RU2237053C1 - Method for stabilization of chlorinated hydrocarbons - Google Patents

Abstract

FIELD: technology of organic synthesis.

SUBSTANCE: invention relates to a method for stabilization of chlorinated hydrocarbons. Stabilization of liquid chlorinated hydrocarbons of fraction C₁₄-C₃₂ with the chlorine content 24-55 wt.-% is carried out by addition of stabilizing mixture taken in the amount 10 wt.-% of chlorinated hydrocarbons to be stabilized. Stabilizing system comprises epoxy-diane resin, 2,6-di-tert.-butyl-4-methylphenol, hexamethylenetetramine and chlorinated hydrocarbons of fraction C₁₄-C₃₂ in the following ratio of components, wt.-%: epoxy-diane resin (sort ED-20, ED-16) : 2,6-di-tert.-butyl-4-methylphenol (ionol) : hexamethylenetetramine of fraction C₁₄-C₃₂ (urotropin) = (10-20):(0-3): (0-0.02):(80-90), respectively. Method provides enhancing stability of goods product, prevention of equipment corrosion caused by hydrogen chloride.

EFFECT: improved stabilizing method.

1 tbl, 10 ex

Description

The invention relates to organic synthesis technology, in particular to a method for stabilizing chlorinated hydrocarbons with a chlorine content of 24-55 wt.%, Obtained by chlorination of waste from the production of oligomerization of ethylene - α-olefins fraction C ₁₄ -C ₃₂ . In practice, these wastes do not find qualified use. Hydrocarbon fractions of the C ₁₄ -C ₃₂ fraction are multifunctional additives to polymeric materials, possessing the properties of a secondary plasticizer and a lubricant. However, they are characterized by low thermal stability.

The destruction of chlorinated hydrocarbons is caused by energy influences: temperature and light. The preferred direction of destruction is the elimination of hydrogen chloride, which is accelerated in the presence of metal salts of variable valence: iron, copper, etc. (Korotkevich S.Kh., Pimenov I.F., Golfand E.A., Sokolovskaya N.G., Zaydman O .A. Methods of obtaining and the scope of application of chloroparaffins in capitalist countries // KP abroad. - 1975. - No. 7. - S.80-88).

A known method of stabilizing chlorinated, mainly linear C ₇ -C ₃₅ paraffins with a chlorine content of 10-72% by adding 0.1-3% (based on paraffin) of fatty aminoxyethylate (Germany, application No. 3928319. Method for stabilizing chlorinated paraffins. Declared 26.08 .89. Published on 02.28.91).

The disadvantage of this method is the use of inaccessible stabilizer.

A known method of stabilizing lower aliphatic chlorocarbons from decomposition by introducing a stabilizing agent containing phosphites: (RO) ₃ P, where R is C ₃ -C ₈ -alkyl, C ₆ -C ₁₀ aryl, together with acid phosphites (RO) ₂ RN (O), where R is lower alkyl, phenyl, higher C ₁₂ -C ₁₆ alkhenyl with a weight ratio of 4-19: 1 and a stabilizing agent concentration of 0.1-5% by weight of chlorohydrocarbon (AS No. 743986 USSR, MKI C 07 C 17/42 Method of stabilization of lower aliphatic chlorohydrocarbons / N. A. Mukmeneva, P. A. Kirpichnikov, V. Kh. Kadyrova, A. G. Liakumovich, D. N. Ziyatdinova, P. V. Ve Shinin, S.I. Agadzhanyan, A.S. Ikhsanov, V.P. Vasiliev, Yu.D. Morozov, M.V. Vagapov, L.V. Verizhnikov. — Publish. 30.06.80, Bulletin No. 24. )

The disadvantage of this method is the use of inaccessible stabilizer.

A known method of stabilizing lower aliphatic chlorocarbons from decomposition by introducing a stabilizing agent containing a phosphoric acid ester: (RO) ₃ PO, where R is ethyl, butyl, cresyl; together with glycerin in the following components, calculated on stabilized chlorohydrocarbon, wt.%:

Phosphoric ester 0.01-0.50

Glycerin 0.01-0.50

The disadvantage of this method is the use of inaccessible stabilizer.

Closest to the claimed invention in technical essence and the expected effect is a method of stabilizing chlorinated paraffins with various epoxy resins (ED-20 and ED-16). The effectiveness of stabilizing compounds was evaluated by the amount of released HCI for 4 hours at 175 ° C (A.A. Molchanov, S.Kh. Korotkevich, N.F. Krishtal. Stabilization of chloroparaffins // Inf. Bulletin for Chemical Industry CMEA. - 1989 . - No. 4. - S.48-52. - Rus.).

The disadvantage of this method is the low thermal stability.

The objective of the invention is to develop an effective stabilization method for chlorinated hydrocarbons. When carrying out the invention, a technical result can be obtained, which is expressed in the possibility of:

- obtaining a marketable product with high thermal stability;

- in preventing corrosion of equipment caused by hydrogen chloride released during the decomposition of chlorohydrocarbons fraction C ₁₄ -C ₃₂ .

To increase thermal stability, a stabilizer is introduced, which is a complex system including an antioxidant - ionol (2,6-di-tert-butyl-4-methylphenol), for the binding of transition metals - urotropin (hexamethylenetetramine) and a hydrogen chloride acceptor - epoxy resin (brand ED -20, ED-16), in the following ratio, wt.%:

Epoxy resin

brands ED-20, ED-16 10-20

Ionol 0-3

Urotropin 0-0.02

Hydrocarbons С ₁₄ -С ₃₂ 80-90

The stabilizing system is prepared by mixing the components in a stream of nitrogen at 40-50 ° C until complete dissolution. Stabilization is carried out by adding to the reactor a stabilizing system in an amount of 10% by weight of the C ₁₄ -C ₃₂ fraction of hydrocarbons and stirring at a temperature of 40-50 ° C in a stream of nitrogen for 0.5 hour. The method is confirmed by examples.

Example 1

The stabilizing system, consisting of 1.48 g (10 wt.%) Of epoxy resin ED-20 and 13.32 g (90 wt.%) Of chlorohydrocarbons of fraction C ₁₄ -C ₃₂ , is prepared by mixing the components in a stream of nitrogen at 40-50 ° C to complete dissolution. 148 g of C ₁₄ -C ₃₂ fraction chlorohydrocarbons (chlorine content of 45.6 wt.%, Mass fraction of acids in terms of HCl 0.0003 wt.%, Mass fraction of iron 0.0013 wt.%) Are charged into the reactor, and 14, 8 g of stabilizing system. Stabilization is carried out at 40-50 ° C in a stream of nitrogen for 0.5 hours. The effectiveness of stabilizing compounds was evaluated according to TU 6-01-16-90 by the amount of released HCl for 4 hours at 175 ° C.

Example 2

Analogously to example 1, a stabilizing system is prepared by mixing 2.22 g (15 wt.%) Of epoxy resin ED-20 and 12.58 g (85 wt.%) Of chlorocarbons fraction C ₁₄ -C ₃₂ .

Example 3

Analogously to example 1, a stabilizing system is prepared by mixing 2.96 g (20 wt.%) Of epoxy resin ED-20 and 11.84 g (80 wt.%) Of chlorocarbons fraction C ₁₄ -C ₃₂ .

Example 4

Analogously to example 1, a stabilizing system is prepared by mixing 2.22 g (15 wt.%) Of epoxy resin ED-20, 0.296 g (2 wt.%) Of ionol and 12.284 g (83 wt.%) Of chlorohydrocarbons of fraction C ₁₄ -C ₃₂ .

Example 5

Analogously to example 1, a stabilizing system is prepared by mixing 2.22 g (15 wt.%) Of epoxy resin ED-20, 0.444 g (3 wt.%) Of ionol and 12.136 g (82 wt.%) Of chlorocarbons of fraction C ₁₄ -C ₃₂ .

Example 6

Analogously to example 1, a stabilizing system is prepared by mixing 0.00148 g (0.01 wt.%) Of urotropin and 14.79852 g (99.99 wt.%) Of chlorohydrocarbons of fraction C ₁₄ -C ₃₂ .

Example 7

Analogously to example 1, a stabilizing system is prepared by mixing 1.48 g (10 wt.%) Of epoxy resin ED-20, 0.00148 g (0.01 wt.%) Of urotropine and 13.31852 g (89.99 wt.%) Of chlorohydrocarbons fractions C ₁₄ -C ₃₂ .

Example 8

Analogously to example 1, a stabilizing system is prepared by mixing 1.48 g (10 wt.%) Of epoxy resin ED-20, 0.0074 g (0.005 wt.%) Of urotropine and 13.31926 g (89.995 wt.) Of chlorohydrocarbons of fraction C ₁₄ - C ₃₂ .

Example 9

Analogously to example 1, a stabilizing system is prepared by mixing 1.48 g (10 wt.%) Of epoxy resin ED-20, 0.296 g (2 wt.%) Of ionol, 0.0074 g (0.005 wt.%) Of urotropine and 13.0166 g ( 87.995 wt.%) Chlorocarbons fraction C ₁₄ -C ₃₂ .

Example 10

Analogously to example 1, a stabilizing system is prepared by mixing 2.96 g (20 wt.%) Of epoxy resin ED-20, 0.296 g (2 wt.%) Of ionol, 0.00148 g (0.01 wt.%) Of urotropine and 11.54252 g (77.99 wt.%) of chlorocarbons fraction C ₁₄ -C ₃₂ .

The data of examples 1-9 are summarized in table.

The proposed stabilization method allows to obtain a stabilizing effect, in its action exceeding the action of individual components (examples 1-3 and 6). The proposed method in its intensity significantly exceeds the known.

Claims (1)

The method of stabilization of liquid chlorinated hydrocarbons fraction C ₁₄ -C ₃₂ with a chlorine content of 24-55 wt.%, Which consists in the introduction of a stabilizing mixture in an amount of 10 wt.% From stabilized chlorohydrocarbons containing epoxy resin, 2,6-di-tert-butyl- 4-methylphenol, hexamethylenetetramine and chlorohydrocarbons fraction C ₁₄ -C ₃₂ in the following ratio, wt.%: Epoxydian resin brand ED-20, ED-16 10-20 2,6-di-tert-butyl-4-methylphenol (ionol) 0-3 Hexamethylenetetramine (urotropin) 0-0.02 Hydrocarbons fraction C ₁₄ -C ₃₂ 80-90