CS225048B1 - The polyesters of sterically hindered propandione acid - Google Patents
The polyesters of sterically hindered propandione acid Download PDFInfo
- Publication number
- CS225048B1 CS225048B1 CS420682A CS420682A CS225048B1 CS 225048 B1 CS225048 B1 CS 225048B1 CS 420682 A CS420682 A CS 420682A CS 420682 A CS420682 A CS 420682A CS 225048 B1 CS225048 B1 CS 225048B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- sterically hindered
- polyesters
- propandione
- acid
- range
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims description 4
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 title 1
- 239000002253 acid Substances 0.000 title 1
- -1 alpha-substituted propanedioic acid Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- JTHRRMFZHSDGNJ-UHFFFAOYSA-N piperazine-2,3-dione Chemical class O=C1NCCNC1=O JTHRRMFZHSDGNJ-UHFFFAOYSA-N 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
Vynález sa týká polyestere typu stéricky bráněných piperazíndionov na báze alfa-substituovanej kyseliny propándiovej zahrnujúcich vo svojom reťazci štruktúrnu jednotku obecného vzorcaThe invention relates to a polyester of the sterically hindered piperazinediones type based on alpha-substituted propanedioic acid comprising in their chain a structural unit of the general formula
tv kde Q je alkylénový reťazec s poétom atómov uhlíka 2 až 6, n má hodnotu v rozmedzí 2 až 15 a spfisobu ich přípravy.wherein Q is an alkylene chain having 2 to 6 carbon atoms, n has a value in the range of 2 to 15 and a method for preparing them.
Spfisob přípravy polyesterov typu stéricky bráněných piperazíndiónov na báze alfa-substituovanej kyseliny propándiovej je založený na preesterifikáoii dimetyl alebo dietylesteru kyseliny 2-(7,15-diazadispiro[5,1,5,5} hexadekán-14,l6-dión-15-yl) propándiovej alifatickými diolmi s poítom atomov uhlíka 2,až 6 ako například 1,2-etándiolom, 1,4-butándiolom, pri teplote v rozmedzí od 100 do 150 °C v suchom uhTovodíkovom rozpúšťadle (xylén, nitrobenzén) v přítomnosti bézického katalyzátore, ako například metoxidu sodného, lítiumamidu, tetrapropyltitanátu ató.The method of preparing sterically hindered piperazinediones of the alpha-substituted propanedioic acid type is based on the transesterification of 2- or 7,15-diazadispiro [5,1,5,5} hexadecan-14,16-dione-15-yl dimethyl ester or diethyl ester. propanedioic aliphatic diols having 2 to 6 carbon atoms such as 1,2-ethanediol, 1,4-butanediol at a temperature in the range of from 100 to 150 ° C in a dry hydrocarbon solvent (xylene, nitrobenzene) in the presence of a basic catalyst; such as sodium methoxide, lithium amide, tetrapropyltitanate and the like.
Stéricky bráněné aminy sú vysokoúčinnými světelnými stabilizátormi mnohých druhov po225048 lymérov. Použitie nízkomolekulových látok tohto typu má však niektoré obmedzenie. Ioh hlavnými nevýhodami sú: veTká prchavosť, značná migráciesohopnosť, 1’ahká extrahovateTnosť a v neposlednom řade dobrá absorbovatelnost do buňkových priestorov živých organtzmov. Prvé tri nežiadúce vlastnosti sú příčinou ich postupného úbytku z úžitkového polyméru so súčasnou stratou ochranného účinku, najprv pri jeho tepélnom spracovanl, potom pri dlhšom skladovaní a nakonlec pri Jeho chemickom čistění alebo praní. Lehká prenikavosť buňkovými stěnami živých organizmov pre značnú toxicitu nízkomolekulových derivátov stérioky bráněných amínov ich vylučuje z aplikácie pri átabilizácii polymérnych materiálov v oblasti potravinářského priemyslu, připadne v oblasti medicíny. Zníženie, alebo eíiminovanie týchto nevýhodných vlastností předpokládá použitie vyšSiemolekulových, oligomérnych alebo polymérnych světelných stabilizátorov s vyhovujúcou znášanlivosťou, alebo naviazanie stabillzujúcich Struktúr na reťazec úžitkového polyméru.Sterically hindered amines are high-efficiency light stabilizers of many kinds of 225048 lymers. However, the use of low molecular weight substances of this type has some limitations. Their main drawbacks are: high volatility, considerable migration capability, easy extractability and, last but not least, good absorbability into the cellular spaces of living orgasms. The first three undesirable properties are the cause of their gradual loss from the utility polymer with a simultaneous loss of protective effect, first in its heat treatment, then in longer storage, and finally in its dry cleaning or washing. The light penetration of cell walls of living organisms due to the considerable toxicity of low molecular weight derivatives of hindered amines excludes them from the application in the stabilization of polymeric materials in the food industry, possibly in the medical field. The reduction or elimination of these disadvantageous properties presupposes the use of higher molecular weight, oligomeric or polymeric light stabilizers with suitable tolerability, or the attachment of stabile structures to the chain of the useful polymer.
Polymérny světelný, stabilizátor piperazínového typu patriaci do skupiny stéricky bráněných amínov, ktorý je predmetom vynálezu, m8že slúžiť k potlačeniu alebo eliminovaniu spomínaných nedostatkov nízkomolekulových látok uvedeného typu.The polymeric light stabilizer of the piperazine type belonging to the group of sterically hindered amines of the present invention can serve to suppress or eliminate said disadvantages of the low molecular weight compounds of the type.
PřikladlEXAMPLE
Zmes 2,0425 g (0,005 mol) dietylesteru kyseliny 2-(7,1 5-diazadispirojjj, 1 ,5,3] hexsdekán-14,l6-dlón-15-yl)propándiovej a 0,3104 g (0,005 mol) 1,2-etándiolu v 10 ml suchého xylénu sa zahřeje na 110 °C a přidá sa 5 mol. % LiNHj· Zmes sa 5alej zahrieva po dobu 4 h pri tej istej teplote, pričom reakčný etanol pomaly oddestilováva. Po uplynulom čase sa zvýši teplota na 130 až 135 °G a udržiava sa áalších 6 h, čím sa oddestiluje zvyšný reakčný etanol. Rozpúšťadlo sa vákuovo oddestiluje a zvyšok sa podrobí vysokému vákuu v priebehu 2 h při teplote 150 °C. Potom sa obsah banky nechá ochladit, rozpustí sa v 30 ml toluénu a premyje sa třikrát malým množstvom vody. Toluénový roztok sa nakonlec vysuší bezvodým síranom sodným a přečistí aktfvnym uhlím. Odpařením rozpúšťadla a vystavením zvyšku vysokému vákuu pri teplote 120 °C sa získá tuhý, sklovitý polymér s teplotou topenia v intervale 37 až 50 °C s priemernou číselnou molekulovou hmotnosťou 960 (stanovená VPO osmometra). Elementárna analýza pre ^,9^26¾¾ vypočítané: 60,32 % C; 6,88 % H; 7,41 % N nájdené: 60,81 % C; 7,12 % H; 7,35 % NA mixture of 2.0425 g (0.005 mol) of diethyl 2- (7,15-diazadispirojjj, 1,5,3] hexsdecan-14,16-dione-15-yl) propanedioic acid diethyl ester and 0.3104 g (0.005 mol) of 1 Of 2-ethanediol in 10 ml of dry xylene is heated to 110 ° C and 5 mol. The mixture is further heated for 4 h at the same temperature, while the reaction ethanol is slowly distilled off. After the time has elapsed, the temperature is raised to 130-135 ° C and held for a further 6 hours to distill off the remaining reaction ethanol. The solvent was distilled off in vacuo and the residue was subjected to high vacuum for 2 h at 150 ° C. The contents of the flask were allowed to cool, dissolved in 30 ml of toluene and washed three times with a small amount of water. The toluene solution was finally dried over anhydrous sodium sulfate and treated with activated charcoal. Evaporation of the solvent and exposure of the residue to high vacuum at 120 ° C gave a solid, glassy polymer having a melting point in the range of 37-50 ° C with an average molecular weight of 960 (as determined by the VPO of an osmometer). Elemental analysis calculated for: C, 60.32; H, 6.88; N, 7.41. Found: C, 60.81; 7.12% H; 7.35% N
Příklad 2Example 2
Postupovalo sa ako v příklade 1 s tým rozdielom, že sa reakcia uskutočnila v přítomnosti 5 mol. % tetrapropyltitanátu. Po izolácii sa získal sklovitý polymér s teplotou topenia 41 až 53 °G a priemernou číselnou molekulovou hmotnosťou 1 150 (stanovené pomocou VPO osmometra).The procedure was as in Example 1 except that the reaction was carried out in the presence of 5 mol. % tetrapropyltitanate. After isolation, a glassy polymer having a melting point of 41-53 ° C and an average molecular weight of 1,150 (determined by VPO osmometer) was obtained.
Elementárna analýza pre GigH26N2°6 vypočítané: 60,32 % C; 6,88 % H; 7,41 % N nájdené: 60,51 % Gj 7,05 % Hj 7,27 % NH, G ig H 26 N 2 ° 6 Calculated: 60.32% C; H, 6.88; 7.41% N found: 60.51% Gj 7.05% Hj 7.27% N
1. Polyestery typu stéricky bráněných piperazíndiónov na báze alfa-substituovanej kyseliny propándiovej, ktoré obsahujú v makromolekule opakujúce sa Strukturně Slánky obecného vzorca1. Polyesters of the sterically hindered piperazinediones type, based on alpha-substituted propanedioic acid, containing in the macromolecule repeating structurally
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS420682A CS225048B1 (en) | 1982-06-07 | 1982-06-07 | The polyesters of sterically hindered propandione acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS420682A CS225048B1 (en) | 1982-06-07 | 1982-06-07 | The polyesters of sterically hindered propandione acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS225048B1 true CS225048B1 (en) | 1984-02-13 |
Family
ID=5384283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS420682A CS225048B1 (en) | 1982-06-07 | 1982-06-07 | The polyesters of sterically hindered propandione acid |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS225048B1 (en) |
-
1982
- 1982-06-07 CS CS420682A patent/CS225048B1/en unknown
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