The products of the oligomerization 10-propenylbenzene as stabilizers for polyolefins
(57) Abstract:The invention relates to the production of products of oligomerization, which can be used in the manufacture of the stabilized polymer compositions of different directions. The purpose of the invention: obtain new derivatives fenotiazina with high stabilizing effect for polyolefins. The products of the oligomerization 10-propenylbenzene General formula
< / BR>where n = 1, 2, m = 1, is obtained by polymerization of the initial monomer at a temperature of 20-25oC in an organic solvent in the presence of a catalyst-epirate boron TRIFLUORIDE in number (3-6)of 10-3mol per 1 mol of the original monomer. table 4. The invention relates to the production of products of oligomerization 10-propenylbenzene that can be used in the production of stabilized polymer compositions for various purposes.It is known that as the stabilizers of the polyolefins used phenolic antioxidants such as 2,2'-Thio-bis(4-methyl-6 - tertbutylphenol) (Toolkit BP) or ether 4-hydroxy-3,5-di-tertbutyl - phenylpropionic acid and PENTAERYTHRITE (Tetralin abdominoperineal resection) (Irganox 1010), as well as stabilizers oligomeres the BR> In addition, to stabilize the polymers are widely used aromatic and heterocyclic amines.Closest to the invention to the technical essence and the achieved positive effect is the stabilization of low molecular weight polymers of ethylene, where the antioxidant is used phenothiazines  as for the use fenotiazina and its alkyl derivatives in the stabilization of other polyolefins or other polymers classes, there are certain limitations to the applicability of these stabilizing additives. It is known that the phenothiazines and its low molecular weight derivatives vyparivayte on the surface of the stabilized polymer during processing and operation that restricts the use of dosages in the polymer to the upper limit of compatibility about 1.5 wt.h. for fenotiazina  in Addition, the phenothiazines and its low molecular weight derivatives are not fully protect polymers from complex factors of aging actions mnogokratnyh deformations, ozone, and heat.The purpose of the invention to obtain new derivatives fenotiazina with high stabilizing effect for polyolefins, the improvement of physical and chemical features, which is achieved by that receive the products of the oligomerization 10-propenylbenzene by the polymerization of the initial monomer at a temperature of 20 25oC in an organic solvent in the presence of catalyst apirat boron TRIFLUORIDE in number (3-6)of 10-3mol per 1 mol of the original monomer.Example 1. In odnogolosy flask is charged with 2.4 g (0.01 M) CIS-10-propenylbenzene (CIS-10-CFT), dissolved in 10 ml of dehydrated organic solvent is ethyl acetate, add 0.1 ml (0,00003 M) solution epirate boron TRIFLUORIDE in acetic acid ethyl ester. The synthesis is carried out at 20 - 25oC until complete conversion of the CIS-10-CFT. The control input of the reaction carried out chromatographic (TLC, Silufol, hexane:ether 6:1). The duration of the synthesis of 2 hours after 25-30 min after addition of the catalyst in the reaction solution in the volume of the reaction mass see the appearance of crystals of a substance, which then form a precipitate on the walls of the flask. Then for 1.5 h observed a significant increase in the volume of sludge. Upon completion of the reaction, the catalyst was neutralized with KOH solution in methyl alcohol. Accumulated in the process of synthesis sediment substance is filtered off, washed successively with 10 ml of ethyl acetate and then 50 ml of ethanol and dried. Obtain 1.6 g (66.6%) with b the acetate, acetone, hexane.IR-spectrum (UR-20, KBr): 760 cm-1(1,2-substituted benzene ring), 790, 740 cm-1(1,2,3-substituted benzene ring), 1600, 1500 cm-1(C=C aromatic ring). In addition, the IR spectra there is no absorption band of the free N-H bond.PMR spectrum (CDCl3) , M. D. contains the signals characteristic of the ethyl groups: of 1.02 (3H, t, J=6 Hz), 1,28 (2H, d, J=7 Hz), and the signals in the region of 1.4 to 1.7 (2H, m), 2,4-2,85 (1H, m), 3,94 of 4.2 (1H, m), 4,8-5,1 (1H, d, J= 11 Hz) and signals of the protons of the aromatic rings of 6.5 to 7.2 (15H, m), M+=478.These data allow us to identify the product of the oligomerization of CIS-10-propenylbenzene as 2-methyl-1-ethyl-3-(10-phenothiazinyl)-2,3-dihydro-1H-pyrido[3,2,1-k,l]phenothiazines (FLOOR-1).< / BR>Elemental analysis:
Found, C 76,70; H 5,69; N 5,43; S 12,99.Calculated C 75,31; H 5,43; N 5,85; S 13,38.In addition to the main reaction product-FLOOR-1, when the duration of the synthesis in the reaction mixture are present oligomeric derivatives of CIS-10-CFT (POL-2). Probable structural formula shown in examples 5-6.Examples 2-4. The product of the oligomerization of CIS-10-CFT (FLOOR-1) are obtained analogously to example 1, but the duration of synthesis varies from 0.67 to 3.2 hours Allocation issue is roducti oligomerization CIS-10-propenylbenzene (POL-2) are obtained analogously to example 1. The resulting precipitate FLOOR-1 leave in the reaction solution. Control over the course of the reaction is carried out by the method of TCX. The duration of the synthesis increases to 18-21 hours During this time, the sediment FLOOR-1 almost completely dissolved. Upon completion of the reaction, the catalyst is neutralized with a solution of KOH in methanol. From the reaction mixture is filtered dropped after neutralization precipitate FLOOR-1. The filtrate is planted in 450 ml of ethanol (methanol) and 20 ml of water. The precipitation is filtered off, washed with 100 ml of ethyl alcohol and dried. Get a light gray powder oligomeric derivatives of CIS-10-propenylbenzene FLOOR-2 output 30-37,5% of T. pl. 140-150oC. M. M. 510-1030 (Kritskaya, naphthalene). FLOOR-2 is highly soluble in most organic solvents, except saturated hydrocarbons.IR Spencer (UR-20, KBr) shows the presence of absorption bands of the free amino group (3370 cm-1), 1,2-substituted (760 cm-1), 1,2,3-substituted (790, 740 cm-1), substituted 1,2,4 (880, 820 cm-1) benzene rings. The structure of the synthesized oligomers can be represented the following structural formula:
< / BR>Proposed structure of the oligomerization products (FLOOR 2) agrees satisfactorily with the data element and the with oligomerization CIS-10-CFT carried out analogously to example 5, but in the solvent used methylene chloride. The duration of the synthesis of 6 hours Products of oligomerization (POL-2) obtained with the yield of 68.8% (table.1).Example 8. Oligomerization CIS-10-CFT carried out analogously to example 5, but in the solvent used toluene. The duration of the synthesis of 6 hours Products of oligomerization (POL-2) obtained with the yield 90,8% (table.1).Thus, the proposed method allows to obtain products of oligomerization CIS-10-FT FLOOR-1 with the outputs of 28.5-75,4% and a half-2 outputs 30-91%
POL-1 and POL-2 was used as the polyolefin stabilizers in the following ratio, wt.The polyolefin 99,7 99,9
FLOOR 1 or FLOOR 2 0,1 0,3
Example 9. Composition on the basis of high-pressure polyethylene (LDPE) prepared by mixing 998 g HDPE with 2 g (0.2 wt.) FLOOR-1 in the mill at 160oC. evaluation of the stabilizing action is performed according to the change of the melt flow index (MFR) in the process of aging of the polymer in air at 200oC for two hours, and time changes the pH of the electrolyte solution on the accumulation of volatile products of decomposition of the polymer during aging at 180oC in a stream of oxygen (pH) TU 301-05-91. Resultater 9, but the stabilizer is added in a concentration of 0.1 wt. and 0.3 wt.Examples 12 to 14. Composition based on HDPE with the addition of 0.1-0.3% FLOOR-2 prepare and test as in example 9 (table.2).Example 15. Prepare and test composition on the basis of LDPE analogously to example 9, but as thermo stabilizer use Irganox-1010 (product of the company Ciba-Geigy) table.2.Examples 16-18. Preparing a composition based on Sevillana brand 11306-075 that as a stabilizer, containing 0.1-0.3% of the FLOOR-1. Mixing of the polymer with the additive was carried out in a high-speed mixer at room temperature for 10 minutes the mixture was extrudible on single-worm extruder with a ratio of the length of the worm and a diameter of 20:1 at temperatures 100-110-120oC zones. From the granules at 130-140oC and a pressure of 80 MPa were cast disks of thickness 1 mmEvaluation of the "oven" effect of additives in compositions based Sevillana spend on THE 301-05-91 time changes the pH of the electrolyte solution on the accumulation of volatile products of decomposition of the polymer during aging at 180oC in a stream of oxygenpH, as well as the change in the melt flow index (MFR) in the process of aging of the composition in air at 200oExamples 19-21. Prepare and test compositions on the basis of Sevillana brand 11306-075 that as a stabilizer, containing 0.1-0.3% of FLOORS-2 (PL. 3).Example 22. Prepare and test the composition based Sevillana analogously to example 17, but as thermo stabilizer use Irganox-1010 (PL. 3).Examples 23 and 24. Composition based on polypropylene is prepared by displacement (polypropylene and thermo stabilizer) in a high-speed mixer at room temperature for 10 min, followed by extrusion in a single screw extruder screw extruder at a temperature of 170-160oC zones of the cylinder. Evaluation of the stabilizing action of additives spend time changing the pH of the electrolyte solution with the accumulation in it of acidic degradation products of the polymer in a stream of oxygen at 180oC and 160oCpHand according to GOST 26996-86 "Polypropylene and copolymers of propylene", paragraph 5.12 at 150oCochre.) (table.4).Example 25. Composition based on PP prepare and test similar to examples 23, 24, but the stabilizer is used as Irganox 1010.From the above table.2-4 data shows that the proposed compositions based on polyolefins containing as thermostabilization on the level of industrial stabilizer make up 1010 or surpass it. According to definition changes VKT both products exceed Irganox 1010, which allows their use as stabilizers for polyolefins.Literature:
1. Chemical additives to polymers. /Ed. by I. P. Maslova. M. Chemistry, 1973 S. 70, 75, 118.2. Murphy C. M. Sanders, C. E. Petroleum Refiner, Vol.26, p. 479, 1947.3. Copyright certificate 1027177, C 08 L 9/00 C 08 K 5/46. Vulcanicola rubber mixture based chain rubber. C. S. Nikulin, Y. F. Shutilin, M. I. Cherkashin, V. M. Andrey, A. P. Zvonkova, M. P. Parinov. Appl. 04.03.82. Publ. 07.07.83. Bull. N 25.4. Skvortsova,, shostakovskii M. F. and benchmarks such, N. Journe. Org. chemistry. 1972, so-8, S. 382-387. The products of the oligomerization 10-propenylbenzene General formula
where n 1, 2;
as stabilizers for polyolefins.
< / BR>Known 2,3-dihydro-3-keto-1H-pyrido[3,2,1]phenothiazines  as antioxidants for lubricants
SUBSTANCE: present invention relates to organic chemistry and specifically to compounds of formula I or to pharmaceutically acceptable salts thereof, where Ar is imidazole or pyrazole, where the said Ar can be substituted with substitute(s) selected from a group consisting of a C1-C6 alkyl group, a phenyl group and a halogen atom, each of Y1, Y2 and Y3 is a carbon ot nitrogen atom, A is an oxygen atom, a sulphur atom or a group of formula -SO2-, R1 is a hydrogen atom, a C1-C6 alkyl group which can be substituted with one phenyl group (where the said phenyl group can be substituted with one substitute selected from a group consisting of a halogen atom and a C1-C6 alkyl group), or a phenyl group, R2 is a C1-C6 alkyl group, R3 is (i) a C1-C18 alkyl group, (ii) C2-C8 alkenyl group, (iii) C2-C8 alkynyl group, (iv) C3-C8 cycloalkyl group, (v) C1-C6 alkyl group substituted with 1-3 substitutes selected from a group given in paragraph 1 of the formula of invention, or (vi) a phenyl group, a naphthyl group, a pyrazolyl group, a pyridyl group, an indolyl group, a quinolinyl group or an isoquinolinyl group, where each of the said groups can be substituted with 1-3 substitutes selected from a group given in paragraph 1, R4 is a hydrogen atom or a C1-C6 alkyl group, and R5 is (i) C1-C10 alkyl group, (ii) C1-C10 alkyl group which is substituted with one or two substitutes selected from a group given in paragraph 1, (iii) C2-C8 alkenyl group which can be substituted with a phenyl group, or (iv) phenyl group, naphthyl group, thienyl group, pyrrolyl group, pyrazolyl group, pyridyl group, furanyl group, benzothienyl group, isoquinolinyl group, isoxazolyl group, thiazolyl group, benzothiadiazolyl group, benzoxadiazolyl group, phenyl group, condensed with a 5-7-member saturated hydrocarbon ring which can contain one or two oxygen atoms as ring members, uracyl group or tetrahydroisoquinolinyl group, where each of the said groups can be substituted with 1-5 substitutes selected from a group given in paragraph 1, provided that when Ar is a group of formula 5, which can be substituted with a C1-C6 alkyl group, R5 is not a C1-C10 alkyl group, and the formula (I) compound is not 5-(3,5-dichlorophenylthio)-4-isopropyl-2-methane-sulfonylaminomethyl-1-methyl-1H-imidazole or 5-(3,5-dichlorophenylthio)-4-isopropyl-1-methyl-2-p-toluene-sulfonylaminomethyl-1H-imidazole. The invention also relates to a pharmaceutical composition based on the formula I compound and to formula II compounds, radicals of which are defined in the formula of invention.
EFFECT: obtaining novel compounds with inhibitory effect on the bond between S1P and its Edg-1 (SIP1) receptor.
32 cl, 43 tbl, 18 ex