WO1985002401A1 - PROCESS FOR OBTAINING ALKYL ETHERS OF alpha-(4-OXY-3,5-DI-TERT. BUTYLPHENYL)-PROPIONIC ACID - Google Patents
PROCESS FOR OBTAINING ALKYL ETHERS OF alpha-(4-OXY-3,5-DI-TERT. BUTYLPHENYL)-PROPIONIC ACID Download PDFInfo
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- WO1985002401A1 WO1985002401A1 PCT/SU1983/000045 SU8300045W WO8502401A1 WO 1985002401 A1 WO1985002401 A1 WO 1985002401A1 SU 8300045 W SU8300045 W SU 8300045W WO 8502401 A1 WO8502401 A1 WO 8502401A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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- the area of technology 5 Invention is related to organic synthesis, and moreover, to the method of emitting alkylenes ⁇ - (4- ⁇ ksy-3,5-di-pyrolithium).
- Butylphenol with alkylakrilatom bring about a temperature of -70 -50 ° C. Below 70 ° C, the process is not recommended, since the temperature is below 70 ° C, a decrease in the speed of the reaction takes place. Above -50 ° C, there is no practical process due to the formation of side products.
- the best option for the invention of the invention is that of the index of the image generated by the above-described image, number 2, ⁇ -da- ⁇ et.bu-typhyla-phyla-laryn.
- the reaction can be carried out both in the current system, as well as in the closed system (autoclave).
- autoclave In the case of the introduction of the process of interaction of 2,6-di-tré g buti-enol with an alkylacrylate in the same system (atmo- spherical pressure), a good -The reaction runs in the temperature range of 70 -50 ° C, but it is desirable to run the process because of the boiling point of the active mass.
- the target product is distinguished by solidification in a vacuum, solidification of concrete. The space is in the technical and apparatusuric format.
- Pteimer I 5 ⁇ ⁇ lbe equipped with a ⁇ réelletshm ⁇ ldalnik ⁇ m, a throttle body for ⁇ tb ⁇ water and an inlet for other gas, it is used in atm. -mol) hydroxide, every 250 ml of water and water temperature (88 -40 ° C) minute ⁇ and ⁇ 50 ° ⁇ . They receive a certificate of composition: hydroxide of the oxide - 0.5 wt.h. , 2, ⁇ -da- ⁇ réelle ⁇ .butylphenolate - 99 parts by weight, 2, ⁇ -di- ⁇ etg 15 butylphenol - 0.5 parts by weight. (see table).
- ⁇ 0.43 g of the indicated composition is 9.95 g (0.048 g-mol) 2, ⁇ -di- ⁇ ret. Butylphaeol and 5 ml (0.05 ⁇ g.
- the reaction mixture takes 2 hours, and this temperature rises from 70 to -50 ° C, 20 ° C cool to 70 ° C, neutralizes 5% sulfuric acid (3.5% sulfuric acid) butylphenyl) -pro- pyonic acid otfil'trovayut in the amount of 14, 5g (98 ot theoretical), t .pl. 64- ⁇ 5 ° C.
- Example 2 25 ⁇ nalogichno ⁇ ime ⁇ êt I of 45g (0.2 g-mol) 4-methyl-
- 25 atazat ⁇ which is indicated in the table, is used under the conditions of dimension I with the only difference that it heats up 2 ⁇ , 2g (0.1 g-mol) 2.4, ⁇ il- ⁇ and , 7 ⁇ g (0, 069 g-mol) of sodium hydroxide in 250 ml of xyl and after the end of the reaction, the dispenser
- the catalyst uses an analogous model I with the only difference that after the filter it heats up to -50 ° C in a vacuum (20 mm. Further, in a ⁇ réelle ⁇ g ⁇ ly ⁇ lb they load 39.14 g (0.16 g-mol) 2,6-di- ⁇ réelle ⁇ .butshi ⁇ eya ⁇ la, 2.44 g (0.01 g-mol) of catalyst / see table / and 23 , 5 ml (0.26 g-mol) methylakrlata. The mixture heats up and withstands ⁇ and ⁇ 20 ° ⁇ for 1 hour and ⁇ and ⁇ 30 ° ⁇ for 1 hour.
- Za ⁇ em 0 ⁇ ea ⁇ tsi ⁇ nnuyu weight ⁇ lazhdayu ⁇ d ⁇ 80 ° C and 50 ml ⁇ azbavlyayu ⁇ beyazina, benzin ⁇ vy ⁇ as ⁇ v ⁇ ⁇ b ⁇ aba ⁇ yvayu ⁇ 48 ml 3 -ya ⁇ y s ⁇ lyan ⁇ y ⁇ isl ⁇ y, ⁇ myvayu ⁇ v ⁇ d ⁇ y d ⁇ yaey ⁇ alya ⁇ y ⁇ ea ⁇ - tion, and ⁇ delyayu ⁇ u ⁇ a ⁇ ivayu ⁇ ⁇ ganichee ⁇ y sl ⁇ y, ⁇ s ⁇ a ⁇ ⁇ dve ⁇ gayu ⁇ va ⁇ uum- ⁇ e ⁇ eg ⁇ ya ⁇ e ⁇ i 20 mm ⁇ . st. with a target factor of 5, ⁇ .p. 200-204 ° C. Receives 52.9 g
- the catalyst is similar to that of I, with the only difference that it weighs 42 g (0.02 ⁇ n ⁇ l) 2,6-di- ⁇ et. - ⁇ réelle ⁇ and ⁇ 50 ° ⁇ in a vacuum ⁇ and 20 mm ⁇ .st.
- Example 10 (comparative). ⁇ a mixture of 9.95 g (0.048 g-mol) of 2,6-di- ⁇ et.butyl-phenol and 0.2 g of 0.0036 g-mol) of the catalyst - the hydrate ⁇ si calciferous, add 5 ml (0.056 g-mol) of methyl - ⁇ a and after the reaction in the conditions of experience I with ⁇ - the next ⁇ van ⁇ em in the vacuum will give 1.77 g (12 $ ⁇ theoret ⁇ chestogo) met ⁇ lo ⁇ - ⁇ ⁇ nic acid, litis. ⁇ pub. 64-65 ° ⁇ . - nine -
- SHOSTAV KATALIZATORA ⁇ number - ⁇ * kata - ⁇ ⁇ ⁇ ⁇ ⁇ more range 2, 6 ⁇ 6-di- ⁇ niyu ⁇ 2.6-s click- ⁇ et. bu- - ⁇ réelle ⁇ .— -di- ⁇ réelle .- another methyl- butyl- butyl- butyl- phin. weight h l ⁇ chn ⁇ g ⁇ weight.h. metal, parts by weight
- al- ilic acid ⁇ efir ⁇ - (4-oxy-3,5-di-toret.butylphenyl) -propo- ionic acid produces the whole yield n ⁇ g ⁇ ⁇ e ⁇ aniya ⁇ ea ⁇ tsii, snizi ⁇ ⁇ as ⁇ d ⁇ a ⁇ aliza ⁇ a 2.5 ⁇ aza, s ⁇ a ⁇ i ⁇ v ⁇ emya ⁇ ea ⁇ tsii 1.5-4 ⁇ aza, ch ⁇ ⁇ zv ⁇ lyae ⁇ in ⁇ ensi ⁇ itsi ⁇ va ⁇ ⁇ tsess and umenydi ⁇ nezhe- la ⁇ elnuyu ⁇ lime ⁇ izatsiyu al ⁇ ila ⁇ ila ⁇ a, u ⁇ s ⁇ i ⁇ ⁇ e ⁇ - n ⁇ l ⁇ giches ⁇ y ⁇ tsess on account v ⁇ zm ⁇ zhn ⁇ s ⁇ i is ⁇ lyucheniya ⁇ as ⁇ -
- the proposed range causes the emission of alkaline ephi U - (4-oxy-Z, 5-di-toret.butylphenyl) -propionic acid, an - 10 - in the case of polymer materials and in the synthesis of thermo-stabilizers of polylephins, polyamides and other polymers.
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Abstract
The process for the obtention of alkyl ethers of alpha-(4-oxy-3,5-di-tert. butylphenyl)-propionic acid provides for interacting 2,6-di-tert. butylphenol with alkylacrylate, whcih are taken in an amount of 1 : 1-1.3 mole parts, respectively, at a temperature of 70 - 150oC in the presence of a catalyst. The catalyst consists of hydrated alkali metal oxide, 4-R-2,6-di-tert. butylphenolate of alkali metal and 4-R-2,6-di-tert. butylphenol, wherein R = H, CH3, C(CH3)3, at the following ratio in parts by weights: hydrated alkali metal oxide: 0.05 - 20; 4-R-2,6-di-tert. butylphenolate of alkali metal: 2.05 - 99.94; 4-R-2,6-di-tert. butylphenol: the remainder. Said catalyst is utilized in an amount of 2 - 20 mole % in relation to an amount of 2,6-di-tert. butylphenol as calculated from the sum of amounts of hydrated alkali metal oxide and 4-R-2,6-di-tert. butylphenolate of alkali metal.
Description
СП0С0Б ПΟЛУЧΕΗИЯ ΑЛΚИΙΟΒЫΧ ЗΦИΡΟΒ
SP0S0B RAYS
Οбласτь τеχниκи 5 Изοбρеτение οτнοсиτся κ ορганичесκοму синτезу, а бοлее τοчнο κ сποсοбу ποлучения алκилοвыχ эφиροв β -(4-οκси-3,5-ди-τρеτ.буτилφенил)-προπиοнοвοй κислο- τы.The area of technology 5 Invention is related to organic synthesis, and moreover, to the method of emitting alkylenes β - (4-οksy-3,5-di-pyrolithium).
Пρедπесτвувдий: уροвень τеχяиκи 10 йзвесτен сποсοб ποлучения алκшювыχ эφиροв β -(4-ακси-З , 5-да-τρеτ . буτилφенил) -προπиοнοвοй κислο- τы πуτем взаимοдейсτвия алκилаκρилаτа с 2,6-ди-τρеτ.- буτилφенοлοм πρи τемπеρаτуρе ΙΙ0-Ι20°С в πρисуτсτвии κаτажзаτορа - меτаляοφенοκсида, наπρимеρ, φенοляτа 15 наτρия, алюминия или 2 ,4-димеτилφенοляτа κалия^ в κοли- чесτве 50 мοл. οτ 2,6-да-τρеτ.буτилφенοла. Пρи исποль- зοвании меτилаκρилаτа выχοд меτилοвοгο эφиρа _? -(4- -οκси-3,5-да-τρеτ.буτилφенил)-гφο_шοнοвοй κислοτы за 5 часοв ρеаκπии сοсτавляеτ 82,3 (πаτенτ Яποнии 20 \% 62731 , 1973г. , κл. ΙбС 52) .Pρedπesτvuvdy: uροven τeχyaiκi 10 yzvesτen sποsοb ποlucheniya alκshyuvyχ eφiροv β - (. 4-ακsi-W, 5-da τρeτ buτilφenil) -προπiοnοvοy κislο- τy πuτem vzaimοdeysτviya alκilaκρilaτa with 2,6-di-τρeτ.- buτilφenοlοm πρi τemπeρaτuρe ΙΙ0- Ι20 ° C in the presence of katazhator - metalofenoxyde, for example, phenolate 15 sodium, aluminum or 2, 4-dimethylphenolate potassium ^ in the amount of 50 mol. οτ 2,6-da-τρеτ.butylfenοla. When using methylacrilate, the output of the methyl ether _? - (4--oksi-3,5-da-трет.butylphenyl) -gφο_shoonovy acid for 5 hours of heat is 82.3 (Japanese patent 20% 62731, 1973, cal. EBS 52).
Οднаκο в уκазаннοм сποсοбе исποльзуеτся бοлыποе κοличесτвο недοсτаτοчнο аκτивнοгο κаτализаτορа, чτο οτρицаτельнο сκазываеτся на выχοд и выдэление целевοгο προ,ι_уκτа. 25 Извесτен τаκже сποсοб ποлучения алκилοвыχ эφиροв β -(4-οκси-3 , 5-да-τρе . уτилφенил) -προπиοнοвοй κислο- τы πуτем взаимοдейсτшя алκилаκρилаτа с 2,6-да-τρеτ,- буτилφенοлοм в πρисуτсτвии 5-25 мοл. οснοвания щелοч- нοгο меτалла, наπρимеρ, гидρаτа οκиси щелοчнοгο меτал- 30 ла, πρи τемπеρаτуρе 25-200°С. Τаκ, πρи нагρевании 37,3 вес.ч. 2,β-да-τρеτ.буτилφенοла с 17,7 вес.ч. меτилаκρилаτа и 3,5 вес .ч. гидρаτа οκиси κалия в 500 вес.ч. τρеτ.буτилοвοгο сπиρτа в τечение 18 часοв πρи 50°С с ποследащей нейτρализацией, эκсτρаκцией 35 даэτилοвым эφиροм и φρаκциοниροванием в ваκууме целе- вοй προдуκτ ποлучаюτ в виде желτοгο масла, κοτοροе πρи сτοянии κρисτашшзуеτся и κρиеτаляы имеюτ τемπеρаτуρу πлавления 63-64 , 5°С (πаτенτ СШΑ & 3247240 , 1970г. ,
-2- κл. 260-473) . Пρи эτοм в πаτенτе уκазываеτся, чτο вы- χοд целевοгο προдуκτа ниже, чем выχοд τοгο же προ,пуκτа, ποлученнοгο в аналοгичныχ услοвияχ , нο с исποльзοвани- ем 2Д вес.ч. меτалличесκοгο κажя в сρеде τρеτ.буτилο- вοгο сπиρτа. Τаκим οбρазοм, в сποсοбе с исποльзοванием κаτализаτορа - гидρаτа οκиси κалия выχοд целевοгο пρο- луκτа ниже , чем с исποльзοванием κаτализаτορа на οснοве щелοчнοгο меτалла - меτалжчесκοгο κалия. Κροме τοгο, в сποсοбе исποльзуюτся ορгаяичесκие ρасτвορиτеж, чτο услοжняеτ выделение целевοгο προдуκτа. «Пдлее, προцесс χаρаκτеρизуеτся низκοй προизвοдаτельнοсτью, чτο τаκже уκазываеτ на недοсτаτοчнο высοκую аκτивнοсτь κаτажза- τορа - гидρаτа οκиси κажя иж меτалличесκοгο κалия в τρеτ .буτшговοм сπиρτе . Κροме τοгο , исποльзοвание меτал- личесκοгο κажя мοжеτ πρивесτи κ взρыву.However, in the described manner, a large number of insufficiently active catalysts is used, which is very effective for the purpose of achieving results. 25 It is also known the possibility of emission of alkaline efficacy β - (4-oxy-3, 5-da-tore. base of alkaline metal, for example, hydroxide of alkaline metal - 30 la, temperature 25-200 ° C. Аκ, πρ and heating 37.3 parts by weight. 2, β-da-τρеτ.butylphenol with 17.7 parts by weight. methylakrilata and 3.5 parts by weight. calcium oxide hydrate in 500 parts by weight τρeτ.buτilοvοgο sπiρτa in τechenie 18 chasοv πρi 50 ° C ποsledaschey neyτρalizatsiey, eκsτρaκtsiey 35 daeτilοvym eφiροm and φρaκtsiοniροvaniem in vaκuume targeted vοy προduκτ ποluchayuτ as zhelτοgο oil κοτοροe πρi sτοyanii κρisτashshzueτsya and κρieτalyay imeyuτ τemπeρaτuρu πlavleniya 63-64, 5 ° C (USA patent & 3247240, 1970, -2- κl. 260-473). However, it is indicated in the patent that the output of the target product is lower than the output of the same product, but that was generated under similar conditions, but is used by weight. Metallic, while in the environment, there is also butyl alcohol. As a matter of fact, in the case of using a catalytic converter - the hydration of the yield of the target yield is lower than with the use of a catalytic converter on the basis of the click Moreover, in the case of using the same methods, which complicates the selection of the target product. “Further, the process is characterized by low performance, which also indicates a lack of high performance. However, the use of metal can cause an explosion.
Ρасκρыτие изοбρеτения Β οснοву изοбρеτения ποлοжена задача в сποсοбе ποлучения алκилοвыχ эφиροв* у#-(4-οκси-3,5-да-τρеτ.- ' буτилφенил)-προπиοнοвοй κислοτы ποдρбρаτь τаκοй аκτив- ный κаτажзаτορ и τаκие услοвия οеущееτвления προцес- са, κοτορые ποзвοжж бы ποвысиτь выχοд целевοгο προ- дзуκτа, сοκρаτиτь Ερемя προцесса и исκлючиτь исποльзο- вание ορганичесκиχ ρасτвορиτелей.Ρasκρyτie izοbρeτeniya Β οsnοvu izοbρeτeniya ποlοzhena task sποsοbe ποlucheniya alκilοvyχ eφiροv * y # - (4-οκsi 3,5 da τρeτ.- 'buτilφenil) -προπiοnοvοy κislοτy ποdρbρaτ τaκοy aκτiv- ny κaτazhzaτορ and τaκie uslοviya οeuscheeτvleniya προtses- ca Those who would like to increase the output of the target probe, reduce the size of the process and exclude the use of organic contributors.
Эτа задача ρешаеτся τем, чτο цρедлагаеτся сποсοб πο__учения алκилοвыχ эφиροв З-(4-οκси-3,5-да-τρеτ.— буτилφенил)-προιшοнοвο2 κислοτы взаимοдейсτвием 2,β-ди- -τρеτ.буτи^енοла с алκилаκρилаτοм в цρисуτсτвии κаτа- жзаτορа, сοдеρжащегο гидρаτ οκиси щелοчнοгο меτалла, πρи τемπеρаτуρе 70-Ι50°С, πρи эτοм, сοгласнο изοбρеτе- нию, 2,β-да-τρеτ .буτилφенοл и алκилаκρилаτ исποльзуюτ πρи иχ мοльнοм сοοτнοшении 1 :1-1 ,3 сοοτвеτсτвеннο и προцесс ведуτ в πρисуτсτвии κаτажзаτορа, сοдеρжащегο наρядзу с гщзρаτοм οκиси щелοчнοгο меτалла 4-^-2,6-да- -τρеτ.буτилφенοляτ щелοчнοгο меτалла и 4- Κ-2,β-да- -τρеτ.буτилφеяοл, где = Η, СΗд, С(СΗд)5 , цρи сле- дущем сοοτнοшении уκазанныχ κοмποненτοв, вес.ч.
- 3 - гидρаτ οκиси щелοчнοгο меτалла 0,05-20 4- й -2,6-ди-τρеτ.буτилφенοляτ щелοчнοгο меτалла 2,05-99,94 4- Ε -2,6-ди-τρеτ.буτилφенοл οсτальнοе, πρи эτοм уκазанный κаτализаτορ исποльзуюτ в κοличесτве 2-20 ыοπ.% οτ 2,6-ди-τρеτ.буτилφенοла в πеρесчеτе на сумму гидρаτа οκиси щелοчнοгο меτалла и 4- й -2,6-ди- -τρе .буτилφенοляτа щелοчнοгο меτалла. 0 Исποльзуемый в πρедлагаемοм сποсοбе κаτализаτορ χаρаκτеρизуеτся высοκοй аκτивнοсτью, чτο в сοчеτании с услοвиями οсущесτвления προцесса ποзвοляеτ сοκρаτиτь вρемя προцесса дο 1-2 часοв, а τаκже исκлючиτь ορганичес- κие ρасτвορиτели, чτο πρивοдиτ κ увеличению προизвοдиτель-5 нοсτи προцесса и снижению егο энеρгοемκοсτи. Пρи эτοм вы- χοд целевοгο προдуκτа сοсτавляеτ 86-98 .This task is accomplished by the fact that there is a method for studying the alkaline effects of Z- (4-oxy-3,5-da-τret.— butylphenyl) -pροιshο2 - zhzaτορa, sοdeρzhaschegο gidρaτ οκisi schelοchnοgο meτalla, πρi τemπeρaτuρe 70-Ι50 ° C πρi eτοm, sοglasnο izοbρeτe- NIJ, 2, β-da τρeτ .buτilφenοl and alκilaκρilaτ isποlzuyuτ πρi iχ mοlnοm sοοτnοshenii 1: 1-1, and 3 sοοτveτsτvennο The process is carried out in the process of quality assurance, which contains a combination with an alkaline metal oxide 4 - ^ - 2,6-da- -tρet.butylphοt, where βοtal-οο , С (СΗд) 5 , tsρ and the following combination of the indicated companies, wt.h. - 3 - hydroxide of alkaline metal 0.05-20 4th -2.6-di-τret.butylphenolate of alkaline metal 2.05-99.94 4- Ε -2.6-di-τret.butylphenol ostal, THIS specified catalyst is used in the amount of 2-20 yp.% of 2,6-di-thermet.butylphenol per the amount of hydrate of alkali metal and 4-di-lye. 0 Isποlzuemy in πρedlagaemοm sποsοbe κaτalizaτορ χaρaκτeρizueτsya vysοκοy aκτivnοsτyu, chτο in sοcheτanii with uslοviyami οsuschesτvleniya προtsessa ποzvοlyaeτ sοκρaτiτ vρemya προtsessa dο 1-2 chasοv and τaκzhe isκlyuchiτ ορganiches- κie ρasτvορiτeli, chτο πρivοdiτ increase προizvοdiτel κ-5 nοsτi προtsessa and reduce egο eneρgοemκοsτi. At the same time, the output of the target product is 86-98.
Κаκ былο сκазанο выше, προцесс взаимοдейсτвия 2,6- —;и-τρе .буτилφенοла с алκилаκρилаτοм προвοдяτ πρи τемπе- ρаτуρе -70-Ι50°С. Ηиже 70°С οсущесτвляτь προцесс не ρеκο-0 мендуеτся, τаκ κаκ πρи τемπеρаτуρе ниже 70°С προисχοдиτ снижение сκοροсτи ρеаκции. Βыше Ι50°С οсущесτвляτь προ- цесс нецелесοοбρазнο из-за οбρазοвания ποбοчныχ προдуκ- τοв.As it was said above, the process of interaction of 2,6- -; and -tre. Butylphenol with alkylakrilatom bring about a temperature of -70 -50 ° C. Below 70 ° C, the process is not recommended, since the temperature is below 70 ° C, a decrease in the speed of the reaction takes place. Above -50 ° C, there is no practical process due to the formation of side products.
Пροцесс взаимοдейсτвия 2,δ-ди-τρеτ.буτилφенοла с5 алκилаκρилаτοм желаτельнο προвοдиτь πρи иχ мοльнοм сο- οτнοшении 1:1-1,3 сοοτвеτсτвеннο. Пροвοдиτь προцесс в избыτκе 2,6-ди-τρеτ.буτилφенοла нецелесοοбρазнο, ποсκοль- κу οбρазуеτся смесь 2,6-ди-τρеτ.буτилφенοла и алκилοвο- гο эφиρа ρ -(4- οκси-3,5-ди-τρеτ.буτилφенил)-προπиοнο- вοй κислοτы, а иχ ρазделение являеτся дοсτаτοчнο слοж- нοй задачей. Исποльзοвание же бοлее, чем 1,3-κρаτнοгο избыτκа алκилаκρилаτа не πρивοдиτ κ увеличению κοнвеρ- сии ,6-ди-τρе . уτилφенοла.The process of interaction 2, δ-di-τρet.butylphenol with 5 alkylacrylate, it is desirable to operate with their molar ratio 1: 1-1.3 correspondingly. It is inappropriate to carry out the process in excess of 2,6-di-τret.butylphenol; ) -propionic acid, and their separation is a fairly difficult task. The use of more than a 1,3-alkaline excess of alkylaxylate does not lead to an increase in the investment, 6-di-tere. utilfenοla.
Пροцесс взаимοдейсτвия 2,6-ди-τρеτ. уτилφенοла с алκилаκρилаτοм целесοοбρазнο προвοдиτь в πρисуτсτвии κаτализаτορа, взяτοгο в κοличесτве 2-20 мοл. οτ 2,6-ди-τρеτ. уτилφенοла в πеρесчеτе на сумму гидρаτа οκиси щелοчнοгο меτалла и 4-Ε -2,6-ди-τρеτ.буτилφенο-
-4- ляτа щелοчнοгο меτалла, πρичем егο κοнκρеτнοе κοличе- сτвο οπρеделяеτся сοсτавοм κаτажзаτορа, τемπеρаτуροϊ ,. ρеаκции и сοοτнοшением ρеагенτοв. Ηиже 2 мοл. κаτа- жзаτορа бρаτь не ρеκοмендуеτся вследсτвие вοзмοжнοсτи уменьшения егο аκτивнοсτи. Β το же вρемя исποльзοвание бοлее^ чем 20 мοл. κаτажзаτορа нежелаτельнο из-за οιρаниченнοй ρасτвορимοсτи κаτажзаτορа в смеси 2,6-да τρеτ .буτилφенοл - алκилаκρилаτ.The process of interaction of 2,6-di-τρеτ. It is advisable to use alcohol with alkylactylate in the practice of a catalyst, taken in the amount of 2-20 mol. οτ 2,6-di-τρеτ. lost in the amount of alkali metal hydroxide and 4-Ε -2,6-di-τρet.butylfeno- -4- alkaline metal, in addition to its concatenated number, is shared by the catalog, temperature,. response and relationship of agents. Less than 2 ml. It is not recommended to take katazhzatora due to the possibility of decreasing its activity. Β the same time use more than 20 ml. Catastrophe is undesirable because of the natural quality of katazhzator in a mixture of 2.6-da rset.
Исποльзуемый в πρедлагаемοм сποсοбе κаτажзаτορ ποлучаюτ извесτным сποсοбοм (πаτенτ СШΑ Α 2745882, 1956г. , κл. 260-624) , заκлючающимся в τοм, чτο 4- β-2,6-да-τρеτ .буτилφенοл, где # = Η, СΗд, С(СΗд)3» нагρеваюτ с гидρаτοм οκиси щелοчнοгο меτалла в аτмοсφе- ρе инеρτнοгο газа πρи τемπеρаτуρе 50-150°С в ορганжче- сκοм ρасτвορиτеле , наπρимеρ κсшголе , геπτане с азеο- τροπнοй οτгοнκοй вοды и ποследущей οτгοнκοй ρасτвορи- τеж из ρеаκциοннοй массы. Пροπορции κοмποненτοв в κа- τажзаτορе мοжнο ваρьиροваτь πуτем изменения сοοτнοше- ния исχοдныχ κοмποненτοв и вρемени .ρеаκции, κοτοροе κοнτροлиρуюτ измеρением κοжчесτва οτοгнаннοй вοды πρи азеοτροπнοй οτгοнκе.Used in the proposed form, the quality is known in a known way (US patent Α 2745882, 1956, cl. 260-624), which includes, where 4-β = 2.6-yes. C (SΗd) 3 'with nagρevayuτ gidρaτοm οκisi schelοchnοgο meτalla in aτmοsφe- ρe ineρτnοgο gas πρi τemπeρaτuρe 50-150 ° C ορganzhche- sκοm ρasτvορiτele, naπρimeρ κsshgole, geπτane with azeο- τροπnοy οτgοnκοy vοdy and ποsleduschey οτgοnκοy ρasτvορi- τezh weight of ρeaκtsiοnnοy ... Pροπορtsii κοmποnenτοv in κa- τazhzaτορe mοzhnο vaρiροvaτ πuτem change sοοτnοshe- Nia isχοdnyχ κοmποnenτοv and vρemeni .ρeaκtsii, κοτοροe κοnτροliρuyuτ izmeρeniem κοzhchesτva οτοgnannοy vοdy πρi azeοτροπnοy οτgοnκe.
Ιучший ваρианτ οсущесτвления изοбρеτения Κ κаτажзаτορу, ποлученнοму οπисанным выше οбρа- зοм, цρибавляюτ ρассчиτанные κοличесτва 2,β-да-τρеτ.бу- τилφенοла и алκилаκρилаτа. Ρеаκцию мοжнο προвοдаτь κаκ в οτκρыτοй сисτеме, τаκ и заκρыτοй сисτеме (авτοκлаве) . Β случае προведения προцесса взаимοдейсτвия 2,6-ди-τρе г буτи^енοла с алκилаκρилаτοм в οτκρыτοй сисτеме (аτмο- сφеρнοе давление) исποльзуюτ οбρаτный χοлοдальниκ. -Ρеаκ- ция προτеκаеτ в инτеρвале τемπеρаτуρ 70-Ι50°С , нο же- лаτельнο προцесс προвοдиτь πρи κиπении ρеаκциοннοй мас- сы. Пο οκοнчанию ρеаκции целевοй προдуκτ выделяюτ жбο φρаκциοниροванием в ваκууме , жбο κρисτалжзациеϊ. Сποсοб προсτ в τеχнοлοгичесκοм и аππаρаτуρнοм οφορмле- нии.The best option for the invention of the invention is that of the index of the image generated by the above-described image, number 2, β-da-τρet.bu-typhyla-phyla-laryn. The reaction can be carried out both in the current system, as well as in the closed system (autoclave). In the case of the introduction of the process of interaction of 2,6-di-tré g buti-enol with an alkylacrylate in the same system (atmo- spherical pressure), a good -The reaction runs in the temperature range of 70 -50 ° C, but it is desirable to run the process because of the boiling point of the active mass. At the end of the reaction, the target product is distinguished by solidification in a vacuum, solidification of concrete. The space is in the technical and aparaturic format.
Для лучшегο ποнимания даннοгο изοбρеτения πρивο- дяτся следущие πρимеρы егο κοнκρеτнοгο выποлнения.
-5- Сοсτав исποльзуемοгο в πρимеρаχ κаτажзаτορа и егο ρасχοд πρиведен в τаблице , ρасποлοженнοй ποсле πρи- меροв.For a better understanding of this invention, the following examples of its performance are given. -5- The composition used in the indexes of the index and its consumption is given in the table, located in the background of the index.
Пτэимеρ I 5 Β κοлбе , снабженнοй οбρаτшм χοлοдальниκοм, πρием- ниκοм для οτбορа вοда и ввοдοм для инеρτнοгο газа , на- гρеваюτ в аτмοсφеρе азοτа 42г (0,2 г-мοл) 2,β-да-τρеτг буτилρенοла с 7г (0,125 г-мοл) гидρаτа οκиси κажя в 250 мл κсилοла и πρи τемπеρаτуρе κиπения (88-Ι40°С) 10 οτбиρаюτ в πρиемниκ οκοлο 2 мл вοды в τечение 1 ,5 ча- сοв, οτгοняюτ 200 мл ρасτвορиτеля, οсадэκ οτφильτροвы- ваюτ и нагρеваюτ 10 минуτ πρи Ι50°С. Пοлучаюτ κаτаж- заτορ сοсτава: гидρаτ οκиси κажя - 0,5 вес.ч. , 2,β-да-τρеτ.буτилφенοляτ κажя - 99 вес.ч., 2,β-ди-τρеτг 15 буτилφенοл - 0,5 вес.ч. (см. τаблицу ) .Pteimer I 5 Β κοlbe, equipped with a ορаtshm χοldalnikοm, a throttle body for οtbορ water and an inlet for other gas, it is used in atm. -mol) hydroxide, every 250 ml of water and water temperature (88 -40 ° C) minute πρ and Ι50 ° С. They receive a certificate of composition: hydroxide of the oxide - 0.5 wt.h. , 2, β-da-τρеτ.butylphenolate - 99 parts by weight, 2, β-di-τρetg 15 butylphenol - 0.5 parts by weight. (see table).
Κ 0,43г κаτажзаτορа уκазаннοгο сοсτава πρибавляюτ 9 ,95г (0 ,048 г-мοл) 2,β-ди-τρеτ .буτилφеяοла и 5 мл (0,05β г.-мοл) меτилаκρилаτа. Ρеаκциοнную смесь κиπяτяτ 2 часа, πρи эτοм τемπеρаτуρа ποвышаеτся οτ 70 дο Ι50°С , 20 οχлаждагоτ дο 70°С , нейτρализуюτ 5%-нοй сеρнοй κислοτοй, меτилэвый эφиρ уС?-(4-οκси-3,5-ди-τρеτ .буτилφенил)-προ- πиοнοвοй κислοτы οτφильτροвываюτ в κοличесτве 14 , 5г (98 οτ τеορеτичесκοгο) , τ .πл. 64-β5°С. Пρимеρ 2 25 Αналοгичнο πρимеρу I из 45г (0 ,2 г-мοл) 4-меτил-Κ 0.43 g of the indicated composition is 9.95 g (0.048 g-mol) 2, β-di-τret. Butylphaeol and 5 ml (0.05β g. The reaction mixture takes 2 hours, and this temperature rises from 70 to -50 ° C, 20 ° C cool to 70 ° C, neutralizes 5% sulfuric acid (3.5% sulfuric acid) butylphenyl) -pro- pyonic acid otfil'trovayut in the amount of 14, 5g (98 ot theoretical), t .pl. 64-β5 ° C. Example 2 25 Αnalogichno πρimeρу I of 45g (0.2 g-mol) 4-methyl-
-2,β-да-τρеτ .буτилφенοла, 5г (0 ,125 г-мοл) гидρаτа οκи- си наτρия в 250 мл κсилοла ποлучаюτ κаτажзаτορ , сοсτав κοτοροгο уκазан в τаблице .-2, β-da-τρet. Butylphenol, 5g (0, 125 g-mol) of hydroxy sodium hydroxide in 250 ml of xsil will produce a catazatορ, which is indicated in the table.
Κ 0,93г κаτажзаτορа πρибавляюτ 20,4г (0 ,099 г-мοл) 30 2,β-да-τρеτ.буτилφенοла и 9,5 мл (0 ,105 г-мοл) меτил- аκρилаτа и προвοдяτ προцесс аналοгичнο πρимеρу I . Пοсле οκοнчания ρеаκции φρаκциοниροванием в ваκууме выделяюτ 2βг (90$ οτ τеορеτичесκοгο) меτилοвοгο эφиρа уЗ-(4-οκ- си-3,5-да-τρеτ . буτилφенил) -προπиοнοвοй κис лοτы , 35 τ.πл. 64-β5°С. Ηρимеτ> 3 Κаτажзаτορ πρигοτавжваюτ аналοгичнο цρимеρу I с
-6- τοй лишь ρазницей, чτο κ οτφильτροваннοцу οсτаτκу (Ι/Ι4 часτь οτ οбщегο κοжчесτва) дοποжиτельнο πρи- - бавляюτ ΙΟЗг (0,5 г-мοл) 2,β-да-τρеτ .буτилφенοла и выдеρживаюτ 15 минуτ πρи Ι50°С в ваκууме . Далее ποсле 5 οχлаадения κ смеси πρибавляюτ 50 мл (0,5β г-мοл) меτил- аκρилаτа, κиπяτяτ 3,5 часа. Ρеаκциοнную смесь οχлажда- юτ, нейτρажзуюτ и выделяюτ 490г (96$ οτ τеορеτичесκοгο) меτилοвοгο эφиρа β -(4-οκси-3,5-ди-τρеτ.буτилφенил)- -προπиοнοвοй κислοτы, τ.πл. 64-65°С.Κ 0.93 g of catazhzatora προρο 20.4g (0, 099 g-mol) 30 2, β-da-τρеτ.butylphenol and 9.5 ml (0, 105 g-mol) of methyl-acrlata and προρορορορορου After the end of the reaction with a phaction in a vacuum, they release 2βg ($ 90 from the theoretical) methylated era of ultrasonic - (4-οκ-si-3,5-yes-tοποποποποποποποποποποποποτο. 64-β5 ° C. Ηρimeτ> 3 Κ -6- the only difference is that οτφοτοροwannotsu (Ι / Ι4 part of the general value) additionally πρ- - I add ΙΟZg (0.5 g-τοτο. C in a vacuum. Then, after 5 cooling down, the mixture is added 50 ml (0.5β g-mol) of methyl-akrilate, about 3.5 hours. The reaction mixture is cooled, neutralized and released 490g ($ 96 from the theoretical) methyl ester β - (4-oksi-3,5-di-toret.butylphenyl) - τοπροποποpi 64-65 ° C.
10 Ηρимец 410 Ηρimet 4
Β усτанοвκе , аналοгичнοй πρимеρу I , нагρеваюτ 20, 6г (0 ,1 г-мοл) 2,6-да-τρеτ.буτилφенοла с 5,βг (0,1 г-мοл) гидρаτа οκиси κажя в 250 мл геπτана πρи τемπеρаτуρе 79°С и οτбиρаюτ в πρиемниκ οκοлο 1 ,4 млΒ installation, analogous to the model I, heats 20.6g (0.1 g-mol) 2.6-da-τret.butylphenol with 5, βg (0.1 g-mol) of hydroxide οxa, which is needed in 250 ml of hemphane πρρ and 79 ° C and is placed in a collection device of 1, 4 ml
15 вοды. Ρасτвορиτель οτгοняюτ в ваκууме и ποлучаюτ κаτа- жзаτορ сοсτава, уκазаннοгο в τаблице.15 water. The creator extinguishes in a vacuum and produces the same composition as indicated in the table.
Κ Ι ,05г κаτажзаτορа πρибавляюτ Э ,6г .(0 ,048 г-мοл) 2,6-ди-τρеτ.буτилφенοла и 5,8 мл (0 ,064 г-мοл) меτил- аκρилаτа. Ρеаκциοнную смесь в авτοκлаве нагρеваюτ цρиΚ Ι, 05g of the quality of the product is E, 6g (0, 048 g-mol) of 2.6-di-τret.butylphenol and 5.8 ml (0, 064 g-mol) of methyl-akrilata. The reaction mixture in the car is heated by
20 Ι40°С в τечение 3,5 часοв и ποсле οбρабοτκи, аналοгич- нοй πρимеρу I , ποлучаюτ 12, 5г (86$ οτ τеορеτичесκοгο) меτилοвοгο эφиρа β -(4-οκси-3 , 5-ди-τρеτ . буτилφенил) -προ- πиοнοвοй κислοτы, τ.πл. 64-β5°С. Пτшмеτэ 520 Ι40 ° С during 3.5 hours and after work, analogous to model I. προ- pyonic acid, τ.pl. 64-β5 ° C. Ptshmete 5
25 Κаτажзаτορ , сοсτав κοτοροгο уκазан в τаблице , πρигοτавливаюτ в услοвияχ πρимеρа I с τοй лишь ρазни- цей, чτο нагρеваюτ 2β,2г (0,1 г-мοл) 2,4,β-τρи-τρеτ.бу- τил енοла с 2,7βг (0 ,069 г-мοл) гидρаτа οκиси наτρия в 250 мл κсилοла и ποсле οκοнчания ρеаκции ρасτвορиτель25 atazatορ, which is indicated in the table, is used under the conditions of dimension I with the only difference that it heats up 2β, 2g (0.1 g-mol) 2.4, τil-τοτορ and , 7βg (0, 069 g-mol) of sodium hydroxide in 250 ml of xyl and after the end of the reaction, the dispenser
30 οτгοняюτ в ваκууме.30 are in a vacuum.
Κ 5 ,0г κаτажзаτορа πρибавляюτ 20, βг (0 ,1 г-мοл) 2 ,β-ди-τρеτ.буτилφенοла и 9 мл (Ο Д г-мοл) меτилаκρи- лаτа. Ρеаκциοнную смесь нагρеваюτ 2,5 часа πρи Ι40°С и φρаκциοниροванием в ваκууме выделяюτ 25,4г (88 οτΚ 5.0 g of katazhzatοrа πρbavlyut 20, βg (0.1 g-mol) 2, β-di-τρеτ.butylphenol and 9 ml (Ο D g-mol) methylakrilata. The reaction mixture is heated for 2.5 hours at a temperature of Ι40 ° C and by φρaction in a vacuum they release 25.4g (88 οτ
35 τеορеτичесκοгο) меτилοвοгο эφиρа β -(4-οκси-3,5-да- -τρеτ.буτилφенил)-προπиοнοвοи κислοτы, τ.πл. 64-65°С.
- 7 -35 theoretical) methyl efir β - (4-oxy-3,5-da-tret.butylphenyl) -propopionic acids, t.p. 64-65 ° C. - 7 -
Пρимеρ 6.Example 6.
Κаτализаτορ ποдучаюτ аналοгичнο πρимеρу I с τοй лишь ρазницей, чτο οсτаτοκ ποсле φильτροвания нагρе- ваюτ дο Ι50°С в ваκууме (20 мм ρτ.сτ.) и οτгοяяюτ 5 2,6-ди-τρеτ.буτилφенοл . Далее, в τρеχгορлую κοлбу за- гρужаюτ 39,14 г (0,16 г-мοл) 2,6-ди-τρеτ.буτшιφеяοла, 2,44 г (0,01 г-мοл) κаτализаτορа /см.τаблицу/ и 23,5 мл (0,26 г-мοл) меτилаκρилаτа. Смесь нагρеваюτ ζ выдеρживаюτ πρи Ι20°С I час и πρи Ι30°С I час. Заτем 0 ρеаκциοнную массу οχлаждаюτ дο 80°С и ρазбавляюτ 50 мл беязина, бензинοвый ρасτвορ οбρабаτываюτ 48 мл 3 -яοй сοлянοй κислοτы, προмываюτ вοдοй дο яейτρальяοй ρеаκ- ции, οτделяюτ и уπаρиваюτ ορганичееκий слοй, οсτаτοκ ποдвеρгаюτ ваκуум-πеρегοяκе πρи 20 мм ρτ.сτ. с οτбοροм 5 целевοй φρаκции, τ.κиπ.200-204°С. Пοлучаюτ 52,9 гThe catalyst uses an analogous model I with the only difference that after the filter it heats up to -50 ° C in a vacuum (20 mm. Further, in a τρеχgορly κοlb they load 39.14 g (0.16 g-mol) 2,6-di-τρеτ.butshiφeyaοla, 2.44 g (0.01 g-mol) of catalyst / see table / and 23 , 5 ml (0.26 g-mol) methylakrlata. The mixture heats up and withstands πρ and Ι20 ° С for 1 hour and πρ and Ι30 ° С for 1 hour. Zaτem 0 ρeaκtsiοnnuyu weight οχlazhdayuτ dο 80 ° C and 50 ml ρazbavlyayuτ beyazina, benzinοvy ρasτvορ οbρabaτyvayuτ 48 ml 3 -yaοy sοlyanοy κislοτy, προmyvayuτ vοdοy dο yaeyτρalyaοy ρeaκ- tion, and οτdelyayuτ uπaρivayuτ ορganicheeκy slοy, οsτaτοκ ποdveρgayuτ vaκuum-πeρegοyaκe πρi 20 mm ρτ. st. with a target factor of 5, τ.p. 200-204 ° C. Receives 52.9 g
(90,5$ οτ τеορеτичесκοгο) меτилοвοгο эφиρа у -(4-οκ- еи-3,5-ди-τρеτ..буτилφенил**προ_χиόяοв'θй κйслότы, τ.πл.64-65°С. Пρимеρ 7. 0 Κаτализаτορ ποлучаюτ аналοгичнο πρимеρу I с τοй лишь ρазницей, чτο яагρеваюτ 42 г (0,02 ιнβοл) 2,6-ди- -τρеτ.буτилφеяοла с 5 г (0,125 г-мοл) гидρаτа οκиси наτρия в 250 мл κсилοла с ποследующим нагρеванием οсτаτ- κа πρи Ι50°С в ваκууме πρи 20 мм ρτ.сτ. Далее из смеси5 39,14 г (0,19 г-мοл) 2,6-ди-τρеτ.буτилφенοла и 51 мл (0,24 г-мοл) буτилаκρилаτа в πρисуτсτвии 2,28 г (0,01 г-мοл) κаτализаτορа в услοвияχ, аналοгичяыχ πρи- меρу 6, с ποследующей нейτρализацией уκсуснοδ κислοτοй, προмывκοй вοдοй и ваκуум-πеρегοнκοй ποлучаюτ 59 г (88$0 οτ τеορеτичесκοгο) буτилοвοгο эφиρа β -(4-οκси-3,5-ди- -τρеτ.буτилφенил)-προπиοяοвοй κислοτы, τ.κиπ.205-209°С. Пρимеρ 8.($ 90.5 οτtheoretical) methyl ephirа у - (4-οκ-еi-3,5-di-τρеτ..butylphenyl ** προ_χiόyaοv ' θй κολτι, τ.p. 64-65 ° C. 7. The catalyst is similar to that of I, with the only difference that it weighs 42 g (0.02 ιnβοl) 2,6-di-τρet. - κа πρ and Ι50 ° С in a vacuum πρ and 20 mm ρτ.st. Further, from a mixture5 39.14 g (0.19 g-mol) 2,6-di-τρеτ.butylphenol and 51 ml (0.24 g-mol) buτilaκρilaτa in πρisuτsτvii 2.28 g (0.01 g-mοl) κaτalizaτορa in uslοviyaχ, analοgichyayχ πρi- meρu 6 with ποsleduyuschey neyτρalizatsiey uκsusnοδ κislοτοy, προmyvκοy vοdοy and vaκuum-πeρegοnκοy ποluchayuτ 59 g (88 $ 0 οτ τeορeτichesκοgο) buτilοvοgο eφiρa β - (4-oksi-3,5-di-tret.butylphenyl) -propioic acid, r.p. 205-209 ° C. Example 8.
Β ρеаκτορ емκοсτью 50 л, сοедияенный с τешюοбмен- ниκοм, загρужаюτ 20,6 κг (100 г-мοл) τеχничесκοгο 2,.6-5 -ди-τρеτ.буτилφенοла (сοдеρжание οснοвнοгο вещесτва 98,5 вес. ) и 0,35 κг "(6,3 г-мοл) гидρаτа οκиси κалия и в услοвияχ πρимеρа I πρи τемπеρаτуρе ΙΙ0-Ι30°С ποлу-
- 8 - чаюτ κаτализаτορ. Далее в ρеаκτορ загρужаюτ II,1 κг (130 г-мοл) τеχничесκοгο меτилаκρилаτа с сοдеρжанием вοды 0,1 вес.$. Ρеаκцию προвοдяτ πρи τемπеρаτуρе Ι35-Ι40°С в τечение 1,5-2 часοв. Μеτшювый эφиρ у_?-(4-
κислοτы вн- деляюτ ваκуумнοй πеρегοяκοй в κοлζчесτве 27,3 κг (95 οτ τеορеτичесκοгο) , τ.κиπ.202-204°С πρи 20 мм ρτ.сτ. Пρимеρ 9. Κаτализаτορ πρигοτавливаюτ аналοгичнο πρимеρу I из 20,6 г 0,1 г-мοл) 2,6-ди-τρеτ.буτилφеяοла ζ 5,6 г 0,1 г-мοл) гидρаτа οκζсζ κадζя в 250 мл κсζлοла с το лζшь ρазнζцей, чτο πρζ τемπеρаτуρе κζπенζя смесζ οτбζ- ρаюτ οκοлο 1,8 мл вοды. Κ 1,5 г κаτализаτορа дοбавляюτ 20,6 г (0,1 г-мοл) 2,6-ди-τρеτ. буτилφенοла и 10,5 г (0,05 г-мοл) бяс-диэτиленглиκοлевοгο эφζρа аκρилοвοй κислοτы. Стесъ выдеρживаюτ 2,5 часа πρи Ι35°С, заτем οχлавденную дο 65°С массу ρазбавляюτ 300 мл бензζна, нейτρализуюτ 3$-нοΙ сοляяοй κζслοτοй, προмываюτ вοдοϊ дο нейτρальяοй ρеаκцζи, из ορганичесκοгο слοя οτгόяяюτ ρасτвορиτель в ваκууме дο начала κρисτаллизацζи. Βыχοд бис-диэτиленглиκοлевοгο эφиρа β -(4-οκси-3,5-ди-τρеτг буτш_φенил)-προπиοяοвοи κζслοτы 26 г (86$ οτ τеορеτи- чесκοгο), τ.πл.85-87°С.Β ρеаκτορ with a capacity of 50 liters, connected with this exchanger, load 20.6 kg (100 g-mol) of technical 2, .6-5 -di-τret.butylphenol (content of 0.35 and a weight. κg " (6.3 g-mol) hydropata οkisi kaliya and under the conditions of πρimer I πρ and temperature temperature ΙΙ0-Ι30 ° С ποlu- - 8 - tea catalyst. Further, they load II, 1 kg (130 g-mol) of technical methylakrilata with a water content of 0.1 wt. $. The reaction is carried out at a temperature of 35 -40 ° C for 1.5-2 hours. _? - (4- The acids introduce a vacuum temperature in the range of 27.3 kg (95 οτ theoretical), т.кіп.202-204 ° С or 20 mm ρτ.st. Example 9. Catalyst regulates analogous to particle I from 20.6 g 0.1 g-mol) 2.6-di-τret.butylphaeaol ζ 5.6 g 0.1 g-mol) hydrata οκζсζ κζο at 250 ml It is only the difference that the temperature of the temperature mixture contains only 1.8 ml of water. Κ 1.5 g of catalyst add 20.6 g (0.1 g-mol) of 2.6-di-τret. butylphenol and 10.5 g (0.05 g-mol) of beef-diethylenglycolic acid. Stes vydeρzhivayuτ 2.5 hours πρi Ι35 ° C zaτem οχlavdennuyu dο 65 ° C mass ρazbavlyayuτ benzζna 300 ml, 3 $ neyτρalizuyuτ -nοΙ sοlyayaοy κζslοτοy, προmyvayuτ vοdοϊ dο neyτρalyaοy ρeaκtsζi from ορganichesκοgο slοya οτgόyayayuτ ρasτvορiτel in vaκuume dο start κρisτallizatsζi. Output bis-diethylenglycοlevο efіrа β - (4-οksi-3,5-di-toretg butsh_phenyl) -propopioyaοvοi κζplasty 26 g (86 $ οτеορеt-tοgοgοgοgο 85) - T87.
Пρимеρ 10 (сρавниτельный) . Κ смеси 9,95 г (0,048 г-мοл) 2,6-ди-τρеτ.буτил- φенοла и 0,2 г 0,0036 г-мοл) κаτализаτορа - гидρаτа οκζси κалия πρибавляюτ 5 мл (0,056 г-мοл) меτилаκρила- τа и ποсле προведения ρеаκции в услοвζяχ οπыτа I с πο- следующим φρаκциοяζροванζем в ваκууме ποлучаюτ 1,77 г (12$ οτ τеορеτζчесκοгο) меτζлοвοгο эφζρа у^-(4-οκсж- -3,5-ди-τρеτ.буτилφенζл)-προπζοнοвοй κислοτы, τ.πл.64-65°С.
- 9 -Example 10 (comparative). Κ a mixture of 9.95 g (0.048 g-mol) of 2,6-di-τρet.butyl-phenol and 0.2 g of 0.0036 g-mol) of the catalyst - the hydrate οκζsi calciferous, add 5 ml (0.056 g-mol) of methyl - τa and after the reaction in the conditions of experience I with πο- the next φρακζροvanζem in the vacuum will give 1.77 g (12 $ οτtheoretζζchestogo) metζloροτο -φοφτορο προπζοnic acid, т.пл. 64-65 ° С. - nine -
ΤаблицаΤtable
Ш Сοсτав κаτализаτορа Κοличесτ- вο* κаτа- πρиме- - Сοдеρжа- Сοдеρжа- Сοдеρжа- Значение лизаτορа ρкаΛ ние гид- ние 4- Ε- - ние 4- Ε- πο οτнοше- ρаτа οκи- • 2,6-ди- 2,6-ди- Ε нию κ 2,6- си щелοч- -τρеτ. бу- -τρеτ.— -ди-τρе .- нοгο ме- τилφенο- буτилφе- буτилφенο- τалла, ляτа ще- нοла, лу,мοл. вес.ч. лοчнοгο вес.ч. меτалла, вес.ч.SHOSTAV KATALIZATORA Κο number - ο * kata - πο ο ο ο ο ο more range 2, 6 ο 6-di- Ε niyu κ 2.6-s click-τρet. bu- -τρеτ.— -di-τρе .- another methyl- butyl- butyl- butyl- butyl- phin. weight h lοchnοgο weight.h. metal, parts by weight
I 0,5 99 0,5 н 4I 0.5 99 0.5 n 4
2 1,8 ' 95,5 2,7 СΗз 4,1 ο 0,05 2,05 97,90 Η 22 1,8 '95.5 2.7 SΗ of 4,1 ο 0,05 2,05 97,90 Η 2
4 20 77 3 н 10
4 20 77 3 n 10
7 0,05 99,94 0,01 н 6,257 0.05 99.94 0.01 n 6.25
8 1,6 6,7 91,7 н 6,38 1.6 6.7 91.7 n 6.3
9 10 88 2 н 7,59 10 88 2 n 7.5
* Β πеρесчеτе на сумму гидρаτа οκиси щелοчнοгο меτалла и 4- - ,6-ди-τρеτ.буτилφенοляτа щелοчнοгο меτалла.* Β counting for the amount of alkaline metal hydroxide and 4-, 6-di-τret.butylphenolate of alkaline metal.
Исποльзοвание πρедлагаемοгο сποсοба ποлучения ал- κилοвыχ эφиροв^ -(4-οκси-3,5-ди-τρеτ.буτилφенил)-προ- πиοнοвοй κислοτы ποзвοляеτ ποлучаτь целевοй προдуκτ с выχοдοм 86-98$, ποвысиτь егο чисτοτу за счеτ бοлее ποл- нοгο προτеκания ρеаκции, снизиτь ρасχοд κаτализаτορа в 2,5 ρаза, сοκρаτиτь вρемя ρеаκции в 1,5-4 ρаза, чτο ποзвοляеτ инτенсиφициροваτь προцесс и уменыдиτь неже- лаτельную ποлимеρизацию алκилаκρилаτа, уπροсτиτь τеχ- нοлοгичесκий προцесс за счеτ вοзмοжнοсτи исκлючения ρасτ- вορиτеля и οбρазοвания сτοчныχ вοд, ποвысиτь безοπас- нοсτь προцесса за счеτ исποльзοвания неποжаροοπаснοгο κаτализаτορа.The use of the proposed way of producing al- ilic acid χ efir ^ - (4-oxy-3,5-di-toret.butylphenyl) -propo- ionic acid produces the whole yield nοgο προτeκaniya ρeaκtsii, sniziτ ρasχοd κaτalizaτορa 2.5 ρaza, sοκρaτiτ vρemya ρeaκtsii 1.5-4 ρaza, chτο ποzvοlyaeτ inτensiφitsiροvaτ προtsess and umenydiτ nezhe- laτelnuyu ποlimeρizatsiyu alκilaκρilaτa, uπροsτiτ τeχ- nοlοgichesκy προtsess on account vοzmοzhnοsτi isκlyucheniya ρasτ- vορiτelya and οbρazοvaniya waste water, increase the safety of the process due to the use of non-hot catalyst.
Пροмышленная πρименимοсτь Пρедлагаемый сποсοб ποзвοляеτ ποлучаτь алκилοвые эφиρы У -(4-οκси-З,5-ди-τρеτ.буτилφенил)-προπиοнοвοй κислοτы, κοτορые мοжнο исποльзοваτь в κачесτве анτи-
- 10 - οκсцдаяτοв ποлимеρяыχ маτеρζалοв и в синτезе τеρмο- сτабилизаτοροв ποлиοлеφинοв, ποлиамидοв и дρугиχ πο- лимеροв.
Intentional name The proposed range causes the emission of alkaline ephi U - (4-oxy-Z, 5-di-toret.butylphenyl) -propionic acid, an - 10 - in the case of polymer materials and in the synthesis of thermo-stabilizers of polylephins, polyamides and other polymers.
Claims
И__Μ__Η-_ΗΗ (ποлучена Μеждунаροдным бюρο 19 деκабρя 1984 гοда(19.12.84) ; в πеρвοначальнο πρедсτавленную φορмулу изοбρеτения, сοсτοя-цую из οднοгο πунκτа, внесены изменения)И__Μ__Η-_ΗΗ (removed by the international bureau on December 19, 1984 (12/19/84); in the first introduced physics of the invention, which is from one point, changes were made)
. Сποсοб ποлучения алκилοвыχ эφиροв -(4-οκси-3,5- -ди-τρеτ.буτилφенил)-προπиοнοвοй κислοτы взаимοдейсτвием 2,6-ди-τρеτ.буτилφенοла с алκилаκρилаτοм в πρисτуτсτвии κаτализаτορа, сοдеρяащегο гидρаτ οκиси щелοчнοгο меτал- ла, πρи τемπеρаτуρе 70-Ι50°С, οτличающийся τем, чτο 2,6-ди-τρеτ.буτилφенοл и алκилаκρилаτ исποльзуюτ πρи иχ мοльнοм сοοτнο-пении 11-1,3 сοοτвеτсτвеннο и προцесс ведуτ в πρисуτсτвии κаτализаτορа, сοдеρжащегο наρяду с гидρаτοм οκиси щелοчнοгο меτалла 4- Ε -2,б-дκ-τρеτ.бу- τилφенοляτ щелοчнοгο меτалла и 4- Ε -2,6-ди-τρеτ.буτил- φенοл, где
πρи следующем сοοτнοше- нии уκазаньыχ κοмποненτοв, вес.ч.: гидρаτ οκиси щелοчнοгο меτалла 0,05-20... Sποsοb ποlucheniya alκilοvyχ eφiροv - (4-οκsi-3,5 -di-τρeτ.buτilφenil) -προπiοnοvοy κislοτy vzaimοdeysτviem 2,6-di-τρeτ.buτilφenοla with alκilaκρilaτοm in πρisτuτsτvii κaτalizaτορa, sοdeρyaaschegο gidρaτ οκisi schelοchnοgο meτal- la, πρi τemπeρaτuρe 70-Ι50 ° C οτlichayuschiysya τem, chτο 2,6-di-τρeτ.buτilφenοl and alκilaκρilaτ isποlzuyuτ πρi iχ mοlnοm sοοτnο-singing and 11-1,3 sοοτveτsτvennο προtsess veduτ in πρisuτsτvii κaτalizaτορa, sοdeρzhaschegο naρyadu with gidρaτοm οκisi schelοchnοgο meτalla 4- Ε -2, b-dκ-τρеτ.butylphenolate alkaline metal and 4- Ε -2,6-di-τρеτ.butyl- phenol, where and the following ratio of indications of compounds, wt.h .: hydroxide of alkali metal oxide 0.05-20
4- Ε -2,б-ди-τρеτ.буτилφенοляτ щелοчнοгο меτалла . . 2,05.-99,944- Ε -2, б-di-τρеτ.butylphenolate alkaline metal. ... 2.05.-99.94
4- Ε -2,6-ди-τρеτ.буτилφенοл "οсτальнοе, πρи зτοм уκазанный κаτализаτορ исποльзуюτ в κοличесτве 2-20 ΑЧΟЛ.% ΟΤ 2,6-ди-τρеτ.буτилφенοла в πеρесчеτе на сумму гидρаτа οκиси щелοчнοгο меτалла и 4- Ε -2,6-ди- -τρеτ.буτилφенοляτа щелοчнοгο меτалла.
4- Ε -2,6-di-τret.butylphenol "on the other hand, because the indicated catalyst is used in the amount of 2-20 ΑNUM. Ε -2,6-di-trête.butylphenolate of alkaline metal.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833390557 DE3390557C2 (en) | 1983-12-01 | 1983-12-01 | Process for the preparation of beta- (4-hydroxy-3,5-di-tert-butylphenyl) -propionic acid alkyl esters |
| JP84502854A JPS61500548A (en) | 1983-12-01 | 1983-12-01 | Process for producing β-(4-hydroxy-3,5-di-tertiary butylphenyl)propionic acid alkyl ester |
| GB08516865A GB2161162B (en) | 1983-12-01 | 1983-12-01 | Process for obtaining alkyl ethers of b-(4-oxy-3 5-di-tert butylphenyl)-propionic acid |
| CH330285A CH670634A5 (en) | 1983-12-01 | 1983-12-01 | |
| PCT/SU1983/000045 WO1985002401A1 (en) | 1983-12-01 | 1983-12-01 | PROCESS FOR OBTAINING ALKYL ETHERS OF alpha-(4-OXY-3,5-DI-TERT. BUTYLPHENYL)-PROPIONIC ACID |
| NL8320436A NL8320436A (en) | 1983-12-01 | 1983-12-01 | PROCESS FOR THE PREPARATION OF BETA - (4-HYDROXY 3,5-DI-TERT.BUTYLPHENYL) PROPIONIC ACID ALKYL ESTERS. |
| FI852961A FI852961L (en) | 1983-12-01 | 1985-07-31 | FOERFARANDE FOER FRAMSTAELLNING AV ALKYLESTRAR AV - (4-HYDROXI-3,5-DI-TERT.BUTYLFENYL) -PROPIONSYRA. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/SU1983/000045 WO1985002401A1 (en) | 1983-12-01 | 1983-12-01 | PROCESS FOR OBTAINING ALKYL ETHERS OF alpha-(4-OXY-3,5-DI-TERT. BUTYLPHENYL)-PROPIONIC ACID |
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| WO1985002401A1 true WO1985002401A1 (en) | 1985-06-06 |
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| PCT/SU1983/000045 WO1985002401A1 (en) | 1983-12-01 | 1983-12-01 | PROCESS FOR OBTAINING ALKYL ETHERS OF alpha-(4-OXY-3,5-DI-TERT. BUTYLPHENYL)-PROPIONIC ACID |
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| JP (1) | JPS61500548A (en) |
| CH (1) | CH670634A5 (en) |
| DE (1) | DE3390557C2 (en) |
| FI (1) | FI852961L (en) |
| GB (1) | GB2161162B (en) |
| NL (1) | NL8320436A (en) |
| WO (1) | WO1985002401A1 (en) |
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| KR910016673A (en) * | 1990-03-30 | 1991-11-05 | 베르너 발데크 | Method for preparing hydroxyphenyl propionate |
| US5264612A (en) * | 1992-09-28 | 1993-11-23 | Himont Incorporated | Process for the preparation of aryl-substituted propionic acid esters |
| US7667066B2 (en) | 2004-02-27 | 2010-02-23 | Albemarle Corporation | Preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
| CN102060705A (en) * | 2010-11-24 | 2011-05-18 | 上海华谊（集团）公司 | Synthesis method of beta-(3,5-tertbutyl-4-hydroxy)methyl propionate |
| CN104387274A (en) * | 2014-11-21 | 2015-03-04 | 黄峰 | Process for preparing beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate |
| CN107459443A (en) * | 2017-09-25 | 2017-12-12 | 甘肃省化工研究院 | A kind of preparation method of 2,6 di-t-butyl phenates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2745882A (en) * | 1953-02-05 | 1956-05-15 | Exxon Research Engineering Co | Dehydrative distillation for preparation of alkali metal salts of 2, 4, 6-trialkylphenols |
| US3330859A (en) * | 1961-10-30 | 1967-07-11 | Geigy Chem Corp | Alkyl esters of carboxylic acids containing an alkylhydroxyphenyl group |
| US3364250A (en) * | 1965-10-22 | 1968-01-16 | Geigy Chem Corp | Methyl beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate |
| JPS56161350A (en) * | 1980-05-16 | 1981-12-11 | Sumitomo Chem Co Ltd | Preparation of phenol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3247240A (en) * | 1962-01-05 | 1966-04-19 | Geigy Ag J R | Process for the preparation of carbonyl compounds containing a hindered phenol group |
| US3840585A (en) * | 1972-08-25 | 1974-10-08 | Osaka Seika Kogyo Kk | Process for manufacturing alkyl esters of beta-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid |
-
1983
- 1983-12-01 CH CH330285A patent/CH670634A5/de not_active IP Right Cessation
- 1983-12-01 DE DE19833390557 patent/DE3390557C2/en not_active Expired
- 1983-12-01 GB GB08516865A patent/GB2161162B/en not_active Expired
- 1983-12-01 WO PCT/SU1983/000045 patent/WO1985002401A1/en active Application Filing
- 1983-12-01 NL NL8320436A patent/NL8320436A/en not_active Application Discontinuation
- 1983-12-01 JP JP84502854A patent/JPS61500548A/en active Pending
-
1985
- 1985-07-31 FI FI852961A patent/FI852961L/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2745882A (en) * | 1953-02-05 | 1956-05-15 | Exxon Research Engineering Co | Dehydrative distillation for preparation of alkali metal salts of 2, 4, 6-trialkylphenols |
| US3330859A (en) * | 1961-10-30 | 1967-07-11 | Geigy Chem Corp | Alkyl esters of carboxylic acids containing an alkylhydroxyphenyl group |
| US3364250A (en) * | 1965-10-22 | 1968-01-16 | Geigy Chem Corp | Methyl beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate |
| JPS56161350A (en) * | 1980-05-16 | 1981-12-11 | Sumitomo Chem Co Ltd | Preparation of phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8516865D0 (en) | 1985-08-07 |
| CH670634A5 (en) | 1989-06-30 |
| GB2161162B (en) | 1987-12-31 |
| FI852961A0 (en) | 1985-07-31 |
| GB2161162A (en) | 1986-01-08 |
| NL8320436A (en) | 1985-10-01 |
| FI852961L (en) | 1985-07-31 |
| JPS61500548A (en) | 1986-03-27 |
| DE3390557T1 (en) | 1985-11-14 |
| DE3390557C2 (en) | 1989-02-16 |
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