SU753853A1 - Nitrogen-containing oligoisobutylene as viscous additive to libricating oils and its preparation method - Google Patents

Description

The invention relates to the synthesis of lubricant additives, in particular to the preparation of nitrogen-containing oligoisobutylene. Polyisobutylene is known as a flj lubricant. Polyisobutylene, in addition to instability to mechanical destruction, gives thickened oils not sufficiently high heat and temperature characteristics. The known oligoisobutyl with terminal carboxyl and ketone groups, which is closest in structure to the new compounds, is also used as a viscosity additive for lubricating oils. The indicated properties are achieved by a new molecular structure of the additive having the eating formula: O —C — CHiClf2 — CHg-d-R where (CH2) m NHj, m-2-5-6; -HN f Ng R-NH (CK2) mNH2,

However, these oligomers are not sufficiently thermostable and slope to mechanical destruction.JJJ

The aim of the invention is to improve the thermal to mechanical stability of the viscosity additive based on oligoisobutylene.

W2,) w / 7i / CHj

prk p - 2O-6O, such nitrogen-containing oligoisobutylene can be obtained by treating oligoisobutylene with terminal carboxyl groups with aliphatic or aromatic amine or diamine at 115: 200 ° С. Oligomers of this formula have a molecular weight of 1500-5OOO, have thickening properties and anti-scoping properties, and can be used as thickening agents: they can reduce the composition of their auxiliary thermal stability, anti-oxidative and mechanical stability, and the amount of their components; em approximately 5-2O weight,%. The method of producing nitrogen-containing oligoisobutylene consists in the condensation of bi-or monofunctional oligo-isobutylene carboxylic acids with organic di- or monoamines in bulk at a temperature of 115-2OO C in an inert atmosphere. In the preparation of nitrogen-containing oligoisobutylene, low molecular weight organic di- or monoamine is taken in excess with respect to oligoisobutylenecarbonic acid to prevent the reaction of H2N- (CH2) 6-NH-C- (H- (CH2-C -) - - CH2-C-W ( CH2) b-KN2,

SNS SNZ

Where

EXAMPLE 2 The experiment is carried out analogously to Example 1, except that 100 g of oligoisobutylene with terminal carboxyl groups and 71.38 g of aniline are taken into the reaction. The reaction is carried out at

175 ° C. The resulting product has a molecular weight of 1986.

Calculated,%: C 82.77; H 14.22; M 1.41: Found: C 82.05: H 14.00; bi 1.39. The product has the formula: 34 polycondensation. Cybo-isobutylene Carboxylic acids are obtained by ozonating in hexane a copolymer of isobutylene with piperylene (bifunctional acids) or a copolymer of isobutylene with isoprene (monofunctional acids). Example 1. In a three-neck flask equipped with a stirrer, a DinaStark nozzle and a reflux condenser, 60 g of oligoisobutylene with xycetic carboxyl groups (DECG) and a molecular weight of 20OO and 61.8 g of hexamethylenediamine (HMDA) are placed. The reaction mass is heated to 180 ° C and is reacted with stirring and purging with argon for 6 hours while removing the separated water from the reaction zone. Unreacted hexamethylenediamine is removed by vacuum distillation. The resulting product has a molecular weight of 3215. Calculated,%: C, 83.98; H 13.29; N1.74. Found,%: C 82.65; H 13.46; N1.76. The product has the formula:

ABOUT

II

C-CH CCH2-C-) tt-CH2-C-SH JI

CH:

SNS

ABOUT

where P is 30, the properties of the obtained oligomers compared to the known additives are presented in Table. 1-3. The data of thermogravimetric analysis are determined on a derivator of the F. Paulik system. The oxidation of the oil is determined by the absorption of oxygen by the oil in the closed system for 60 min. TermodestruktUktsii oils, thickened with additives studied at 2OO C for 12 hours. Mechanodestruction is carried out on an ultrasonic low-frequency disperser at 50 ° C with an operating frequency of 22 kHz for 20 minutes. PRI me R 3. In the three-neck flask. equipped with a stirrer, a Dean nozzle. Starck, and a reflux condenser are placed 80 g of oligoisobutine with terminal carboxyl groups - (QdKi)

where n 21.

Example 4: The test was carried out analogously to Example 3, except that 80 g of oligoisobutane with terminal carboxyl groups and 28 g of diethylenetriamine (DETA) were taken into the reaction. The reaction is carried out at. The reaction product is washed from unreacted polyethylenestuffs with isopropyl alcohol. The resulting product has a molecular weight of 5123.

ABOUT

H2N- (CH2) 2-TJH-C-CH CHfCCHi

Calculated,% (well, according to diethylenetriam):

C 84.3; H 14.1; N 1.6.

Found,%: C 79.6; H 13,, 8.

EXAMPLE 5 The experiment is carried out analogously to Example 3, except that 80 g of opigoazobutylene with terminal carboxyl groups and 33 g of ethylenediamine (3QA) are taken into the reaction. The reaction is carried out at 115 ° C. The resulting product has. molecular weight 1989.

Calculated: C 82.2; K 1O, 65; M2.8.

Found,%: C 80.9, H 13.6, N 1.69. The product has the formula:

ski

about

- CH2-C-7 "H - (((1H2)

sn,

P

where

Antioxidant activity of additives in diisosilicladipate

Additive

Opigoisobutylene with carboxyl groups

Oligokzobutklen on the basis of OIKG and FDA

Oligoisobutylene based on OIKG and PZPA

Opikoizobutylene on the basis of OICT and ELA

The drop in barometric pressure during oxidation in 18O min at, mm Hg. when the concentration of the additive 3/10, wt.%

74/52

48/28 59/55 6J / 56 775 Example. In a three-necked flask equipped with a stirrer, a DinaStark nozzle with a reflux condenser, 80 g of oligoisobutylene with carboxylic and ketsnnyh groups with a molecular weight of 2340 and containing 0.75% of carboxyl groups () and 11.7 g of aniline are placed. The reaction mass is heated to 175 ° C and the reaction is carried out with stirring and purging with argon for 6 hours while removing the precipitated water from the reaction zone. Unreacted aniline is removed by vacuum extraction. The product obtained has a molecular weight of 2430 and the formula:

Heat Resistance Additives

Oligoisobutylene with terminal carboxyl groups

Syoizobutylene based on HECA and HMDA Oppoisobutylene based on HECA and aniline Antioxidative activity of an additive in oil

Additive

with terminal carboxyl-based OICG

based on HFG

Table 1

Decomposition temperature, ° С

end

38О 450 440

Barometric pressure drop during oxidation in 60 minutes at 2OO C, mm Hg, at an additive concentration of 3/10 mass%

6О / 55 47/22

43/26 60 | jNH-C-CH (cHj-C -) - CH, C-CH, CHjСН where П «4 О Calculated,: С 84.44; H 10.41; BUT, 54. Found,%: C 83.98; H 10.23; N0.52. As can be seen from the tables, nitrogen-containing oligoisobutylene has good thickening properties. In addition, the presence of nitrogen-containing groups provides the best antioxidant properties and increased resistance to thermo-mechanical destruction in comparison with oligoisobutylene with terminal carboxyl and ketsnN1,1MI groups. T0 Face 2 based on 1/6 of Balakhonskaya

9753853

Drop in viscosity of oils on the basis of 1/6 of Balakhonskaya, thickened with additives during thermal and mechanical destructions

MoleculeIndex l vis viscosity mass.

4OOO

149

3215

137

148

1986

1O

Table 3

Claims (2)

Claim Nitrogen-containing oligoisobutylene, formulas About SNZO II I ¹¹ 1 k-s-sn- (sn ₂ - ¢ -% CH ₂ - CR, II CHs CHs where K-YAN ((EDLN _{2 7} where nz = 2 ^ 6 -14 or -UN or CH ₃ at Ή -20-60 as a viscosity additive for lubricating oils, 2. The method of producing nitrogen-containing oligoisobutylene according to paragraph 1, which consists in processing oligoisobutylene with terminal carboxyl groups with an aliphatic or aromatic amine or diamine at 115-200 ° C.