SU1238132A1 - Oxidized atactic polypropylene with functional groups as polyfunctional lubricating oil additive - Google Patents

Description

I

The invention relates to the chemistry of polymers, specifically to new oxygen-containing derivatives of atactic polypropylene, and can be used in the chemical industry.

The aim of the invention is the synthesis of oxidized atactic polypropylene with functional groups, which can be used as a multifunctional lubricant additive in the petrochemical industry.

Example 1 30 g of atactic polypropylene (ALL) are loaded into a stirred reactor under a stream of nitrogen. The reactor is heated to 140 ° C and held at this temperature until the polymer is completely dissolved. The stirrer is turned on and 0.15 g (0.5%) of dicomyl peroxide HK is metered into the molten polymer. The temperature in the reactor was raised to 280 ° C and kept at this temperature for 1 hour. The reaction product was cooled to 20 ° C, 350 ml of heptane were added and stirred for 1.5 hours. The solution was decanted, separated from the insoluble precipitate by decantation and the solvent was distilled off. 28.7 g of thermally degraded ASH1 containing double bonds are obtained, with a mol.m. 15200, The product is oxidized with air oxygen in a stirred reactor at 240 ° C for 4.5 hours at an air flow rate of 6 ml / min. 28.0 g of a modified light-yellow polypropylene is obtained with a mol.m. 4500, viscosity 4.46 cSt at. The bromine oxidation number is 3.57 g, / 100 g, which corresponds to an unsaturation level of 1.03. The hydroxyl number is 34.9 mgKOH / G, which corresponds to K of 2.8. The content of carbonyl groups calculated from the integrated intensity of the peak at 1720 cm in the IR spectra is 0.93%, which corresponds to I 1.5 and n 100.3.

Found,%: C 84.29; H 14.13; About 1.40.

Calculated: C 84.48; H 14.02; About 1.53.

Example 2. The experiment was carried out similarly to Example 1, except that the thermal destruction was carried out at 280 ° C in the presence of 0.2% PC, and the oxidation was carried out for 4.5 hours and the air flow rate was 6 ML / MIN: g. A polymer is obtained with a mol.m5, viscosity of 4.68 cSt at.

five

 5 20 30 35 0, 5

50

55.

238132X

The content of carbonyl groups is 0.56%, which corresponds to f. 1.0 Bromine number of oxidation product 1.92 g /

/ 100 g, Hydroxyl number of 22.5 mg KOH / G, which corresponds to V 0.6 and k 2.0. The resulting substance has h 113,9.

Paydeno,%: C 85.03; H 14.10; About 1.07.

Calculated: C 84.92; H 14.12, O 0.96.

Example 3. The synthesis was carried out analogously to example 1, except that the thermal destruction was carried out at 260 ° C in the presence of 0.5% PC and oxidized at 220 ° C for 3.5 hours with an air flow rate of 4 ml / min . Get the product with the mol. 4900, viscosity 4.83 cSt at 100 C. The oxidation product contains 0.57% carbonyl groups, has a bromine number of 3.3 rBti / lOO g and hydroxyl number equal to 22.9 mg KOH / g, 4 that corresponds to: f 1.0; TI 1.0; h 1 11, 6; k 2,0.

Found,%: C 84.80; H 14.02; About 1.06.

Calculated: 84.91; H 14.11; About 0.98. (Example 4. The experiment was carried out analogously to example 1, except that the thermal decomposition was carried out in the presence of 0.2% PC and was oxidized for 3.5 hours. The product was obtained at a molar of 4650 and containing 0 , 90% of carbonyl groups, bromine: the number is 2.03 g g, the hydroxyl number is 33.9 mg KOH / G, which corresponds to: f 0.6, k 2.8, n 104.2, E 1.5.

Found,% About 1.55.

Calculated O 1.48.

Example 4a The test was carried out analogously to Example 4, except that the extraction was carried out with heptane at 30 ° C. Product feature is identical.

Example 4S. The test was carried out analogously to Example 4, except that the extraction was carried out with benzene at 25 ° C. Product feature is identical.

Example 46. The experiment was carried out analogously to example 4, except that the extraction was carried out with chloroform at. The characteristic of the product is identical.

C 84.67; H 14.22; C 84.48; H 14.04;

Example 5. The synthesis was carried out analogously to Example I, except that the thermal destruction was carried out at 260 ° C in the presence of 0.5% tert-butyl peroxide. The product is obtained from mol.m. 4700, containing 0.77% carbonyl groups, a bromine number of 2.72 g of Br / 100 g, a hydroxyl number of 31.0 mg KOH / g, which corresponds to fT 0.8; , 6; P 1,3; 1 105.8,

Found,%: C 84.40; H 14.23; About 1.25.

Calculated: C 84,61; H 14.06; About 1.33.

Example 6 (prototype), In the reactor with a mixer load 30 g of the APP with mol.m. 38000, melted at 40 ° C and oxidized for 2.5 hours and an air flow rate of 150 ml / min. Receive 28.3 g of modified APP with mol.m. 23700 containing 0.3% carbonyl groups, which corresponds to 2.5 groups per polymer macromolecule. According to the results of iodometric titration, oxidized polypropylene contains 1.63% hydroperoxide groups (11.7 groups per mole). According to the results of ozonation on the device of the ADS-4, the resulting product does not contain double bonds. Hydroxyl and carboxyl groups were not found in the product. The resulting product is practically insoluble in MS-8 oil and partially soluble in heptane. For the tests, the oxidized APP fraction with mol.m. 6800, obtained by sequential deposition of the polymer from the solution in heptane with alcohol.

The number of double bonds is determined on an ADF-4 instrument and according to the Kaufman-Baltes method. The content of hydroperoxide groups in the samples is determined by the odometric method, and the amount of carboxyl. groups - by titration with an alcohol solution of alkali. The amount of hydroxyl groups at the secondary carbon atom is determined by the standard procedure by acylation with acetic anhydride in pyridine.

Based on the data of elemental analysis, the determination of molecular weight, IR and NMR spectra, the structure of the compounds obtained is confirmed.

Research institute

In the IR spectrum there are peaks in the range of 1,200 and 1,280 cm, which in

5 o

S

0 5 0

0 5 0

five

in combination with a broad band of 3,200–3,350 (maximum of 3,280) cm, confirm the presence of a hydroxyl group. The NMR-H spectrum of the oxidation product recorded on a device with an operating frequency of 100 MHz contains chemical shifts of protons in the region of 4.26 and 4.79 MD, corresponding to the protons of the hydroxyl and CH groups with terminal double bonds.

The thickening ability (P of the synthesized samples in relation to the basement of the MS-8 oil is determined at temperatures of 50 and 100 ° C, the concentration of the additive is 5 wt.%. The viscosity index (IV) of the oils is determined by the known nomogram. Tests for thermal-oxidative stability for fretting, corrosion oxidation is carried out by a well-known method in a flow reactor for 5 h at 165 ° C in the presence of copper element, the additive concentration in oil is 10%. The accumulation of oil oxidation products was monitored by changing the optical density at 440 them.

Mechanical destruction of the 10% solution of the additive in MS-8 oil is carried out on an ultrasonic low-frequency dispersion device UZDN-1 at an operating frequency of 35 kHz at 100 ° C for 30 minutes. Determination of the thermal stability of the oil with additives is carried out by heating the sample at 200 ° C for 12 hours. The resistance to mechanical destruction is characterized by the resistance of the viscosity of the thickened oil.

Table 1 shows the thickening properties of additives in MS-8 oil. B.2 - thermo and mechanical destruction of thickened oils, as well as antioxidant activity of additives.

The test results confirm the positive effect of the proposed substance when using MS-8 oil.

The resulting oxidized atactic polypropylene with functional groups is a light yellow, viscous liquid with a spe- has a glass transition temperature of 54 ° C. According to thermogravimetric analysis, the resulting product has a decomposition start temperature of 280-285 ° C.

Thus, the proposed polypropylene with functional groups has the best antioxidant

S12381326

properties, high resistance to a sufficiently high complex, thickened thermo- and mechanical destruction and retains these properties.

Table 1

Substance by example

Claims (1)

Oxidized atactic polypropylene with functional groups of the general formula sn; R Sn ₃ 1 “ ch ₂ = s - -CH-CHI -sn ₂ -sn- -sn ₂ -s-sn ₃ t ¹ he to η ^and 0 where n> = 0.6-1.0; K = 2.0-2.8; l = 100,3-113,9; ^c = 1.0-1.5 with mol.m. 4500-5000 as a multifunctional lubricant additive. 1238132 <1238132