Derivatives of s-triazine and method of production thereof

 

(57) Abstract:

Usage: create ozone rubber products. The inventive product F. - ly (I), where R3- C6-cycloalkyl, unsubstituted or substituted 1 - 21- C4-alkyl or C3- C7-alkyl branched chain, which can be used as antiozonant for thermosetting resin compositions. Reagent 1: cyanuric chloride. Reagent 2: the corresponding N-alkyl-n-phenylenediamine. 2 S. and 3 C. p. F. - ly, 7 PL.

The invention relates to a process for the preparation of new derivatives of S-triazine of General formula (I)

RHNHNNHR where R3-7the alkyl branched chain or3-6cycloalkyl, unsubstituted or substituted WITH 1-21-4altergroup that can be used as antiozonants for thermosetting resin compositions.

Known derivative paraphenylenediamine used for protivoatomnoi protection in static and dynamic conditions. However, even the best of them have a significant tendency to wear and discoloration.

The purpose of the invention to provide new derivatives of S-triazine highly effective antiozonants to protect the mate is th invention provide exceptionally long life protivoatomnoi protection in static conditions without the use of waxing. The advantages of the compounds of the substituted triazine are as follows: they are mostly not painting antiozonants with high molecular weight; they gradually form a plaque on the surface of rubber products; provide exceptional dynamic protection without the use of waxing, which is achieved by mixing the above-mentioned triazine compounds with other known antiozonants and antioxidants; exhibit no tendency to increase the propensity to podocarpaceae rubber mixture, in which they are included, which increases the safety of handling other paraphenylenediamine of antiozonants.

The way to obtain new derivatives of S-triazine of General formula (I) is that the corresponding N-alkyl-n-phenylenediamine is subjected to interaction with cyanuric chloride in an inert organic solvent to obtain the reaction mixture containing trichlorohydrin the target product, which is neutralized with a solution of alkali metal hydroxide, followed by separation of the target product usually by crystallization.

P R I m e R 1. 2,4,6-Tris(N-1,4-dimethylpentyl-n-phenylendiamine)- 1,3,5-triazine.

The 3-liter chetyrehosnuju bottom of canola. Isopropanol cooled to a temperature of -10aboutWith and add 184,4 g (1 mol) of cyanoalanine. To this stirred suspension was added 680 g (3.3 mol) of 4-amino-N-(1,4-dimethylpentyl)aniline (dropwise) over 1 h, keeping the temperature between -10 and -5aboutC. for 1 h, the reaction mixture is heated to a temperature of 30aboutC, and then maintained for 16 h 30aboutC. the Reaction mixture is heated with reverse cooling for 1 h at a temperature of approximately 80aboutC. the Reaction is then accompanied by liquid chromatography under high pressure by observing the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final product is a triple substitution. After cooling to a temperature of 60aboutWith 240 g (3 mol) of a 50% aqueous sodium hydroxide solution are added dropwise within 1 h sodium Chloride is removed by filtration at a temperature of 40aboutC. the Filtrate is cooled to a temperature of 10aboutWith and the solvent decanted. Oily bottom layer is extracted with water at a temperature of 60aboutWith, then crystallized from fresh isopropanol. Specified in the title compound is recrystallized from hexane, and it melts at a temperature 128-132aboutC. the Output is 79,1% IR SP% purity.

P R I m m e R 2. 2,4,6-Tris(N-isopropyl-n-phenylendiamine)1,3,5 - triazine.

A 2-liter chetyrehosnuju round-bottom flask equipped with thermometer, drive stirrer, condenser and addition funnel, is placed 650 ml of isopropanol. Isopropanol cooled to a temperature of 5aboutWith, then add to 36.8 g (0.2 mol) of cyanuric chloride. To this stirred suspension was added a solution of 90 g (0.6 mol) of 4-amino-N-isopropylaniline in 100 ml isopropanol (dropwise) over 1 h, maintaining the temperature between -5 and 0aboutC. for 0.5 h, the reaction mixture is heated to a temperature of 30aboutC, then heated under reflux for 2 hours the Reaction is accompanied by liquid chromatography under high pressure by observing the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final product is a triple substitution. The reaction mixture is cooled and defend during the night. Chloride-hydrogen amine salt is neutralized by adding 96 g (0.6 mol) of 25% aqueous sodium hydroxide solution for 0.5 h, after which the mixture is heated under reflux for 0.5 hours Specified in the title compound precipitated upon cooling, and select the filtration, washed isoprop is tstuat structure. Liquid chromatography high resolution shows that the product has a purity of 95.3% of

P R I m e R 3. 2,4,6-Tris(N-cyclohexyl-n-phenylendiamine)-1,3,5 - triazine.

Repeat the procedure of example 2, except for using a 0.1 molar scale with 4-amino-N-cyclohexylaniline used to obtain specified in the title compound, melting point 215-217aboutC. the Output is 89,9% of the IR spectrum corresponds to the structure. Liquid chromatography high resolution shows that the product has a purity of 90.1% of

P R I m e R 4. 2,4,6-Tris(N-sec-butyl-n-phenylendiamine)1,3,5 - triazine.

Repeat the procedure of example 2, except that 4-amino-N-Deut-butylaniline used to produce specified in the procurement compound, melting point 167-169aboutC. the Output is 90.8% of the IR spectrum corresponds to the structure. Liquid chromatography high resolution shows that the product has a purity of 94.6%

P R I m e R 5. 2,4,6-Tris(N-1,3-dimethylbutyl-n-phenylendiamine)- 1,3,5-triazine.

The 3-liter chetyrehosnuju round-bottom flask equipped with thermometer, drive stirrer, a condenser and a bulk funnel, was placed a solution 316,8 g (of 1.65 mol) of 4-amino-N-(1,3 - dimethylbutyl)aniline is orida for 0.5 h, maintaining the temperature between 30-40aboutC. the Reaction mixture is heated under reflux for 1-1/2 hours the Reaction is accompanied by liquid chromatography under high pressure by observing the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final product is a triple substitution. After cooling the reaction mixture to a temperature of 60aboutWith added dropwise 120 g (1.5 mol) of a 50% aqueous solution of sodium hydroxide for 1 h sodium Chloride is removed by filtration at a temperature of 40aboutC. the Filtrate is loaded back into the reaction flask, which added dropwise to 250 ml of water. Specified in the title compound precipitates and is removed by filtration, melting point 124-127aboutC. the Output is 82.6% of the IR spectrum corresponds to the structure. Liquid chromatography high resolution shows that the product has a purity of 95.3% of

P R I m e R 6. 2,4,6-Tris(N-1-methylhept-n-phenylendiamine)-1,3,5-triazine.

Repeat the procedure of example 5, except 0,225 molar scale with 4-amino-N-(1-methylheptan)aniline leading to the specified in the procurement of the connection. After recrystallization from 28% mixture of toluene-hexane temperature PL is anyone's permission shows the product has a purity of 90.7 percent

P R I m e R 7. 2,4,6-Tris(N-2,4-di-tert-butylcyclohexyl-n - phenylendiamine)-1,3,5-triazine.

Repeat the procedure of example 5, except for using a 0.25 molar scale with 4-amino-N-(2,4-di-tert-butylcyclohexyl) aniline leading to the specified in the title compound, melting point 147-152aboutC. the Output is 85.7% of the IR spectrum corresponds to the structure.

P R I m e R 8. 2,4,6-Tris(N-2-second-butylcyclohexyl-n - phenylendiamine)-1,3,5-triazine.

Repeat the procedure of example 5, except for using a 0.25 molar scale with 4-amino-N-(2-Deut-butylcyclohexyl)-aniline, conductive to getting listed in the workpiece connection. The product is not crystallized and was isolated as a residue from distillation, melting point 122-130aboutC. the Output is 95,8% of the IR spectrum corresponds to the structure and liquid chromatography high resolution shows that the product has a purity of 86.6 per cent

P R I m e R 8A. 2,4,6-Tris(N-1,4-dimethylpentyl-2-methyl-n-phenylendiamine)1,3,5 - triazine.

In chetyrehosnuju a round bottom flask of 1 l equipped with a thermometer, mechanical stirrer and condenser, was placed a solution weight 176 g (0.80 mol) of the compound 4-amino-N-(1,4 - dimethylpent is after 15 min at 25aboutTo add to 36.8 g (0.30 mol) of cyanuric chloride. The reaction mixture was incubated for 15 min at 25aboutWith, then warm condensing in the reflux for 2 hours the reaction is monitored, conduct high-speed liquid chromatography by observing the disappearance of the original amine, and the conversion of the intermediate mono - and biznesowych compounds in the final tizamidine product. The reaction mixture is cooled to 25aboutWith and trihydrochloride these compounds are removed by filtration. Trihydrochloride load back into the reaction flask and add 500 ml of isopropanol. The temperature of the support 60aboutWith and add 96,0 g (of 0.60 mol) of 25% aqueous sodium hydroxide solution. When cooled isopropanolamide layer named connection was wimbleball. It is extracted with three times 20% aqueous isopropyl and vacuum distillation of the lead up to dry. The substance melted at 70-73aboutC. the Yield amounts to 57.8 per cent Infrared spectrum is in agreement with the structure. Relative area on the chromatogram obtained by HPLC, find that the purity of the product is 94.7% of

P R I m e R 8B. 2,4,6-Tris(N-1,4-dimethylpentyl-2-ethyl-n - phenylendiamine) is inane using 4-amino-N-(14-dimethylpentyl)-2-ethylaniline; melting point is 79-83aboutC. Output 97,2% of the Infrared spectrum is in agreement with the structure. Relative area on the chromatogram obtained by HPLC, find that the purity of the product is 93,6%

P R I m e R 8C. The compound 2,4,6-Tris-(N-isopropyl-2-ethyl-n - phenylendiamine)-1,3,5-triazine.

In chetyrehosnuju a round bottom flask of 1 l equipped with a thermometer, mechanical stirrer and condenser, was placed a solution of 122,4% (0.66 mol) of 4-amino-N-(isopropyl)-2 - ethylaniline in 300 ml of isopropanol. The temperature of the solution to support equal to 10aboutFrom and after 1/2 h at 15aboutTo add to 36.8 g (0.20 mol) of cyanuric chloride. The reaction mixture is warm with condensation under reflux for 2 hours For reaction watching conducting liquid chromatography high pressure by monitoring the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final tiszaladany product. After cooling to 60aboutWith dropwise during 1/2 h add 120 g (of 0.60 mol) of a 20% aqueous sodium hydroxide solution. The aqueous layer was removed and discarded. A named connection, fell upon cooling, ethanole. The substance melts at 173-175aboutC. the Output is 94,4% of the Infrared spectrum is in agreement with the structure. Relative area on the chromatogram obtained by the method of liquid chromatography high pressure, found that the purity of the product is 96,3%

P R I m e R 8E. 2,4,6-Tris(N-isopropyl-2-methyl-n - phenylendiamine)-1,3,5-triazine.

The procedure of example 8C is repeated, except that to obtain these compounds are used 4-amino-N-(isopropyl)-2-methylaniline, melting point is 185-186aboutC. the Yield 82.3% Of the Infrared spectrum is in agreement with the structure. Relative area on the chromatogram obtained by the method of liquid chromatography high pressure, found that the purity of the product is 92.7% of

P R I m e R 8E. 2,4,6-Tris(N, N-bis(isopropyl)-n-phenylendiamine)- 1,3,5-triazine.

In chetyrehosnuju a round bottom flask of 1 l equipped with a thermometer, mechanical stirrer and condenser, was placed a solution consisting of 99 g (0,515 mol) of N, N-bis(isopropyl)-n - phenylenediamine dissolved in 100 ml of toluene. The temperature of the solution support the 25aboutAnd add a 30.7 g (to 0.17 mol) of cyanuric chloride, doing it for the time during which the temperature reinicia in the reflux for 3 hours The reaction is monitored, conducting high-performance liquid chromatography by observing the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final tizamidine product. The reaction mixture is cooled to 80aboutWith, and add 140 g (0.50 mol) of 14.3%-aqueous sodium hydroxide solution. After warming up with condensation under reflux for 1 h, the water layer is removed. Toluene layer is evaporated. The residue is transferred into hexane and a small amount of insoluble matter is removed by filtration. The filtrate is evaporated and the named compound is isolated in the form of residue, melting point is 156-170aboutC. the Yield 74.3% Infrared spectrum is in agreement with the structure, and the relative area on the chromatogram obtained by HPLC, find that the purity of the product is 77.8%

P R I m e R 8F. 2,4,6-Tris(N,N-bis-1,4-(dimethylpentyl)-n - phenylendiamine)-1,3,5-triazine.

The procedure of example 8E repeated, except that to obtain these compounds are used N,N-bis(1,4 - dimethylpentyl)-n-phenylenediamine. The product is isolated in the form of an oily residue. The output is 97.9% of InfraCrete high-performance liquid chromatography, find that the purity of the product is 67,1%

P R I m e R 8C. 2,4,6-Tris(N-isopropylphenyl-n-phenylendiamine)- 1,3,5-triazine.

In chetyrehosnuju a round bottom flask of 1 l equipped with a thermometer, mechanical stirrer and condenser, was placed a solution, composed of 58.8 g (0.25 mol) of n-amino-2-isopropyl - diphenylamine dissolved in 177 g of isopropanol. The temperature of the solution supports equal 15aboutTo add to 14.7 g (0.08 mol) of cyanuric chloride in a period of 1/2 h with increasing the reaction temperature to 25aboutS, then the solution is heated to 75aboutAnd it was incubated for 5 hours For reaction monitor the conduct of high-performance liquid chromatography by observing the disappearance of the original amine, and the conversion of the intermediate mono - and benzamidine compounds in the final tiszaladany product. The reaction mixture is cooled to 20aboutWith and trihydrochloride neutralize with diluted sodium hydroxide solution. After cooling to 25aboutWith the water layer is removed. Isopropanolamine layer evaporated. The residue is removed by filtration. The filtrate is evaporated and the named compound is isolated in the form of residue. The compound melts at 85aboutC. the Yield Of 57.6% relative area on the chromatogram obtained Meton. The compound 2,4,6-Tris(N-2-isopropylphenyl-3 - isopropyl-n-phenylendiamine)-1,3,5-triazine.

In a three-neck round bottom flask 2 l, equipped with a mechanical stirrer, thermometer and an additional funnel, place of 46.1 g (0.25 mol) of cyanuric chloride and 400 ml of acetone. The resulting solution is cooled to -8aboutC (ice in acetone). A solution containing of 53.6 g (0.26 mol) of 4-amino-(N-1,4-dimethylpentyl) aniline and 200 ml of acetone is added dropwise via an additional funnel to a cold solution of cyanuric chloride for 45 minutes during the whole time of adding the temperature of the reaction solution to support equal -5aboutWith and give rise to the 26aboutAfter completion of the addition. The amine hydrochloride is then neutralized by adding an aqueous solution of sodium carbonate (13.3 g, 0.13 mol in 100 ml of water).

The second flask of 2 l, equipped as before, put to 66.3 g (0.51 mol) of a 60% aqueous sodium sulfide solution and 200 ml of water. Substituted triazine solution is transferred into an additional funnel and then added dropwise to byistroprodavaemoy the sodium sulfide solution. The temperature of the solution remained equal 26aboutWith throughout the 20-minute period is added. The resulting solution with a pH of 13.4 neutrons is given under reduced pressure, getting dark residue. This residue is extracted with 300 and 100 ml of methylene chloride, the extracts are combined and dried over sodium sulfate. The solution is filtered and carry out the crystallization of the product, adding hexane to the filtrate. The total yield for the three crystallization mass was 92.0% (melting point 201-205aboutC). Relative area on the chromatogram obtained by HPLC, find that the purity of the product is 93.2% if we assume the existence of a mixture tinawag and thiol tautomers. Infrared spectra of the product were in agreement with the proposed structures.

P R I m e R s 9-24 on the suitability of antiozonant.

N-alkylenediamines connection of the present invention function as a wonderful antiozonants in rubber polymers no inclination to migratory staining is evident at this time. The following examples demonstrate the suitability of compounds in a wide range of test conditions for resistance to ozone and light. All tests use triazine in the compounds of vulcanizates, typical in the industry. The following recipe for testing is a typical rubber compound.

< / BR) 50,0

Carbon black

(N-326) 50,0

Zinc oxide 3,0

Microcrystalline

wax 1,5

Stearic acid 1,0

Aromatic

oil oil 5,0

Benzothiazolone-

named 1,0

Sulfur 2,0

Antiozonant

The antiozonants:

Comparative And N-phenyl - N'- (1,3-dimethylbutyl)-n - phenylenediamine (commercially available as Flexcon TM7F from Uniroyal chemical company).

Comparative In mixed diaryl-n-phenylenediamine (commercially available as Novasan TMAS from Uniroyal chemical company).

The above formula for the test is used for all test samples, unless stated otherwise. The recipe is an approximate expression of the typical compounds of the sidewall of the tire. The identity and level of antiozonant represent variables that are measured in the following examples.

The composition of the test used to obtain unvulcanized test sheets by pre-mixing of natural rubber and polybutadiene. After mixing all of the other components except for sulfur and benzothiazolesulfenamide add with the formation of non-productive compounds, and in the next stage of mixing between the hot plates in the course of time, sufficient to achieve a complete cure. For the purposes of tests used mode of curing: 15 min at a temperature of 160aboutC. the Exact configuration of the test samples for testing on aging in the ozone varies depending on the description of the used test method ASTM (American standard test method). The link is to test methods of the American society for testing and materials.

The results of tests on aging in ozone are presented in table.1.

Aging test in ozone carried out using standard test method ASTM d 1149-81 called "Wear rubber surface cracking in a chamber (flat pattern)". This method involves evaluating the resistance of vulcanized rubber to cracking when exposed to an atmosphere containing ozone. Rubber specimens with surface relative tensile strain, and the ozone content in the test chamber is maintained at a level of 50 ppm at a temperature of 100aboutF (38aboutC). The General designation for this test is a test method in a curved loop, because the test sample is placed under strain so that it forms configkey loop is a very simple test configuration, at which destruction can be expected for several hours at high temperature and the atmosphere of ozone, which placed the samples.

Samples of age annaprasana at room temperature at the sixth month and the twelfth month of study. Consequently, presents three groups of test data: to aging, aging 6 months and aging 12 months. Example 9 (control) refers to a composition that does not contain protection antiozonant. This unprotected sample decays through 6-17 h of exposure, depending on the degree of aging, which received a sample before exposure to ozone. Example 10 (comparative A) represents the result of adding a traditional paraphenylenediamine (Flaxton 71) with 4 parts of the PHR, it cracks between 600 and 24 h exposure. In example 11 rubber composition, protected substituted triazine of the present invention shown in example 1, is maintained in the range of 1040 and 1128 h for different, not subjected to aging and subjected to aging of the samples. It is clear that the protection of the ozone provided by the compounds of the present invention, is best compared with traditional antiozonants, which are well known in the field of rubber.

aboutF (38aboutC) at 20% elongation or stretch. This additional degree of deformation is an additional characteristic of a sample, which is different from the tests conducted, as shown in the table.1. All other details regarding the test method are similar to those for the results table.1.

Unprotected control samples of example 12 are stored in the range from 8 up to 552 hours depending on how long the sample was subjected to aging. The composition of comparative And not subjected to the aging condition at 600 h shows very minor cracking. Example 13 sample aging 6 and 12 months. shows cracking in the range from 56 to 24 hours of Compounds of the present invention shown in example 14, again showing a significant improvement in quality compared with the known antiozonants regarding protection from exposure to ozone, which exceeds one compared with traditionally used antiozonants class paraphenylenediamine.

Rubber products can be protected against the effects of ozone when they are so affected in atmospheric conditions. One of the most challenging applications is the use of the bus when the vehicle remains on the air and in sancturay atmosphere for an unlimited period of time. The true conditions under which the bus operates, it is difficult to play as the aging test in ozone in static conditions, which are described in the table.1 and 2, and the testing methods in dynamic conditions, as, for example, test the fatigue strength under bending Demattia.

When you try to play a typical surface condition of the tires using the following test method. The samples are installed in the test fixture on the air, facing South, exposing the full impact of the environmental conditions (e.g. Naugatuck, Connecticut). Samples continuously bend for 8 h at an angle of about 78about. After this period, the bending of the sample weaken and leave this weakened static condition at 16 o'clock the Method is repeated day after day to deterioration of the sample, indicated by the appeared the W (relaxation in good agreement with actual conditions, when the bus is operating, i.e., the bus is moving for many hours and during this time she makes a loop with the same movements that accompany her work during bending during the test. Then the bus is a long time in static conditions that are played during the 16-hour static cycle. The results of the test are expressed in thousands of periods. During bending of the specimen bent at an angle 78aboutat 8,5 thousand periods per hour.

This test fatigue strength under bending under dynamic conditions involves the use of rectangular samples (12 x 76 mm) with 3-mm radius of the annular groove through the center of the sample.

The results show that the example 15, containing antiozonant, lasts less than 3000 thousand periods in this test. Examples 16 and 17, which are protected by paraphenylenediamine, known in the art, and a triazine of the present invention, respectively, showing a significant improvement in the ability to withstand ageing under natural conditions outdoors. The triazine is a compound of the present invention protects the sample of example 17 with almost the same result as imicheskih applications.

P R I m e R s 18-21. Mixing antiozonants.

The triazine-compounds of the present invention in comparison with N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine (comparative A-Flaxton 7F), usually manifests much better protection in static conditions and slightly worse defense in a tough dynamic conditions, as estimated by various methods of laboratory testing. However, quite unexpectedly discovered that the properties of a dynamic protection can be significantly improved by mixing the triazine-compounds with the traditional p-phenylendiamine. This is carried out without damage to the ozone protection in static conditions. Examples 18-21 below demonstrate this synergistic effect.

In examples 18 and 19 antiozonant of example 1 is mixed with two traditional antiozonants in order to assess cumulative effects both in static and in dynamic conditions testing on aging in the ozone. The results are compared with the results of unmixed control samples 20 and 21. Used rubber composition is the same as previously used arrangement for testing all tests, except that the microcrystalline wax cancelled to ensure that the anti-Christ.], in ozone in dynamic conditions outdoors carry out so, as described for test 8 h bending/16 h in static conditions for examples 12-24 table.3, except that bending at 8,5 thousand periods per hour perform continuously. No period of relaxation. The test continues, and therefore none of the sample has not reached the end point of cracking (fracture).

Aging test in the ozone in the chamber, held in static conditions, carried out as described for examples 9-11.

The results are shown in table.4 to test on aging in the ozone in the chamber under dynamic conditions, show that the comparative And (Flexzone 7F) crack through 216 h (example 20), whereas the compound of example 1 used in examples 18, 19, 21, alone or in combination with comparative And or allows to obtain excellent protection, as evidenced by the fact that no cracks are not visible through 1016 h tests.

Testing under dynamic conditions outside (examples 18-20) shows that the mixture of example 1 with comparative and provide excellent protection in dynamic conditions. Mixtures of examples 18 and 19 unexpectedly increase the dynamic ozone resistance as compared with example 21, which uses the compound of example 1.

P R and m is for testing the above, however, without wax. The composition for testing compendious, mix and vulcanized in a flat test sheet for further analysis of the characteristics of discoloration and staining. Specific test carried out in accordance with the method of ASTM-D-925-83. Method evaluates the degree of inclination to the coloring material by determining the amount of discoloration that occurs from the raw material through the coating white lacquer, which is applied on the test sample. Use the track for testing, are given for all samples of the invention. After the test sample is mixed and vulcanized, it is covered with veneer white lacquer in accordance with the method of ASTM-D-925. Then it is exposed to the light source lamp "mountain sun", in a suitable test chamber for a set period of time. Use the apparatus for testing a Hunter colorimeter LabTMin order to objectively determine the color change of white lacquer within 4 h of exposure lamp "mountain sun". ASTM d 2244-79, entitled "Color differences of opaque materials", leads a number of characteristics with standard letters a, b, and l As the characteristics of the coloring normally the th scale from 0 to 100, where 0 means completely black and 100 means absolutely white. Therefore, the higher the L value, the more white is the sample. The composition of test example 22 is received as a control, which does not contain antiozonants. Example 24 contains antiozonant of the present invention described in example 1, i.e., 2,4,6-Tris(N-1,4-dimethylpentyl-n - phenylendiamine)-1,3,5-triazine.

P R I m e R 23. Use the comparative substance And representing N-phenyl-N'-(1,3-dimethylbutyl)-n - phenylenediamine (Flexzone 7F received from Uniroyal chemical company, Inc.). The test results for the three samples are presented in table.5, showing the value of "L" Hunter after 4 h of exposure.

The results above clearly show that the traditional substance paraphenylenediamine example 23 shows significant staining (32,6) after 4 h of exposure. In contrast, the formula for the test containing the compound of the invention of example 1 has a color saturation equal 81,5, which is very close to the value 987,9 set forth for the control sample of example 22. Thus, the connection of the present invention has a minimum diffusion staining, which is extremely unusual result dolzani as antiozonants without accompanying action problems of diffusion of the coloring and all such which shows, for example, the results of the comparative composition A. This class of materials can be described as naikrasiveyshaya the antiozonants.

Compounds of the present invention can be used with advantage in mixtures of antioxidants and antiozonants, known in the art, to enhance specific properties. Despite the fact that compounds substituted triazine of the present invention is described here only as antiozonants, it is clear that substances can also function as antioxidants for rubber, thereby providing protection against oxidative degradation, as well as protection from exposure to ozone. It should be noted that when used as an antioxidant levels are generally much lower than 100 wt.h. hydrocarbon rubber than when using as antiozonant.

Unsaturated polymers can be protected against oxidation and ozone destruction by mixing the triazine-compounds of the invention with conventional antioxidants. Many classes of phenolic, amine, etc. function as antioxidants. Index of industrial antioxidants and antiozonants (3rd edition, published Goodyear Taye is haunted properties. Typical classes of such antioxidant materials are spatial employed phenols, alkyl-substituted diphenylamine, aryl-substituted diphenylamine, aralkyl-substituted diphenylamines, naphthylamines, the reaction products of diarylamino and ketone, monophenol, bisphenola, polyphenols, hydroquinone derivatives and the polymerized quinoline. System antioxi - data may contain one or more of such substances. Optimal levels added (PHR) for antioxidants can easily be determined by simple experiment, and they can vary widely depending on the end use.

2,4,6-Tris(N-alkyl-n-phenylendiamine)-1,3,5-triazine can be most favorably used in the tire as a component of any or all thermoeconomics kouchakzadeh parts of the tire. They include the tread, the side frame parts truck tires, car or off-road vehicles, and the bus also contains a lot of different reinforcing layers. These components usually contain more than one termotehnica polymer in the mixture, which can be protected from destruction under the action of ozone and oxidative destruction.

Methods introduction etisal rubber compound, in which they are introduced, compared with the traditional paraphenylenediamine.

P R I m e R s 25-33. The composition of the sidewall of the tire.

The following examples illustrate the preferred suitability of triazines in the joints of the outer sidewall of a pneumatic tire containing a mixture of highly unsaturated rubber such as EPDM (rubber-based copolymer of ethylene, propylene and diene monomer), which has a lower unsaturation.

Examples 25, 26 and 27 are comparative and not included in the scope of the invention. Example 25 does not contain any significant component triazine (1) of the present invention or EPDM. Examples 26 and 27 do not contain the triazine. These test cases show cracking in the 72-hour aging test in ozone (ASTM d-3395B-82), which is an extremely hard test method for aging in ozone in dynamic conditions, and this test method involves the vulcanization of sample compounds on a fabric belt. The belt rests on a number of rollers in order to cause surface deformation in the ozone chamber at 50 ppm of ozone at a temperature of 100aboutF (38aboutC).

Examples 25 and 26 illustrate cracking during exposure to ozone belt, eastview EPDM.

Example 28 illustrates the improvement in the art in the preparation of the recipe rubber compound. This compound having triazine and EPDM, is saved when testing on the ozone belt in a dynamic state, in General, without the formation of any cracks.

P R I m e R s 29-33 illustrate the humidity levels add significant components, EPDM or triazine. Not adhering to the scientific justification, believe that optional protection can be achieved with the use of adequately high levels of either EPDM or triazine compounds. I believe that it is not necessary to have high levels of both compounds to obtain the exceptional properties of resistance to ozone and fatigue strength. However, it should be noted that excellent ozone resistance can be achieved at lower levels of any significant component in comparison with other methods of protection from exposure to ozone.

The effect of progressively higher levels of triazine-compounds (example 1) shown in the results of exposure to ozone (test with a curved loop, examples 29 and 30 (two parts triazine-compounds), which show the development of cracks during ISPA.

The positive effect of progressively higher levels of EPDM shown by comparison of examples 29, 30 and 33, which has a more progressive EPDM. The level of protection from exposure to ozone increases with increasing levels of EPDM. Significant triazine connection is present at a constant level in all three examples. Thus, we can conclude that the desired properties can be obtained by changing the level of elastomer with less unsaturation (i.e., DM) and triazine-compounds.

The results are shown in table.6.

P R I m e R s 34-41. Examples 34, 35, 36 and 40 are comparative examples and are not included in the scope of the present invention. Examples 34, 35 and 40 do not contain triazine antiozonant, and examples 34 and 36 do not contain EPDM (polymer with less unsaturation). The test results on the fatigue strength under bending Monsanto are decisive results have a good correlation to the properties of the service life of the tire carcass. Example 37 shows the value of fatigue during repeated bending, equal to 106 against the much lower values of comparative examples 34, 35, 36, all of which do not contain at least one key component of the present invention.

The following is the comparison of test results on the fatigue strength under bending comparative examples 35 (13.3), 39 and 41 (75 and 162,6 respectively). The choice of curing group is another important factor. Vulcanization using a combination of peroxide/sulfur improves the results of fatigue during repeated deformation.

The importance of triazine antiozonant shown when comparing the values of fatigue during repeated bending of comparative example 35 (13,3) against example 37 (106). Example 41 shows the optimal results of the tests on the fatigue strength under repeated deformation with the use of high molecular weight EPDM, triazine antiozonant and vulcanizing groups peroxide/sulfur.

The results are shown in table.7.

Tire new connection is only useful when it has good adhesion with adjacent layers of rubber tires. The results of the test on adhesion under static conditions is always good for all of the mixtures of the present invention, where a value of 10, generally regarded as fully adequate to the result of this test for adhesion. The adhesion characteristics of each of the compounds of the examples evaluated for their adhesion with the standard composition for testing protector shown below.

Standard tread test composition for the>Polybutadiene (PBD 1203) 25,0

Natural rubber

(SMR 5CV) 20,0

Carbon black (N-234) 55,0

Zinc oxide 3,0

Microcrystalline wax 0,5

N-phenyl-N'-(1,3-dime-

Tilbury)-n - phenylenediamine 1,0

Stearic acid 1,0

Aromatic oil

oil 20,0

2-(Morpholinothio)benzo-

the thiazole 0,5

Thiocarbamoylation 0,5

Sulfur 2,0

The test connection is duplicated in comparison with a standard tread composition with a layer of latex containing resorcinolformaldehyde resin, which is treated cloth on both sides, which forms the test pad. Pillow vulcanized under pressure for 15 minutes at a temperature of 177aboutC. Vulcanized pillow stretch in a tensile testing machine Scott (or the bursting machine brand "Instron") with the formation of the force required to make the test compound to separate from the standard composition for testing protector. Re-sampling test and they are listed in the table.7 kN/m

The suitability of rubber products in the dynamics.

2,4,6-Tris(N-alkyl-n-phenylendiamine)- 1,3,5-triazine the most beneficial can be used as a component in most UDA is edstone exposed to sancturay environment. In industry there is a strong need for naikrasiveyshaya antiozonants material, which can effectively protect the rubber product both in static and dynamic States of the ozone environment.

The following sections describe specific rubber products that are most beneficial are protected by materials of the present invention. In a large range of industrial rubber products that will be discussed are many different types of rubbers, previously disclosed as suitable in the present invention. It should be noted that the triazine-compounds of the invention can be used to improve the wear resistance of any polymer system, used in any traditional building rubber products. Major progress can be achieved through the use of triazine antiozonants to improve protection oil-resistant polymers in the first place, copolymers of butadiene and Acrylonitrile (nitrile rubber or nitrile rubber). These types of polymers are extremely oil-resistant and with high otnositelnosti of the invention can be used to replace the neoprene (polychloroprene) in many priebe also be noted, what variety of highly unsaturated polymers used in these industrial rubber products, can be further improved in respect of their otnositelnosti and fatigue strength under bending by mixing rubber with less unsaturation, such as EPDM, with traditional highly unsaturated rubbers used in the present time.

The straps.

Among the different types of belts that are produced in the rubber industry, the drive belts are the types that are most improved by using materials and compounds described in this invention. The drive belt is usually described as V-belts, and belt force transmission and timing belt. All of these types of belts can be greatly improved with the use of the compounds of the invention. Rubber mixtures, which are described above and which contain the compounds of structure (I), can be most favorably used on external surfaces of the structure of the belt. In wedge, forced and toothed drive belts these compounds can replace the neoprene in the lower regions of engagement of the belt pulleys, the alternative described is to better understand the suitability of belts, given a General description of the structure of the belt.

The drive belt has an elastomeric body, which makes up a large portion of the belt. There is geometrically defined neutral axis of the majority of the belt that passes over a set of pulleys. Neutral axis simply indicates that the area above the neutral axis is in tension as it passes through the pulley, and the area below the neutral axis is described in the compression state. Therefore, a typical drive belt has a section of the tension and the compression section, which divides the plane of the neutral axis. The main longitudinal reinforcement are completely conventional in the art and represent layers of cords or fabric or steel strands that are approximately on the plane of the neutral axis. Riparian belt consists of one or more rubber compounds having the same or different rubbers on a polymer basis. As indicated, the outer tissue layers of the belt can be most beneficial enhanced with the use of the rubber mixtures of the present invention. In addition, the compression section, which is experiencing significant repeated bending during the life of the belt can extract Vova mixture type unsaturated diene. These areas are traditionally used rubber-based neoprene (polychloroprene), which can now be overridden with the use of cheap, high-, oil - and rastvoriteleyj polymers such as nitrile rubber (NBR) and NBR in mixtures with other polymers, such as the best choice rubber (SBR), natural rubber, EPDM and so on Because the rubber compound used in the elastomeric body of the belt, should be able to be sealed inside multiple layers of different types of reinforcing materials, adhesion of rubber compounds to adjacent layers has absolutely crucial to the success of the operations of manufacturing belts. Discovered that excellent levels of adhesion can be achieved by using materials of the present invention.

Conveyor belts.

Conveyor belts are widely used in industry and are an endless variety of payloads. Conveyor belt is usually made of an elastomeric body formed by one or more rubber mixtures containing embedded in the elastomeric body plenty of reinforcements in position between the upper and lower housings. It cover materials may be most beneficial to use a rubber triazine substances of the present invention is a hallmark of neokrashivanija.

1. Derivatives of S-triazine of General formula

< / BR>
where R3WITH7-alkyl branched chain or3- C6-cycloalkyl, unsubstituted or substituted by one or two1- C4-altergroup.

2. Derivatives under item 1, wherein R3- C7-alkyl branched chain.

3. Derivatives under item 1, wherein R is chosen from 1,4-dimethylpentyl, isopropyl, cyclohexyl, terbutyl, 1,3-dimethylbutyl, 1-methylheptane, 2,4-di-tert-butylcyclohexyl and 2-verbalintelligence.

4. The method of obtaining derivatives of S-triazine of General formula

< / BR>
where R3WITH7-alkyl branched chain or3- C6-cycloalkyl, unsubstituted or substituted by one or two1- C4-accelgroup,

characterized in that the corresponding N-alkyl-p-phenylenediamine is subjected to interaction with cyanuric chloride in an inert organic solvent to obtain the reaction mixture containing trichlorohydrin the target product, which is neutralized with a solution of alkali metal hydroxide, followed by separation of the target product.

5. The method according to p. 4, characterized in that the target product widely

 

Same patents:

The invention relates to construction materials and can be used for the manufacture of roofing bezrulonnaya and waterproofing mastics and coating masses of roofing material, roofing tiles

Polymer composition // 2058347

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The invention relates to the timber and woodworking industry and can be used in the furniture industry, construction, road and rail carriage, packaging, etc

The invention relates to the field of production of rubber products, particularly to x-ray shielding and radiation resistant rubbers used in medicine

The invention relates to the production of plate materials of dispersed wood materials, such as wood fiber or from machining chips and sawdust, which is a waste of mechanical processing of wood, and can be used to obtain material, operated in high humidity conditions (container, the outer lining material)

The invention relates to methods of producing modified polymer binder materials for the preparation of asphalt concrete mixtures used in road paving

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of melamine adducts with acids of the order: cyanuric, phosphoric, boric acid in the presence of liquid medium that are modifying agents of polymers. Method involves homogenization of melamine and acid powders in a mixer at temperature from 20°C to 80°C and then prepared mixture is subjected for effect by deformation shift at temperature from 20°C to 150°C at the shift rate value 5-400 s-1 and the total deformation shift value from 1.5 x 103 to 2.0 x 105%. The ratio of melamine to acid is from 2:1 to 1:2 preferably. Effect by the deformation shift is carried out in mechanical reactor of auger type. Invention provides simplifying process in synthesis of end substances, significant decreasing consumptions and avoiding pollution of environment.

EFFECT: improved method of synthesis.

2 cl, 10 ex

FIELD: synthesis of phosphorus-containing derivatives of organic compounds.

SUBSTANCE: invention relates to method of preparing polyphosphates of organic compounds, to mixture of polyphosphates of organic nitrogenous bases, and to use of polyphosphates and mixture of polyphosphates as fire retardants for plastics, preferably thermoplastics and, more particularly, polyamides and polyesters. Polyphosphates of organic compounds are prepared via exchangeable decomposition of mixture of phosphorus pentoxide and at least one organic nitrogenous base with a compound releasing water when decomposed under reaction conditions, the latter compound being used in such molar proportion that water would release in amount corresponding to essentially two moles of water per one mole of phosphorus pentoxide. Water-releasing compound can be compound forming, along with water, only volatile decomposition products and this compound can be selected from group including anhydrous oxalic acid, oxalic acid dehydrate, and formic acid. Exchangeable decomposition reaction is conducted at 100 to 250°C. Mixture of polyphosphates of organic nitrogenous bases is characterized by following properties: when heated to 320°C it looses less than 2% of its mass; pH value of its 10% water suspension exceeds 5 at 25°C, preferably from 5.2 to 7.7 and, more preferably, from 5.8 to 7; its solubility in water is less than 0.1 g and preferably less than 0.01 g per 100 mL water.

EFFECT: expanded synthetic possibilities.

6 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is an improved method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) by reacting 2,5,8-trichloro-sim-heptazine with an azidation agent in form of sodium azide in the medium of aqueous acetone at room temperature, followed by extraction of the end product via deposition from water. The invention can be used in organic synthesis.

EFFECT: high-tech and cheap method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) from commercially available 2,5,8-trichloro-sim-heptazine and a cheap azidation agent in simpler conditions for synthesis and extraction of the end product with high output and purity.

FIELD: chemistry.

SUBSTANCE: described is an improved method of producing melamine cyanurate which is used in different compositions as a flame retardant. The method involves reaction of cyanuric acid and melamine in molar ratio of 1:1 in the presence of 2-30% water of the weight of dry reactants at temperature ranging from 10 to 100°C in countercurrent air streams at pressure of 2-10 kgf/cm2. The method can be realised continuously.

EFFECT: end product is obtained with high output with low power consumption.

1 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a compound of formula (1) where R1 denotes hydrogen or SO3, R2 denotes hydrogen or SO3, R3 denotes hydrogen or CH2CO2, R4 denotes CH2CO2, CH(CO2)CH2CO2 or CH(CO2)CH2CH2CO2, and where M denotes a stoichiometric cation equivalent required to balance the anionic charge in formula (1) and is a combination of Mg2+ with at least 1 additional cation. The additional cations are selected from a group consisting of H+, a cation of an alkali metal, a cation of an alkali-earth metal other than Mg2+, ammonium, mono-C1-C4 alkyl-di-C2-C3-hydroxyalkylammonium, di-C1-C4-alkyl-mono-C2-C3-hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, and mixtures thereof. The invention also relates to versions of the method of producing said compound and use of said compound in binding compositions for bleaching paper.

EFFECT: compound is a more efficient paper bleaching agent.

8 cl, 4 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention includes (a) at least one optical bleaching agent of formula (1) , wherein R1 denotes hydrogen or SO3M, R2 denotes hydrogen or SO3M, R3 denotes hydrogen or CH2CO2M, R4 denotes CH2CO2M, CH(CO2M)CH2CO2M or CH(CO2M)CH2CH2CO2M, where M denotes hydrogen, a cation of an alkali metal, ammonia, mono-methyl-di-C2-C3-hydroxyalkylammonium, dimethyl-mono-C2-C3- hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, or a mixture of said compounds, (b) a magnesium salt or (c) binder, which is selected from a group consisting of natural starch, enzyme-modified starch, and chemically modified starch, wherein there are 0.1-15 parts of component (b) for one part of component (a). The invention also relates to a method of bleaching paper using said composition.

EFFECT: composition is a more efficient means of achieving high paper whiteness.

9 cl, 4 ex, 3 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to novel compounds of general formula (1), which possess affinity for µ-opioid receptor and ORL1-receptor, to medications, containing said compounds, and to application of said compounds for obtaining medications, suitable for treating pain, fear, stress and other diseases or conditions. In general formula (1) Y1, Y1', Y2, Y2', Y3, Y3', Y4 and Y4' stand for -H; R1 and R2 independently on each other stand for -H or -CH3; on condition that R1 and R2 both simultaneously do not stand for -H; Q stands for: -C6-16-aryl, non-substituted or mono- or poly-substituted with -F, -Cl, -Br or -I; or heteroaryl; R3 stands for: -C1-8-alkyl, non-substituted or mono- or poly-substituted -OR0, where R0 stands for non-substituted -C1-3-alkyl; non-substituted -C3-6-cycloalkyl-C1-4-alkyl; non-substituted -C1-4-alkyl-C3-6-cycloalkyl; -C6-16-aryl, non-substituted or mono- or poly-substituted with -F, -Cl, -Br, -I, -CN, -R0 or -OR0, where R0 stands for non-substituted -C1-8-alkyl; or heteroaryl; n stands for 0; X stands for -NRA-; RA stands for -H or -R0; where R0 stands for non-substituted -C1-4-alkyl; and RB stands for -C(=O)R0; where R0 stands for non-substituted -C2-8-alkenyl-C6-16-aryl or non-substituted -C1-8-alkyl-(C6-16-aryl)1-2.

EFFECT: obtaining compounds for obtaining medications, suitable for treatment of pain, fear, stress and other diseases or conditions.

10 cl, 14 tbl, 164 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (1), which possess an affinity to the µ-opiod receptor and the ORL1-receptor. The invention also relates to the application of the said compounds for obtaining medications, which can be used in treatment of fear, stress and associated with stress syndromes, depressions, epilepsy, Alzheimer's disease, senile dementia, general cognitive dysfunctions, learning and memory disorders (as nootropic), withdrawal syndromes, alcohol and/or drug abuse and/or abuse of medications and/or alcohol, narcotic and medication addiction, etc. In general formula (1) (1) Y1, Y1', Y2, Y2', Y3, Y3', Y4 and Y4' in each case stand for -H; Q stands for -R0, -C(=O)-R0, -C(=O)OR0, -C(=O)NHR0, -C(=O)N(R0)2 or-C(=NH)-R0; R0 in each case stands for -C1-8-aliphate, -C3-12-cycloaliphate, -aryl, -heteroaryl, -C1-8-aliphate-C3-12-cycloaliphate, -C1-8-aliphate-aryl, -C1-8-aliphate-heteroaryl, -C3-8-cycloaliphate-C1-8-aliphate, -C3-8-cycloaliphate-aryl or -C3-8-cycloaliphate-heteroaryl; R1 and R2 independently on each other stand for -C-1-8-aliphate; R3 stands for -C1-8-aliphate, -aryl, -heteroaryl or -C1-8-aliphate-C3-12-cycloaliphate; n stands for 0; X stands for -NRA-;RA stands for -C1-8-aliphate; RB stands for -C1-8-aliphate; on condition that R1, R2, RA and RB simultaneously do not stand for the non-substituted-C1-8-aliphate.

EFFECT: increased efficiency of the application of the compounds.

9 cl, 11 tbl, 164 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a concentrated storage-stable aqueous solution (S) comprising components (a), (b) and (c), wherein component (a) is at least one optical brightening agent of formula (1), in which the anionic charge on the brightener is balanced by a cationic charge composed of one or more cations selected from a group consisting of hydrogen, alkali metal cation, alkali-earth metal cation, ammonium, ammonium which is mono-, di- or trisubstituted by a C1-4 linear or branched alkyl radical and ammonium which is mono-, di- or trisubstituted by a C1-4 linear or branched hydroxyalkyl radical, and the concentration of component (a) is 0.08-0.3 mol/kg, based on the total weight of the concentrated storage-stable aqueous solution (S); component (b) is at least one inorganic salt (SA), in a concentration of 2-15 wt %, based on the total weight of the concentrated storage-stable aqueous solution (S), where the salts (SA) are preferably by-products of the production process and component (c) is water, in a concentration of 10-88 wt %, based on the total weight of the concentrated storage-stable aqueous solution (S).

EFFECT: invention relates to a method of producing a concentrated storage-stable aqueous solution (S), a method for use thereof as an optical brightening agent for bleaching cellulose substrates, fabrics or nonwoven materials, a sizing solution or suspension when processing paper and a pigmented coating composition containing the solution (S).

23 cl, 1 dwg, 7 tbl, 14 ex

FIELD: highway building and repair, in particular surface treatment of pavements.

SUBSTANCE: claimed emulsion contains (mass %) mineral material 83.5-87.5 and cation bitumen emulsion 11.5-14.5. Mineral material additionally contains cement 1.0-2.0; cation bitumen emulsion contains (mass %) bitumen 60/90 59.0-65.0; cation emulsifier 0.7-0.9; surfactant admixture 0.15-0.25; calcium chloride 0.07-0.13; hydrochloric acid 0.35-0.60; oxyethylated phenolic alcohol 0.65-0.80; and balance: water.

EFFECT: mixture with improved adhesive quality of binder with mineral acidic and basic rocks; improved strength characteristic, increased water resistance coefficient, enhanced emulsion decay time.

1 ex, 4 tbl

Bitumen emulsion // 2244725

FIELD: road-building materials.

SUBSTANCE: pavement-intended bitumen emulsion contains, wt %: bitumen, 45-49; surfactant-type emulsifier in the form of amines, diamines, polyamines, and quaternary ammonium salts, 0.125-0.25; aqueous hydrochloric acid for neutralization of emulsifier, 1-2; additionally, polyalkylbenzene resin produced as by-product in isopropylbenzene production process, 1-15; and water, the balance.

EFFECT: increased resistance of bitumen component to oxidative ageing processes without losses in other performance characteristics.

2 tbl, 12 ex

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