on 1.0 mole of amine) was added under stirring. It was. The temperature was raised from 8 ° C. to 12 ° C. and stirred at 12 ° C. for 5 minutes, then the reaction mixture was slowly heated from 12 ° C. to 26 ° C. and stirred at 26 ° C. for another 15 minutes. The temperature was increased from 26 ° C. to 86 ° C. over 1 hour 30 minutes and stirred at 86 ° C. for 3 hours. The reaction temperature was increased to a pot temperature of 115 ° C. with stirring for 1 hour until all reaction water was collected and carried out as in Example 1. The reaction product was stripped in vacuo at a pot temperature of 178 ° C. and a pressure of 22 mm. 75 g of very dark viscous reaction product was obtained. GPC analysis showed the apparent molecular weight range of THF as follows:

Molecular weight area (%)

1064 13.3

728 18.0

357 68.0

Example 6

The conditions of Example 1, except that 56.5 g of N- (2-methylethyl) -N'-phenyl-p-phenylenediamine, 1.0 g of toluene sulfonic acid and 125 g of toluene were made into a solution by heating to 65 ° C. with stirring. And the process was repeated. 14.0 g of 99% acetaldehyde (former 1.25 M based on 1.0 mole of amine) was added and the temperature was raised from 8 ° C. to 12 ° C. and the reaction mixture was stirred at 12 ° C. for 5 minutes and ¾ hours at 12 to 28 ° C. Stir over. The reaction mixture is heated at 28-86 ° C. over ½ hour, stirred and heated at 86 ° C. for an additional 2 hours. The reaction mixture is heated to a pot temperature of 114 ° C. for 1 hour 15 minutes until all reaction water has evaporated to the end of the reaction. The reaction was carried out as in Example 1 and stripped in vacuo at a pot temperature of 178 ° C. and a pressure of 22 mm. 65 g of dark viscous reaction product were obtained. GPC analysis showed the apparent molecular weight range of THF as follows:

Molecular weight area (%)

814 13.9

566 15.7

296 70.4

Example 7

56.5 g of N- (2-methylethyl) -N'-phenyl-p-phenylenediamine, 1.0 g of toluene sulfonic acid and 125 g of toluene were stirred to a solution by heating to 65 ° C., and the solution was cooled to 10 ° C. Except that, the conditions and treatment of Example 1 were repeated. 7.0 g of 99% acetaldehyde (1.25 M formaldehyde based on 1.0 mole of amine) was added and the mixture was increased from 10 ° C to 14 ° C. The reaction mixture was stirred at 14 ° C. for 5 minutes and slowly heated to 24 ° C. over 15 minutes. The reaction mixture was stirred at 24 ° C. for 15 minutes, heated slowly to 91 ° C. for 30 minutes, and stirred at 91 to 89 ° C. for an additional 3 hours. The reaction mixture was then reacted over 50 minutes at a pot temperature of 114-115 ° C. until all reaction water was evaporated to complete the reaction. The reaction was carried out as in Example 1 and stripped in vacuo at a pot temperature of 185 ° C. and a pressure of 18 mm.

61 g of black highly viscous oil was obtained. GPC analysis indicated the molecular weight range of THF as follows:

Molecular weight area (%)

793 5.9

561 9.1

298 82.7

Example 8

Example, except that 335 g of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 5.0 g of xylene sulfonic acid and 600 g of toluene were heated and stirred at 55 ° C. under N ₂ atmosphere. 1 treatment and conditions were repeated. To this solution was added 77 g of 37% formalin (0.75 M formaldehyde based on 1.0 M of amine) at 55 ° C. and stirred at 55-70 ° C. for ½ hour. The reaction mixture was allowed to react at 70 to 108 ° C. for 2 hours until all reaction water was evaporated to the end of the reaction. The process was carried out in the same manner as in Example 1 using excess sodium carbonate in water. The reaction mixture was vacuum stripped to a pot temperature of 192 ° C. at a pressure of 25 mm. 353 g of reaction product were obtained (dark black hard dendritic solid). GPC analysis showed the apparent molecular weight range of THF as follows:

Molecular weight area (%)

2935 30.5

1850 30.9

777 20.1

452 18.6

Example 9

The conditions and treatment of Example 8 were repeated except that 2.0 g of xylene sulfonic acid was used. The product was stripped to a pot temperature of 190 ° C. and a pressure of 25 mm to give 350 g of reaction product. GPC analysis indicated the molecular weight range of THF as follows:

Molecular weight area (%)

1103 8.8

750 26.2

448 65.0

Example 10

The conditions and treatment of Example 8 were repeated except that 1.0 g of xylene sulfonic acid and 96 g of 37% formalin (formula 0.938 M based on the weight of the amine) were used. The product was stripped at a pot temperature of 192 ° C. and a pressure of 25 mm to give 349 g of reaction product. The reaction product did not solidify at room temperature.

Example 11

Example 1 conditions and treatment, except that 335 g of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 8.8 g of xylene sulfonic acid and 500 g of toluene were heated to 45 ° C. with stirring. The process was repeated. 130 g 37% formalin (former 1.25 M based on 1.0 mole of amine) are added and the mixture is stirred for 15 minutes at a temperature between 45 and 49 ° C. The reaction mixture is heated to 49-112 ° C. for 2 hours until all reaction water has evaporated to the end of the reaction. The process was carried out as in Example 1 using 9 g sodium carbonate in 71 mL water and the reaction mixture was stripped to a pot temperature of 195 ° C. and a pressure of 14 mm. 350 g of very dark brittle resin was obtained. Data from GPC analysis is provided in Example 14.

Example 12

Example 1 conditions and treatment, except that 335 g of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 5.0 g of xylene sulfonic acid and 625 g of toluene were heated to 45 ° C. with stirring. The process was repeated. 130 g of 37% formalin (former 1.25 M based on 1.0 mole of amine) are added and the mixture is stirred at 45-40 ° C. for 30 minutes. The reaction mixture is slowly heated to 83 ° C. for 30 minutes and stirred at 83 ° C. for 2 hours. The reaction mixture is heated for 3 hours and 15 minutes at a pot temperature of 83 to 110.5 ° C. until all reaction water has evaporated to the end of the reaction. The process was carried out as in Example 1 using 5.0 g sodium carbonate in 31 ml of water and the mixture was stripped in vacuo at a pot temperature of 182 ° C. and a pressure of 12 mm. 355 g of dark brittle resin was obtained. Data from GPC analysis is provided in Example 14.

Example 13

Example 12 conditions and treatment were repeated except that 600 g toluene and 65 g 37% formalin (0.625 mole formaldehyde based on 1.0 mole amine) were used. The mixture was kept at 83 ° C. for 2 hours. The aerobic time was 1 hour 5 minutes. The mixture was carried out as in Example 12 and stripped in vacuo at a pot temperature of 181 ° C. and a pressure of 11 mm. 347 g of a very dark and somewhat viscous resin were obtained. Data from GPC analysis is provided in Example 14.

Example 14

The process and conditions of Example 13 were repeated except that 95 g of 37% formalin (0.938 M formaldehyde based on 1.0 M amine) were added at 45 ° C. The process was carried out in the same manner as in Example 12. The mixture was vacuum stripped to a pot temperature of 184 ° C. and a pressure of 12 mm. 350 g of very dark brittle resin was obtained. GPC analysis of Examples 11-14 was performed using polystyrene standards. The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (poly D or Mw / Mn) were determined.

Example Mw Mz Mn Poly D

11 4604 10225 1682 2.7365

12 360 1 7222 1619 2.2245

13 1466 2213 1002 1.4632

14 2228 3766 1271 1.7528

Example 15

Natural rubber, cis-polybutadiene [butene (BUDENE 1207], a rubber composition containing carbon black, processing aids and a typical sulfur accelerated curing system for tire sidewalls was prepared in a laboratory Banbury mixer using two separate addition steps. Sulfur and accelerators were added to the Banbury mixer in the second stage, while processing aids were added and passed in the first stage along with the rubber and carbon black. Different amounts of ozone degradation inhibitor [Santo Flex ^TM (Santoflex ^TM) 13], or carried the reaction product of Examples 12 to 14 was added to the mixture of the first step. Santoplex ^TM 13 is N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine manufactured by Monsanto. Table 1 below shows the vulcanization characteristics of the rubber composition. In Table I, only the composition difference of a rubber composition is shown.

The effect of increasing the amount of N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (Santoplex ^TM 13) ozone deterioration agent on the curing behavior and the curing properties of the compositions A, B and C Shown by comparison. The most dramatic effect is when comparing static and dynamic ozone resistance. As their amount increased from 1 phr (composition A) to 5 phr (composition C), the sample appeared from numerous large ozone cracks to its surface after static testing to no ozone cracks, and many dynamic cracks after dynamic testing. Only the edges are cracked. Addition of the high molecular weight product of Example 13 in an amount of 5 phr (Composition D) provides the same static and dynamic ozone protection as Composition C containing 5 phr of low molecular weight Santoplex ^™ 13. High molecular weight products will have the advantage of having low volatility in the cured compounds and superior persistence compared to low molecular weight Santoplex ^™ 13. Using 5 phr of the high molecular weight product of Example 14 (composition G) provided static ozone barrier properties equivalent to using 5 phr of Santoflex ^™ 13 (composition C), but dynamic ozone barrier properties were somewhat inferior. The high molecular weight product (composition H) of Example 12 does not provide static or dynamic ozone barrier properties comparable to Santoplex ^™ 13 5 phr (composition C).

Example 16

Natural rubber, cis-polybutadiene (butene 1207), rubber compositions containing carbon black, processing aids and a typical sulfur accelerated curing system on the tire sidewalls were prepared in a laboratory Banbury mixer using two separate addition steps. Sulfur and accelerators were added to the Banbury mixer in the second stage, while processing aids were added and passed in the first stage along with the rubber and carbon black. Only the difference in composition of the rubber composition is shown in Table 2.

The reaction products of Santoplex ^™ 13 and Example 13 were compared to Compounds I and K, each containing 5 phr, and also to a blend (composition J) containing 2.5 phr of each product. These results clearly show that a mixture of low molecular weight Santoplex 13 and the high molecular weight reaction product of Example 13 can be used to provide good curing properties and adequate ozone barrier properties.

[Oxygen Absorption]

Styrene-butadiene rubber without ozone deterioration agent [Flioplex (Plioflex 1712] was combined with the anti-ozonation agent of the present invention. Plioplex 1712 is commercially available from The Goodyear Tire and Rubber Company. For comparison purposes, various commercially available ozone deterioration inhibitors were also formulated. Various parts by weight of ozone deterioration agent were used for oxygen absorption studies. The amount of the ozone deterioration inhibitor was expressed in parts by weight based on 100 parts by weight of rubber, respectively.

Oxygen uptake tests were performed by dissolving the blended SBR in the toluene moiety. The cement thus formed was poured onto aluminum foil to form a thin film. After drying, the weight of rubber for each sample was obtained. The foil with the adhesive rubber strip was then placed in a coral absorber and the time needed to absorb 1.0, 2.0 and 3.0% oxygen was measured and recorded in Table 3 below. Such testing procedures are described in more detail in Industrial and Engineering Chemistry, 43, p. 456 (1951) and Industrial and Engineering Chemistry, 45, p. 392 (1953).

Claims (9)

(1) an aldehyde selected from the group consisting of formaldehyde, acetaldehyde and mixtures thereof, and general formula N, N'-disubstituted, wherein R ¹ and R ² are independently selected from the group of radicals consisting of C ₃ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl and C ₇ -C ₁₂ aralkyl a reaction material comprising an amine-containing compound selected from the group consisting of -p-phenylene diamine, (i) conditions of presence of an acid catalyst, (ii) molar ratio conditions of an aldehyde: amine-containing compound in the range of about 1.01: 2 to 2: 1. And (iii) reacting under condensation conditions, including dissolving the amine-containing compound in an organic solvent to form a condensation product; (2) removing the reaction water from the condensation product; (3) adjusting the pH of the condensation reaction product to at least 7 to form a basic reaction mixture; (4) filtering off the neutralized catalyst to form a solvent reaction mixture; (5) heating the solvent reaction mixture to a temperature in the range of about 110 to 250 ° C. in vacuo; And (6) a reaction product of a multistage process comprising isolating a reaction product derived solely from the aldehyde and the amine, the reaction product exhibiting anti-ozonation activity in a diene-containing rubber from a heated solvent reaction mixture. A compound which shows ozone deterioration prevention activity in diene containing rubber, characterized by the above-mentioned. The compound of claim 1, wherein the amine containing compound is N, N′-disubstituted-p-phenylene diamine. The compound according to claim 1, wherein the amine containing compound is substituted diphenylamine. Deterioration of the diene-containing rubber, characterized in that the rubber selected from the group consisting of natural rubber, homopolymer of conjugated diolefin, copolymer of conjugated diolefin and ethylenically unsaturated monomer, and mixtures thereof is mixed with the compound of claim 1. Method for reducing. The method of claim 4, wherein the compound of claim 1 is added in an amount ranging from about 0.5 phr to 10 phr. (A) a rubber selected from the group consisting of natural rubbers, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers, and mixtures thereof; And (B) 1) an aldehyde selected from the group consisting of formaldehyde, acetaldehyde and mixtures thereof, and a general formula N, N'-disubstituted, wherein R ¹ and R ² are independently selected from the group of radicals consisting of C ₃ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl and C ₇ -C ₁₂ aralkyl a reactant comprising an amine containing compound selected from the group consisting of -p-phenylene diamine, (i) aldehydes in the range of about 1.01: 2 to 2: 1 in the presence of an acid catalyst; Reacting under condensation conditions including molar ratio conditions of the amine-containing compound and (iii) dissolving the amine-containing compound in an organic solvent to form a condensation product; 2) removing the reaction water from the condensation product; 3) adjusting the pH of the condensation reaction product to at least 7 to form a basic reaction mixture; 4) filtering off the neutralized catalyst to form a solvent reaction mixture; 5) heating the solvent reaction mixture to a temperature in the range of about 110 to 250 ° C. in vacuo; And 6) Characterizing the reaction product of a multistage process comprising isolating the reaction product derived solely from the aldehyde and the amine, the reaction product exhibiting anti-ozonation activity in the diene containing rubber, from the heated solvent reaction mixture. Rubber composition made into. 7. The rubber composition according to claim 6, wherein the amine containing compound is N, N'-disubstituted-p-phenylene diamine. The rubber composition according to claim 6, wherein the amine containing compound is substituted diphenylamine. The rubber composition of claim 6, wherein the reaction product is in an amount ranging from about 0.5 to about 10 phr.