CS219192B1

CS219192B1 - Higher molecular light stabilizers based on aliphatic dicarboxylic acid esters and 2-hydroxy-1,3-disubstituted propane derivatives and processes for their preparation

Info

Publication number: CS219192B1
Application number: CS651681A
Authority: CS
Inventors: Frantisek Vas; Jozef Luston; Zdenek Manasek
Original assignee: Frantisek Vas; Jozef Luston; Zdenek Manasek
Priority date: 1981-09-04
Filing date: 1981-09-04
Publication date: 1983-03-25

Abstract

Vynález sa týká vyššiemolekulových světelných stabilizátorov na báze esterov alifatických dikarboxylových kyselin a 2-hydroxy-1,3-disubstituovaných derivátov propánu a spósobu ich přípravy, ktorý spočívá v tom, že sa na zlúčeniny typu 2-hydroxy-l,3-bis(7,15-diazadispiro-[5,l,5,3]hexadekán-14-16-dión-15-yl) propánu pósobí zlúčeninami typu dichloridu kyseliny šťavelovej v prostředí suchého organického rozpúšťadla v přítomnosti organickej bázy, ako napr. trietylamín, tri-nbutylamín, benzyldimetylamín, pyridin a pod. Význam vynálezu spočíváv prípravevyššiemolekulových světelných stabilizátorov piperazínového typu, ktoré majú nižšiu prchavosť a vypieratelnosť z polymérnych výrobkov, vyznačujúcich sa velkým povrchom oproti nízkomolekulovým látkám na báze stéricky tienených amínov.The invention relates to higher molecular weight light stabilizers based on esters of aliphatic dicarboxylic acids and 2-hydroxy-1,3-disubstituted derivatives of propane and a method for their preparation, which consists in treating compounds of the 2-hydroxy-1,3-bis(7,15-diazadispiro-[5,1,5,3]hexadecan-14-16-dion-15-yl) propane type with compounds of the oxalic acid dichloride type in a dry organic solvent environment in the presence of an organic base, such as triethylamine, tri-n-butylamine, benzyldimethylamine, pyridine, etc. The significance of the invention lies in the preparation of higher molecular weight light stabilizers of the piperazine type, which have lower volatility and leachability from polymer products, characterized by a large surface area compared to low molecular weight substances based on sterically hindered amines.

Description

The present invention relates to higher molecular weight stabilizers based on aliphatic dicarboxylic acid esters and 2-hydroxy-1,3-disubstituted propane derivatives which are substituted in the 1 and 3 positions with 7,15-diazadispiro (5,1,5,3) he. -xadecane-14,16-dione, of formula I 219192

wherein R 1 and R 2 are the same or different alkyl groups having from 1 to 15 carbon atoms, or with the carbonyl group to which they are attached form a monocyclic ring of 5 to 10 carbon atoms, the compound of formula III is o

11 H

Cl - c - (C 1-6) n - C - Cl

wherein R 1 and R 2 are the same or different alkyl groups having from 1 to 15 carbon atoms, or with the carbon atom to which they are attached form a monocyclic ring of 5 to 10 carbon atoms and n is from 0 to 16 and a method for their preparation.

A disadvantage of the low molecular weight substances on the base-shaded amines is their considerable fleece of wasp and washability from polymeric products characterized by large surfaces such as films and fibers. There is already high high-temperature processing already in the loss of concentration of low molecular weight stabilizers from polymer systems. The washability of these stabilizers is negatively reflected in the chemical purification of the stabilized textile materials. Low molecular weight stabilizers include sterically shielded amines, due to their volatility and erosion, it is necessary to take into account their toxicity, which excludes them from application in the 1st stabilization of polymeric materials in the food industry. A partial solution to these problems provides the use of higher molecular weight stabilizers and satisfactory polymer compatibility.

It is a further object of the present invention to provide a process for the preparation of said higher molecular weight light stabilizers of the general formula (I), characterized in that the compound of the formula (II)

wherein n is 0-16 at room temperature in a dry organic solvent such as benzene, toluene, xylenes, hexane, octane, diethyl ether, chloroform, dichloromethane and the like, in the presence of an organic base such as triethylamine, tri-n. -butylamine, benzyldimethylamine, pyridine and the like.

The above-described piperain-type light stabilizers of the present invention are within the group of sterically hindered amines and may serve to suppress or eliminate the aforementioned drawbacks of low molecular weight amine species. Example 1 To a solution of 0.8351 g (0.0015 mol) of 2-hydroxy-1,3-bis (7,15-diazadispiro- [5,1,5,3] hexadecane-14-16-dione-15-yl) propane in 15 ml of dry toluene and 1 ml of triethylamine, a solution of 0.1794 g (0.00075 mol) of sebol koyl chloride in 10 ml of dry toluene is slowly dropped under stirring. The reaction mixture was allowed to stir at room temperature for 5 hours. The triethylamine hydrochloride formed was evaporated in a vacuum evaporator. Upon complete drying of the residue under high vacuum, a yellowish-colored product was obtained, m.p. 44-46 ° C, which had a molecular weight of 1230 (determined by thermosmometry). Elemental analysis for C 72 H 110 N 8 O 12: Calculated: C = 67.57% H = 8.66% N = 8.76% Found: C = 66.92% H = 8.57% N = 8.70% IR spectrum (CHCl 3) : vmax = 840, 870, 900, 930, 950, 980, 1030, 1050, 1090, 1140, 1185, 1210, 1240, 1280, 1295, 1350, 1465, 1680, 1730, 2960, 3360 cm -1 NMR spectrum (CDCl 3): δ = 1.25 (multiplet, 4H), 1.65 (broad band, 80H), 25, (broad band, 12H), 3.45 (multiplet, 2H), 3.9 (multiplet 8H) ppm Example 2. To a 0.835 g solution (0.0315 fnol) 2-hydroxy-1,3-bis (7,15-diazadispiro [5,1,5,3] hexadecane-14,16-dione-15-yl) propane in 15 mL dry hexane and 1 mL of pyridine a solution of 0.0952 g (0.00075 mol) of oxalic dichloride in 10 ml of dry hexane was slowly added dropwise with stirring, and the reaction mixture was allowed to stir at room temperature for 5 hours. The mixture was worked up as in Example 1 to give a product of molecular weight 1160 ( memory phase).

Claims

1. High molecular weight light stabilizers based on aliphatic dicarboxylic acid esters and 2-hydroxy-1,3-disubstituted propane derivatives which are substituted in the 1 and 3 positions with 7,15-diazadispiro (5,1,5,3) hexadecane -14,16-dione of formula I

Example 3

The procedure was as in Example 1 except that diethyl ether was used as the solvent and pyridine was used as the base. INVENTION

2. A process for the preparation of a compound of formula (I) according to claim 1, characterized in that the compound of formula (II) is formed

OH (¾ - 4h - 0 '' where R ¹ and R ² "are the same or different alkyl groups having 1 to 15 carbon atoms, or with the carbon atom to which they are attached, form a monocyclic ring having 5 to 10 carbon atoms, of the formula Clay oo II |

Cl - C - (CH 2 H - C - Cl where R _x and R ² are the same or different alkyl groups having 1 to 15 carbon atoms or with the carbon atom to which they are attached form a myocyclic ring having 5 to 10 carbon atoms and is 0 to 16.

wherein n is 0 to 16 at room temperature in a dry organic solvent such as benzene, toluene, xylene, hexane, octane diethyl ether, chloroform, dichloromethane, in the presence of an organic base such as triethylamine, tri-n-butylamine, benzyldimethylamine, pyridine.