CZ472788A3

CZ472788A3 - Process for preparing a liquid concentrate for polymeric materials stabilization

Info

Publication number: CZ472788A3
Application number: CS884727A
Authority: CZ
Inventors: Antonin Ing Humplik; Tibor Rndr Csc Gogh; Milan Ing Csc Karvas; Julius Ing Csc Durmis; Ivo Ing Orlik; Marcela Rndr Csc Goghova; Renata Ing Horakova; Jiri Ing Zmitko
Original assignee: Vucht As
Priority date: 1988-07-01
Filing date: 1988-07-01
Publication date: 1994-02-16
Also published as: SK472788A3; SK278615B6

Abstract

The concentrate containing 30 up to 70 weight percent of mixture closed to the compounds with a general formula (I), where the symbols R1 and R2 are of the same meaning or of the different one and they mean alpha methyl benzyl or alpha dimethylbenzyl, the symbol x means integer in a value of 0 up to 2 and the symbol y means integer in a value of 0 up to 3 and this mixture is soluble in 70 up to 30 % of softener, while this softener consists of the mixture closed to aromatic and/or naphthenic hydrocarbons, is being prepared based on the alyklation of diphenylamine with styrene or with the mixture of styrene and alpha methyl styrene, at the temperature of 80 up to 120 Celsius degrees, while bleaching clay is present and acting as the catalyst, however the ration of diphenylamine and styrene is 1 : 1,5 up to 2,0. Water contained in the product, carried in that process by the used bleaching clay, however this product is created as a result of the reaction mixture filtration, is removed with the use of vacuum distillation, and the filtration cake is prepared which consists of the part closed to the reaction product and of the used catalyst, this cake is washed at the temperature of 80 up to 180 Celsius degrees, at the pressure of 2,5 up to 40 kPa, with the use of softener in a multiply excess (3 up to 8) related to the reaction product quantity contained in the filtration cake, and the such colature is mixed with the above mentioned isolated reaction product and softener, while water was removed of this cake before this mixing started. Water carried in this process also can be removed with the use of the vacuum distillation closed the starting the starting consisting of diphenylamine and bleaching clay, before feeding of styrene is started and the rest of water can be removed based on the distillation closed to the resulted reaction mixture, while the used catalyst can be removed of it. The liquid concentrate is applied to stabilise polymers, related to caoutchouc family especially, to prevent the thermic or thermo-oxidising degradation.

Description

The present invention relates to a process for preparing a liquid concentrate for stabilizing polymeric materials, especially rubbers against thermal and thermo-oxidative degradation, based on aralkylated diphenylamines and an aromatic softener.

The diphenylamine and p-phenylenediamine derivatives represent a group of important and widely used polymeric stabilizers, especially rubber. Due to the relatively high viscosity, they are often used in the form of oil solutions.

The prior art processes for producing alkylated diphenyl amine derivatives result from the alkylation of diphenylamine with olefins, for example diisobutene (US 3,714,258), styrene or alpha-methylstyrene (US 2,943,112) under the catalysis of BF 4 etherate, H 2 SO 4, p-toluenesulfonic acid , A1C13 (US 2,943,112; US 3,714,257; US 3,714,258; US 2,017,253). Their disadvantage is that, in addition to the various alkyl-substituted diphenylamine isomers, a considerable amount of unreacted diphenylamine remains in the reaction mixture. This can be eliminated by demanding high-temperature fractional distillation, respectively. low vacuum. Commercial Technical Products Include! free diphenylaraine up to 10% by weight. In their application in the rubber industry, under the conditions of processing rubber mixtures at temperatures above 100 ° C, it is volatilized, resulting in no air pollution in the working areas, but in fact a lower dose of anti-degradation agent. This fact is consequently reflected in the application of less effective protection of polymeric materials against degradation effects. A further drawback of the aforementioned known methods of producing alkyl substituted diphenylamines is that after the alkylation process is complete, the alkylation catalyst used is to be washed off. Because of this, the process is mostly done in organic solvents, from which - 2 - 38 then they wash the catalysts with water. • There is a considerable amount of wastewater that can be disposed of? [0009] The high degree of reacting of the starting diphenylamine with the appropriate olefin and the simple isolation of the alkylation catalyst used in the resulting reaction mixture provides a process according to CS 191 570, which operates with a mixture of insoluble catalysts such as polyphosphated impregnated clay acid. Its significant disadvantage is that it takes a lot of time? the final product (9 to 15%) remains adsorbed on the filtered catalyst, resulting in significant economic losses.

The diphenylamine derivatives thus prepared as well as the p-phenylenediamine derivatives are advantageous, due to their relatively high viscosity, adapted to oil solutions, but this is connected with the building up of the storage economy, including reservoirs, pipelines, pumps and scoops, especially for the stabilizer. and especially for oil. The components are kept at the necessary heat treatment viscosity by heating. In fact, mixing oil and stabilizer requires additional equipment - a mixer with stirrer and heating and a measuring cup with a pump. It has now been found that most of the aforementioned drawbacks are avoided by the preparation of a liquid concentrate for stabilizing polymeric materials, in particular rubber-metal, against thermal and thermo-oxidative degradation containing 30 to 70% by weight of a mixture of aralkylated diphenylamines of formula I

(AND)

or alpha, alpha-dimethylbenzyl, x is an integer from 0 to 2 and y is an integer from 1 to 3 dissolved in 70 to 30% by weight of a plasticizer, consisting of a mixture of aromatic and / or naphthenic hydrocarbons, alkylation of diphenylamine with styrene or a mixture of styrene and alpha-methyl styrene at 80-120 ° C, in the presence of a bleaching clay catalyst, and at a ratio of diphenylamine to styrenes of 1: 1.5 to 2.0 relative to each other according to the invention. The present invention is based on the fact that after filtration of the resulting reaction mixture, the filtrate consisting of the reaction product is freed from the water introduced into the ores with the used bleaching clay by vacuum distillation, the filter cake consisting of the reaction product and the catalyst used is washed in 80 to 120 ° C and 2.5 to 40 kPa with a 3 to 8-fold excess of softener, calculated on the content of the reaction product in the filter cake, and the filtrate thus obtained is mixed with the already isolated dewatered reaction product and softened. onu

It has also been found to be advantageous to remove the major portion of the water introduced into the process by bleaching the clay by vacuum distillation of the starting mixture of diphenylamine and bleaching earth prior to the addition of styrene or a mixture of styrene and alpha-methylstyrene and the residual water removed by vacuum distillation of the resulting reaction mixture optionally depleted the catalyst used, saving in particular pumping operations ·

As the solvent-acting softener, it is possible, for example, to use a plasticizer based on a mixture of predominantly mono-, di- and tri-aromatic hydrocarbons (Furex 433), a mixture of aromatic and naphtha hydrocarbons (Triumpf), optionally on the basis of naphthenic hydrocarbons. the filter cake by the softener, the content of the absorbed reaction product on the alkylation catalyst used is reduced to a minimum of 1 to 2%.

The decisive advantage of the process of the invention compared to the known processes for producing similar products is that it efficiently combines the isolation of the technical product from the resulting reaction mixture into an oil concentrate in one operation, thus reducing the investment cost by about 50 reducing energy consumption and laboriousness. The considerable elimination of the losses on the technical product as a result of its sorption to the alkylating catalyst used significantly improves not only the economic but also the ecological characteristics of the process. The liquid concentrate prepared by the process of the present invention is a low viscosity, low viscosity, low volatility liquid, very low coloring polymer substrate. It is harmless to health and its production is raw material, energy and technology less demanding than in the case of naphthylamine and p-phenylenediamine derivatives. Even if its oil component adequately adjusts the amount of rubber hydrocarbon, thereby reducing the cost per unit amount of rubber produced, respectively. replaces a commonly used softener / its pomp / rubber compound. The liquid form of the concentrate allows the use of an automatic dosing system and subsequent immediate incorporation, for example, into the prepared non-stabilized latex without prior treatment.

The liquid concentrate of the present invention excels in the versatility of use for all common types of synthetic rubber latexes (butadiene-styrene, isoprene, butadiene and butadiene-acrylonitrile), respectively. rubber mixtures.

The polymer substrate is added in an amount of 0.5 to 5.0% by weight, preferably 1 to 3% by weight, and can be used in conjunction with other additives suitable for the substrate to which it is incorporated by conventional processing techniques. like other sets.

The following examples illustrate, but do not limit the invention. Example 1

215.5 kg (1.27 kmol) of diphenyl-amine are introduced into a 600 l reactor equipped with a stirrer, a low temperature condenser, a thermometer and a measuring cup and thawed. At 75 ° C, the stirrer is switched on and 44 kg of bleaching earth (catalyst) is metered in. The reaction mixture is heated to 95 ° C and the styrene is metered in at a rate such that the reaction temperature is between 98 ° C and 105 ° C. After dispensing 225.5 kg (2.16 kmol), the reaction mixture was further stirred for 3 h and then filtered on a pressure filter. 397 kg (90%) of filtrate are obtained, from which excess water is removed by vacuum distillation. 50% wt. (44 kg) of a mixture of aralkylated diphenylamines is washed with 285 kg of a purex 433 aromatic softener at 80 ° C and a pressure of 2.5 to 10 kPa · Filtered oil solution of a substituted diphenylamine mixture in an amount of 168 kg containing 23 wt. % of the oil component is mixed with the undiluted product and finalized by the addition of a corresponding amount of aromatic oil to a concentration of 50% by weight of the active ingredient * Liquid concentrate is characterized by: viscosity kinematic at 50 ° C * 293 mm 2 / s,% Ň and 2.21 * Example 2

The procedure is as in Example 1 from the same weights. 369 kg of filtrate (84% by weight) were obtained, from which water was distilled off. A filter cake containing 62% (72 kg) of aral - 5 -

Icyl-diphenylamines are washed with 504 kg of Furex 433 aromatic softener at 110 ° C and a pressure of 30 to 40 kPa. A filtered 327-kg oil solution containing 84% by weight of active ingredient and 84% of oil is further mixed with the isolated reaction product. finalizing with the addition of a corresponding amount of aromatic oil to a concentration of 40% of the active ingredient. Liquid concentrate is characterized by: viscosity ki nematic, 50 224 minvs, fo N »1.64 · Example 3

169.23 g (1 mol) of diphenylamine are introduced into a 4-neck flask equipped with a stirrer, a low-temperature condenser, a thermometer and a dropping funnel, and 39.2 bleaching earth is added after thawing, mixed > the temperature is raised to 100 ° C and 104.2 g (1 mol) of styrene and 118.2 g (1 mol) of alpha-methylstyrene are added · After filtering off the catalyst, 359.0 g of filtrate are obtained, the active ingredient being distilled off. water · Filter cake containing 44% by weight of the active ingredient - a mixture of aralkylated diphenylamines, is washed with five times the Triumph type aromatic-naphthenic softener at 100 ° C and 3 to 6 kPa · Further processing according to Examples 1 and 2 · The product is finalized to a concentration 70% by weight of aralkylated diphenylamine mixture · Liquid concentrate is characterized by: kinematic viscosity at 50 ° 0 * 485 mm ^ / s,% N * 2.52 * Example 4

The liquid concentrate prepared according to Example 1 (stabilizer 1) was added to the creamy latex latex of butadiene - styrene rubber type 1 500 * in a concentration of 2.2% by weight (i.e., 1.1% active ingredient) per dry weight of rubber. After coagulation and drying of the obtained rubber, the stabilizing efficacy of the subject stabilizer was monitored by thermo-oxidative stress of the raw rubber in air-circulating dryers at 130 ° C for 0 to 8 hours · The change in viscosity of ou00ΝΕΥ ° ML 1 - 4V100 ° C rubber is always the measure of stabilizing efficiency due to degradation processes during oxidation at higher temperatures · Measured values show # 1 * - 6 -

Table 1

Stabilizer Viscosity Μ00ΪΠ2Υ ML - 4/100 ° C ([% by weight] 0 1 2 4 6 8 h - 53.0 56.5 66.0 77.0 82.0 84.0 Stabilizer 1 47.5 51.0 51 , 5 53.5 55.0 54.0 Phenyl-beta-naphthylamine - 1.6% 49.5 55.0 54.0 51.0 50.0 52.5 (mixed di-phenyl-phenylenediamine + + aromatic softener 1: 2) - 2.1% 51.0 54.0 54.0 51.5 53.5 50.0

The stabilizing activity of the subject stabilizer with respect to the active ingredient content exceeds the stabilizing activity of the phenyl-ata-naphthyl amine as well as the p-phenylenediamine derivative with two functional groups in terms of the concentration of H-compounds in the stabilizer.

The quaternary concentrate for thermal and thermo-oxidative stabilization of the polymeric materials of the present invention, prepared according to Example 2 (Stabilizer 2), was applied to the scrambled latex in a 2.5% w / w (i.e., 1.0% active ingredient) dry weight rubber 1 712 butadiene-styrene rubber, Example 4 * Measured viscosity values MOOHEY ML - 4/100 ° 0 in Table 2.

Table 2

Stabilizer Viscosity MOONSY ML - 4/100 ° 0 (% by weight) 0 1 i ·· 2 4 6 8 h Stabilizer 2 46.0 44.0 43.0 38.5 24.5 21.0 phenyl-beta-naphthyl -amine 2.0% 44.0 36.5 34.5 20.0 13.0 11.0 (mixed di-phenyl-p-phenylenediamine + + aromatic-46.5 41.0 38.0 25.0 19.0 17.5 Handler, 1: 2) - - 2.4% - 7 -

The stabilizing efficacy of the subject stabilizer exceeds the stabilization efficiency of known, commonly used arainic stabilizers, based on the concentration of -NH-groups in the stabilizer.

The liquid concentrate prepared according to Example 3 (Stabilizer 3) was added to a mixture of chlorine-prene rubber type GS, containing carbon black, HAF type, at a concentration of 3% by weight (2.5% per active ingredient) calculated on rubber. aromatic wetting agent, stearic acid and cross-linking system formed by the MgO / ZnO / tetraethylsulfuric disulfide / ethylenediurea crosslinking system The following values of selected physical-mechanical properties were achieved in the vulcanizates prepared by compressing the crude mixture to optimum at 160 ° C thermo-oxidative aging according to CSU 02 1511 at 130 ° C for 1 to 7 days, the critical magnitude / most pronounced during the period of time / ductility ·

Table 3

Parameter - mixed styrene diphenylamine (2.5%) Stabilizer 3 polymerized 2,2,4-trimethyl-1,2-dihydro-quinoline (2.5%) residual strength 2 days 59 66 65 54 (rel. ) 3 days 42 51 56 35 4 days 30 42 48 27 5 days 6 35 41 23 7 days - 15 20 10 dynamic fatigue by Mattia (cracks) kc 5, 8 8.6 12.5 10.6 The subject stabilizer shows the highest stabilizing treatment * Example 7

Working with the same starting material weights and with the same equipment as in Example 1 # From the mixture of thawed di-8 phenylamine and bleaching earth heated to 95 ° C, the major portion of the bleached water is removed by vacuum distillation prior to dosing. The resulting reaction mixture was freed from the residual water by vacuum distillation and filtered on a pressure filter to give 394 kg (89%) of the reaction product, which was further processed similarly to Example 1.

Claims

what about PATENT CLAIMS

w) -O [n ' α o 1. A method for preparing a liquid end of a copolymer to stabilize the copolymer materials, in particular rubbers, against thermal and thermo-oxidative degradation containing 30 to 70% by weight of a mixture of aralkylated diphenylamines of the formula I

Wherein R and R are the same or span and are alpha-methylbenzyl or alpha, alpha-dimethylbenzyl, x is an integer from 0 to 2 and y is an integer from 0 to 3 dissolved in 70 to 30% by weight of a plasticizer consisting of an aromatic mixture and / or naphthenic hydrocarbons, by alkylation of diphenylamine with styrene or a mixture of styrene and alpha-methylstyrene at a temperature of 80 to 120 ° C, in the presence of a bleaching clay catalyst and at a mutual molar ratio of diphenylamine to styrenes of 1: 1.5 to 2.0; by filtering the resulting reaction mixture, the filtrate consisting of the reaction product is dewatered with the bleaching earth using vacuum distillation, the filter cake consisting of the reaction product part and the catalyst used is washed at 80-120 ° C and pressure 2.5 to 40 kPa with 3 to 8 fold excess of softener, calculated on the content of the reaction product in the filter and the filtrate thus obtained is mixed with the already de-watered reaction product and the plasticizer. Process according to Claim 1, characterized in that the main portion of the water introduced into the process with the bleaching earth used is removed by vacuum distillation of the starting mixture of diphenylamine and bleaching earth before the addition of styrene or a mixture of styrene and alpha-methylstyrene and the remainder of the water is removed by vacuum distillation. the subsequent reaction mixture, or depleted catalyst used;