CS254696B1 - 3,3-bis (chloromethyl) -1,5-dioxa-8,8,10,10-tetramethyl-9-azaspiro [5,5] undecane and its preparation - Google Patents

Abstract

The solution relates to 3,3-bis(chloromethyl)-1,5--dioxo-S.S.lOjlO-tetramethyl-O-azaspiro[5,5]-undecane of formula I and the method of its preparation, which consists in reacting 2,2,6,6-tetramethyl-4-oxopiperidine of formula II with 1,3-dichloro-2,2-dihydroxypropane of formula III at reflux 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. The compound of formula I is used as a light stabilizer for polymers and for the preparation of polymeric light stabilizers by polycondensation reactions, the preparation of polyethers, polythioethers, polyesters or polycarbonates.

Description

254636

The invention relates to 3,3-bis (chloromethyl) -1,5-dioxa-8,8, -0,10-tetramethyl-9-azaspiro [5.5] undecane and to a process for its preparation.

The sterically hindered amines are currently the most effective light stabilizer for polymers [FE Karrer, Makromol. Chem., 181, 595 (1980), JJ Usilton, ARPatel, Amer. Chem. Soc. Polym. Prep., 18 (1), 393 (1977), F. Guguinus, Developments Polymer Stabilization-1, ed. G. Scott, App. Svience Publishers, London, 1979, chap.8) Various derivatives of 2,2,6,6-tetraalkylpiperidine, 1,2,2,6,6-pentaalkylpiperidine, 2,2 , 6,6-tetraalkylpiperazine or 7,15-diaza-dispiro [5,1,5,3] hexadecane. These compounds inhibit the undesired degradation reaction that occurs in the photooxidation of polymers, especially polyolefins. The disadvantage of the light stabilizers of the sterically shielded amine class is their high volatility and the extractability of the utility polymers. By preparing the compound of the invention, the molecular weight of the stabilizer is increased, which reduces the volatility and extractability of the polymer stabilizer. At the same time, the presence of functional chloromethyl groups allows the preparation of polymeric stabilizers by polycondensation reactions, the preparation of polyethers, polytioethers, polyesters, and polycarbonate.

The subject of the invention is 3,3-bis (chloromethyl) -1,5-dioxa-8,8,10,16-tetramethyl-9-azaspiro [5,5] undecane of formula I. t. 0 - CH, z C m, - Cl-Cw, -Ci / 4- ó

The invention furthermore relates to a process for the preparation of compound I, characterized in that 2,2,6,6-tetramethyl-4-oxopiperidine of formula II

Tar Ch3 Η -M

XCG 5 (II 1

reacts with 1,3-dichloro-2,2-dihydroxymethylpropane of formula III H-O-CH 2 CH 2 -Cl

H — O — CH 2 CH 2 —C1 (III) at the low flux temperature of the hydrocarbon solvent which forms an azeotropic mixture with water such as benzene, toluene, or xylenes in the presence of an acidic catalyst such as 4-toluene sulfonic acid. Example 1

A 15.5 g (0.1 mSlu) of 2.2.6 6 6-tetrabethyl-4-oxopiperidine, 20 gi (0 g) is placed in a flask equipped with an azeo-tropical water separator and a poor condenser. 105 moles of 4-toluenesulfonic acid x. 1H2O and 200 ml of benzene. The reaction mixture was heated at the reflux temperature for 1 hour, separating the crystal water from the acid and the system moisture. At the same time, the acid salt and the piperidine derivative are formed. Then 17.3 g (0.1 mol) of 1,3-dichloro-2,2-dihydroxymethylpropane is added. The reaction mixture is further refluxed until a theoretical amount of water is eliminated in the azeotropic attachment. Then, the cooled reaction mixture was poured into cold 20% sodium hydroxide solution and well sprayed. The organic layer was separated, washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to give a solid cake (30 g, 97% of theory), which was recrystallized from hexane. The compound of formula (I) is obtained as a white crystalline solid, m.p. 86-87 ° C.

Elemental Analysis calculated for C14H25Cl2NO2: C, 54.19; H, 8.12; N, 4.51%. 1! C 54.25%, H 8.39%, N 4.42%. @ 1 H NMR Spectrum (CDCl3) .delta. (Ppm): 1.13 (b.s., CH3, 12H), 1.60 (s, - 2 -, 4H), 3.62 (s, --CH2 - Cl, 4H); 3.70 (s, -1CH2-O-, 4H). Example 2

The procedure is the same as in Example 1, except that a mixture of xylenes boiling in the range of 137-140 ° C is used as the solvent. 30 g (97% of theory) of crude product are obtained. Example 3 100 parts by weight of unstabilized polypropylene powder are impregnated in dichloromethane with 0.1 wt. parts of 2,6-di-tert-butyl-4-methylphenol, 0.15 wt. of calcium stearate and 0.2 wt. of the die compound prepared according to Example 1. Po

Claims (2)

Evaporation of the solvent from the mixture was compressed to a thickness of 0.2 mm at a pressure of 20 MPa and a temperature of 190 ° C for 5 minutes. The films thus prepared are irradiated with a mercury lamp 125 W at a distance of 7 cm from the source. The degradation of the polymer is monitored by the evolution of the carbonyl passage in the infrared spectra. While the carbonyl index of 0.2 in pure polypropylene is 220 hours, the stabilized polymer reaches this value after 1880 hours. PRED Μ ET 1. 3,3-bis (chloromethyl) -5-dioxa-8,8,10,10-tetramethyl-9-azaspiro [5,5] undecane of formula (I): In o-cu., Cm-c - - 2. The process for the preparation of 3,3-bis (chloromethyl) -1,5-dioxa-8,8,10,10-tetramethyl-9-azaspiro [5,5] -undecane of the formula I, step 1, characterized by wherein the 2,2,6,6-tetramethyl-4-oxopiperidine of formula (II) of the invention reacts with 1,3-dichloro-2,2-dihydroxymethylpropane of formula III H-O-CH 2 CH 2 -Cl H-O-CH 2 CH 2 -Cl (III) at the low flux temperature of the hydrocarbon solvent which forms with the water an azeotropic mixture such as benzene, toluene or xylenes, catalysed with 4-toluenesulfonic acid until the theoretical amount of the reaction is eliminated. water.