RO122453B1 - Asymmetric adipic diesters and process for preparing the same - Google Patents

Abstract

The invention relates to adipic diesters to be used in polymer processing and to a process for preparing the same. According to the invention, the adipic diesters are defined by the general formula R1OOC-(CH2)4-COOR2 where R1 is an n-butyl, n-hexyl, 2-ethyl-hexyl, isodecyl and isotridecyl, R2 is an aliphatic-aromatic radical exhibiting a flowing temperature of -39A C...-42A C, an ignition temperature of 200A C...238A C, a viscosity index of 76...186, they being obtained in two successive steps, namely: a semi-ester obtained in the first step and the corresponding asymmetric diester obtained subsequently, under solution acid catalysis conditions.

Description

The invention relates to asymmetric adipose diesters and to a process for obtaining them, used in the processing of polymers.

It is known that the problem of synthesis and development of new classes of lubricants, with precise industrial applicability in the mechanical field, continues to be a priority theme of fundamental and applied research [Zasutomi Seijiro, Japan, Toraiboroisuto, 2005, 50 (4), 295-300 ], The lubricants used in polymer processing, in order to reduce the energy consumption required in this operation, are also the motivation for starting extensive theoretical and practical studies [Vainstak VV et al., Chemistry and Technology of Fuels and Oils, 2005, 41 (2), 151-158], the fundamental knowledge regarding the basic oils, respectively the production techniques, the types and properties of the synthetic oils, the test methods, the principles of selection, as well as the management aspects in this field are recent research objectives (Watanabe Seiichi, Petrotech [Tokyo, Japan), 2004, 27 (10), 821-826; Yoshida Toshio, Petrotech (Tokyo, Japan), 2004, 27 (11), 881-888].

Methods for obtaining complex citric esters, synthesized on the basis of mixtures of alcohols used as additives for processing polymers, such as the plasticizer direction, for a variety of polymers are described in the literature [Alber Frank et al., IP Corn. Journal, 2004, (July 13), 4 (8), 15]. The synthesis and biodegradability characteristics of adipose and sebaceous esters are recent reports of fundamental research [Gryglewicz S. et al., J. Synthetic Lubrication, 2003, 20 (2), 99-107; Gryglewicz S. et al., J. Synthetic Lubrication, 2004, 20 (4), 281-288]. The synthesis of new types of plasticizers with a mixed structure, such as glycidyl ethyl hexyl phthalate, is the subject of a study that indicates the possibility of using these derivatives as plasticizers for PVC [Kim Sang-Woo et al., J. of Applied Polymer Science, 2005, 96 (4), 1347-1356]. Plasticizers with a mixed structure, based on n-octyl and n-decile fats, have resistance to cold and suitable specific properties [Wang Shuging et al. Xiandai Suliao Jiagong Yingyong, 2004, 16 (4), 34-36], By using less branched C ₉ alcohols, small trimelitic esters are obtained, which are especially useful for application directions that impose resistance to higher temperatures, such as wire insulation. and cables (US 6969736).

In order to obtain polymeric processing aids that possess suitable properties of either plasticizer or lubricant, respectively, in order to achieve fluids with suitable lubrication characteristics in the tribological field, it is necessary to design such molecular models that contain in their structure a multitude of functions, both polar and nonpolar. In order to achieve these desires, the principles of polyfunctionality, respectively of asymmetry of the molecule thus constructed prove to be valid.

On the basis of these principles and considering the adipic acid as the basic framework, small esters with an asymmetrical structure can be made, based on aliphatic alcohols of variable length, in conjunction with special alcohols, with complex structure, of aliphatic-aromatic type. In order to gain an additional contribution of asymmetry element, an aliphatic pendant chain, of variable length, is attached to the aromatic core of these special alcohols.

In order to reach structures as close to the theoretical one as possible, the synthesis is performed in two stages. Thus, in the first stage, a semiester is made based on alcohol with an aliphatic aromatic complex structure, followed by the second step, when the asymmetric ester is obtained under the conditions of adding an aliphatic alcohol of variable length. Both steps are conducted in appropriate ratios between the reaction partners, in acid catalysis; In order to obtain a product that does not have a residual acidity, or even of small value, it is necessary to add at the end of the synthesis of a lower alcohol which corrects this character, but which does not cause a disturbance or deviation from the theoretical structure expected.

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Methods for the synthesis of aliphatic unordesters with lower disturbance points are known, 1 which are used either as lubricants or as plasticizers for thermoplasts (EP 1516865).

There is also known a method of obtaining mixtures of italic alkyl esters, 3 which provides flexibility in controlling their viscosity, the products obtained can be used as plasticizers for PVC, as lubricants and as hydraulic fluids 5 (WO 0329180). Also known is a process for obtaining mixed-structure adipose diesters, based on 2-phenoxy ethanol, respectively n-butanol and 2-ethyl hexanol, which 7 has the disadvantage of processing in a single phase, without providing a closer to the theory and without a proper correction of the remaining acidity (RO 104393). 9

The technical problem that the invention solves consists of the elaboration of molecular structures on the basic skeleton of adipic acid, having stable reproducible characteristics, 11 which possess plasticizer / lubricant properties for polymer processing.

Asymmetric adipose diesters, with complex structure, defined by general formula 13

R ₁ OOC- (CH ₂ ) ₄ -COOR ₂ 15 according to the invention eliminates said disadvantages by the fact that the radical R is a n-butyl, n-hexyl, 2-ethyl-hexyl, isodecyl and isotridecyl radical, R ₂ is a radical with an aliphatic-aromatic type structure of the form: 19

-ch ₂ -ch2-o- (g5 ^ ^{21 3} 23 wherein R ₃ = H, o-secbutyl and / or p-nonyl, which exhibit critical solvation temperatures of

126 ... 156 ° C, the maximum torque in the Brabender plastogram 22.56 ... 37.77 Nm, number of lubricants - 25 balls 8.11 ... 13.3, diameter of the wear stain 0.95. .1.40 mm for unadjusted specimens, respectively 0.38-1.10 mm for additive specimens, flow temperature -39 .., -42 ° C, 27 ignition temperature 2OO ... 238 ° C, index of viscosity 76 ... 186.

The process of obtaining asymmetric adipose diesters in two successive stages, with 29 obtaining initially a semiester and subsequently the corresponding asymmetric distention, under acid catalytic solution in accordance with the invention, eliminates the disadvantages mentioned by 31 that the adipic acid is esterified in the first step with an alcohol selected from 2-phenoxyethanol, 2 - [(o-secbutyl) phenoxy] ethanol and 2 - [(p-nonyl) phenoxy] ethanol, under strict stoichiometry, with 33 extracting the reaction water and obtaining the corresponding semester. , followed by the addition, in the second step, of aliphatic alcohol, selected from n-butanol, n-hexanol, 2-ethyl hexanol, 35 isodecanol and isotridecanol, with the extraction of the reaction water and the corresponding asymmetric diester in the presence of an aromatic solvent. chosen from benzene, toluene or xylene, in 37 quantities of 20 ... 200% relative to the mass of the reactants, in acid catalysis based on p-toluene sulfonic acid, in can titrated from 1 ... 10% relative to the mass of the reactants, with the mixture being brought to 39 reaction at reflux, the synthesis taking place in a period of 5-7 h, in which the blast temperature increases progressively, with the final addition of 0 , 1 ... 1.0 moles lower alcohol selected from ethanol, 41 n-propanol and n-butanol, additional reflux for 2 ... 4 h, stripping of excess solvent and lower alcohol to a dew point temperature. 245-255 ° C, the crude mass of 43 reaction being treated with dilute basic aqueous solutions, of alkaline carbonates with a concentration of 1 ... 5%, until neutral pH, then repeated washing, with demineralized water, devolatilization in 45 vacuum up to a blast temperature of 235-250 ° C and a residual vacuum of 3-8 mm col Hg, followed by hot discoloration, with activated carbon, and filtration. 47

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By applying the invention, the following advantages are obtained:

- the complex structure ensures the possibility of using these products in a wide range of application directions, either in the field of polymer and PVC processing in particular, both as plasticizers, as lubricants or as tribological fluids;

- the process ensures the reproducibility of the structures and the absence of any remaining acidity.

The following are 12 examples of embodiments of the invention.

Example 1. In a 2000-ml two-necked flask, fitted with a thermometer and Dean-Stark head, to extract the reaction water and return the solvent, coupled with an upward reflux refrigerant, 1.0 moles are introduced. (146 g) adipic acid, 1.0 mol (264 g) 2 - [(p-nonyl) phenoxy] ethanol, 6.0 g p-toluene sulfonic acid, 150 ml toluene, and about 20 ml toluene in the head extractor, and porous porcelain granules, to ensure a quiet boil. The mixture is brought to reflux at a temperature that increases progressively, from about 115 ° C to 145 ° C, during 5 hours, during which the theoretical quantity of water is extracted. After cooling below 100 ° C, 1.0 mol (200 g) isotridecanol is added, then reduced to reflux and kept under these conditions for a further 5 hours, during which the theoretical amount of developed water is also extracted. The reaction mixture is cooled to below 100 ° C, 0.54 moles (40 g) is added n-butanol, it is restored to reflux, where it is kept for another 3 hours, after which the excess toluene and n-butanol are extracted from the system. reaction mass, up to a dew point of 255 ° C. The gross mass of the asymmetric diester is treated with dilute 5% aqueous sodium carbonate solutions to neutralize and remove p-toluenesulfonic acid at about 50-55 ° C, in the ratio of 1: 1 to 1: 2 mass. crude: aqueous solution, then repeated with still hot demineralized water, until neutral pH, followed by devolatilization in vacuo, up to a blast temperature of 235'C and a residual vacuum of 3 mm col Hg, treated warm, with bleaching charcoal, and filter.

The asymmetric adipose diester obtained, ie the mixed adipate of isotridecyl and 2 - [(p-nonyl) phenoxy] ethyl, called iso-13-p-N, has the essential physico-chemical parameters shown in table 1.

Characteristics 2 - [(p-nonyl) phenoxy] ethanol, self-synthesis, are the following:

- molecular formula C ₁₇ H ₂₈ O ₂ ;

- the structure formula

- molecular mass M = 264;

- density, g / cm ³ d = 0.978;

- refractive index n ²⁰ = 1,5113.

Example 2. In an installation similar to that described in Example 1, 1.15 moles (168 g) adipic acid, 1.15 moles (223.1 g) 2 - [(o-secbutyl) phenoxy] ethanol are introduced, 6.0 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene in the extractor head, after which the synthesis is carried out in the first step as in Example 1. 15 moles (230 g) isotridecanol and proceed to the second step and the sequences for processing the gross reaction mass, as in example 1. The asymmetrical adipic diester obtained, ie the mixed adipate of isotridecyl and 2 - [(o- secbutyl) phenoxy] ethyl, called iso 13-OSECBUT, has the essential physico-chemical parameters shown in Table 1.

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Characteristics 2 - [(o-secbutyl) phenoxy] ethanol, self-synthesis, are the following:

- molecular formula C ₁₂ H ₁₈ O ₂ ;

- the structure formula

HO-CH ₂ ^ H ₂ -O- / Q ₃ -ch-ch ₂ -ch ₃

- molecular mass M = 194;

- density g / cm, d = 1.0146;

- refractive index n ²⁰ = 1,5175.

Example 3. In an installation similar to that described in Example 1, 1.3 moles (189.8 g) adipic acid, 1.3 moles (179.4 g) 2-phenoxyethanol, 7.0 g p -toluene toluene, porous porcelain granules and 150 ml toluene, plus about 20 ml toluene, in the extractor head, after which the first step is carried out, as in example 1. Next 1.3 moles (260 g) are added. ) isotridecanol and proceed to perform the second step and the sequences for processing the gross reaction mass, as in example 1.

The asymmetrical adipose diester obtained, ie the mixed adipate of isotridecyl and 2-phenoxyethyl, called iso-13-FE, has the essential physico-chemical parameters shown in table 1.

The characteristics for 2-phenoxy ethanol, own synthesis, are the following:

- molecular formula C ₈ H ₁₀ C ₂ ;

- the structure formula ho-ch ₂ -ch ₂ - ° -O

- molecular mass M = 138;

- density, g / cm ³ d = 1,109;

- refractive index n ²⁰ = 1,5370.

Example 4. In an installation similar to that described in Example 1, 1.10 moles (160.6 g) adipic acid, 1.10 moles (290.4 g) 2 - [(p-nonyl) phenoxy] are introduced. ethanol, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, followed by the first step, as in Example 1. add 1,10 moles (173.8 g) isodecanol and proceed to the second step and the successions of processing the gross reaction mass, as in example 1. The asymmetrical adipose diester obtained, ie the mixed adipate of isodecyl and 2 - [(p-nonyl) phenoxy] ethyl, called iso 10-pN, has the essential physico-chemical parameters shown in table 1.

Example 5. In an installation similar to that described in Example 1, 1.27 moles (185.42 g) adipic acid, 1.27 moles (246.38 g) 2 - [(o-secbutyl) phenoxy] are introduced. ethanol, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, followed by the first step, as in Example 1. add 1.27 moles (200.66 g) of isodecanol and proceed to the second step and the sequences for processing the gross reaction mass, as in Example 1. The asymmetrical adipose diester obtained, ie the mixed isodecyl adipate and 2 - [(o-secbutyl) phenoxy] ethyl, called iso-10-OSECBUT, has the essential physico-chemical parameters shown in table 1.

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Example 6. In an installation similar to that described in Example 1, 1.45 moles (211.7 g) adipic acid, 1.45 moles (200 g) 2-phenoxyethanol, 6.5 g p-toluene acid are introduced. sulfonic acid, porous porcelain granules and 150 ml toluene, plus about 20 ml toluene, in the extractor head, followed by the first step, as in Example 1. 1.45 mol (229 g) isodecanol is further added. and proceed to perform the second step and the sequences for processing the gross reaction mass, as in example 1. The asymmetrical adipic diester obtained, ie the mixed adipate of isodecyl and 2-phenoxyethyl, called iso-10-FE, has the physical parameters - essential chemicals shown in table 1.

Example 7. In an installation similar to that described in Example 1, 1.15 mol (168 g) adipic acid, 1.15 mol (303.6 g) 2 - [(p-nonyl) phenoxy] ethanol are introduced, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, after which the first step is carried out, as in Example 1. , 15 moles (149.5 g) 2-ethyl hexanol and proceed to the second step and the sequences of processing the crude reaction mass, as in example 1. The asymmetric adipose diester obtained, ie the mixed adipate of 2- ethyl hexyl and 2 - [(p-nonyl) phenoxy] ethyl, termed 2EH-pN, have the essential physico-chemical parameters shown in Table 1.

Example 8. In an installation similar to that described in Example 1, 1.35 moles (197.1 g) adipic acid, 1.35 moles (261.9 g) 2 - [(o-secbutyl) phenoxy] are introduced. ethanol, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, followed by the first step, as in Example 1. add 1.35 moles (175.5 g) 2-ethyl hexanol and proceed to the second step and the sequences for processing the gross reaction mass, as in Example 1. The asymmetrical adipose diester obtained, ie the mixed adipate 2-ethyl hexyl and 2 - [(o-secbutyl) phenoxy] ethyl, called 2EH-OSECBUT, have the essential physico-chemical parameters shown in Table 1.

Example 9. In an installation similar to that described in Example 1, 1.25 moles (182.5 g) adipic acid, 1.25 moles (330 g) 2 - [(p-nonyl) phenoxy] ethanol are introduced, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, after which the first step is carried out, as in Example 1. , 25 moles (127.5 g) n-hexanol and proceed to perform the second step and the sequences for processing the gross reaction mass, as in Example 1. The asymmetric adipose diester obtained, ie the mixed n-hexyl adipate and 2 - [(p-nonyl) phenoxy] ethyl, referred to as HEX-pN, has the essential physico-chemical parameters shown in Table 1.

Example 10. In an installation similar to that described in Example 1, 1.50 moles (219 g) adipic acid, 1.50 moles (291 g) 2 - [(o-secbutyl) phenoxy] ethanol, 7 are introduced. 0 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, followed by the first step, as in Example 1. 1.50 is added. moles (153 g) n-hexanol and proceed to the second step and the successions of processing the gross reaction mass, as in example 1. The asymmetrical adipose diester obtained, ie the mixed adipate of n-hexyl and 2- [ (o-secbutyl) phenoxy] ethyl, called HEX-OSECBUT, has the essential physico-chemical parameters shown in table 1.

Example 11. In an installation similar to that described in Example 1, 1.30 moles (189.8 g) adipic acid, 1.30 moles (343.2 g) 2 - [(p-nonyl) phenoxy] are introduced. ethanol, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head, followed by the first step, as in Example 1.

The following is added 1.30 moles (96.2 g) n-butanol and proceed to the second step and the sequences for processing the gross reaction mass, as in example 1. The asymmetric adipose diester obtained , ie the mixed adipate of n-butyl and 2 - [(p-nonyl) phenoxy] ethyl, 3 called BUT-pN, has the essential physico-chemical parameters shown in table 1.

Example 12. In an installation similar to that described in Example 1, 5 1.55 moles (226.3 g) adipic acid, 1.55 moles (300.7 g) 2 - [(o-secbutyl) phenoxy] are introduced. ] ethanol, 6.5 g of p-toluene sulfonic acid, porous porcelain granules and 150 ml of toluene, plus about 20 ml of toluene, in the extractor head 7, followed by the first step, as in Example 1. 1.55 moles (114.7 g) of n-butanol are then added and the second step 9 and the sequences for processing the gross reaction mass are carried out, as in Example 1. The asymmetric adipose diester obtained, ie The mixed adipate of n-butyl and 2 - [(o-secbutyl) phenoxy] ethyl, 11 BUT-OSECBUT codes, presents the essential physico-chemical parameters shown in table 1.

The gelling characteristics were determined on a BRABENDER type PL / 3S plastograph, 13 under the conditions of standard prescriptions, based on vinyl polychloride, namely: PVC suspension (Kw = 67) 33.6 g (100: 3), plasticizer 16.6 g (50: 3), Ba-Cd stearate stabilizer 0.2 g 15 (0.6: 3), at a speed of 50 rpm, tank of 50 cm ³ and at a temperature of 160 ° C. The critical solvation temperature, the TCS criterion, was determined using a Boetius microscope, with 17 plate heaters, on a suspension PVC Kw = 67. The lubrication figure was determined on a Brabender PL / 3S type plasterboard, on a standard polychloride mixture of wine, according to 19 recipes: PVC suspension (Kw = 67) 100 g, lead tribasic sulphate stabilizer 2 g, lubricant 1 g, working temperature 160 ° C, rotation speed 30 rpm, tank 30 cm ³ , range 21 5; for the effective test, a fraction of receipt calculated for 30 g PVC is used.

The lubrication figure was calculated using the Bottner-Rosenthal relation (Kunststoffe, 23 1972, 62, 10, 685):

C, = 1000 ——— where:

C _L = lubrication figure;

E = total quantity of ingredients, as a percentage of PVC; 33

T = temperature of the kneaded mass, ° C;

M _min = the minimum torque, kg.m. 35

The dynamic viscosity was determined with a Rheotest RV (VEB Prufgerăte-Werk Medingen / Dresden) rotational viscometer, at 20 ° C, the SI measuring device, the shear speed of 37 in the range 1.6-1310 s' ¹ .

The diameter of the wear stain was determined on a machine with 4 SETA type balls, according to 39 ASTM D 4172.

The kinematic viscosity, respectively the viscosity index was determined with the help of an Ubbelohde viscometer 41, according to ASTM 445.

The flash point was determined according to ASTM D 92, and the point of 43 flow, according to ASTM D 97.

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Table 1

The values of the essential physico-chemical parameters

Nr. crt. Feature Adipat code Formula molecular Table mole- ticular Μ Density g / cm 3, 20 ° C Refractive index n ²⁰ Viscosity dynamics mPa.s 20 ° C 1 iso 13-p-N C ₃₆ H ₆₂ O ₅ 574 .9596 1.4824 113.92 2 iso 13-OSECBUT ^ 3ΐΗ ₅₂ Ο ₅ 504 .9696 1.4782 46.74 3 iso 13-FE * C27H44O5 448 1.0309 1.4760 - 4 iso 10-p-N θ33 ^ 56θ5 532 .9715 1.4830 113.67 5 iso 10-OSECBUT 462 .9818 1.4790 36.34 6 iso-10-FE * ^ 24 ^ 38θ5 406 .9939 1.4773 - 7 2EH-p-N θ31 ^ 52θ5 504 .9728 1.4831 95.72 8 2EH-OSECBUT C26H42O5 434 0.9927 1.4803 41.64 9 HEX-p-N ^ 29 ^ 48θ5 476 .9865 1.4833 77.17 10 HEX-OSECBUT θ24 ^ 38θ5 406 1.0075 1.4810 27.18 11 BUT-p-N ^ 27 ^ 44θ5 448 .9963 1.4872 89.13 12 BUT-OSECBUT ^ 22 ^ 34θ5 378 1.0282 1.4884 34.64

Slow crystallization tendency over time.

Table 2

Values of tests for assessing the qualities of polymer processing aids, respectively, plasticizer and lubricant

Nr. crt. Characteristic Adipate code TCS, ° C Maximum torque from the Brabender plastogram, N.m Lubrication figure c _L 1 iso 13-p-N * 163-165 17.66 13.39 2 iso 13-OSECBUT 145-148 25.50 10.41 3 iso 13-FE 140-141 31.39 11.71 4 iso 10-p-N 155-158 22.56 8.11 5 iso 10-OSECBUT 140-141 35.80 7.97 6 iso-10-FE 126-128 37.77 9.61 7 2EH-p-N 156-159 23.54 - 8 2EH-OSECBUT 141-142 34.33 - 9 HEX-p-N 147 26.00 - 10 HEX-OSECBUT 133-135 35.32 -

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Table 2 (continued)

Nr. crt. Characteristic Adipate code TCS, 'C Maximum torque from the Brabender plastogram, N.m Lubrication figure c _L 11 BUT-p-N 147-149 26.00 - 12 BUT-OSECBUT 136-138 34.58 - 13 DO A, di-2-ethyl hexyl adipate ** 134-135 26.49 -

* Net character of lubricant ** Dz-2-ethyl hexyl adipate, considered as a comparison term

Table 3

Representative tribological parameters

Nr. crt. Parameter Adipate code Kinematic viscosity, mm ² / s Index of viscozitat e Flash point,' C Point of flow, 'C 40 ° C 100 ° C 1 iso 13-p-N 52.00 7385 102 238 <-42 2 iso 13-OSECBUT 22.71 4365 99 224 <-42 3 iso 13-FE 49.37 6648 82 202 - 4 iso 10-p-N 19.46 3957 96 225 <-42 5 iso 10-OSECBUT 15.12 4087 186 212 <-42 6 iso-10-FE 16.80 3575 88 202 - 7 2EH-p-N 45,62 6288 79 220 -39 8 2EH-OSECBUT 19.75 3930 87 215 <-42 9 HEX-p-N 35,90 5563 88 216 -39 10 HEX-OSECBUT 15:28 3376 87 210 <-42 11 BUT-p-N 43.12 6067 79 208 -39 12 BUT-OSECBUT 17.72 3623 76 two hundred <-42 13 DOA, d / -2-ethyl adipate hexyl * 8.12 2381 113 142 <-42

* DOA, d / -2-ethyl-hexyl adipate, considered as a comparison term

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Table 4

Lubrication properties (4-ball machine test)

Nr. crt. Parameter Adipate code Non-additive oil Additive oil dia- meter patch of Wear, mm 40 daN / 60 min Welding, daN with 1.5% zinc dithiophosphate by 1.5% ash-free dithiocarbamate Diame- ter Wear stain, mm 40 daN / 60 min Welding, daN Diame- ter Wear stain, mm 40 daN / 60 min Welding, daN 1 iso 13-p-N 0.95 130 0.50 140 0.80 160 2 iso 13-OSECBUT 1.02 120 0.49 140 0.80 160 3 iso 13-FE 1.04 160 - - 1.10 160 4 iso 10-p-N 1.12 120 0.40 160 0.90 170 5 iso 10-OSECBUT 1.30 120 0.43 140 0.90 160 6 iso-10-FE 1.07 160 - - 1.05 160 7 2EH-p-N 1.05 150 0.50 160 0.90 180 8 2EH-OSECBUT 1.30 150 0.60 150 0.88 170 9 HEX-p-N 1.20 150 0.57 150 0.70 180 10 HEX-OSECBUT 1.15 150 0.38 150 0.95 170 11 BUT-p-N 1.03 150 0.40 150 0.83 170 12 BUT-OSECBUT 1.05 150 0.40 150 1.00 170 13 DOA, d / '- 2-ethyl adipate hexyl 1.20 two hundred - - 1.30 190

DOA, d / -2-ethyl hexyl adipate, considered as a comparison term

Claims (2)

1. Asymmetric adipose diesters, used for polymer processing, defined by the general formula 3 R ₁ OOC- (CH ₂ ) ₄ -COOR ₂ characterized in that the radical R! is an n-butyl, n-hexyl, 2-ethyl-hexyl, isodecyl 7 and isotridecyl radical, R ₂ is a radical with an aliphatic-aromatic type structure of the form: wherein R ₃ = H, o-secbutyl and / or p-nonyl, has critical solvation temperatures 13 of 126 ... 156 ° C, the maximum torque in the Brabender plastogram 22.56 ... 37.77 Nm, figure lubrication 8.11 ... 13.3, diameter of the wear stain 0.38 ... 1.40 mm, 15 flow temperature -39 ...- 42 ° C, ignition temperature 200 ... 238 ° C, viscosity index 76 ... 186. 2. Process for obtaining asymmetric adipose diesters, as defined in claim 1, in 17 successive stages, with the first obtaining a semiester and subsequently the corresponding asymmetric distention, under acid catalytic solution, characterized in that the 19 adipic acid is esterified, in the first step, with an alcohol selected from 2-phenoxyethanol, 2 - [(o-secbutyl) phenoxy] ethanol and 2 - [(p-nonyl) phenoxy] ethanol, under strict stoichiometry conditions, with 21 water extraction. reaction and obtaining the appropriate semiester, followed by the addition, in the second step, of aliphatic alcohol, selected from n-butanol, n-hexanol, 2-ethyl hexanol, 23 isodecanol and isotridecanol, with the extraction of the reaction water and the corresponding asymmetric diester being obtained, in the presence of an aromatic solvent selected from benzene, toluene or xylene, in an amount of 25 to 20% by weight of the reactants, in acid catalysis based on p-toluene sulfonic acid, in an amount of d is 1 ... 10% from the mass of the reactants, with the mixture of 27 reacting to reflux, the synthesis taking place within 5-7 hours, in which the blast temperature increases progressively, with the final addition of 0, 1 ... 1.0 moles of alcohol selected from ethanol, 29 n-propanol and n-butanol, additional reflux for 2 ... 4 h, stripping of excess solvent and lower alcohol to a blast temperature of 245 -255'C, the crude mass of 31 reaction being treated with dilute basic aqueous solutions of alkaline carbonates with a concentration of 1 ... 5%, then repeated washing with demineralized water to neutral pH, devolatilization in 33 vacuum to a temperature de blaz of 235-250'C and a residual vacuum of 3-8 mm col Hg, followed by hot discoloration, with activated carbon, and filtration. 35