CS270897B1 - Method of mixed triarylphosphates preparation - Google Patents
Method of mixed triarylphosphates preparation Download PDFInfo
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- CS270897B1 CS270897B1 CS89832A CS83289A CS270897B1 CS 270897 B1 CS270897 B1 CS 270897B1 CS 89832 A CS89832 A CS 89832A CS 83289 A CS83289 A CS 83289A CS 270897 B1 CS270897 B1 CS 270897B1
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- phenol
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- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 150000002989 phenols Chemical class 0.000 claims abstract description 8
- 235000021317 phosphate Nutrition 0.000 claims abstract description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 5
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical class CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- ZEFOXNBIQIPHOP-UHFFFAOYSA-N 2,3-di(propan-2-yl)phenol Chemical class CC(C)C1=CC=CC(O)=C1C(C)C ZEFOXNBIQIPHOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 238000007664 blowing Methods 0.000 claims 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 abstract 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical class CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 13
- 230000029936 alkylation Effects 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- -1 2 to 10% by weight Chemical class 0.000 description 1
- MFFHOTWDYMNSLG-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)phenol Chemical compound CC(C)C1=CC=C(O)C(C(C)C)=C1C(C)C MFFHOTWDYMNSLG-UHFFFAOYSA-N 0.000 description 1
- KEUMBYCOWGLRBQ-UHFFFAOYSA-N 2,4-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC=C(O)C(C(C)C)=C1 KEUMBYCOWGLRBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZINJLDJMHCUBIP-UHFFFAOYSA-N ethametsulfuron-methyl Chemical compound CCOC1=NC(NC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(=O)OC)=N1 ZINJLDJMHCUBIP-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
(57) Je popísaná esterifikácia zmesi fenolov, obsahujúcej 30 až 50 % hmot, monoizopropylfenolov, 2 až.10 % hmot, diisopropylfenolov, 0,2 až 2 % hmot, triizopropyl-. fenolov a 30 až 70 % hmot· fenolu s oxychloridom fosforečným diskontinuálnym a kontinuálnym spbsobom tvořeným kaskádou prietokových miešaných reaktorov s róznou teplotou od 80 do 180 °C.(57) The esterification of a mixture of phenols containing 30 to 50% by weight, monoisopropylphenols, 2 to 10% by weight, diisopropylphenols, 0.2 to 2% by weight, triisopropyl- is described. of phenols and 30 to 70% by weight of phenol with phosphorus oxychloride in a batch and continuous manner consisting of a cascade of flow stirred reactors with a different temperature of from 80 to 180 ° C.
Tento sposob eeterifikác^e je možné uplatni ť v organickej technologii pri přípravě i zmesných triarylfosfátov so širokými možnostem! uplatnenia в využitím vlastnosti jednotlivých .izomerov, alebo ich zmesi<This method of etherification can be applied in organic technology in the preparation of mixed triaryl phosphates with a wide range of possibilities. application in the use of properties of individual isomers, or mixtures thereof
270 897270 897
Sposob přípravy zmesných triarylfosfátov vznikajúcich esterifikáciou oxychloridu fosforečného s fenolom a izopropylfenolmi za katalytického účinku kovového horčíka, alebo jeho zlúčenin. Zmes alkylfenolov sa připraví alkyláciou fenolu propánom tak, že v alkylačnej zmesi je 30 až 40 % hmotnostných izopropylfenolov a 60 až 70 % hmotnostných fenolu. Získaný triarylfosfát sa následné spracuváva destiláciou, rek-» „ tifikáciou a extrakciou, kde sa odstránia nezreagované fenoly, nežiadúce esterifikačné produkty a katalyzátor. Takto sa získá produkt o požadovaných fyzikálno-chemických vla8tnostiach. *Process for preparing mixed triaryl phosphates formed by esterification of phosphorus oxychloride with phenol and isopropylphenols under the catalytic action of magnesium metal or its compounds. The alkylphenol mixture is prepared by alkylating phenol with propane such that the alkylation mixture contains 30 to 40% by weight of isopropylphenols and 60 to 70% by weight of phenol. The triaryl phosphate obtained is subsequently treated by distillation, recrystallization and extraction to remove unreacted phenols, unwanted esterification products and catalyst. A product of the desired physico-chemical properties is thus obtained. *
Příprava zmesných triarylfosfátov je popísaná například v US patentoch 1 858 659,The preparation of mixed triaryl phosphates is described, for example, in U.S. Patents 1,858,659,
840 325, 2 851 476, 2 931 823 a v československých autorských osvedčeniach 186 971,840 325, 2 851 476, 2 931 823 and in Czechoslovak author certificates 186 971,
230 995, 233 262 a 260 173. ·230 995, 233 262 and 260 173. ·
Vyššie uvedené spísoby přípravy sú odlišné a uvádzajú iný technologický postup a zloženie strojno-technologického zariadenia, sú náročné na spotřebu energií, pričom sú značné straty materiálu v technologickom procese.The above preparation methods are different and indicate a different technological process and composition of the machinery, are energy-intensive, with considerable material losses in the technological process.
Podlá uvedených patentov sa výroba uskutoČnovala tak, Že sa fenol alkyloval propanem za použitia aktivovanej bieliacej hlinky kyselinou fosforečnou ako katalyzátora na zmes fenolu a izopropylfenolov,· v ktorých převažoval 2-izopropylfenol. Táto zmes sa rektifikovala, kde sa oddělil nezreagovaný fenol, tak aby ho bolo v zmesi pod 20 % hmotnostných. Takáto alkylačná zmes sa esterifikovala pri teplote 150-160 °C 8 POCly Po doreagovaní sa do reakčnej zmesi přidal čistý fenol a reakcia sa dokončila za vzniku zmesných. triarylfosfátov, kde obsah trifenylfosfátu bol pod 35 % hmotnostných.According to the above patents, production was carried out by phenol alkylation of propane using activated phosphoric clay with phosphoric acid as a catalyst to a mixture of phenol and isopropylphenols, in which 2-isopropylphenol predominated. This mixture was rectified where unreacted phenol was separated so that it was below 20% by weight in the mixture. Such an alkylation mixture was esterified at 150-160 ° C. 8 POCly After the reaction was complete, pure phenol was added to the reaction mixture and the reaction was complete to give a mixture. triarylphosphates wherein the triphenylphosphate content was below 35% by weight.
Podstatou sposobu výroby zmesných triarylfosfátov podlá vynálezu je, Že sa připraví alkylačná zmes fenolu, 30 až 50 % hmot, izopropylfenolov, 2 až 10 % hmot. 2,4- a 2,6-diizopropylfenolov a 0,2 až 2 % hmot, triizopropylfenolu alkyláciou fenolu s propénom. Uvedená reakčná zmes sa neupravuje destiláciou na odstránenie nezreagovaného fenolu, ale táto pri celkovom obsahu fenolu 30 až 70 % hmotnostných fenolu 8 výhodou 60 % sa priamo esterifikuje s oxychloridom fosforečným tak, že molárny poměr fenolov ku POClj je rovný 1 ku 3—3,5. Uvedené fenoly sa vyhrejú na teplotu 80 °C až 100 °C a postupné sa do tejto zmesi nadávkuje katalyzátor a hořčík alebo jeho zlúčeniny a oxychlorid fosforečný. Teplota reaktora sa zvyšuje na 160 - 180 °C. Při teplote do 120 °C zreaguje fenol, 2-izopropylfenol a 2,4-diizopropylfenol. V Salšom stupni pri zvýšení teploty na 150-160 °C doreaguje predovšetkým 2-izopropylfenol, nakolřko ostatně zložky už v reakčnej zmeBi nie sú přítomné a 2-izopropylfenol reaguje | s třetím chlorom z POCl^ na zmesný triarylfosfát o požadovaných fyzikálno-chemických vlastnostiach. Po skončení reakcie sa reakčná zmes vyfúka suchým dusíkom, aby sa z nej odstránil rozpuštěný chlorovodík. To sa prevádza pri 160 - 180 °C. ’The process according to the invention is based on the preparation of an alkylation mixture of phenol, 30 to 50 wt.%, Isopropylphenols, 2 to 10 wt. 2,4- and 2,6-diisopropylphenols and 0.2 to 2% by weight of triisopropylphenol by alkylation of phenol with propene. Said reaction mixture is not treated by distillation to remove unreacted phenol, but at a total phenol content of 30 to 70% by weight of phenol 8, preferably 60%, it is directly esterified with phosphorus oxychloride so that the molar ratio of phenols to POCl 3 is equal to 1 to 3 - 3,5 . Said phenols are heated to a temperature of 80 ° C to 100 ° C and the catalyst and magnesium or its compounds and phosphorus oxychloride are gradually added to this mixture. The temperature of the reactor is raised to 160-180 ° C. Up to 120 ° C phenol, 2-isopropylphenol and 2,4-diisopropylphenol are reacted. The salsa step of increasing the temperature to 150-160 ° C to complete the reaction in particular, 2-isopropylphenol, co Nakol ° the other components already in the reaction are present zmeBi and 2-isopropylphenol treated | with third chlorine from POCl 2 to a mixed triaryl phosphate having the desired physicochemical properties. After completion of the reaction, the reaction mixture is blown with dry nitrogen to remove dissolved hydrogen chloride. This is carried out at 160-180 ° C. '
Unikajúce odplyny sú chladené a skondenzované produkty (POCl^ a alkylfenoly) sa vracajú naspat do reakčnej zmesi.The off-gases are cooled and the condensed products (POCl 4 and alkylphenols) are returned to the reaction mixture.
Hlavně výhody navrhovaného riešenia sú v tom, že na začiatku reakcia je vedená pri bode varu POCl^, ušetří sa energia na rektifikáciu alkylačnéj zmesi, využije sa exotermickoeť reakcie, plynule sa zabezpečí odvod vznikajúceho chlórovodíka a zároveň proces sa dá usporiadať do kaskády prietokových miešaných reaktorov, z ktorých každý bude vyhrievaný na rožnu teplotu, čím sa zabezpečí plynulostí procesu, zníží sa na minimum vplyv na životné prostredie a zabráni úniku POCl^ a fenolovz reakčného systému.The main advantages of the proposed solution are that at the beginning of the reaction is carried out at the boiling point of POCl 2, energy is saved to rectify the alkylation mixture, the exothermic reaction is utilized, the evacuation of hydrogen chloride is continuously ensured. each of which will be heated to a different temperature, thereby ensuring process continuity, minimizing environmental impact and preventing leakage of POCl 2 and phenols from the reaction system.
Příklad č. 1Example # 1
Do kondenzačního reaktora typu trojhrdlej banky sa předloží 245 g zmesi alkylfenolov o obsahu 62 % hmotnostních fenolu a 38 % hmotnostních izopropylfenolov, ktorých zloženie je následujíce 65,6 % hmotnostných fenolu, 31,5 % hmotnostných monoizopropylfenolov a 3 % hmotnostní diizopropylfenolov. Do tejto zmesi sa nadávkuje 0,5 g katalyzátora MgClg, zmes sa zahřeje na 80 °C a nadávkuje sa do nej 55,5 g POCI3. Za stálého miešania a odvodu chlórovodíka cez spatný chladič sa plynule zvyšuje teplota počas 2 hodin na 120 °C a v priebehu SalŠích 4 hodin na 160 °C. Po dosiahnutí 160 °C. sa reakčná zmes nechá 2 hodiny doreagovat a vyfuka sa dusíkom. Po ochladení sa získá suro· vý fosfát, .ktorého obsah chlóru je pod 0,1 % hmotnostných a číslo kyslosti je 6,2 mg KÓH/g.A three-neck flask condensation reactor is charged with 245 g of a mixture of alkylphenols containing 62% by weight of phenol and 38% by weight of isopropylphenols, the composition of which is 65.6% by weight of phenol, 31.5% by weight of monoisopropylphenols and 3% by weight of diisopropylphenols. To this mixture was added 0.5 g of MgCl 2 catalyst, heated to 80 ° C and 55.5 g of POCl 3 was charged therein. While stirring and evacuating the hydrogen chloride through a bad cooler, the temperature is continuously raised to 120 ° C for 2 hours and 160 ° C for 4 hours. After reaching 160 ° C. The reaction mixture was allowed to react for 2 hours and purged with nitrogen. After cooling, a crude phosphate is obtained having a chlorine content below 0.1% by weight and an acid number of 6.2 mg KOH / g.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS89832A CS270897B1 (en) | 1989-02-08 | 1989-02-08 | Method of mixed triarylphosphates preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS89832A CS270897B1 (en) | 1989-02-08 | 1989-02-08 | Method of mixed triarylphosphates preparation |
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| Publication Number | Publication Date |
|---|---|
| CS83289A1 CS83289A1 (en) | 1989-12-13 |
| CS270897B1 true CS270897B1 (en) | 1990-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS89832A CS270897B1 (en) | 1989-02-08 | 1989-02-08 | Method of mixed triarylphosphates preparation |
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| Country | Link |
|---|---|
| CS (1) | CS270897B1 (en) |
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1989
- 1989-02-08 CS CS89832A patent/CS270897B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS83289A1 (en) | 1989-12-13 |
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