CS232189B1 - 2,3-Bis (2,2,6,6-tetramethyl-4-piperidylamino) butanedioic acid dialkyl ester and its preparation - Google Patents

2,3-Bis (2,2,6,6-tetramethyl-4-piperidylamino) butanedioic acid dialkyl ester and its preparation Download PDF

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CS232189B1
CS232189B1 CS507883A CS507883A CS232189B1 CS 232189 B1 CS232189 B1 CS 232189B1 CS 507883 A CS507883 A CS 507883A CS 507883 A CS507883 A CS 507883A CS 232189 B1 CS232189 B1 CS 232189B1
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Czechoslovakia
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preparation
formula
piperidylamino
tetramethyl
bis
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CS507883A
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Czech (cs)
Slovak (sk)
Inventor
Frantisek Vass
Anna Papalova
Zdenek Manasek
Jozef Luston
Gabriela Hercegova
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Frantisek Vass
Anna Papalova
Zdenek Manasek
Jozef Luston
Gabriela Hercegova
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Application filed by Frantisek Vass, Anna Papalova, Zdenek Manasek, Jozef Luston, Gabriela Hercegova filed Critical Frantisek Vass
Priority to CS507883A priority Critical patent/CS232189B1/en
Publication of CS232189B1 publication Critical patent/CS232189B1/en

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Abstract

Podstatou vynálezu je dialkylester kyseliny 2,3-bis(2,2,6,6-tetrametyl-4- **piperidylamino)butándiovej vzorca Ikde R je metylová alebo etylová skupina. Podstatou vynálezu je dálej spJsob přípravy zlúčeniny vzorca I, ktorý sa vyznačuje tým,.že sa na dialkylester kyseliny 2,3- dibrombutandiovej vzorca II 0kde R je metylová alebo etylová skupina, ptfsobí 4-amino-2,2,6,6-tetrametylpiperidínom vzorca III v suchom benzéne alebo toluéne pri teplote 20 až 30 °C v přítomnosti trietylamínu. Vynález má použitie v chémii polymérov pre přípravu polymerizovatelného světelného stabilizátora polymérov.The essence of the invention is a dialkyl ester of 2,3-bis(2,2,6,6-tetramethyl-4-**piperidylamino)butanedioic acid of the formula Ikwhere R is a methyl or ethyl group. The essence of the invention is also a method for the preparation of the compound of formula I, which is characterized by the fact that the dialkyl ester of 2,3-dibromobutanedioic acid of formula II 0 where R is a methyl or ethyl group is treated with 4-amino-2,2,6,6-tetramethylpiperidine of formula III in dry benzene or toluene at a temperature of 20 to 30 °C in the presence of triethylamine. The invention has application in polymer chemistry for the preparation of a polymerizable light stabilizer of polymers.

Description

- 1 - 232 189

Vynález sa týká dialkylesteru kyseliny 2,3-bis(2,2,6,b--tetrametyl-4-piperidylamino)butándiovej,a sposobu jeho pří-pravy.

Stéricky bráněné aminy sú vysokoúčinné světelné stabili-zátory polymérov. Ihhibujú radikálové procesy, ktoré prebieha-jú pri fotooxidácii polymérov. Nevýhodou nízkomolekulovýchzlúčenín tejto skupiny je ich značná prchavosť a extrahovatel-nosť, čo sposobuje ich postupný úbytok z úžitkového polyméruuž pri samotnom spracovaní, alebo neskor pri skladovaní, che-mickom čistění alebo praní.

Uvedené nevýhody tento vynález odstraňuje. Podstatou vy-nálezu je dialkylester kyseliny 2,3-bis(^,2,6,6-tetrametyl-4--piperidylamino)butándiovej vzorca I

0

OR /1/ kde R je metylová alebo etylové skupina. Podstatou vynálezu

V

je dalej sposob přípravy zlúčeniny. vzorca I, ktorý sa vyzna-čuje ťým, že sa na dialkylester kyseliny 2,3-dibrómbutándiovejvzorca II

RO

CH - OH - C.i i \

Br Br

OR /11/ — 2 — 232 188

kde R je metylová alebo etylová skupina, pósobí 4-araino-2,2,6,ó-tetramětylpiperidínom vzorca III

/111/ v suchom benzéne alebo toluene pri teplote 20 až 30 °G v přítomno-sti trietylamínu Výhodou uvedeného vynálezu je zváčšenie raolekulovej hmotno-sti samoého stabilizátore a příprava polymerizovatelného svě-telného %oilizátora polymérov piperidínového typu dávajúcehomožnost značného eliminovania sporaínaných nedostatkov nízkomole-kulových zlúčenín tejto skupiny· Příklad 1 K roztoku 3»1255 g (0,θ2 mol) 4-amino-2,2,6,6-tetrametylpi-peridínu a-2,8 ml trietylamínu v 50 ml suchého benzénu sa pri te-plotě 20 °G za stálého miešania pomaly prikvapkáva roztok 3,0395 g(0,01 mol) dime tyle steru kyseliny o( ,o(-dibrómjantárovej v 20 ml v suchého benzénu. Reakčná. zmes sa nechá pri tej istej teplote dá-le j miešat 24 h. Vzniknutý tuhý podiel sa odsaje, rozpustí v na-sýtenóm roztoku uhličitanu draselného a roztok sa dokladné vyextra-huje éterom. Benzenový filtrát a éterické extrakty sa spoja, do- a kladné .premyjú destilovanou vodou, vysušia bezvodým síranom sod-ným a rozpúštadlá sa odparia. K lepkavému zvyšku sa prileje 20 mlpetrolóteru, pričom nastane jeho stuhnutie. ho filtrácii sa zís- Λ ka žltkastá, spráškovatelná látka s teplotou topenia 83 až 85 G.

Elementáma analýza pre

Vypočítané* G = 63,40% , H = 10,20 % , Nájdenés G = 63,10 % , H = 10,33 % , B = 12,32 %B = 12,16 % IG spektrum (chloroform) = 970, 1000, 1025, 1080, 1150, 1430, 1600, 1650, 1730, 2870 1175, 1230, 1265, 1365,2950, 3^90 cm”1 - 3 - Přiklad. 2 232 K roztoku 1,56 g 4-amino-2>2,6,6-tetramětylpiperidínu v1,4 ml trietylamínu v 20 ml suchého toluenu aá pri teplote . 30 °G za stálého miešania prikvapká roztok 1,66 g dietylesterukyseliny ¢4, ^dibřóm jantar ověj v 20 ml suchého toluénu. Re'akč·ná zmes sa miesa 20 h, ďalej sa spracuje ako v příklade 1. Zís-rka sa produkt s .teplotou topenia 90 až 93 °G. Příklad 3 z Z 36 g práškového polypropylénu sa homogenizáciou s50,72 gzlúceniny podlá příkladu 1 připravili miesaním v plastografe -Brabender a ónsledovným lisováním folie o hrúbke 0,2 m, ktorésa ozařovali v rotačnom oiarovacom zariadení výbojkou Tesla RW125 W. Sledoval sa vývoj karbonylových skupin v nestabilizovaneja stabilizovanéj folii. Kým néstabilizováhá folia dosiahla karbonylový index 0,1 za 190 hodin, stabilizovaná vzorka dosiahlaten istý stupeň degradácie za 1200 hodin.

Vynález má použitie pre přípravu polymérneho světelnéhostabilizátora piperidínového typu.

- 1-232 189

The present invention relates to dialkyl 2,3-bis (2,2,6, b-tetramethyl-4-piperidylamino) butanedioic acid and its preparation.

The hindered amines are highly efficient polymer stabilizers. They inhibit the radical processes that take place in photooxidation of polymers. A disadvantage of the low molecular weight compounds of this group is their considerable volatility and extractability, resulting in their gradual loss from the useful polymer in the processing itself or later in storage, chemical purification or washing.

The above-mentioned disadvantages are eliminated by the present invention. The present invention relates to dialkyl 2,3-bis (2,6,6,6-tetramethyl-4-piperidylamino) butanedioic acid of the formula I

0

OR (1) wherein R is methyl or ethyl. SUMMARY OF THE INVENTION

IN

is further a method for preparing a compound. of formula (I), characterized in that the dialkyl ester of 2,3-dibromobutanedioic acid (II)

RO

CH - OH - Ci i \ t

Br Br

OR / 11 / - 2 - 232,188

wherein R is methyl or ethyl, with 4-amino-2,2,6,6-tetramethylpiperidine of formula III

(111) in dry benzene or toluene at 20-30 ° C. in the presence of triethylamine. of the compounds of this group. Example 1 To a solution of 3: 1255 g (0, 2 mol) of 4-amino-2,2,6,6-tetramethylpiperidine and-2.8 ml of triethylamine in 50 ml of dry benzene at room temperature. 20 ° C, with stirring, a solution of 3.0395 g (0.01 mol) of dime tyle of acid (o (o (-dibromosuccinic acid) in 20 ml in dry benzene is slowly added dropwise). The resulting solid is filtered off with suction, dissolved in a saturated solution of potassium carbonate and extracted extensively with ether, and the benzene filtrate and the ethereal extracts are combined, washed and distilled. The solvent was evaporated, dried over anhydrous sodium sulfate, and the solvents were evaporated, and 20 ml of a peterol ether was added to the sticky residue, solidifying. The filtrate gave a yellowish, dustable substance with a melting point of 83-85 G.

Elementary analysis for

Calculated G = 63.40%, H = 10.20%, Found G = 63.10%, H = 10.33%, B = 12.32% B = 12.16% IG Spectrum (Chloroform) = 970 , 1000, 1025, 1080, 1150, 1430, 1600, 1650, 1730, 2870 1175, 1230, 1265, 1365, 2950, 3 ^ 90 cm ”1-3 - Example. 2,232 To a solution of 1.56 g of 4-amino-2, 2,6,6-tetramethylpiperidine in 1.4 ml of triethylamine in 20 ml of dry toluene at a temperature of. With stirring, a solution of 1.66 g of diethyl ester ¢4 dibromide succinate in 20 ml of dry toluene is added dropwise with stirring. The reaction mixture was stirred for 20 h, further worked up as in Example 1. The product was obtained with a melting point of 90-93 ° C. Example 3 From 36 g of polypropylene powder, homogenizing with 50.72 g of the composition of Example 1 was prepared by mixing in a plastograph-Brabender and a 0.2 m thick film, which was irradiated in a rotary irradiation apparatus with Tesla RW125 W lamp. in a non-stabilized and stabilized film. While the carbonate index was 0.1 to 190 hours, the stabilized sample achieved some degree of degradation at 1200 hours.

The invention is of use for the preparation of a polymeric light stabilizer of the piperidine type.

Claims (2)

- 4 - PR B DM B ϊ V Y R Ál B Z O 232 189 1 · Dialkylester kyseliny 2,3-bixs(2,2,6,6-tetrametyl-4-piperidyl-amino)butándiovej vzoroaI- 4 - PR B DM B ϊ Y B B Z Z 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 189 kde R je metylová alebo etylová skupina· 2· Spdsob přípravy elúčeniny vzorce, I podlá bodu 1, jrcorý savyznačuje tým, že s,a na dialkylester kyseliny 2,3-dibrom-butándiovej vzoroa IIwherein R is a methyl or ethyl group. A process for the preparation of a compound of formula I according to claim 1, characterized in that s, and dialkyl 2,3-dibromo-butanedioic acid of formula II OH i BrOH and Br /11/ kde R je metylová alebo etylová skupina, pdsobí 4-amino--2,2,6,6-tetrametylpiperidínom vzoroa III(11) wherein R is methyl or ethyl, 4-amino-2,2,6,6-tetramethylpiperidine of formula III is used /111/ v suohom benzéne alebo toluéne pri teplote 20 až 30 °Gv přítomnosti trietylamínu·/ 111 / in benzene or toluene at 20 to 30 ° C in the presence of triethylamine ·
CS507883A 1983-07-04 1983-07-04 2,3-Bis (2,2,6,6-tetramethyl-4-piperidylamino) butanedioic acid dialkyl ester and its preparation CS232189B1 (en)

Priority Applications (1)

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CS507883A CS232189B1 (en) 1983-07-04 1983-07-04 2,3-Bis (2,2,6,6-tetramethyl-4-piperidylamino) butanedioic acid dialkyl ester and its preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CS507883A CS232189B1 (en) 1983-07-04 1983-07-04 2,3-Bis (2,2,6,6-tetramethyl-4-piperidylamino) butanedioic acid dialkyl ester and its preparation

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