CS198676B1 - Method of preparing dicumyl peroxide - Google Patents
Method of preparing dicumyl peroxide Download PDFInfo
- Publication number
- CS198676B1 CS198676B1 CS168878A CS168878A CS198676B1 CS 198676 B1 CS198676 B1 CS 198676B1 CS 168878 A CS168878 A CS 168878A CS 168878 A CS168878 A CS 168878A CS 198676 B1 CS198676 B1 CS 198676B1
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- Czechoslovakia
- Prior art keywords
- dicumyl peroxide
- reaction
- cumene hydroperoxide
- weight
- mixture
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 10
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 7
- -1 organometallic iron compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- HABLENUWIZGESP-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O.CCCCCCCCCC(O)=O HABLENUWIZGESP-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález sa týká spůeobu přípravy dikumylperoxidu reakciou kuménhydroperoxidu alebo Jeho roztokov a kyslíka za katalytického účinku solí alebo organokovovýoh zlúčenin železa,The invention relates to a process for the preparation of dicumyl peroxide by reacting cumene hydroperoxide or its solutions and oxygen under the catalytic action of salts or organometallic iron compounds,
Diktunylperoxid podobné ako mnoho Jalších organických peroxidoy možno prippaviť viacerými lostupmi. Dosiať. sa vychádza z příslušného hydroperoxidu alebo organokovovej zlúčeniny připadle samotného uhťovodíka. Hydroperoxidy alebo peroxid vodíka íahko reagujú a terciálnymi esp. ínými rezonančně stabilizovanými karboniovými iónmi, ktoré sa vytvárajú účinkom kataytických množstiev kyselin na alkény, alkoholy, étery, estery alebo hydroperoxidy a přitom ko produkty vznikajú peroxidy. Reekčné podmienky sa menia podía použitých reagentov, pričom ýmto spdsobom možno pripraviť aj asymetrické peroxidy.Dictunylperoxide similar to many Other organic peroxides can be prepared by multiple peelings. Dosi. is based on the respective hydroperoxide or organometallic compound, which is the hydrocarbon itself. Hydroperoxides or hydrogen peroxide readily react with tertiary esp. other resonantly stabilized carbon ions, which are formed by the action of catalytic amounts of acids on the alkenes, alcohols, ethers, esters or hydroperoxides, and the products form peroxides. The reaction conditions vary with the reagents used, and asymmetric peroxides can also be prepared.
Vznik peroxidov priamo oxidáciou uhíovodíkov je obmedzený na případy» ked vznikájúce adikály sú vysoko stabilné. Výhodnéjšla je syntéza z hydroperoxidov katalyzovaná kovovými ínmi. Ako katalyzátory sa používaju soli médi kobaltu, mangánu, olova alebo komplexy ruténia. íroxy-radikály vznikájúce pri tomto rozklade vzájomne interagujú za vzniku alkoxyradikálov, ioré rekombináoiou poskytujú prevážne peroxidy a to v závislosti od prostredia, teploty štruktúry alkoxy-radikálu.The formation of peroxides directly by the oxidation of hydrocarbons is limited to cases where the resulting addicals are highly stable. More preferred is the synthesis from hydroperoxides catalyzed by metal tin. As catalysts, cobalt, manganese, lead media or ruthenium complexes are used. The hydroxyl radicals formed in this decomposition interact with each other to form alkoxy radicals, which, by recombination, give predominantly peroxides, depending on the environment, the temperature of the alkoxy radical structure.
Podstata spflsobu přípravy dikumylperoxidu reakciou kuménhydroperoxidu alebo jeho rozkov v alifatických alebo aromatických uhíovodíkov a alkoholoch, chlorovaných, uhíovodíkoch ípadne v oxidačněj zmesi z výroby kuménhydroperoxidu resp. Jej vákAových konoentrátovThe principle of the process for the preparation of dicumyl peroxide by the reaction of cumene hydroperoxide or its decomposition in aliphatic or aromatic hydrocarbons and alcohols, chlorinated hydrocarbons or in an oxidation mixture from the production of cumene hydroperoxide resp. Its vacuum concentrates
676676
199 Β7Β alebo v zmesi rozpúšťadiel podťa vynálezu qcčíva v tom, že reakoia sa uskutočňuje v přítomnosti kyslíka připadne lnáho plynu obsahujúoeho kyslík za katalytického účinku solí alebo organokovovýoh zlúčenín železa.199-7Β or in a solvent mixture according to the invention, characterized in that the reaction is carried out in the presence of oxygen or an oxygen-containing gas, under the catalytic action of salts or organometallic iron compounds.
Reakoia sa sukutočňuje prl teplotáoh kedy ešte nedochádza k výraznéjnejšlemu termickému homolytiokému rozkladu hydroperoxidu, obvykle v intervale 60 až 125°C. Konoentráoia kuménhydroperoxidu je závislá od použitého rozpúšťadla a pohybuje sa od 0,1 do 96%. Rozpúšťadlom m8žu byť alifatioké alebo aromatické uhťovodíky a alkoholy, chlorované uhlovodíky, oxidačná zmes z výroby kuménhydroperoxidu a jej vákové koncentráty alebo zmesi niekoťkých rozpúšťadiel. S nízkými koncentráeiami kuménhydroperoxidu sa míže praoovať v kuméne, kde v přiebehu reakcie dochádza k jeho oxidáoii, čím sa výťažok dikumylperoxidu v porovnaní.s východiskovým množstvom kuménhydroperoxidu podstatné zvyšuje. V takomto případe počiatočné množstvo kuménhydroosroxidu v kuméne funguje ako iniciátor reakoia.The reaction is carried out at temperatures where no significant thermal homolytic decomposition of the hydroperoxide occurs, usually in the range of 60 to 125 ° C. The concentration of cumene hydroperoxide is dependent on the solvent used and ranges from 0.1 to 96%. The solvent may be aliphatic or aromatic hydrocarbons and alcohols, chlorinated hydrocarbons, an oxidation mixture from the manufacture of cumene hydroperoxide and its vacuum concentrates, or mixtures of several solvents. With low concentrations of cumene hydroperoxide, it can be treated in cumene, where it is oxidized during the reaction, thereby substantially increasing the yield of dicumyl peroxide compared to the starting amount of cumene hydroperoxide. In such a case, the initial amount of cumene hydrooside in cumene acts as a reacoia initiator.
V případe vysoko koncentrovanýoh roztokov kuménhydroperoxidu je možné postupovať tak, že na reakolu sa použije len časť koncentrovaného roztoku kuménhydroperoxidu a Óalšia časť sa přidá po určltej době alebo periodiky po menších dávkách, čím sa dosiahne vačšej bezpečnosti.In the case of highly concentrated cumene hydroperoxide solutions, only a portion of the concentrated cumene hydroperoxide solution can be used on the reacol and another portion is added after a certain period of time or periodically in smaller portions to achieve greater safety.
Katalyzátory sú obyčajne vo forma rozpustnéj v reakčnom prostředí vo formo solí alifatiokýoh alebo aromatických karboxylovýoh kyselin, aoetylacetonátov, síranov, ohelátov, komplexov (napr. typu FeXgPyg» fcúe X je halogén ap.) a používajú se v množstve 0,001 až 2% hm železa. Reakčná doba je určovaná experimentálnymi podmienkami a pohybuje sa od 1 do 8 hodín. DOležité je tiež udržovat intenzívny styk medzi kvapalnou a plynnou fázou. Dosahuje sa to vhodnou konštrukoiou reaktora s intenzívnym premiešavanlm fáz či už samotným plynom obsahujúoim molekulový kyslík alebo kombináoiou β rfiznymi typmi rozpúšťadiel.The catalysts typically are soluble in the reaction medium as salts alifatiokýoh or aromatic karboxylovýoh acid aoetylacetonátov, sulphates, ohelátov, complexes (e.g. type FeXgPyg »fc ÚE X is a halogen, etc.) And is used in an amount of 0.001 to 2% by weight of iron . The reaction time is determined by experimental conditions and ranges from 1 to 8 hours. It is also important to maintain intensive contact between the liquid and gas phases. This is achieved by a suitable design of the reactor with intensive mixing of the phases, either by the gas containing molecular oxygen itself or by a combination of β-different types of solvents.
Výhody sp8sobu přípravy dikumylperoxidu podťa vynálezu spočívajú okrem iného v tom, že je jednoduohý a ekonomicky nenáročný.The advantages of the process for the preparation of dicumylperoxide according to the invention are, inter alia, that it is simple and economically undemanding.
Příklad 1Example 1
V roztoku obsahujúoom 7,6 % hm kuménhydroperoxidu a 0,4% bm kumylalkoholu v kuméne sa rozpustí kaprinát žsleznatý v množstve 0,35 % hm. Po vyhrlatí roztoku na 94°O sa za intenzívneho premiešavania vhéňa do zmesi vzduoh v množstve 145 litrov/h počítané na 1 1 reakčnej zmesi. Po 6,5 hodinách reakoie vzniklo 21,7% hm dikumylperoxidu, 12,5 % hm aoetofenónu a 22,2 % hm kumylalkoholu. V nepřítomnosti katalyzátore pri týohto podmienkaeh dikumylperoxid v8beo nevzniká.In a solution containing 7.6% by weight of cumene hydroperoxide and 0.4% by weight of cumyl alcohol in cumene, dissolve capric acid caprate in an amount of 0.35% by weight. After the solution was heated to 94 ° C, the mixture was purged with vigorous stirring at 145 L / h, calculated per 1 L of reaction mixture. After 6.5 hours of reaction, 21.7% by weight of dicumyl peroxide, 12.5% by weight of oetophenone and 22.2% by weight of cumyl alcohol were formed. In the absence of a catalyst, dicumyl peroxide does not form under these conditions.
Příklad 2Example 2
Kuménhydroperoxid obsahujúoi 8,0 % hm kumylalkoholu a 0,1 % hm aoetofenónu sa zmisša s izooktánom v ohjemovom pomere 2,5:1· K tejto zmesi sa přidá 280 ppm železa vo formě solí mastných kyselin a oelá zmes sa vyhřeje na 97°0. Po dosiahnutí tejto teploty sa za miešania zavádza do zmesi kyslík ryohlosťou 100 1/h ha 1 1 roztoku. V přiebehu reakoie sa rozpúšťadlo postupné oddestiluje. Po 3 hodináoh trvania pokusu výsledná zmes obsahovala 91,6 % hm dikumylperoxidu, 2,1% hm aoetofénónu, 5,2 % hm kumylalkoholu a 1,1 % hm inýeh látok.Cumene hydroperoxide contains 8.0% by weight of cumyl alcohol and 0.1% by weight of o-oetophenone and is mixed with isooctane in a 2.5: 1 ratio by volume. . Upon reaching this temperature, oxygen is introduced into the mixture with stirring at a rate of 100 l / h and 1 l of solution. During the reaction, the solvent is gradually distilled off. After 3 hours, the resulting mixture contained 91.6 wt% dicumyl peroxide, 2.1 wt% α-oetophenone, 5.2 wt% cumyl alcohol, and 1.1 wt% other substances.
198 878198 878
Příklad 3Example 3
Kuménhydroperoxid obsahujúci 8,0 % hm kumylalkoholu, 0,1 % hm aoetofenónu a 0,04 % hm Pe++ reaguje pri teplote 97°C a prietoku vzduchu 120 1/h na 1 1 roztoku 3,5 hodiny. Potom sa k zmesi přidá Íaláí kuménhydroperoxid s čistotou ako má východiskový roztok bez katalyzátore a to v polovičnom množstve ako pSvodná násada. Po dalších 3 hodinách re akcie pri rovnakých podmienkach reakčná zmes obsahovala 90,6% hm. dikumylperoxidu, 4,0% hm aoetofenónu,Cumene hydroperoxide containing 8.0 wt% cumyl alcohol, 0.1 wt% aoetophenone and 0.04 wt% Pe ++ reacted at 97 ° C and 120 l / h air flow per 1 l of solution for 3.5 hours. Then, additional cumene hydroperoxide is added to the mixture with the purity of the starting solution without catalyst in half the amount of the aqueous feed. After an additional 3 hours of reaction under the same conditions, the reaction mixture contained 90.6 wt. dicumyl peroxide, 4.0 wt.% of o-oetophenone,
4,1 % hm kumylalkoholu a zbytok tvořili iné látky.4.1% by weight of cumyl alcohol and the rest were other substances.
Příklad 4Example 4
Roztok 28,6% hm kuménhýdroperoxidu v kuméne obsahujúci 1,8% hm kumylalkoholu a 0,25% hm acetylacetonátu železitého sa nechá reagoval? 4 hodiny pri teplote 103°C a prietoku vzduchu 100 1/h na 1 1 roztoku. Po tejto době vznikol dikumylperoxid v množstve 21,1 % hm.A solution of 28.6 wt% cumene hydroperoxide in cumene containing 1.8 wt% cumyl alcohol and 0.25 wt% ferric acetylacetonate was allowed to react? 4 hours at 103 ° C and 100 l / h air flow per 1 l of solution. After this time, dicumyl peroxide was formed in an amount of 21.1% by weight.
Dikumylperoxid podobné ako mnohé peroxidické zlúčeniny možno použil? ako zdroj voťňých radikálov pri polymerizačnýoh reakciách nenasýtených látok alebo ako zosietfovaoie činidlo v gumárenskom priemysis.Dicumyl peroxide similar to many peroxidic compounds can be used? as a source of free radicals in polymerization reactions of unsaturated substances or as a crosslinking agent in rubber industry.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS168878A CS198676B1 (en) | 1978-03-17 | 1978-03-17 | Method of preparing dicumyl peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS168878A CS198676B1 (en) | 1978-03-17 | 1978-03-17 | Method of preparing dicumyl peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS198676B1 true CS198676B1 (en) | 1980-06-30 |
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ID=5351871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS168878A CS198676B1 (en) | 1978-03-17 | 1978-03-17 | Method of preparing dicumyl peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS198676B1 (en) |
-
1978
- 1978-03-17 CS CS168878A patent/CS198676B1/en unknown
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