SK560190A3 - Composition containing an elastomer and stabiliser mixture, use thereof and method of elastomer stabilisation - Google Patents
Composition containing an elastomer and stabiliser mixture, use thereof and method of elastomer stabilisation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C08K5/375—Thiols containing six-membered aromatic rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
Description
Kompozícia obsahujúca elastomér a stabilizátorovú zmes, jej použitie a spôsob stablizácie elastomérovA composition comprising an elastomer and a stabilizer composition, its use and a method for stabilizing the elastomers
Oblasť. technikyArea. technique
Vynález sa týka kompozície obsahujúcej elastomér a stabilizátorovú zmes, jej použitia a spôsobu stablizácie elastomérov.The invention relates to a composition comprising an elastomer and a stabilizer composition, to its use and to a method of stabilizing the elastomers.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Deriváty fenolu obsahujúce alkyltiometylovú skupinu v zmesiach so zlúčeninami obsahujúcimi fosfor a/alebo síru sú známe ako stabilizátory pre elastoméry. Napríklad v európskom patente č. 049 133 A je opísaná zmes, ktorá obsahuje 4 zložky. Zmes pozostáva z difenylamínu, trifenylfosfitu, dialkyltiodipropionátu a aspoň jedného alkylfenolu alebo bisfenolu, ako je napríklad bis-(4-hydroxybenzyl)tioéter.Phenol derivatives containing an alkylthiomethyl group in mixtures with phosphorus and / or sulfur containing compounds are known as stabilizers for elastomers. For example, in European patent no. 049 133 A discloses a composition comprising 4 components. The mixture consists of diphenylamine, triphenylphosphite, dialkylthiodipropionate and at least one alkylphenol or bisphenol such as bis- (4-hydroxybenzyl) thioether.
Z US patentu č. 3 658 743 A je známa zmes pre elastoméry, ktorá pozostáva z troch zložiek. Zmes je tvorená fenolom alebo bisfenolom, ako bola predtým uvedená v európskom patente č.049 133 A, organickým sulfidom alebo dialkyltiodialkanolátom a epoxidom alebo fosfitom, ako je napríklad trifenylfosfit.U.S. Pat. No. 3,658,743 A is a known compound for elastomers which consists of three components. The mixture consists of a phenol or bisphenol, as previously disclosed in European Patent No. 049 133 A, an organic sulfide or dialkylthio dialkanolate and an epoxide or phosphite, such as triphenylphosphite.
V DE patentovom spise č. 23 34 163 A je opísaná zmes tvorená 2 zložkami, ktorá pozostáva z fenolu a fosfitu. Stabilizátorová zmes obsahuje napríklad 2,6-dialkyl-substituovaný 4-(alkylmerkaptometyl)fenol, ako fenolickú zložku a 4-alkylalebo 2,4-dialkyl-substituovaný trifenylfosfit.In DE patent no. 23 34 163 A discloses a mixture of 2 components consisting of phenol and phosphite. The stabilizer mixture comprises, for example, 2,6-dialkyl-substituted 4- (alkylmercaptomethyl) phenol as a phenolic component and 4-alkyl or 2,4-dialkyl-substituted triphenyl phosphite.
V US patente č. 3 637 585 A je ďalej uvedená dvojzložková zmes, ktorá obsahuje alkylmerkaptometylfenol, v ktorom alkylový zvyšok nesie 2 alkanoyloxylové substituenty, ako aj dialkyltioalkanoát.U.S. Pat. No. 3,637,585 A is a further two-component composition comprising an alkyl mercaptomethylphenol in which the alkyl moiety carries 2 alkanoyloxy substituents as well as a dialkylthioalkanoate.
V EP patente č. 0 224442 je ako stabilizátor uvedenýIn EP patent no. 0 224442 is disclosed as a stabilizer
6-alkyl-2,4-bis(tiometyl)fenol.6-alkyl-2,4-bis (thiomethyl) phenol.
Samotné fenoly obsahujúce alkyltiometylovú skupinu sú tiež známe ako stabilizátory elastomérov. V európskom patente č. 0 165 209 A sú napríklad opísané 2,4-bis(merkaptometyl)-6-alkylfenoly, ako zvlášť účinné stabilizátory.The alkylthiomethyl-containing phenols themselves are also known as elastomer stabilizers. In European patent no. For example, 2,4-bis (mercaptomethyl) -6-alkylphenols are described as particularly effective stabilizers.
Naďalej však trvá potreba účinných stabilizátorov pre elastoméry> ktoré sú citlivé proti oxidatívnemu odbúravaniu.However, there remains a need for effective stabilizers for elastomers that are sensitive to oxidative degradation.
Podstata vynálezuSUMMARY OF THE INVENTION
Predmetom tohto vynálezu je kompozícia obsahujúca elastomér a stabilizátorovú zmes, ktorá pozostáva zIt is an object of the present invention to provide a composition comprising an elastomer and a stabilizer composition comprising:
a) 2,4-bis-(n-oktyltiometyl)-6-metylfenolu a(a) 2,4-bis- (n-octylthiomethyl) -6-methylphenol; and
b) aspoň jednu zlúčeninu zo skupiny tris(4-nonylfenyl)fosfit, tris(2,4-di-t-butylfenyl)fosfit,b) at least one compound from the group tris (4-nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite,
3.9- bis(stearyloxy)-2,4,8,10-tetraoxa-3,9-difosfaspiro[5,5]undekán, tetrakis(3-dodecyltio-propionyloxymetyl)metán, bis[β-(n-tridecyloxykarbony1)etyl]merkaptán,3.9-bis (stearyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, tetrakis (3-dodecylthio-propionyloxymethyl) methane, bis [β- (n-tridecyloxycarbonyl) ethyl] mercaptan,
3.9- bis(2,4-di-t-butylfenoxy)-2,4,8,10-tetraoxa-3,9-difosfaspiro[5.5]undekán,3,9-bis (2,4-di-t-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane;
3.9- bis(2,4-di-t-butyl-6-metylfenoxy)-2,4,8,10-tetraoxa-3,9-difosfaspiro[5.5]undekán, pričom pomer a) a b) je v rozsahu od 9:1 do 1:9.3,9-bis (2,4-di-t-butyl-6-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, wherein the ratio a) and b) range from 9 : 1 to 1: 9.
Kompozícia podlá tohto vynálezu môže napríklad ako elastoméry obsahovať ďalej uvedené materiály:For example, the composition of the present invention may include the following materials as elastomers:
1. Polydiény, ako napríklad polybutadién, polyizoprén alebo polychloroprén, blokové polyméry, ako napríklad styrén-butadién-styrénový, styrén-izoprén-styrénový alebo akrylonitrilbutadiénový kopolymér alebo styrén-butadiénový kopolymér.Polydienes such as polybutadiene, polyisoprene or polychloroprene, block polymers such as styrene-butadiene-styrene, styrene-isoprene-styrene or acrylonitrile-butadiene copolymer or styrene-butadiene copolymer.
2. Kopolyméry monoolefínov a diolefínov vytvorené navzájom alebo s inými vinylovými monomérmi, ako sú napríklad etylén-alkylakrylátové kopolyméry, etylén-alkylmetakrylátové kopolyméry, etylén-vinylacetátové kopolyméry, rovnako ako terpolyméry etylénu s propylénom a diénom, ako je hexadién, dicyklopentadién alebo etylidénnorbornom.2. Copolymers of monoolefins and diolefins formed with each other or with other vinyl monomers, such as ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers, as well as terpolymers of ethylene with propylene hexene or diene, such as ethylene-diene pentene or diene, such as.
3. Polyméry obsahujúce halogén, ako je napríklad polychloroprén, chlórkaučuk, chlórovaný alebo chlórsulfónovaný polyetylén, epichlórhydrínové homopolyméry a kopolyméry, chlórtrifluóretylénové kopolyméry, polyméry z vinylových zlúčenín obsahujúcich halogén, ako je napríklad polyvinylidénchlorid, polyvinylidénf luorid, ako aj ich kopolyméry, ako je vinylchlorid-vinylidénchlorid, vinylchlorid-vinylacetát alebo vinylidénchlorid-vinylacetát.3. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homopolymers and copolymers, chlorotrifluoroethylene copolymers, polymers of halogen-containing vinyl compounds such as polyvinylidene chloride, such as polyvinylidene chloride vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
4. Polyuretány, ktoré sú odvodené od polyéterov, polyesterov a polybutadiénu s hydroxyskupinami na konci reťazca a od alifatických alebo aromatických polyizokyanátov, rovnako ako ich predprodukty.4. Polyurethanes derived from polyethers, polyesters and polybutadiene with end-chain hydroxy groups and from aliphatic or aromatic polyisocyanates, as well as precursors thereof.
5. Prírodný kaučuk.5. Natural rubber.
6. Zmesi vyššie uvedených polymérov.6. Mixtures of the above polymers.
7. Vodné zmesi prírodných a syntetických kaučukov, ako napríklad mlieko prírodného kaučuku alebo latexy karboxylovaných styrén-butadiénových kopolymérov.7. Aqueous mixtures of natural and synthetic rubbers such as natural rubber milk or latexes of carboxylated styrene-butadiene copolymers.
Tieto elastoméry sa tiež môžu predkladať ako latexy a ako také sa môžu stabilizovať.These elastomers may also be presented as latexes and as such may be stabilized.
Výhodné sú kompozície, ktoré ako elastoméry obsahujú polydién, ako je polybutadiénový kaučuk, halogénovaný polymér, ako je polyvinylidénfluorid alebo polyuretán. Zvlášť výhodné sú kompozície, ktoré ako elastomér obsahujú polybutadiénový kaučuk.Preference is given to compositions which comprise as elastomers a polydiene such as polybutadiene rubber, a halogenated polymer such as polyvinylidene fluoride or polyurethane. Particularly preferred are compositions which contain polybutadiene rubber as elastomer.
Podlá tohto vynálezu kompozícia účelne obsahuje 0,01 až 10 % hmotn. stabilizátorovej zmesi tvorenej zložkou a) a b) , vzťahujúce sa na elastomér, zvlášť 0,05 až 5,0 % hmotn., napríklad 0,05 až 3 % hmotn., predovšetkým 0,1 až 2 % hmotn. zmesi stabilizátorov všeobecného vzorca I a/alebo vzorca II a IV a všeobecného vzorca III, V a VI sa môže takisto používať. Vzájomný pomer obidvoch zložiek a) a b) sa môže meniť v širokom rozsahu. Hmotnostný pomer zložky a) k zložke b) je účelne 9:1 až 1:9, napríklad 2:8 až 8:2 alebo 3:7 až 7:3. Výhodný pomer je v rozsahu od 2:1 do 1:2 a zvlášť predstavuje asi 1:1 až 1:2.Suitably, according to the invention, the composition comprises 0.01 to 10 wt. a stabilizer mixture of components a) and b), based on the elastomer, in particular from 0.05 to 5.0% by weight, for example from 0.05 to 3% by weight, in particular from 0.1 to 2% by weight. mixtures of stabilizers of formula I and / or formula II and IV and formula III, V and VI may also be used. The ratio of the two components a) and b) can vary widely. The weight ratio of component a) to component b) is suitably 9: 1 to 1: 9, for example 2: 8 to 8: 2 or 3: 7 to 7: 3. A preferred ratio is in the range of from 2: 1 to 1: 2, and is especially about 1: 1 to 1: 2.
Zapracovanie do elastomérov sa môže uskutočňovať napríklad primiešaním substancií a) a b) a prípadne ďalších prísad, ako napríklad urýchíovača vulkanizácie, plniva, zmäkčovadla alebo pigmentu, metódami zodpovedajúcimi obvyklým technickým postupom, pred alebo v priebehu vytvárania alebo tiež nanášaním rozpustených alebo dispergovaných zlúčenín na polymér, prípadne s nasledujúcim odparením rozpúšťadla. K stabilizovaným plastickým hmotám sa zlúčeniny vzorca I až VI môžu tiež pridávat vo forme masterbača, ktorý obsahuje tieto zlúčeniny napríklad v koncentrácii od 2,5 do 25 % hmotn..The incorporation into elastomers can be carried out, for example, by mixing substances a) and b) and optionally other additives, such as vulcanization accelerator, filler, plasticizer or pigment, by methods corresponding to conventional techniques, before or during formation, or optionally followed by evaporation of the solvent. The stabilized plastics can also be added in the form of a masterbatch containing these compounds, for example in a concentration of from 2.5 to 25% by weight.
Výroba zlúčenín a) a b) sa uskutočňuje podía známych spôsobov, ako sú v súvislosti so zlúčeninou a) popísané v EP A 0 165 209 a v US A 3 227 677. Môžu sa tiež získať reakciou fenolu všeobecného vzorca laThe preparation of the compounds a) and b) is carried out according to known methods, as described in connection with compound a) in EP-A-0 165 209 and US-A-3 227 677. They can also be obtained by reaction of a phenol of the formula Ia
kde R1 j e metyl a R3 je vodík, s formaldehydom alebo zlúčeninou, ktorá za reakčných podmienok formaldehyd uvolňuje a s aspoň jedným merkaptanom všeobecného vzorca R2-SH, kde R2 je Cg_C12 alkyl v prítomnosti bázi, ktorou je monometylamín, dimetylamín, trimetylamín, monoetylamín alebo diétylamín.wherein R 1 is methyl and R 3 is hydrogen, with formaldehyde or a compound which liberates formaldehyde under the reaction conditions and with at least one mercaptan of the formula R 2 -SH, wherein R 2 is C 8 -C 12 alkyl in the presence of a monomethylamine, dimethylamine base, trimethylamine, monoethylamine or diethylamine.
Príklady uskutočnenia vvnálezuDETAILED DESCRIPTION OF THE INVENTION
Nasledujúce príklady ďalej objasňujú vynález. Percentá a diely uvádzané v príkladoch sú percentá hmotnostné a hmotnostné diely.The following examples further illustrate the invention. The percentages and parts given in the examples are percentages by weight and parts by weight.
Príklad 1Example 1
Spôsob výroby 2,4-bis(n-oktyltiometyl)-6-metylfenoluA process for the preparation of 2,4-bis (n-octylthiomethyl) -6-methylphenol
160,74 g (0,72 mol) 2,4-bis(dimetylarainometyl)-6-metylfenolu a 210,65 g (1,44 mol) n-oktántiolu sa zohrieva v zariadení vybavenom miešadlom a chladičom na intenzívne miešanie na teplotu 150 ’C počas 36 hodín, pričom pri tlaku 5,3 2 MPa sa odvádza dimetylamín. Získa sa 291,6 g (95 %) žltého oleja. Čistý 2,4-bis-(n-oktyltiometyl)-6-metylfenol sa získa stĺpcovou chromatografiou surového produktu na silikagé6 li vo forme bezfarebného oleja.160.74 g (0.72 mol) of 2,4-bis (dimethylarainomethyl) -6-methylphenol and 210.65 g (1.44 mol) of n-octanethiol are heated to 150 with a stirrer and cooler for vigorous stirring. Dimethyl amine is evacuated at 36 psi. 291.6 g (95%) of a yellow oil are obtained. Pure 2,4-bis- (n-octylthiomethyl) -6-methylphenol was obtained by column chromatography of the crude product on silica gel 11 as a colorless oil.
Elementárna analýza:Elemental analysis:
Vypočítané: 70,69 % C, 10,44 % H, 15,09 % S,Calculated: C 70.69, H 10.44, S 15.09,
Nájdené: 70,85 % C, 10,42 % H, 15,11 % S.Found:% C, 70.85;% H, 10.42;% S, 15.11.
Príklad 2Example 2
Spôsob stabilizácie polybutadiénového kaučuku (starnutie v silikónovom oleji)Method of stabilization of polybutadiene rubber (aging in silicone oil)
100 g polybutadiénu, ktorý bol predstabilizovaný 0,4 %100 g of polybutadiene which has been pre-stabilized 0,4%
2,6-di-terc-butyl-p-krezolu, sa mieša na miešacom kalandri pri teplote 50 ’C v priebehu 6 minút na homogénny produkt s 0,15 % stabilizátorovej zložky a) a 0,3 % stabilizátorovej zložky b). Z valcovanej hmoty sa pri teplote 80 ’C lisujú dosky s hrúbkou 2 mm. Týmto spôsobom sa tiež vyrobia ďalšie dosky bez stabilizátora.2,6-di-tert-butyl-p-cresol, is mixed on a stirring calender at 50 ° C for 6 minutes to a homogeneous product with 0.15% stabilizer component a) and 0.3% stabilizer component b). Sheets of 2 mm thickness are pressed from the rolled material at 80 ° C. Other boards without stabilizer are also produced in this way.
Skúšobná vzorka starne ponorením do silikónového oleja s teplotou 160 ’C počas 30 minút. Ako merítko slúži obsah gélu na konci starnutia. Obsah gélu sa stanovuje takto:The test specimen ages by immersion in silicone oil at 160 ° C for 30 minutes. The gel content at the end of aging serves as a measure. The gel content is determined as follows:
Skúšaná vzorka sa po starnutí rozpustí v 100 ml toluénu pri laboratórnej teplote. Po 24 hodinách sa roztok filtruje cez drôtové sito (pódia normy ASTM E 11 č. 400) a zachytený zvyšok sa starostlivo premyje a vysuší. Obsah gélu sa stanoví zo vzorcaAfter aging, the test sample is dissolved in 100 ml of toluene at room temperature. After 24 hours, the solution is filtered through a wire mesh (ASTM E 11 No. 400) and the collected residue is carefully washed and dried. The gel content is determined from the formula
Gelgel
EE
X 100 (%) kdeX 100 (%) where
Fg znamená hmotnosť filtra s gélom,Fg means the weight of the gel filter,
Fo znamená hmotnosť prázdneho filtra aFo means the mass of the empty filter and
E znamená navážku skúšanej vzorky.E is the test sample.
Výsledky sú zhrnuté v ďalej uvedenej tabuíke 1.The results are summarized in Table 1 below.
Tabulka 1Table 1
Ak sa nahradí vo vyššie opísanom príklade stabilizátor A 2,4-bis-(n-oktyltiometyl)-6-terc-butylfenolom z príkladu 2, dosiahnu sa s analogickými kombináciami stabilizátorov podobné dobré hodnoty stabilizácie.If, in the above-described example, the stabilizer A is replaced with the 2,4-bis- (n-octylthiomethyl) -6-tert-butylphenol of Example 2, similar good stabilization values are obtained with analogous stabilizer combinations.
Príklad 3Example 3
Spôsob stabilizácie polybutadiénového kaučuku (starnutie v silikónovom oleji)Method of stabilization of polybutadiene rubber (aging in silicone oil)
Vykonanie pokusu sa uskutočňuje analogickým spôsobom, ako je opísaný v príklade 3 s tým rozdielom, že starnutie prebieha v silikónovom oleji s teplotou 160 “C počas 45 minút. Výsledky sú zhrnuté v nasledujúcej tabulke 2.The experiment was carried out in an analogous manner to that described in Example 3 except that aging was carried out in silicone oil at a temperature of 160 ° C for 45 minutes. The results are summarized in Table 2 below.
Tabulka 2Table 2
Claims (6)
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KR (1) | KR0172941B1 (en) |
BR (1) | BR9005755A (en) |
CA (1) | CA2029708C (en) |
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US6512032B1 (en) | 1997-07-28 | 2003-01-28 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride resin compositions and articles molded therefrom |
JPH09208783A (en) * | 1996-01-31 | 1997-08-12 | Kureha Chem Ind Co Ltd | Vinylidene fluoride resin composition and molded product |
GB2355463B (en) * | 1999-10-18 | 2001-12-05 | Ciba Sc Holding Ag | Stabilisers for emulsion crude rubbers, synthetic latex and natural rubber latex |
KR101693875B1 (en) * | 2008-05-15 | 2017-01-17 | 바스프 에스이 | Basic stabilisation systems for emulsion polymerised rubbers |
JP5278179B2 (en) * | 2009-06-09 | 2013-09-04 | 信越化学工業株式会社 | Adhesive composition, and adhesive sheet and coverlay film using the same |
KR101173215B1 (en) | 2009-09-10 | 2012-08-13 | 금호석유화학 주식회사 | Novel thio compounds and Preparing method of the same |
KR101146246B1 (en) * | 2009-12-17 | 2012-05-16 | 금호석유화학 주식회사 | Anti-oxidants for rubber and Synthetic rubber with thereof |
US8729169B2 (en) | 2011-04-08 | 2014-05-20 | Korea Kumho Petrochemical Co., Ltd. | Synthetic rubber with anti-oxidants for rubber |
KR101195233B1 (en) * | 2011-05-19 | 2012-10-29 | 금호석유화학 주식회사 | Heat resistant dopes for polymer resin and polymer resin composition comprising the same |
CN106905206B (en) * | 2017-03-03 | 2018-08-14 | 湘潭大学 | The preparation of bis- (n-octyl sulfidomethyl) phenol of 2- methyl -4,6- |
DE102017220555A1 (en) | 2017-11-17 | 2019-05-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Stabilizing compounds, process for their preparation, compositions containing these stabilizing compounds, methods for stabilizing an organic component and use of stabilizing compounds |
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DE3671241D1 (en) * | 1985-11-13 | 1990-06-21 | Ciba Geigy Ag | SUBSTITUTED PHENOLES AS STABILIZERS. |
-
1990
- 1990-11-09 CA CA002029708A patent/CA2029708C/en not_active Expired - Lifetime
- 1990-11-12 EP EP90121610A patent/EP0428973B1/en not_active Expired - Lifetime
- 1990-11-12 DE DE59009983T patent/DE59009983D1/en not_active Expired - Lifetime
- 1990-11-12 ES ES90121610T patent/ES2081335T3/en not_active Expired - Lifetime
- 1990-11-13 SK SK5601-90A patent/SK279833B6/en not_active IP Right Cessation
- 1990-11-13 CZ CS905601A patent/CZ284773B6/en not_active IP Right Cessation
- 1990-11-13 BR BR909005755A patent/BR9005755A/en not_active IP Right Cessation
- 1990-11-14 KR KR1019900018383A patent/KR0172941B1/en not_active IP Right Cessation
- 1990-11-14 JP JP02308443A patent/JP3099127B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0428973B1 (en) | 1995-12-20 |
CA2029708A1 (en) | 1991-05-15 |
CZ560190A3 (en) | 1998-11-11 |
JPH03177442A (en) | 1991-08-01 |
ES2081335T3 (en) | 1996-03-01 |
DE59009983D1 (en) | 1996-02-01 |
EP0428973A1 (en) | 1991-05-29 |
SK279833B6 (en) | 1999-04-13 |
KR0172941B1 (en) | 1999-03-30 |
CZ284773B6 (en) | 1999-02-17 |
BR9005755A (en) | 1991-09-24 |
KR910009837A (en) | 1991-06-28 |
CA2029708C (en) | 2003-07-29 |
JP3099127B2 (en) | 2000-10-16 |
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Legal Events
Date | Code | Title | Description |
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MK4A | Expiry of patent |
Expiry date: 20101113 |