CS257379B1 - Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation - Google Patents

Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation Download PDF

Info

Publication number
CS257379B1
CS257379B1 CS868573A CS857386A CS257379B1 CS 257379 B1 CS257379 B1 CS 257379B1 CS 868573 A CS868573 A CS 868573A CS 857386 A CS857386 A CS 857386A CS 257379 B1 CS257379 B1 CS 257379B1
Authority
CS
Czechoslovakia
Prior art keywords
tetramethyl
preparation
piperidylamino
ethylene
vinyl acetate
Prior art date
Application number
CS868573A
Other languages
Czech (cs)
Slovak (sk)
Other versions
CS857386A1 (en
Inventor
Zdenek Manasek
Alzbeta Pajchortova
Gabriela Vassova
Frantisek Vass
Original Assignee
Zdenek Manasek
Alzbeta Pajchortova
Gabriela Vassova
Frantisek Vass
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zdenek Manasek, Alzbeta Pajchortova, Gabriela Vassova, Frantisek Vass filed Critical Zdenek Manasek
Priority to CS868573A priority Critical patent/CS257379B1/en
Publication of CS857386A1 publication Critical patent/CS857386A1/en
Publication of CS257379B1 publication Critical patent/CS257379B1/en

Links

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

(54) Etylén-vinylacetátový kopolymér obsahujúci 2,2,6,6-tetrametyl-4-piperidylamínoskupiny a sposob jeho přípravy(54) Ethylene-vinyl acetate copolymer containing 2,2,6,6-tetramethyl-4-piperidylamino and a process for its preparation

Vynález sa týká etylén-vinylacetátového kopolyméru obsahujúceho 2,2,6,6-tetrametyl-4-piperidylamíno skupiny a sposobu jeho přípravy.The invention relates to an ethylene-vinyl acetate copolymer containing 2,2,6,6-tetramethyl-4-piperidylamino groups and to a process for its preparation.

Nízkomolekulové a polymérne zlúčeniny obsahujúce v svojej štruktúre sféricky tienené amínoskupiny sú účinné světelné stabilizátory užitkových polymérov [F. Gugumus, Developments in Polymer Stabilisation-1, ed. G. Scott, Applied Science Publishers, London, 1979, kap. 8, F. E. Karrer, Makromol. Chem., 181, 595 (1980)].Low molecular weight and polymeric compounds containing spherically shielded amino groups in their structure are effective light stabilizers for utility polymers [F. Gugumus, Developments in Polymer Stabilization-1, ed. G. Scott, Applied Science Publishers, London, 1979, Chap. 8, F. E. Karrer, Makromol. Chem., 181, 595 (1980)].

Medzi zlúčeniny s vysokým stabilizačným efektom sa zaraďujú rožne deriváty 2,2,6,6-tetrametylpiperidínu, 1,2,2,6,6-pentametylpiperidínu, 2,2,6,6-tetraalkylpiperazínu, 7,15diazadispirof 5,1,5,3 Jhexadekánu, 2,2,5,5-tetraalkylpyrolidínu. Sféricky tienené aminy účinné inhibujú degradačné reakcie, ktoré prebiehajú v podmienkach prírodného starnutia polymérov. Nevýhodou nízkomolekulových derivátov sféricky tienených amínov je ich prchavosť a vypieratetnost, čo spůsobuje ich postupný úbytok z úžitkového polyméru už pri samotnom spracovaní, alebo pri působení různých látok s extrakčným účinkom.Compounds with a high stabilizing effect include various derivatives of 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetraalkylpiperazine, 7,15-diazadispirof 5,1,5 3, 3-hexadecane, 2,2,5,5-tetraalkylpyrrolidine. The spherically shielded amines effectively inhibit the degradation reactions that occur under the natural aging conditions of the polymers. The disadvantage of the low molecular weight derivatives of the spherically shielded amines is their volatility and washability, which causes them to gradually disappear from the useful polymer, either during processing or under the action of various substances with an extractive effect.

Přípravou kopolyméru pódia predmetu vynálezu sa eliminuje prchavosť a znižuje extrahovatetnosť tohto vysokomolekulového stabilizátora najma z polyolefínov. Zlúčenina na báze kopolyméru, ktorá je predmetom vynálezu nebola doteraz v odbornej literatúre popísaná.The preparation of the copolymer according to the invention eliminates volatility and reduces the extractability of this high-molecular-weight stabilizer, especially of polyolefins. The copolymer-based compound of the present invention has not been described in the prior art.

Podstatou vynálezu je etylén-vinylacetátový kopolymér obsahujúci 2,2,6,6-tetrametyl-4-piperidylamíno skupiny vzorca I kde R je . fnxThe present invention provides an ethylene-vinyl acetate copolymer containing a 2,2,6,6-tetramethyl-4-piperidylamino group of formula I wherein R is. FNX

CHCH

-CHCH

II

OABOUT

I c--oI c - o

II

Ct-íf-CHp-RCt-if-CHP-R

ÍI) m = 4 až 60, n = 2 až 4, p = 1 až 3, x má hodnotu v rozmedzí od 40 do· 2.(I) m = 4 to 60, n = 2 to 4, p = 1 to 3, x having a value in the range of 40 to 2.

Podstatou vynálezu je ďalej spůsob přípravy kopolymerů vzorca I vyznačujúceho sa tým, že sa na etylén-vinylacetátový kopolymér vzorca II kdeThe present invention further provides a process for the preparation of copolymers of formula (I), characterized in that the ethylene-vinyl acetate copolymer of formula (II):

~CHrCHr~ CH r CH r - - - — - - - - CH— CH. i i. CH— CH. i i. rnx RNX 0 1 O-C-CH^ 0 1 O-C-CH rozmedzí od t ranging from t

nx (II) m = 4 až 60, n = 2 až 4, x má hodnotu v kyseliny 3- (2,2,6,6-tetrametyl-4-piperidylamínojpropánovej vzorca IIInx (II) m = 4 to 60, n = 2 to 4, x has the value in 3- (2,2,6,6-tetramethyl-4-piperidylamino-propanoic acid III)

CH, CHaCH, CHa

ΗN y— NCH?· CH?· C, um ch3 ch3 kdeYN y— NCH? · CH? · C, um ch 3 ch 3 where

R1 je metylová alebo etylová skupina v suchom toluene alebo xyléne pri teplote spatného toku a v atmosféře dusíka za katalýzy amidu lítneho alebo zmesou amidu lítneho a amidu sodného.R 1 is a methyl or ethyl group in dry toluene or xylene at reflux temperature and under nitrogen atmosphere with catalysis of lithium amide or a mixture of lithium amide and sodium amide.

Příklad 1 g granulovaného, etylén-vinylacetátového kopolymeru (II] [Mn = 17 800), obsahujúceho 23,5 % hmot. (0,041 molu] vinylacetátu sa po vysušení za použitia vákua 0,1-0,3 kPa (pri teplote 50 °C po dobu 4 h) rozpustí v 120 ml xylénu (zmes xylénov, po destilácii za přítomnosti sodíka). Po rozpuštění pri teplote 100 °C za miešania a prietoku sušeného dusíka sa přidá 0,6 g (0,026 molu) amidu lítneho suspendovaného v práškovitej formě v 10 mí sušeného xylénu. V časovom intervale 45 minút sa potom za miešania přidá 11 g (0,0432 molu) etylesteru 3-(2,2,6,6-tetrametyl-4-piperidylammo) propanové] (III).Example 1 g of a granulated, ethylene-vinyl acetate copolymer (II) [Mn = 17,800] containing 23.5 wt. (0.041 mol) of vinyl acetate is dissolved in 120 ml of xylene (a mixture of xylenes, distilled in the presence of sodium) after drying under a vacuum of 0.1-0.3 kPa (at 50 ° C for 4 h). At 100 ° C with stirring and dried nitrogen flow, 0.6 g (0.026 mol) of lithium amide suspended in powder form in 10 ml of dried xylene is added, followed by 11 g (0.0432 mol) of ethyl ester with stirring over 45 minutes. 3- (2,2,6,6-tetramethyl-4-piperidylamino) propanoic acid] (III).

Teplota sa zvýši v priebehu 30 min. na 125 °C, po 20 min. sa pridajú 2 g (0,0079 molu) etylesteru III a v inertnej atmosféře pokračuje polyméranalogická reakcia za miešania po dobu 110 min. pri teplote spatného toku. Roztok sa potom ochladí na 60 stupňov Celsia a postupné sa přidává za miešania do 500 ml 90 %-ného vodného etanolu. Vyzrážaný kopolymer sa filtráciou separuje a potom extrahuje v 200 ml 90 °/o-ného vodného etanolu po dobu 10 h. Po izolácii sa nažltlý produkt suší na vzduchu pri teplote 20 °C a potom sa v práškovitej formě dosuší vo vákuovej sušiíarni pri 40 stupňoch Celsia za tlaku 0,2-0,5 kPa. Vysušený produkt s čselným priemerom molekulové j hmotnosti 18 400 (stanovenie Mn metodou VPOJ, obsahuje 4,64 % hmot. dusíka.The temperature is raised within 30 min. to 125 ° C, after 20 min. 2 g (0.0079 mol) of ethyl ester III are added and the polymer-analogous reaction is continued under stirring for 110 min under an inert atmosphere. at reflux temperature. The solution was then cooled to 60 degrees Celsius and added gradually to 500 ml of 90% aqueous ethanol with stirring. The precipitated copolymer is separated by filtration and then extracted in 200 ml of 90% aqueous ethanol for 10 h. After isolation, the yellowish product is air dried at 20 ° C and then dried in powder form in a vacuum oven at 40 degrees Celsius at 0.2-0.5 kPa. The dried product having an average molecular weight of 18,400 (Mn by VPOJ) contains 4.64% nitrogen by weight.

Příklad 2Example 2

Použije sa analogický postup ako v příklade 1 s tým rozdielom, že sa na polyméranalogickú reakciu použije 15 g etyléu-vinylacetátového kopolyméru (Mn = 27 400) o obsahu vinylacetátovej zložky 18 % hmot. (0,031 molu), 9,5 g (0,040 móluj metylesteru kyseliny 3-(2,2,6,6-tetrametyl-4-piperidyl amíno jpropiónovej a ako katalyzátor sa použije zmesný systém 0,4 g (0,0174 móluj amidu lítneho· a 0,3 g (0,0065 móluj amidu sodného, suspendovaný v práškovitej formě v 10 ml absolutného o-xylénu. Po izolácii sa získá nažltlá látka v práškovitej formě s obsahom dusíka 4,28 % hmot. a Mn 28 200.An analogous procedure to that described in Example 1 was followed except that 15 g of ethylene-vinyl acetate copolymer (Mn = 27,400) with a vinyl acetate content of 18% by weight was used for the polymer-analogous reaction. (0.031 mol), 9.5 g (0.040 mol) of 3- (2,2,6,6-tetramethyl-4-piperidyl-amino) propionic acid methyl ester, and a mixed system of 0.4 g (0.0174 mol of lithium amide) is used as catalyst. And 0.3 g (0.0065 mol of sodium amide, suspended in powder form in 10 ml of absolute o-xylene. After isolation, a yellowish powder is obtained with a nitrogen content of 4.28 wt% and an Mn of 28,200.

Příklad 3Example 3

100 hmotnostných dielov nestabilizovaného práškovitého polypropylénu sa zmieša s 0,1 hmot. dielmi 2,6-di-terc.butyl-4-metylfenolu, 0,5 hmot. dielmi kopolyméru připraveného podfa příkladu 1 a 0,15 hmot. dielmi stearanu vápenatého a zmes sa homogenizuje v tavenine v miešacej komoře plastografu Brabender v dusíkovej atmosféře pri teplote 190 °C po 5 min. Zo získánej zmesi sa vylisuje folia o hrúbke 0,15 milimetrov pri tlaku 5 MPa a teplote 210 stupňov Celsia. Vzorky připravené z tejto fólie sa potom ožarujú ortuťovou výbojkou o výkone 125 W vo vzdialenosti 7 cm od zdroja. Degradácia polymeru sa sleduje vývojom karbonylového pása v infračervených spektrách. Doba dosiahnutia karbonylového indexu 0,2 pri týchto podmienkach u polypropylénové) fólie neobsaliujúcej světelný stabilizátor sa dosahuje za 140 hodin, zatial' čo u stabilizovanej fólie sa dosiahne táto hodnota za 1 620 hodin.100 parts by weight of unstabilized powdered polypropylene are mixed with 0.1 wt. parts by weight of 2,6-di-tert-butyl-4-methylphenol, 0.5 wt. parts by weight of the copolymer prepared according to Example 1 and 0.15 wt. The mixture is homogenized in a melt in a mixing chamber of a Brabender plastograph under nitrogen at 190 ° C for 5 min. A sheet of 0.15 mm thickness at a pressure of 5 MPa and a temperature of 210 degrees Celsius is pressed from the obtained mixture. The samples prepared from this film are then irradiated with a 125 W mercury lamp at 7 cm from the source. The degradation of the polymer is monitored by the development of the carbonyl band in the infrared spectra. The time to reach the carbonyl index of 0.2 under these conditions for the polypropylene film not containing the light stabilizer is reached in 140 hours, while for the stabilized film this value is reached in 1,620 hours.

Claims (2)

PREDMET VYNÁLEZUOBJECT OF THE INVENTION 1. Etylén-vinylacetátový kopolymér obsahuj úci 2,2,6,6-tetrametyl-4-piperidylaroíno skupiny vzorca I1. An ethylene-vinyl acetate copolymer containing a 2,2,6,6-tetramethyl-4-piperidylamino group of the formula I - C/<- C/-L- — (Z (Z - C / <- C / -L- (Z (Z -— · « -—- -— · «-—- — CH - Cl·/.— | íZ - CH - Cl · /.— | iZ — ® * — - ® * - — CH - CH.— 1 C - CH - CH.— 1 C 0 0 0 i 0 and c = o I c = o I c=o I c = o I CH3 CH 3 1 CH.-CH.~R 1 CH.-CH. ~ R (n-p) X (n-p) X
ť íl) kde R je in --- 4 až 60, n = 2 až 4, p = 1 až 3, x má hodnotu v rozmedzí od 40 do 2.where R is in --- 4 to 60, n = 2 to 4, p = 1 to 3, x has a value in the range of 40 to 2.
2. Sposob přípravy zlúčeniny I podl'a bodu 1, vyznačujúci sa tým, že sa na etylén-vinylacetátový kopolymér vzorca II2. A process for the preparation of a compound of claim 1, wherein the ethylene-vinyl acetate copolymer of formula II is: Γ τ Γ τ ~ * ~ * £ iZ £ iZ - —, ch- CH I -, ch- CH I O ABOUT 0=CCHA 0 = CCH A mx mx M * M *
nx dl) kde ni -- 4 až 60, n — 2 až 4, x má hodnotu v rozmedzí od 40 do 2, posobí alkylesterom kyseliny 3- (2,2,6,6-tetrametyl-4-piperidylaminojpropánovej vzorca IIInx dl) where ni-4 to 60, n-2 to 4, x having a value in the range of from 40 to 2, has an alkyl ester of 3- (2,2,6,6-tetramethyl-4-piperidylamino) -propanoic acid of formula III O XOR (lil) kdeO X OR (III) where R1 je metylová alebo etylová skupina, v suchom. toluéue alebo xylene pri teplote spatného toku v atmosféře dusíka za katalýzy amidu lítneho alebo zmesi amidu lít něho a amidu sodného.R 1 is a methyl or ethyl group, in the dry state. toluene or xylene at reflux under a nitrogen atmosphere with catalysis of lithium amide or a mixture of lithium amide and sodium amide. Severografia, n. p. závod 7, MostSeverography, n. p. Race 7, Most Sena 2,40 KčsSena 2,40 Kčs
CS868573A 1986-11-24 1986-11-24 Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation CS257379B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CS868573A CS257379B1 (en) 1986-11-24 1986-11-24 Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CS868573A CS257379B1 (en) 1986-11-24 1986-11-24 Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation

Publications (2)

Publication Number Publication Date
CS857386A1 CS857386A1 (en) 1987-09-17
CS257379B1 true CS257379B1 (en) 1988-04-15

Family

ID=5436467

Family Applications (1)

Application Number Title Priority Date Filing Date
CS868573A CS257379B1 (en) 1986-11-24 1986-11-24 Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation

Country Status (1)

Country Link
CS (1) CS257379B1 (en)

Also Published As

Publication number Publication date
CS857386A1 (en) 1987-09-17

Similar Documents

Publication Publication Date Title
US4304882A (en) Polymer from peroxy compounds containing acylating groups
CA1282899C (en) ISOPROPANOLAMINES AS CATALYST DEACTIVATORS IN SOLUTION PROCESS FOR POLYMERIZATION OF .alpha.-OLEFINS
US4331586A (en) Novel light stabilizers for polymers
EP0042589B1 (en) Norbornene polymers stabilized with hindered aromatic alcohols
US3466261A (en) Polyolefins stabilized by thioesters of antimonious acid
US4769457A (en) Glycoluril derivatives and their use as stabilizers for polymers
US4057530A (en) 2-Phenyl-indole derivatives and process for preparing the same
Alvaradejo et al. Maleimide end-functionalized poly (2-oxazoline) s by the functional initiator route: synthesis and (bio) conjugation
US4356287A (en) Novel polymeric light stabilizers for polymers
JPH06234808A (en) Method for finishing polymer
EP0022501A1 (en) Polycondensates of substituted piperidines and use thereof as stabilizers for polymers
CS257379B1 (en) Ethylene vinylacetate copolymere containing 2,2,6,6-tetramethyl-4-piperidylamino group and method of its preparation
EP0426499B1 (en) Polymeric additives
Chmela et al. Stabilising effect of monomers, homopolymers and copolymers of vinyl derivatives of sterically hindered amines on the photo-oxidation of polypropylene
CA1336194C (en) Siliconic stabilizer compounds for organic polymers, and process for their preparation
JPH08259535A (en) Composition and method for stabilizing synthetic polymer
CS257380B1 (en) Ethylene-vinylacetate copolymere containing 7,15-diaxadispiro(5,1,5,3)hexadecyle groups
US4386177A (en) Light stabilizers for polymers containing hindered piperidinyl-substituted 1,3,5 triazine groups
Ferruti et al. Synthesis and exchange reactions of some polymeric benzotriazolides
US4370430A (en) Hindered amine light stabilizers for polymers
JPH02174775A (en) 2, 6-polyalkylpiperidine-substituted benzimidazole-2- carboxylic acid anilide and method for stabilizing organic material therewith
US5281645A (en) Benzophenones containing an ester functional group and their use in polymers
SU429070A1 (en) METHOD FOR OBTAINING A COLORLESS COPOLYMER. TESTER WITH ACRYLONITRILE 1 The invention relates to the production of polystyrene plastics, in particular, to the preparation of styrene and acrylonitrile copolymers that are resistant to color change under the conditions of processing into products. slightly yellowish materials. Heating them briefly at 50–180 ° C, especially at 200–220 ° C, associated with the processing of the material, leads to a change in color. The copolymer becomes much yellower and even darker. A method is known for preparing color-resistant copolymers by thermal polymerization in an inert gas atmosphere of 80–60 wt. % styrene and 20-40 weight. % acrylonitrile in the presence of 0.05 ^ 0.25 wt. % organophosphorus compound of general formula 1015 where RI is alkyl (Ci — € 4); Ro is alkyl (Ci — Sat); Rs is alkyl (Ci — GS), aryl or alkaryl. This method makes it possible to obtain copolymers that are resistant to color change at a processing temperature of 200–220 ° C for 30–40 minutes. The purpose of the invention is to obtain copolymers that are resistant to temperatures of 200–220 ° C for a long time. . This is achieved by copolymerization in an inert gas atmosphere at elevated temperatures of 80–60 wt. % styrene with 20-40 weight. % acrylonitrile in the presence of a mixture consisting of 0.05-0.25 weight. % 2,4,6-trialkylphenol of the general formula 2025CCH ^) ^ CCICH ^) ^ where R is alkyl (Ci — 4), and an organophosphorus compound with a total of 30 formulas
CZ257691A3 (en) liquid photo-stabilizing ingredients for polymers and process for preparing thereof
US4371695A (en) Stabilizers for polymers and polymers stabilized thereby