CS272639B1 - 1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane - Google Patents
1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane Download PDFInfo
- Publication number
- CS272639B1 CS272639B1 CS22189A CS22189A CS272639B1 CS 272639 B1 CS272639 B1 CS 272639B1 CS 22189 A CS22189 A CS 22189A CS 22189 A CS22189 A CS 22189A CS 272639 B1 CS272639 B1 CS 272639B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- tetramethyl
- propenyloxymethyl
- dioxa
- undecane
- bis
- Prior art date
Links
- ALDHHPYPKQQDBC-UHFFFAOYSA-N 8,9,10,10-tetramethyl-3,3-bis(prop-2-enoxymethyl)-1,5-dioxa-9-azaspiro[5.5]undecane Chemical compound C(C=C)OCC1(COC2(OC1)CC(N(C(C2)(C)C)C)C)COCC=C ALDHHPYPKQQDBC-UHFFFAOYSA-N 0.000 title 1
- -1 2-propenyloxymethyl Chemical group 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- RUVGXVRFQYHCRO-UHFFFAOYSA-N 8,8,10,10-tetramethyl-3,3-bis(prop-2-enoxymethyl)-1,5-dioxa-9-azaspiro[5.5]undecane Chemical compound C(C=C)OCC1(COC2(OC1)CC(NC(C2)(C)C)(C)C)COCC=C RUVGXVRFQYHCRO-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Vynález sa týká l,5-dioxa-3,3-bis(2-propenyloxymetyl)8,8,10,10-tetrametyl-9-azaspirop, 5jundekánu.The invention relates to 1,5-dioxa-3,3-bis (2-propenyloxymethyl) 8,8,10,10-tetramethyl-9-azaspirop, 5 -undecane.
Stéricky tienené aminy patria v súčastnosti medzi najúčinnejšie světelné stabilizátory pre polyméry (P,E. Karrer, Makromol, Chem., 181, 595 (1980), E. Gugumus, Developments in Polymer Stabilisation-1, ed, G, Scott, Applied Science Publishers, London, 1979, kap. 8, J.J. Usilton, A.R. Patel, Am. Chem. Soc. Polym. Prep., 18(1), 393(1977). Sú to rozličné deriváty 2,2,^;6-tetraalkylpiperidínu, 1,2,2,6,6-pentaalkylpiperidínu, 2,2,6,6-tetraalkylpiperazínu alebo 7,15-diazadispiro£5,l,5,33hexadekánu. Tieto zlúčeniny inhibujá nežiadúce degradačné procesy, ktoré prebiehajú pri interakci! světla a kyslíka s polymérmi, Nevýhodou tejto triedy světelných stábilizátorov je vysoká prchavosť a extrahovatelnosť nizkomolekulových derivátov z polymérov. Zlúčenina, ktorá je predmetom vynálezu, obsahuje vo svojej molekule dve funkčně nenasýtenó vazby. Přítomnost’ týchto skupin v molekule světelného stabilizátora umožňuje pripravu vysokomolekulových světelných stábilizátorov polymerizáoiou nenasýtených vazieb alebo ich kopolymerizáciu s inými nenasýtenými monomérmi. Táto zlúčenina nebola doteraz popísaná v odborné J literatúře.Sterically shielded amines are currently among the most effective light stabilizers for polymers (P, E. Karrer, Macromol, Chem., 181, 595 (1980), E. Gugumus, Developments in Polymer Stabilization-1, ed, G, Scott, Applied Science Publishers, London, 1979, Chapter 8, JJ Usilton, AR Patel, Am Chem Soc Polym Prep, 18 (1), 393 (1977), which are various derivatives of 2,2,6,6-tetraalkylpiperidine 1,2,2,6,6-pentaalkylpiperidine, 2,2,6,6-tetraalkylpiperazine or 7,15-diazadispiro [eta] < 5 >, 1, 5.33 hexadecane. The disadvantage of this class of light stabilizers is the high volatility and the extractability of the low molecular weight derivatives of the polymers.The compound of the invention contains two functionally unsaturated bonds in its molecule. Light stabilizers by polymerizing unsaturated bonds or copolymerizing them with other unsaturated monomers. This compound has not been previously described in the literature.
Podstatou vynálezu je l,5-dioxa-3,3-bis(2-propenyloxymetyl)-8,8,10,10-tetrametyl-9-azaspirof5,5]undekán vzorca IThe present invention provides 1,5-dioxa-3,3-bis (2-propenyloxymethyl) -8,8,10,10-tetramethyl-9-azaspirof5,5] undecane of formula I
Spósob přípravy zlúčeniny vzorca I spočívá v tom, že 2,2,6,6-tetrametyl-4-oxopiperidín vzorca IIA process for the preparation of a compound of formula I is characterized in that 2,2,6,6-tetramethyl-4-oxopiperidine of formula II
H-,θ CH,H-, θ CH,
H-ií \= O . V (ii) H = 1. V (ii)
NjC CH3 reaguje s 2,2-di(2-propenyloxymetyl)-l,3-přopándiolom vzorca III ho-ch2 ci^-o-ci^-ch=ch2 ho-ch/^ 'kch2-o-ch2-ch=ch2 (III) rfCS 272639 Bl pri teplote spatného toku uhlovodíkového rozpúšťadla, ktoré tvoří s vodou azeotropiokú zmes, ako je například benzén, toluén alebo xyleny, za přítomnosti kyslého katalyzátora, ako je například kyselina 4-toluénsulfonová.NJC CH 3 is reacted with 2,2-di (2-propenyloxymetyl) -l, 3-propanediol of formula III it -CH 2 C ^ -O-C-CH-CH 2 -CH him / ^ 'of CH2 -O -ch 2 -ch = ch 2 (III) rfCS 272639 B1 at a low flow temperature of a hydrocarbon solvent which forms an azeotropic mixture with water such as benzene, toluene or xylenes in the presence of an acid catalyst such as 4-toluenesulfonic acid.
Předmětná látka sa mSže použit' ako světelný stabilizátor pre polyméry alebo je medziproduktom pre pripravu polymérnych světelných stabilizátorov polymerizačnými alebo kopolymerizačnými reakciami.The subject substance can be used as a light stabilizer for polymers or is an intermediate for the preparation of polymeric light stabilizers by polymerization or copolymerization reactions.
Příklad 1Example 1
Do banky opatrenej nástavcom na azeotropické oddelovanie vody a spatným chladičom sa vloží 4,66 g (0,03 mol) 2,2,6,6-tetrametyl-4-oxopiperidínu, 6,28 g (0,033 mol) kyseliny 4-toluénsulfónovejxH2O a 60 ml benzénu. Reakčná zmes sa za miešania zahrieva na teplotu spatného toku 0,5 hodiny, pričom sa oddestiluje kryštálová vody a vlhkost’zo systému. Súčasne vzniká sol' kyseliny a derivátu piperidinu. Potom sa přidá 6,49 g (0,03 mol) 2,2-di(2-propenyloxymetyl)-l,3-propándiolu v 10 ml benzénu. Reakčná zmes sa refluxuje, kým sa nevylúči teoretické množstvo vody (5 hodin). Po ochladení sa reakčná zmes vleje do 100 ml 10 % chladného vodného roztoku hydroxidu sodného a dobré pretrepe. Oddělí sa organická vrstva a vodná fáza sa dvakrát extrahuje 30 ml benzénu. Spojené extrakty sa perú vodou a solankou a vysušia sa bezvodým síranom sodným. Benzén sa oddestiluje na rotačněj vakuovéj odparke, pričom sa získá 10,6 g nažltlej kvapaliny (100 % teoretického výtažku), ktorá sa vákuovo destiluje. Zachytává sa bezfarebná viskózna kvapalina v teplotnom intervale 150 až 160 °C pri tlaku 133 Pa,A flask equipped with an azeotropic water separator and a reflux condenser was charged with 4.66 g (0.03 mol) of 2,2,6,6-tetramethyl-4-oxopiperidine, 6.28 g (0.033 mol) of 4-toluenesulfonic acidxH 2. 0 and 60 ml benzene. The reaction mixture was heated to reflux for 0.5 hours with stirring while crystalline water and moisture were distilled off from the system. A salt of the acid and piperidine derivative is formed simultaneously. 6.49 g (0.03 mol) of 2,2-di (2-propenyloxymethyl) -1,3-propanediol in 10 ml of benzene are then added. The reaction mixture was refluxed until the theoretical amount of water had precipitated (5 hours). After cooling, the reaction mixture is poured into 100 ml of 10% cold aqueous sodium hydroxide solution and shaken well. The organic layer was separated and the aqueous phase was extracted twice with 30 ml of benzene. The combined extracts were washed with water and brine and dried over anhydrous sodium sulfate. The benzene was distilled off on a rotary evaporator to give 10.6 g of a yellowish liquid (100% of theory) which was vacuum distilled. A colorless viscous liquid is collected over a temperature range of 150 to 160 ° C at a pressure of 133 Pa,
Elementárna analýza pre C2OH35WO4! Elemental Analysis for C 20 H 35 WO 4 ?
Vypočítané; C - 67,95 %, H 9,98 %, N « 3,96 %calculated; C - 67.95%, H 9.98%, N «3.96%
Nájdené: C » 68,09 %, H «10,02 %, N « 3,84 % ΧΗ NMR spektrum (CDCl-j):Found: C »68.09%, H '10.02%, N' 3.84% Χ Η NMR (CDCl-j):
cf(ppm) » 1,12 (s,0H3-, 12 H), 1,60 (s.-CHg-, 4 H), 3,36 (s,-0H2-0-, 4 H), 3,67 (b,cf (ppm) »1.12 (s, OH 3 -, 12 H), 1.60 (s, -CH 2 -, 4 H), 3.36 (s, -0H 2 -O-, 4 H), 3.67 (b,
-OHg-0-,4 H), 3,88 (m,-0H2-0-, 4 H), 5,11 (m,CH2»CH-, 4 H), 5,79 (m, CH2=CH-, 2 H)-OHg-O-, 4 H), 3.88 (m, -OH 2 -O-, 4 H), 5.11 (m, CH 2 · CH-, 4 H), 5.79 (m, CH 2 = CH-, 2 H)
Příklad 2Example 2
Postupuje sa rovnako ako v příklade 1 s tým rozdielom, že sa ako rozpúštadlo použije toluén a doba reakcie je 3 hodiny. Získá sa 10,6 g surového produktu (100 % teoretického výtažku). Produkt destiluje v teplotnom intervale 151 až 158 °0 pri tlaku 133 Pa.The procedure was as in Example 1 except that toluene was used as the solvent and the reaction time was 3 hours. 10.6 g of crude product are obtained (100% of theory). The product distilled over a temperature range of 151 to 158 ° 0 at 1 mm Hg.
Elementárna analýza pre θ2ΟΒ35ΒΟ4: Elemental analysis for θ2Ο Β 35 ΒΟ 4 :
Vypočítané; 0 « 67,95 %, H - 9,98 %, N « 3,96 %calculated; 0 «67.95%, H - 9.98%, N« 3.96%
Nájdené; C « 67,90 %, H - 9,88 %, N « 4,02 % *Ή NMR spektrum je totožné so spektrom zlúčeniny pripravenej podl’a příkladu 1.found; C 67 67.90%, H 9 9.88%, N% 4.02% * The NMR spectrum is identical to that of the compound prepared according to Example 1.
Příklad 3Example 3
100 hmotnostných dielov nestabilizovaného práškovitého polypropylénu sa impregnuje v dichlormetáne s 0,1 hmot. dielmi 2,6-di-terc.butyl-4-metylfenolu, 0,15 hmot. dielmi stearanu vápenatého a s 0,1 hmot. dielmi zlúčeniny, pripravenej podía příkladu 1.100 parts by weight of unstabilized powdered polypropylene are impregnated in dichloromethane with 0.1 wt. parts by weight of 2,6-di-tert-butyl-4-methylphenol, 0.15 wt. parts by weight of calcium stearate and with 0.1 wt. parts of the compound prepared according to Example 1.
Po odpaření rozpúšťadla sa zo zmesi vylisujú folie o hrúbke 0,2 mm pri tlaku 20 MPa a teplote 190 °C po dobu 3 minút. Takto připravené fólie sa ožarujú ortuťovou výbojkou o výkone 125 W vo vzdialenosti 7 cm od zdroja, Degradácia sa sleduje vývojom karbonylového pásu v infračervených spektrách. Kým doba dosiahnutia karbonylového indexu 0,2 je u čistého polypropylénu 200 hodin, stabilizovaný polymér dosiahne túto hodnotu až «iAfter evaporation of the solvent, 0.2 mm thick sheets are pressed from the mixture at 20 MPa at 190 ° C for 3 minutes. The films thus prepared are irradiated with a 125 W mercury lamp at a distance of 7 cm from the source. The degradation is monitored by developing the carbonyl band in the infrared spectra. While the carbonyl index time of 0.2 is 200 hours for pure polypropylene, the stabilized polymer reaches this
CS 272639 Bl po 980 hodinách.CS 272639 B1 after 980 hours.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS22189A CS272639B1 (en) | 1989-01-12 | 1989-01-12 | 1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS22189A CS272639B1 (en) | 1989-01-12 | 1989-01-12 | 1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS22189A1 CS22189A1 (en) | 1990-05-14 |
| CS272639B1 true CS272639B1 (en) | 1991-02-12 |
Family
ID=5333934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS22189A CS272639B1 (en) | 1989-01-12 | 1989-01-12 | 1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS272639B1 (en) |
-
1989
- 1989-01-12 CS CS22189A patent/CS272639B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS22189A1 (en) | 1990-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Harpp et al. | Organic sulfur chemistry. 26. Synthesis and reactions of some new sulfur transfer reagents | |
| JP4153031B2 (en) | Polymerizable monomers and polymers | |
| JPS6176519A (en) | Polymer substance showing liquid crystal phase | |
| US5223591A (en) | Initiators for polymerization | |
| CA1052799A (en) | Phenol-acetals | |
| JPH0321619A (en) | New polyacetal copolymers of trioxane and trimethylol propane formal derixatives | |
| US3704311A (en) | Functional bis(perfluoroalkylsulfonyl)alkyl compounds | |
| CS272639B1 (en) | 1,5-dioxa-3,3-bis (2-propenyloxymethyl)-8,9,10,10-tetramethyl-9-azaspiro(5,5)undecane | |
| US2619491A (en) | Tetrahydropyranyl ethers | |
| US3758593A (en) | Functional bis(perfluoroalkylsulfonyl)alkyl | |
| US3578717A (en) | Perfluoroalkyl vinyl sulfones and process for producing same | |
| US3449340A (en) | Triazines containing oxetane groups | |
| CS254697B1 (en) | 4,4-bis (2-chloroethoxy) -2,2,6,6-tetramethylpiperidine and its preparation | |
| US3758531A (en) | Functional bis (perfluoroalkylsulfonyl) alkyl compounds | |
| CS259396B1 (en) | 1,2,2,6,6-Pentamethyl-4- (n-bromoalkoxy) piperidines and a process for their preparation | |
| CS259250B1 (en) | 1,6-Dioxa-9,9,11,11-tetramethyl-10-azaspiro [6,5] dodecene-3 and its preparation | |
| US4282343A (en) | Poly-(alpha-alkoxy)acrylamide and poly-(alpha-alkoxy)acrylamide complexes | |
| US3700737A (en) | Perfluoroalkyl vinyl sulfones | |
| CS216273B1 (en) | Polymerizable luminous stabilizers of the piperazine type | |
| RU1835405C (en) | Oligomer stibazane as antipyrene for epoxy resin and a technique of production of oligomer stibazane | |
| Bilgici et al. | Synthesis and polymerizations of novel bisphosphonate‐containing methacrylates derived from alkyl α‐hydroxymethacrylates | |
| Samyn et al. | Synthesis, polymerization, and copolymerization of lactams containing vinyl groups | |
| JPS6154789B2 (en) | ||
| US5189184A (en) | 2-(3'-butenyl)-3,4-dihydro-2h-pyrans, their synthesis and use | |
| US4329480A (en) | Cyclic meta-sulfonium-phenoxide zwitterions |