CS252979B1 - Poly(ethylene-2,5-bis/2,2,6,6-tetramethyl-4-piperidyloxy/hexandionate)and method of its preparation - Google Patents

Poly(ethylene-2,5-bis/2,2,6,6-tetramethyl-4-piperidyloxy/hexandionate)and method of its preparation Download PDF

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CS252979B1
CS252979B1 CS859501A CS950185A CS252979B1 CS 252979 B1 CS252979 B1 CS 252979B1 CS 859501 A CS859501 A CS 859501A CS 950185 A CS950185 A CS 950185A CS 252979 B1 CS252979 B1 CS 252979B1
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Czechoslovakia
Prior art keywords
tetramethyl
bis
piperidyloxy
preparation
poly
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CS859501A
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Czech (cs)
Slovak (sk)
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CS950185A1 (en
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Frantisek Vass
Jozef Luston
Zdenek Manasek
Gabriela Vassova
Andrej Romanov
Anna Bielikova
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Frantisek Vass
Jozef Luston
Zdenek Manasek
Gabriela Vassova
Andrej Romanov
Anna Bielikova
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Priority to CS859501A priority Critical patent/CS252979B1/en
Publication of CS950185A1 publication Critical patent/CS950185A1/en
Publication of CS252979B1 publication Critical patent/CS252979B1/en

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  • Hydrogenated Pyridines (AREA)

Description

Riešenie týchto problémov može poskytnut použitie vhodných polymérnych stabilizátorov. Podstatou vynálezu je poly[etylén-2,5-bis(2,2,6,6-tetrametyl-4-piperidyloxy)hexándionát] vzorca IThe use of suitable polymeric stabilizers can provide a solution to these problems. The present invention provides a poly [ethylene-2,5-bis (2,2,6,6-tetramethyl-4-piperidyloxy) hexanedionate] of the formula I

kde n je 2 až 100. Podstatou vynálezu je ďalej sposob přípravy zlúčeniny I, ktorý sa vyznačuje tým, že sa na dialkylestery kyseliny 2,5-bis(2,2,6,6-tetrametyl-4-piperidylo xyjhexándiovej vzorca IIwherein n is from 2 to 100. The present invention further provides a process for the preparation of compound I which is characterized in that to 2,5-bis (2,2,6,6-tetramethyl-4-piperidyloxyhexanedioic acid dialkyl esters II)

kde R je metylová, alebo etylová skupina, působí 1,2-etándiolom v suchom xylene v přítomnosti metanolátu sodného, lítiumamidu, alebo tetraalkyltitanátu pri teplote v rozmedzí od 110 do 160 °C po dobu 7 až 10 hodin.wherein R is methyl or ethyl, treated with 1,2-ethanediol in dry xylene in the presence of sodium methanolate, lithium amide, or tetraalkyl titanate at a temperature ranging from 110 to 160 ° C for 7 to 10 hours.

Výhodou uvedeného vynálezu je příprava oligomérneho, až polymérneho světelného stabilizátora polyalkylpiperidínového typu so zvýšenou molekulovou hmotnosfou, který pri aplikácii v polymérnych materíáloch může do značnej miery eliminovat spomínané nedostatky vyskytujúce sa u nízkomolekulových zlúčenín tejto skupiny.An advantage of the present invention is the preparation of an oligomeric to polymeric light stabilizer of polyalkylpiperidine type with increased molecular weight which, when applied in polymeric materials, can largely eliminate the aforementioned drawbacks occurring in the low molecular weight compounds of this group.

Přiklad 1Example 1

K reakčnej zmesi pozostávajúcej z 0,51 g (0,001 molu] dietylesteru kyseliny 2,5-bis(2,2,6,6-tetrametyl-4-piperidyloxy)hexándiovej, 0,125 g (0,002 molu] 1,2-etándiolu v 10 ml suchého toluénu, zahriatej na 110 °C sa přidá 0,03 g tetrapropyltitanátu ako katalyzátore. Zmes sa zahrieva 1 h pri tej istej teplote, pričom část reakčného etanolu sa postupné oddestiluje. Potom sa teplota zvýši na 130 až 135 °C a udržiava sa po dobu 5 hodin. Počas tejto doby oddestiluje zvyšná část reakčného etanolu a teplota sa zvýši na 160 °C. Po odstránení rozpúšťadla sa zvyšok pri nezmenenej teplote podrobí vákuu 0,1 kPa po dobu dalších 4 hodin. Po ochladení sa surový polymér rozpustí v 20 mililitroch toluénu, přečistí aktívnym uhlím, dokladné premyje destilovanou vodou a roztok sa vysuší bezvodým síranom sodným. Po odpaření toluénu a vysušení zvyšku vo vákuovej sušiarni pri teplote 120 °G a tlaku 0,2 kPa po dobu 4 h, sa získá tuhý, žltkastý, křehký polymér s teplotou máknutia 72 až 75 °C a priemernou číselnou molekulovou hmotnosfou 2 800.To a reaction mixture consisting of 0.51 g (0.001 mol) of 2,5-bis (2,2,6,6-tetramethyl-4-piperidyloxy) hexanedioic acid diethyl ester, 0.125 g (0.002 mol) of 1,2-ethanediol in 10 ml of dry toluene heated to 110 [deg.] C. is added 0.03 g of tetra-propyltitanate as a catalyst, and the mixture is heated at the same temperature for 1 hour, while part of the reaction ethanol is gradually distilled off, then raised to 130-135 [deg.] C. During this time, the remainder of the ethanol is distilled off and the temperature is raised to 160 DEG C. After removal of the solvent, the residue is subjected to a vacuum of 0.1 kPa for a further 4 hours at unchanged temperature. After toluene is evaporated and the residue is dried in a vacuum oven at 120 ° C and 0.2 kPa for 4 h, a solid, yellowish solid is obtained. 100% brittle, brittle polymer with a softening point of 72-75 ° C and an average molecular weight of 2,800.

P r i k 1 a d 2Example 1 and d 2

Pri polykondenzácii 0,483 g (0,001 mólu) dimetylesteru kyseliny 2,5-bis(2,2,6,6-tetrametyl-4-piperidyloxy)hexándlovej a 0,125 g (0,002 mólu) 1,2-etándiolu sa postupuje ako v příklade 1 len s tým rozdielom, že ako katalyzátor sa použije lítiumamid v množstve 0,03 g a reakčná zmes sa zahrieva 7 h v rozmedzí teplůt 110 až 160 °C. Získá sa tuhý, žltkastý, l'ahko spráškovateTný polymér, ktorý vykazuje teplotu maknutla v rozmedzí· 73 až 77 °C a priemernú číselná molekulová hmotnost 3100, (pri stanovení pomocou VPO).The polycondensation of 0.483 g (0.001 mol) of 2,5-bis (2,2,6,6-tetramethyl-4-piperidyloxy) hexanedioic acid dimethyl ester and 0.125 g (0.002 mol) of 1,2-ethanediol is followed as in Example 1 only with the difference that 0.03 g of lithium amide is used as the catalyst and the reaction mixture is heated for 7 h in a temperature range of 110 to 160 ° C. A solid, yellowish, easily dustable polymer is obtained which has a melt temperature in the range of 73-77 ° C and an average molecular weight of 3100 (as determined by VPO).

Elementárna analýza pre C26H46N2O6Elemental analysis for C 26 H 46 N 2 O 6

Vypočítané: N = 5,80 %Calculated: N = 5.80%

Nájdené: N = 5,73 %Found: N = 5.73%

IC spektrum (chloroform)IC spectrum (chloroform)

360 (s) — v (N—H),360 (s) - in (N-H),

980 (s),980 (s)

940 (s) - uas, vs (C-H),940 (s) - at as , in s (CH),

1740 (s) v (C=O),1740 (s) in (C = O),

1450 (s) — S (C—H),1450 (s) -S (C-H),

380 (s) + 1 360 (s) dublet — 5 (gem.380 (s) + 1,360 (s) doublet - 5 (gem.

CH3),CH 3 ),

1300 (s) — v (C—H),1300 (s) - in (C-H),

260 (s) + 1240 (s) — v (C—O—C ester) cm-1 260 (s) + 1240 (s) - in (C-O-C ester) cm -1

Vynález má použitie pre přípravu oligomérneho, až polymérneho světelného stabilizátora polymérov, najma polyolefínov.The invention is of use for the preparation of an oligomeric to polymeric light stabilizer of polymers, in particular polyolefins.

PREDMET VYNALEZUOBJECT OF THE INVENTION

Claims (2)

PREDMET VYNALEZUOBJECT OF THE INVENTION 1. Poly[etylén-2,5-bis(2,2,6,6-tetrametyl-4-ipiperidyloxy)hexándiovej vzorca II1. Poly [ethylene-2,5-bis (2,2,6,6-tetramethyl-4-ipiperidyloxy) hexanedioic acid II C-CH-(CH2)2 ilC-CH- (CH 2 ) 2 il CH~ C-0 c/^CH-C-O c CH-, ch^ch^okde n je 2 až 100.CH 2, where n is 2 to 100. 2. Sposob přípravy zlúčeniny I podTa bodu 1, vyznačujúei sa tým, že sa na dialkylestery kyseliny 2,5-bis(2,2,6,6-tetrametyl-4-piperidyloxyjhexándiovej vzorca II kde R je metylová, alebo etylová skupina, posobí 1,2-etándiolom v suchom xylene v přítomnosti metanolátu sodného, lítiumamidu, alebo tetraalkyltitanátu pri teplote v rozmedzí od 110 do 160 °C po dobu 7 až 102. A process for the preparation of compound (I) according to claim 1, characterized in that to the dialkyl esters of 2,5-bis (2,2,6,6-tetramethyl-4-piperidyloxy) hexanedioic acid of the formula II wherein R is methyl or ethyl, 1,2-ethanediol in dry xylene in the presence of sodium methanolate, lithium amide, or tetraalkyl titanate at a temperature ranging from 110 to 160 ° C for 7 to 10
CS859501A 1985-12-19 1985-12-19 Poly(ethylene-2,5-bis/2,2,6,6-tetramethyl-4-piperidyloxy/hexandionate)and method of its preparation CS252979B1 (en)

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