CS259250B1 - 1,6-Dioxa-9,9,11,11-tetramethyl-10-azaspiro [6,5] dodecene-3 and its preparation - Google Patents

Abstract

The solution relates to 1,6-dioxa-9,9,11,11- -tetramethyl-10-azaspiro- [6,5] dodecene-3 of formula I and a method for its preparation, which consists in reacting 2,2,6,6- -tetramethyl-4-oxopiperidine of formula II with 2- -butene-1,4-diol of formula III at the reflux temperature of a hydrocarbon solvent that forms an azeotropic mixture with water, such as benzene, toluene or xylenes, in the presence of an acid catalyst, such as 4-toluenesulfonic acid. The compound of formula I has use as a light stabilizer for polymers.

Description

The present invention relates to 1,6-dioxa-9,9,1,1,11-tetramethyl-10-azaspiro [6,5] dodecene-3 and a process for its preparation.

Sterically shielded amines are currently among the most effective light stabilizers for polymers (FE Karrer, Makromol. Chem., 181, 595 (1980), F. Gugumus, Developments in Polymer Stabilization-1, edited by G. Scott, Applied Science Publishers, London , 1979, Chapter 8, JJ Usilton, AR Patel, Am. Chem. Soc., Polym Prep., 18 (1), 393 (1977)).

They are various derivatives of 2,2,6,6-tetraalkylpiperidine, 1,2,2,6,6-pentaalkylpiperidine, 2,2,6,6-tetraalkylpiperazine or 7,15-diazadispiro [5,1,5,3] hexadecane.

These compounds inhibit undesirable degradation processes that occur in the interaction of light and oxygen with polymers. A disadvantage of this class of light stabilizers is the high volatility and extractability of low molecular weight derivatives from polymers. The compound of the invention contains a functional unsaturation in its molecule.

The presence of this group in the light stabilizer molecule allows the preparation of high molecular weight light stabilizers by polymerizing an unsaturated bond, or copolymerizing it with other unsaturated monomers. This compound has not been previously described in the literature.

The present invention provides 1,6-dioxa-9,9,11,11-tetramethyl-10-azaspiro [6,5] dodecene-3 of formula I

CH ·, ³ \

Η-Γ

CH3

CH

CH

O-CH ₂ -CH ₂ O-CH ₂ -CH (I)

The present invention provides a process for the preparation of a compound of formula I, characterized in that 2,2,6,6-tetramethyl-4-oxopiperidine of formula II ch ₃ .

, ch ₂ hi

CHg ΌΗ 3 (IX) is reacted with 2-butene-1,4-diol of formula III

HO-CH ₂ -CH = CH-CH ₂ -OH (III) at a low flow temperature of a hydrocarbon solvent which forms an azeotropic mixture with water such as benzene, toluene or xylenes in the presence of an acid catalyst such as 4-toluenesulfonic acid.

Example 1

To a flask equipped with an azeotropic water separator and a reflux condenser was charged 31.05 g (0.2 mol) of 2,2,6,6-tetramethyl-4-oxopiperidine, 41.84 g (0.22 mol) of 4- toluene sulfone H2O and 300 ml toluene. The reaction mixture was heated at reflux for 0.5 hours, separating the crystal water from the acid and the moisture from the system. At the same time, the acid salt of the piperidine derivative is formed. Then, 19.38 g (0.22 mol) of 2-butene-1,4-diol is added and the reaction mixture is refluxed until the theoretical amount of water is precipitated (4 hours).

After cooling, the reaction mixture is poured into 200 ml of 20% cold aqueous sodium hydroxide solution and shaken well. The organic layer was separated, washed with water and brine and dried over anhydrous sodium sulfate. Toluene was distilled off in a vacuum rotary evaporator to give a yellowish crystalline solid (42 g, 93%).

The product is purified by distillation under reduced pressure and a fraction is collected at a temperature range of 90 to 92 ° C at a pressure of 66.7 Pa, which solidifies to a crystalline substance with a melting point of 64-66 ° C.

Elemental analysis for C ^ HjjN NCO ^:

Calculated: C = 69.29%, H = 10.29%, N = 6.22%

Found: C = 69.21%, H = 10.12%; N, '6.09%; ^H NMR (chcípnu:

A (PPm) = 1.02 (S, -CH ₃ , 12H) 1.48 (s, -CH ₃ -, 4H), 4.05 (d, -CH ₂ -O-, 4H, J = 2 Hz) ,.

5.48 (t, -CH =, 2H, J = 1.5Hz)

Example 2

The procedure was as in Example 1 except that the solvent used was a mixture of xylenes boiling in the range of 137-140 ° C. The reaction time is 3 hours. Yield: 42.4 g (93% of theory);

Example 3

100 parts by weight of unstabilized powdered polypropylene are impregnated in dichloromethane with 0.1 wt. parts by weight of 2,6-di-tert-butyl-4-methylphenol, 0.15 wt. % of calcium stearate and 0.2 wt. After evaporation of the solvent, 0.2 mm thick sheets are pressed from the mixture at 20 MPa at 190 ° C for 3 minutes. The films thus prepared are irradiated with a 125 W mercury lamp at a distance of 7 cm from the source.

The degradation of the polymer is monitored by the development of the carbonyl band in the infrared spectra. While the time of reaching the carbonyl index of 0.2 for pure polypropylene is 240 hours, the stabilized polymer does not reach this value until 1,720 hours.

Claims (2)

3 259250 sodium and good shaking. The organic layer was separated, washed with water and brine and dried over anhydrous sodium sulfate. The toluene was distilled off in a vacuum rotary evaporator to give a yellowish crystalline solid (42 g, 93% of theory). The product is purified by distillation under reduced pressure and a fraction at 90-92 ° C is collected at a pressure of 66.7 Pa, which solidifies to a crystalline material with a temperature of 64-66 ° C. Elemental analysis for C ^ HHj ^N ^O:: Calculated: C = 69.29%, H = 10.29%, N = 6.22% Found: C = 69.21%, H = 10.12%, N « 6.09% 1H NMR spectrum (CHCl 3: A (PPm) = 1.02 (S, -CH 3, 12H), 1.48 (s, -CH 3 -, 4H), 4.05 (d, -CH 2 --O- , 4H, J = 2 Hz), 5.48 (t, -CH =, 2H, J = 1.5 Hz) Example 2 The procedure is as in Example 1 except that xylenes with a temperature of The reaction time is 3 hours, 42.4 g (93% of theory) of the crude product is obtained Example 3 100 parts by weight of unstabilized polypropylene powder are impregnated with dichloromethane with 0.1 parts by weight of 2.6 -di-tert-butyl-4-methylphenol, 0.15 wt.% calcium di-stearate and with 0.2 wt .-% of the compound prepared according to Example 1. Evaporation of the solvent from the mixture is pressed to a film thickness of 0.2 mm at a pressure of 20 MPa and temperature of 190 ° C for 3 minutes The films thus prepared are irradiated with a mercury lamp The performance of the polymer is monitored by the evolution of the carbonyl band in the infrared spectra. While the carbonyl index of 0.2 "in pure polypropylene is 240 hours, the stabilized polymer reaches this value after 1720 hours. SUBJECT TO 1. 1. 1,6-dioxa-9,9,11,11-tetramethyl-10-azaspiro [6,5 | dodecene-3 of formula 1 CH 3 (CH 3 / O-CH 3 -CH 3 -X 1 -X-o-ch 2 -CH 3 CH 3 (I)) 2. A method for preparing 1,6-dioxa-9,9,11,11-tetramethyl-10-azaspiro [beta], [delta] dodecene-3 of formula I according to claim 1, wherein the 2,2,6,6-tetramethyl -4-oxopiperidine of formula II CH 3 CH 3 O (IX) 259250 is reacted with 2-butene-1,4-diol of formula III HO-CH 2 -CH = CH-CH 2 -OH (III) at the hydrocarbon solvent low flux temperature which forms azeotropes with water such as is benzene, toluene or xylenes, in the presence of an acid catalyst such as 4-toluenesulfonic acid, until a theoretical amount of reaction water is formed. Severografia, n. P., MOST Price 2; 40 Kcs