CS225022B1 - Polyester light stabilizer based on alpha, alpha'-disubstituted aliphatic dicarboxylic acid tetrasubstituted piperazinedione and 1,2-ethanediol and a method for its preparation - Google Patents

Polyester light stabilizer based on alpha, alpha'-disubstituted aliphatic dicarboxylic acid tetrasubstituted piperazinedione and 1,2-ethanediol and a method for its preparation Download PDF

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CS225022B1
CS225022B1 CS655181A CS655181A CS225022B1 CS 225022 B1 CS225022 B1 CS 225022B1 CS 655181 A CS655181 A CS 655181A CS 655181 A CS655181 A CS 655181A CS 225022 B1 CS225022 B1 CS 225022B1
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Czechoslovakia
Prior art keywords
alpha
ethanediol
tetrasubstituted
piperazinedione
light stabilizer
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CS655181A
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Czech (cs)
Slovak (sk)
Inventor
Frantisek Prom Chem Vass
Zdenek Ing Csc Manasek
Jozef Ing Csc Luston
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Vass Frantisek
Manasek Zdenek
Luston Jozef
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Priority to CS655181A priority Critical patent/CS225022B1/en
Publication of CS225022B1 publication Critical patent/CS225022B1/en

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Abstract

Vynález sa týká polyesterového svjtelného stabilizátora na báze alfa,alfa -disubstituovanej alifatickej dikarboxyiovej kyseliny tetrasubstituovaným piperazíndionom a 1,2-etándiolu. Podstata vynálezu přípravy zlúčeniny polyesteru na báze alfa,alfa -disubstituovanej alifatickej dikarboxyiovej kyseliny tetrasubstituovaným piperazíndionom a 1,2- -etándiolu spočívá v reesterifikécii dietylesteru kyseliny 2,5-bis/7,15-diazadispiro[5,1,5,3]hexadekán-14,16-dion-15-yl/- hexéndiovej s 1,2 etándiolom pri teplote 100 ač 150 °C v suchom uhTovodíkovom rozpúSťadle za přítomnosti bázického katalyzátore. Vynález má použitie na přípravu světelného stabilizátora polymérov.The invention relates to a polyester light stabilizer based on alpha,alpha-disubstituted aliphatic dicarboxylic acid with tetrasubstituted piperazinedione and 1,2-ethanediol. The essence of the invention for the preparation of a polyester compound based on alpha,alpha-disubstituted aliphatic dicarboxylic acid with tetrasubstituted piperazinedione and 1,2-ethanediol consists in the reesterification of 2,5-bis/7,15-diazadispiro[5,1,5,3]hexadecan-14,16-dion-15-yl/-hexanedioic acid diethyl ester with 1,2 ethanediol at a temperature 100 to 150 °C in a dry hydrocarbon solvent in the presence of a basic catalyst. The invention is used for the preparation of a polymer light stabilizer.

Description

225022 2

Vynález sa týká polyesterového světelného stabilizátore polyesterového typu na bázealfa,alfa'-dišubstituovanej dikarboxylovej alifatickej kyseliny tetrasubstituovaným pipera-zíndiónom a 1,2-etándiolu vzorca I

O

II -C-CH-CH,-CHj-CH-C-0-CH3-CH,-0- (I) kde n má hodnotu 2 až 40 a spOsobu jeho přípravy.

SpOsob přípravy polyesterového světelného stabilizátora na báze alfa,alfa'-disubsti-tuovanej alifatickej dikarboxylovej kyseliny tetrasubstituovaným piperazíndiónom a 1,2—-etándiolu je založený na reesterifikácii zlúčeniny vzorca XI

s 1,2-etandiolom pri teplote 100 až 150 °C v suchom uhl’ovodíkovom rozpúšťadle (toluén,xylén, nitrobenzén) v přítomnosti bázického katalyzátore, ako například litiumamidu, hydro-xidu draselného, tetrapropyltitanátu.

Stéricky bráněné aminy sú vysokoúčinnými světelnými stabilizátormi mnohých druhoy po-lymérov. Použitie nízkomolekulových látok tohto typu má vgak niektoré obmedzenia. Ich hlav-nými nevýhodami sú: vel*ká prchavosť, značná schopnost migrovat, 1’ahká extrahovateTnosť av neposlednom radě dobrá absorbovateTnosť do buňkových priestorov živých organizmov. Prvétri nežiaduce vlastnosti sú příčinou ich postupného úbytku z úžitkového polyméru so súčas-nou stratou ochranného účinku, najprv pri jeho tepelnom spracovaní, potom pri dlhfiom skla-dovaní a nakoniec pri jeho chemickom čistění alebo praní. Lehká pronikavost buňkovými stě-nami živých organizmov pre značnú toxicitu nízkomolekulových darivátov sféricky bráněnýchamínov ich vylučuje z aplikácie pri stabilizácii polymérnych materiálov v oblasti potravi-nářského priemyslu, připadne v oblasti medicíny. Zniženie, alebo elimlnovanle týchto nevý-hodných vlastností předpokládá použitie vySSiemolekulových, oligomérnych alebo polymérnychsvětelných stabilizátorov s vyhovujúcou znéSanlivosťou, alebo naviazanie stabilizujúcichStruktúr na retazec úžitkového polyméru.

Polymérny světelný stabilizátor piperazínového typu patriacl do skupiny stéricky brá-něných amínov, ktorý je prédmetom vynálezu na potlačenie alebo k eliminovaniu spomínanýchnedostatkov nízkomolekulových látok uvedeného typu. Příklad 1

Zmes 1,7472 g (0,0025'mol) dietyleateru kyseliny 2,5-biš/7,15-diazadispiro[5,1,5,3]·-hexadekén-14,16-dión-15-yl/hexándiovej a 0,1677 g (0,0025 mol) 1,2-etándiolu v 10 ml suché-ho xylénu sa zahřeje na 110 °C a přidá sa 5 mol % litiumamidu. Zmes sa áalej zahrieva podobu 4 h pri tej istej teplote, pričom reakčný etanol pomaly oddestilováva. Po uplynulomčase sa zvýči teplota na 130 až 135 °G a udržiava sa áal&ích 6 h, čím sa oddestiluje zvyšný

225022 2

BACKGROUND OF THE INVENTION The present invention relates to a polyester type polyester light stabilizer for base-alpha, alpha-substituted dicarboxylic aliphatic acid with tetrasubstituted piperazine and 1,2-ethanediol of formula I.

O

II -C-CH-CH, -CH 2 -CH-C-O-CH 3 -CH, -O- (I) wherein n has a value of 2 to 40 and a process for its preparation.

The process for preparing a polyester light stabilizer based on alpha, alpha-disubstituted aliphatic dicarboxylic acid by tetrasubstituted piperazinedione and 1,2-ethanediol is based on the reesterification of the compound of formula XI

with 1,2-ethanediol at 100-150 ° C in a dry hydrocarbon solvent (toluene, xylene, nitrobenzene) in the presence of a basic catalyst such as lithium amide, potassium hydroxide, tetrapropitanate.

The sterically hindered amines are high performance light stabilizers for many species of polymers. However, the use of low molecular weight substances of this type has some limitations. Their major drawbacks are: large volatility, considerable ability to migrate, ease of extractability and, last but not least, good absorbability into the cellular spaces of living organisms. The first undesirable properties are the cause of their gradual loss from the useful polymer with the simultaneous loss of protective effect, first in its heat treatment, then in long-term storage and ultimately in chemical cleaning or washing. The slight permeability of the cell walls of living organisms, due to the high toxicity of low molecular weight spherically hindered amines, excludes them from application in the stabilization of polymeric materials in the food industry, possibly in the medical field. The reduction or elimination of these disadvantageous properties implies the use of high molecular weight, oligomeric or polymeric light stabilizers, or the attachment of stabilizing structures to the useful polymer strand.

A piperazine-type polymeric light stabilizer belonging to the group of sterically hindered amines, which is the subject of the invention for the suppression or elimination of said low molecular weight deficiencies of said type. Example 1

A mixture of 1.7472 g (0.0025 mol) of 2,5-bis / 7,15-diazadispiro [5,1,5,3] -hexadecene-14,16-dione-15-yl / hexanedioic acid diethyl ether and 0.1677 g (0.0025 mol) of 1,2-ethanediol in 10 ml of dry xylene is heated to 110 ° C and 5 mol% of lithium amide is added. The mixture was further heated for 4 h at the same temperature, while the reaction ethanol was slowly distilled off. After a period of time, the temperature was raised to 130-135 ° C and maintained for 6 hours, thereby distilling off the remaining

Claims (3)

3 225022 reakčný etanol. Rozpúšťadlo sa vákuovo oddestiluje a na zvyšok sa pflsobí tlakem i,3 Pa podobu 2 h. Potom sa obsah nechá ochladit, rozpustí sa v 50 ml toluénu a premyje třikrát ma-lým množstvom vody. Toluénový roztok sa nakoniec vysuší bezvodým síranom sodným a přečistíaktívnym uhlím. Odpařením rozpúšťadla a vystavením získaného zvyšku tlaku 1,3 Pa sa získátuhý, sklovitý, l’ahko spráškovateTný polymér s teplotou topenia v intervale 68 až 75 °Cmolekulovou hmotnos.ťou 2 070 (stanovené termoosmometricky). Elementáma analýza pre Ο^Η^Ν^Οθ: Vypočítané: N = 8,38 Kájdené: N = 8,30 IČ spektrum (chloroform): vmax “ ®55, 970, 1 010, 1 075, 1 200, 1 265, 1 350, 1 370, 1 450, 1 680, 1 730, 2 940 οιη-1 Příklad 2 Postupovalo sa ako v příklade 1, s tým rozdielom, že sa reakcía vykonala v přítomnosti5 mol % tetrapropyltitánu. Po izolácii sa získal polymér s teplotou topenia v intervale 69až 78 °C a molekulovou hmotnosťou 2 230 (stanovené termoosmometricky). Elementárna analýza pre C36H52N4°8! Vypočítané: N - 8,38 Kájdené: N = 8,27 PREDMET VYNÁLEZU3 225022 Reaction Ethanol. The solvent is distilled off under vacuum and the residue is subjected to a pressure of 1 mbar for 2 hours. The contents are then allowed to cool, dissolved in 50 ml of toluene and washed three times with a small amount of water. The toluene solution is finally dried over anhydrous sodium sulfate and purified carbon. Evaporating the solvent and subjecting the obtained pressure to 1.3 Pa to yield a vitreous, readily dustable polymer having a melting point of 68 to 75 ° C with a molecular weight of 2070 (determined thermo-isometric). Elemental analysis for ΟΟΗΗΝ: :Ο:: N = 8.38. 1350, 1370, 1450, 1680, 1730, 2940. Example 1 The procedure was as in Example 1 except that the reaction was carried out in the presence of 5 mol% tetrapropyl titanium. After isolation, a polymer having a melting point of 69 to 78 ° C and a molecular weight of 230 ° (determined thermo-isometric) was obtained. Elemental analysis for C36H52N4O8! N - 8.38. Calculated: N = 8.27 1. Polyesterový světelný stabilizátor na báze alfa,alfa*-disubstituovanej alifatickejdikarboxylovej kyseliny tetrasubstituovaným piperazíndiónom a 1,2-etándiolu obecného vzor-ce 1 O O II II -C-CH-CH2-CH2-CH-C-O-CH2-CH2-O-A polyester light stabilizer based on alpha, alpha-disubstituted aliphatic dicarboxylic acid with tetrasubstituted piperazinedione and 1,2-ethanediol of the general formula O-II-C-CH-CH 2 -CH 2 -CH-C-O-CH 2 -CH 2 -O- kde n má hodnotu 2 až 40. ,2. Spdsob přípravy polyesterového světelného stabilizátora na báze alfa,alfa'-disub-stituovaňej alifatickej dikarboxylovej kyseliny tetrasubstituovaným piperazíndiónom a 1,2--etándiolu podle bodu 1, vyznačujúci sa tým, že na zlúčeninu vzorca IIwherein n is 2 to 40. 2. Process for preparing a polyester light stabilizer based on alpha, alpha-disubstituted aliphatic dicarboxylic acid by tetrasubstituted piperazinedione and 1,2-ethanediol according to claim 1, characterized in that the compound of formula II sa pdsobí 1,2-etándiolom. (XI) 225022 4is treated with 1,2-ethanediol. (XI) 225022 4 3. Spflsob podl’a bodu 2, vyznaSujúci sa tým, že sa reakcia uskutečňuje za přítomnostibázických katalyzátorov ako například litiumamidu, tetrapropyltitanátu, hydroxidu draselné-ho a táto reakcia sa vykonává pri teplote 100 až 150 °C v suchom uhlovodlkovom rozpúěťadle,ako například toluéne, xyléne, nitrobenzéne. Severografia, n. p„ MOST Cena 2,40 Kčs3. A process as claimed in claim 2, wherein the reaction is carried out in the presence of a basic catalyst such as lithium amide, tetrapropyl titanate, potassium hydroxide and is carried out at a temperature of 100 to 150 [deg.] C. in a dry hydrocarbon solvent such as toluene. , xylene, nitrobenzenes. Severografia, n. P „MOST Price 2.40 Kcs
CS655181A 1981-09-04 1981-09-04 Polyester light stabilizer based on alpha, alpha'-disubstituted aliphatic dicarboxylic acid tetrasubstituted piperazinedione and 1,2-ethanediol and a method for its preparation CS225022B1 (en)

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CS655181A CS225022B1 (en) 1981-09-04 1981-09-04 Polyester light stabilizer based on alpha, alpha'-disubstituted aliphatic dicarboxylic acid tetrasubstituted piperazinedione and 1,2-ethanediol and a method for its preparation

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