CS224809B1 - Manufacturing process of 5-norbornen-2,3-dikarboxyl acidand/or its anhydride - Google Patents
Manufacturing process of 5-norbornen-2,3-dikarboxyl acidand/or its anhydride Download PDFInfo
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- CS224809B1 CS224809B1 CS165582A CS165582A CS224809B1 CS 224809 B1 CS224809 B1 CS 224809B1 CS 165582 A CS165582 A CS 165582A CS 165582 A CS165582 A CS 165582A CS 224809 B1 CS224809 B1 CS 224809B1
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- Prior art keywords
- anhydride
- maleic anhydride
- acid
- maleic
- dicyclopentadiene
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- 150000008064 anhydrides Chemical class 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 28
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 16
- 239000011976 maleic acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 11
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 230000000707 stereoselective effect Effects 0.000 description 5
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález sa týká výroby kyseliny 5-norbornón-2,3-dikarboxylovej a/alebo jej anhydridů (endometyléntetrahydrof talanhydridu) z dostupných petroohemickýoh alebo koksoohemiokých surovin technicky a ekonomicky nenáročným spósobom, s využitím běžných aparatur a zariadení·The present invention relates to the production of 5-norbornone-2,3-dicarboxylic acid and / or its anhydrides (endomethylenetetrahydrophthalic anhydride) from available petro-chemical or coke-chemical raw materials in a technically and economically undemanding manner, using conventional apparatus and equipment.
Je dávno známo fíaosermann A. i Diele-Alder-Reaotien, Organic Background and Physioo-Chemioal Aspeots. Elsevier Publ. Co· (1965)» Eisler B., Vassermann A·: J. Chem· Soc· 1953. 19^3» Benford G, A·, Vassermann A·: J. Chem· Soc· 362, 367; Kaufmann H«, Vassermann A·: J. Chem· Soc. 1939« 870; Goppoldová M., Goppold M.: Chem. prům· 30, 362 (198O)J příprava 5-norbornén-2,3-dikarbónove j (dikarboxylove j ) kyseliny (endometyléntetrahydroftalpvej kyseliny), ako aj jej anhydridů ^endometyléntetrahydroftalanhydridj bicyklo«*(2,2,1 )-heptón- (5 )-dikarbón- (2,3 )-anhydridJ Diels-Alderovou adíciou oyklopentadiónu na kyselinu maleínovú, resp· maleínanhydrid· Přitom cykl open tadión je dién a maleínanhydrid, resp· kyselina mal eí nová dienofil· Známe sú tiež výsledky takej to adície viaoerýoh konjugovaných diénov s maleínanhydridom, pričom k najv&čšim pozoruhodnostiam patří zistenié {^Craig D., Shipman J« J., Fowler F. B.: J. Am· Chem· Soc· 83« 2825 (I9ól)j Craig D.: J. Am· Chem· Soo· 85. 1006 (1963 )J, že rýohlostná konétanta reakcie adície oyklopentadiénu s maleínanhydridom fedťc,Fiaosermann A. and Diele-Alder-Reaotien, Organic Background and Physioo-Chemioal Aspeots have long been known. Elsevier Publ. Co (1965) Eisler B., Vassermann A: J. Chem Soc 1953 19 ^ 3 Benford G, Vassermann A J. Chem Soc 362, 367; Kaufmann H., Vassermann A., J. Chem. Soc. 1939 «870; Goppold, M., Goppold, M .: Chem. 30, 362 (198O) J preparation of 5-norbornene-2,3-dicarboxylic acid (endomethylenetetrahydrophthalic acid) as well as its anhydrides, bicyclo (2.2.1) -heptone- ( 5) -dicarbonate- (2,3) -anhydride Diels-Alder addition of cyclopentadione to maleic acid or maleic anhydride · Open tadione is a diene and maleic anhydride or a small dienophile · The results of such a multi-functional addition are also known of the conjugated dienes with maleic anhydride, the most noteworthy of which are those found by Craig D., Shipman J, Fowler FB, J. Am. Chem., Soc., 83, 2825 (19). Soo · 85, 1006 (1963), that the rate-limiting constant of the reaction of addition of cyclopentadiene with maleic anhydride fedtc,
CH a CHCH and CH
I + I +
CH a CHCH and CH
CHCH
IIII
CHCH
COWHAT
CO XCH ' I XCO X CH 1 IX
CH XCH - COCH X CH - CO
CHCH
CH,CH,
CH X coCH X co
CHCH
224 809 je až o tri poriadky vyššia než iných. diénov. To sa technicky racionálně využilo ^Kubička R., Goppoldová M.: Čs. autorské o svedčenie 149 504; Goppoldová M.: Chem· pr&m· 30· 408 (1980) ] na odstraňovanie oyklopentadiénu z pyrolýznej C^-frakoie maleínanhydridom alebo vodným roztokom kyseliny maleínovej za súčasnej výroby adičného produktu 5-norbomén-2,3-dikarboxylovej kyseliny, resp· jej anhydridu· Avšak cyklopentadién vystupuje v Diels-Alderevej reakci i nielen ako konjugovaný dién, ale tiež dienofil, takže je aj v pyrolýznej C^-frakoii nestabilný, 1’ahko sa dimerizuje na dioyklopentadién224 809 is up to three orders higher than others. diene. This was technically rationally used ^ Kubička R., Goppoldová M .: Cs. author's testimony 149 504; Goppoldová M .: Chem · pr · m · 30 · 408 (1980)] for the removal of cyclopentadiene from pyrolysis of C 1 -C 4 -fracoic acid with maleic anhydride or aqueous maleic acid solution while producing the 5-norbomene-2,3-dicarboxylic acid or anhydride adduct thereof However, cyclopentadiene acts not only as a conjugated diene in the Diels-Alderev reaction, but also as a dienophile, so that it is unstable in the pyrolysis C 1 -fracoia too, and is easily dimerized to dioyclopentadiene
CH = CH CH j CH - CH 2 I I 11CH = CH CH 1 CH - CH 2 II 11
CH = CH CH ] - CH CH ^CH CH2 CH CH CH] - CH CH CH CH 2
To zapříčiňuje znižovanie obsahu volného cyklopentadiénu v uhlovodíkových frakoiách, tým znižovanie výťažkov adičnýoh produktov a sčasti i znočisťovanie finálneho produktu. Dimerizáoia cyklopentadiénu na dioyklopentadién sa tak využívá právo na izoláciu cyklopentadiénu zo zmesí s inými konjugovanými diénmi a áalšími ufalovodíkmi s blízkými alebo dokonoa prokrývajúoimi sa teplotami varu £uS|l pat. 2 439 307; Palo tas, Horakovios, Lili: Period. Póly tooh., Chem. Bag· (Budapost) 1969)· 13 (1-2), 149], pričom vytvořený adičný pfcodukt C^ sa už 1’ahko oddělí od nízkovrúcioh. C^-uhl’ovodíkov· Potom pri syntézách či procesech využívá júcioh cyklopentadién ako východisková surovinu či monomér sa postupuje tak, že sa naj skór spravidla termicky štiepi či krakuje dicyklopontadién na cyklopentadién £nSR pat· 1 951 320; 2 019 596; USý pat.This causes a decrease in the content of free cyclopentadiene in the hydrocarbon fractions, thereby reducing the yields of addition products and, in part, also contaminating the final product. Thus, the dimerization of cyclopentadiene to dioyclopentadiene exploits the right to isolate cyclopentadiene from mixtures with other conjugated dienes and other hydrocarbons with near or even overlapping boiling points. 2,439,307; Palo Tas, Horakovios, Lili: Period. Poles tooh., Chem. Bag · (Budapost) 1969) · 13 (1-2), 149], and the addition product C ^ already separates easily from low boiling. Hydrocarbons · Then, in the synthesis or process, using cyclopentadiene as the starting material or monomer, proceeds as a rule by thermally cleaving or cracking dicyclopontadiene to cyclopentadiene £ nSR pat · 1 951 320; 2,019,596; US Pat.
372 237 í 2 490 866; 2 831 904; Kononov a iní: Bull· Akad« nauk SSSR,, ser· Chim. 1953 · 101; Vraný H·, Bohdaneoký M.: Chem· listy <£, 936 (1955)] a *en » v Salto, otupni hneá vedie na adíolu e na leinanhydridom, kyselinou maleínovou alebo na využitie· Bepolymerizáoia sa často robí v trubkovém reaktore, dokonoa v organických inertnýoh rozpúšťadláoh ap·; najčastejšie pri teplotáoh v rozsahu 230 až 340 °C a čiastočne zvýšeném tlaku [Maáarský pat· 151 720 (1964); Kovacs H·, Raskai B·: Chim· prom· 1962 > (1O), 712; VS< pat* 3 016 4.10; 769 813; 771 65Ο; Kčbrioh G·, Flory K«: Tetrahedron Lett· 1966 , 973} V· Brit· pat· 573 592; NSR pat· 881 943] Tieto postupy však v případe potřeby vyrábať adičné produkty372 237 s 2,490,866; 2,831,904; Konon and others: Bull · Akad «nauk USSR ,, ser · Chim. 1953 · 101; Vraný H., Bohdaneoký M .: Chem. Leaves <£, 936 (1955)] and in Salto, dull brown leads to adiol e to leinanhydride, maleic acid or for use. Bepolymerization is often done in a tubular reactor, even in organic inert solvents and; most commonly at temperatures in the range of 230 to 340 ° C and partially elevated pressure (Maáarský pat · 151 720 (1964); Kovacs H, Raskai B: Chim prom 1962> (10), 712; VS <pat * 3,016 4.10; 769 813; 771 65Ο; Kčbrioh G ·, Flory K «: Tetrahedron Lett · 1966, 973} V · British · 573 592; NSR Pat · 881 943] These processes, however, produce addition products if necessary
224 809 cyklopentadiénu s maleínanhydridom, resp· kyselinou maleinovou si vyžadujú len izoláoiu cyklepentadiénu zo zmesí uhTovodíkov oestou tvorby dioyklopentadiénu, ale tiež osobitné endotermioké štiepenie na cyklopentadién, vrátane potřebných strojných a technologických zariadení· Tieto problémy rieái spósob podl’a tohto vynálezu·224 809 cyclopentadiene with maleic anhydride and / or maleic acid require not only isolation of cycllepentadiene from hydrocarbon mixtures from the formation of dioyclentadiene, but also specific endothermic cleavage to cyclopentadiene, including the necessary machinery and technological equipment.
PodTa tohto vynálezu sa spósob výroby kyseliny 5-norbomón-2,3-dikarboxylovéj a/alebo jej anhydridu uskutočňuje tak, že sa na dicyklopentadión pósobí maleínanhydridom a/alebo kyselinou maleinovou pri teplote 130 až 340 °C a celkovom tlaku 0,05 až 10 MPa, připadne za přítomnosti pomocných látok·According to the invention, the process for the preparation of 5-norbomone-2,3-dicarboxylic acid and / or its anhydride is carried out by treating dicyclopentadione with maleic anhydride and / or maleic acid at a temperature of 130 to 340 ° C and a total pressure of 0.05 to 10 MPa, if appropriate in the presence of excipients ·
Výhodou spósobu výroby podTa tohto vynálezu je nižšia energe tická náročnost’ výroby adičnýoh produktov cyklopentadiénu s maleínanhydridom a/lebo kyselinou maleinovou, lebo v jednom teohnologickom stupni prebieha praktioky súčasne endotermický rozklad dioyklopentadiénu na cyklopentadién so súčasnou exotermickou adíciou in šitu cyklopentadiénu na dienofil - maleinarthydrid, resp· kyselinu maleínovú· Ďalej menšia možnost’ priebehu vedTajáích reakci! cyklopentadiénu, menšia aparatúraa náročnost’ prooesu a dobrá reprodúktovateThosť výroby·An advantage of the process according to the invention is the lower energy consumption for the production of cyclopentadiene addition products with maleic anhydride and / or maleic acid, since in one theological stage the endothermic decomposition of dioyclopentadiene to cyclopentadiene with concomitant exothermal dihydrophenitide adenitentin is also practiced simultaneously. · Maleic acid · Further, less possibility of side reactions! cyclopentadiene, smaller apparatus and prooes and good reproducibility
Dicyklopentadión potřebný na výrobu anhydridu 5-norbomón-2,3-dikarboxylovej kyseliny podTfL tohto vynálezu móže byť petrochemického/ koksochemického alebo iného póvodu. Podobné je to aj s maleínanhydridom a' kyselinou maleinovou, ktoré navýše móžu obsa hovať aj áalšie komponenty ako příměsi, ako kyselinu fumarovú, ky selinu jantarová ap· Molový poměr maleínanhydridu, resp· kyseliny maleínovej k dioyklopentadiénu je v rozsahu 1 : 0,1 až 1,0, spravidla najvhodnejší je však 1 : 0,5, počítané na čisté východiskové suroviny.The dicyclopentadione required for the production of 5-norbomone-2,3-dicarboxylic acid anhydride according to the invention may be of petrochemical / coke-chemical or other origin. The same is true of maleic anhydride and maleic acid, which may additionally contain other components such as fumaric acid, succinic acid and the molar ratio of maleic anhydride or maleic acid to dioyclopentadiene is in the range of 1: 0.1 to 1.0, but generally 1: 0.5, based on the pure starting material, is most preferred.
Reakčná teplota móže byt’ v rozsahu 130 až 3^0 °C, ale najvhodnejšie, ako z hTadiska rýohlosti rozkladu dioyklopentadiénu, tak aj ešte dostatočnej termiokej stability vytvořeného adičného produktu s maleínanhydridom, resp· kyselinou maleinovou (rovnováha dostatočne posunutá na pravá stranu rovnice), je teplota IČO až 240 °C. Proces možno uskutočňovať pri zníženom i zvýšenom tlaku, z hTadiska nenáročnosti výrobného zariadenia je najvhodnejšie pracovat’ pri tlaku blízkom atmosferickému· Reakčné prostredieThe reaction temperature may be in the range of 130 ° C to 30 ° C, but most preferably, both in terms of the decomposition rate of the dioyclopentadiene and the sufficient thermal stability of the maleic anhydride or maleic acid addition product formed (equilibrium sufficiently shifted to the right side of the equation) , the temperature of the Reg. The process can be carried out under reduced or elevated pressure, from the point of view of the inexpensive production equipment it is best to work at a pressure close to atmospheric · Reaction environment
- 4'- 4 '
224 809 a připadne aj suroviny je vhodné inert izovať, napr* odsáním vzduchu, prefúkaním dusíkom, oxidom uhličitým alebo inými inertnými plynini. Ako pomocné látky prlchádza jú do úvahy hlavně inertné organické rozpúšťadla, vhodné sú najmá čisté látky alebo užšie frakcie, ak sa pracuje pri tlaku blízkom atmosferickému, spravidla s teplotou varu nad aplikovanou teplotou procesu výroby adičnýoh produktov. Přednost’ majú termicky stále organické zlúčeniny, ako alkylbenzény (xylóny, diizopropylbenzén, dodecylbenzén) a iné alkylarylzlóčeniny, n-alkány až C^» ropné frakcie s teplotou varu 100 až 300 °C ap. Menej vhodná je voda a chlorované uhlovodíky. Ďalej pomocným látkám pa tria stabilizátory, zvlášť inhibitory-radikálové j polymerizácie, teplotně dostatočne stále antioxydanty (napr. 2,6-di-terc-butyl-4-metylfenol, alkylsubstituovaný p-fenyléndiamín ap.), připadne katalyzátory Diels-Alderovej adície.224 809 and, if appropriate, the raw materials may be inerted, for example by sucking in air, purging with nitrogen, carbon dioxide or other inert gases. Suitable excipients are, in particular, inert organic solvents, in particular pure substances or narrower fractions are suitable when operating at a pressure close to atmospheric, generally with a boiling point above the applied temperature of the addition process. Preference is given to thermally stable organic compounds such as alkylbenzenes (xylones, diisopropylbenzene, dodecylbenzene) and other alkylaryl compounds, n-alkanes to C ^-petroleum fractions having a boiling point of 100-300 ° C and the like. Less suitable are water and chlorinated hydrocarbons. In addition, the auxiliaries include stabilizers, in particular radical polymerization inhibitors, temperature-stable antioxidants (e.g., 2,6-di-tert-butyl-4-methylphenol, alkyl-substituted p-phenylenediamine, etc.), and Diels-Alder addition catalysts.
Kritériom ukončenia vlastnej syntézy je spravidla úplná konverzia dicyklopentadiénu.As a rule, the complete conversion of dicyclopentadiene is the criterion for completing the synthesis itself.
Surový adičný produkt možno aplikovat’ jednak bez dalšej úpravy ako taký (spravidla po šupinkovaní, granulovaní či práškovaní), najčastejšie sa však prekryštalizuje z organického rozpúšťadla či organických rozpúšťadiel alebo vody, ďalej předeštiláoiou, najmá za zníženého tlaku, destiláciou s vodnou parou, extrakciou polárnými alebo nepolárnými rozpúšťadlami, rafináoiou alebo pósobením adsorbentov, ako bieliaoej hlinky, syntetických alebo prírodných zeolitov, aktívneho uhlia ap.The crude addition product can be applied without further treatment as such (usually after scales, granulation or dusting), but is most often recrystallized from an organic solvent or organic solvents or water, followed by pre-distillation, in particular under reduced pressure, steam distillation, polar extraction or by non-polar solvents, by refining or by adsorbing adsorbents such as white clay, synthetic or natural zeolites, activated carbon and the like.
Spósob po dl’a tohto vynálezu sa na j jednoduchšie uskutočňuje diskontinuálne, ale možno ho realizovat’ aj polokontinálne a kontinuálně ·The method of the present invention is easier to carry out batchwise, but it can also be realized semi-continuously and continuously.
Ďalšie podrobnosti, ako aj výhody spósobu výroby podTa tohto vynálezu sú zřejmé z príkladov.Further details as well as advantages of the production method of the present invention are evident from the examples.
Příklad 1Example 1
Do trojhrdlej banky o objeme 250 cm opatrenej miešadlom, spátnýra chladičom a teplomerom sa dá 66 g dicyklopentadiénu a 98 g maleínanhydridu, takže molový poměr maleínanhydridu k dicyklopentadiénu je 1 í 0,5. Zmes sa za neustálého miešania vyhřeje na teplotu 170 °θ β- při tejto teplote a tlaku rovnajúcemu sa atmosferickému v laboratoriu, t. j. 98,9 kPa, sa udržuje počas 5 h. Potom sa '5'A 250 cm 3-necked flask equipped with a stirrer, a reflux condenser and a thermometer is charged with 66 g of dicyclopentadiene and 98 g of maleic anhydride, so that the molar ratio of maleic anhydride to dicyclopentadiene is 1 to 0.5. The mixture is heated to 170 ° θ β at this temperature and pressure equal to atmospheric pressure in the laboratory, with stirring. j. 98.9 kPa, held for 5 h. Then '5'
224 809 produkt ochladí, zváží a analyzuje· Získá sa 163,1 g pevného produktu slabožltézo sfarbenia tohto zloženia ($ hmot.): 0,05 dicyklopentadién; 9»3 maleínanhydrid; 33,9 anhydrid-5-norbomén-2,3-dikarboxylovej kyseliny fexo stereošpeoifleká forma); 22,3 amhydrid-5-norbornén-2,3-dikar boxy love j kyseliny (endo stereošpeoif loká forma); 0,5 5-norbornén-2,3-dikarboxylová kyselina· Zvyšok do 100 % tvoria látky živičná t ého oharek toru. Konverzia dioyklopentadiénu dosahuje 99»9 $· Získaný produkt má brómové číslo 75,67 g Br/100 g; číslo kyslosti 422,5 mg K0H/g a číslo zmydelnenia 630,9 mg KOH/g·224 809 the product is cooled, weighed and analyzed. 163.1 g of solid product are obtained in the following form ($ w / w): 0.05 dicyclopentadiene; 9 → 3 maleic anhydride; 33,9-5-norbomene-2,3-dicarboxylic anhydride (fexo stereospecific form); 22,3-5-norbornene-2,3-dicarboxylic acid amide hydride (endo stereosphoifal form); 0.5 5-norbornene-2,3-dicarboxylic acid · The remainder to 100% consists of bitumen substances. Conversion of dioyclopentadiene reaches 99.9 $ · The product obtained has a bromine number of 75.67 g Br / 100 g; acid number 422.5 mg KOH / g and saponification number 630.9 mg KOH / g ·
Příklad 2Example 2
Postupuje sa podobné, ako v příklade 1, len s tým rozdielom, že před vyhrievaním sa reakčný priestor inertizuje prefákanim dusíkom a navýše doreakčného prostredia sa dá 0,5 g 2,6-di-terč-butyl- 4-me ty lf enolu a na spatný chladič sa dá vodný uzávěr proti přístupu vzduchu· Získá sa 163,8 g pevného produktu slabožltého sfarbenia, v ktorom na rozdiel od příkladu 1 je len 1,3 % hmot· nezřeagovaného maleínanhydridu·The procedure is similar to that of Example 1, except that before heating, the reaction space is inerted with nitrogen soak and 0.5 g of 2,6-di-tert-butyl-4-methylphenol is added to the reaction medium and 163.8 g of a solid, slightly yellowish color product is obtained, in which, unlike Example 1, there is only 1.3% by weight · unreacted maleic anhydride ·
Přiklad 3Example 3
Do trojhrdlej banky o objeme 250 cm opatrenej miešadlom, spatným ohladičom a teplomerom sa dá 7^,6 g dioyklopentadiénu koksochemického póvodu (čistoty 88,5 $ hmot.) a 98 g maleínanhydridu, takže mólový poměr dioyklopentadién : maleínanhydrid = = 0,5 : 1· Zmes sa za neustálého miešania vyhřeje na teplotu 170 °θ a pri tejto teplote a tlaku rovnajáoemu sa tlaku vzduchu v laboratoriu, t· j. 98,9 kPa, sa udržuje počas 5 h· Potom sa produkt ochladí, zváži a analyzuje sa· Získá sa 171,3 β pevného produktu tmavohněděj farby tohto zloženia (% hmot·): 0,67 maleínanhydrid; 30,35 anhydrid 5-norbomén-2,3-dikarboxylovej kyseliny (exo stereošpecifioká forma); 16,93 anhydrid 5-norbornén-2,3~dikarboxylovej kyseliny (endo stereošpecifioká forma)· Zvyšok do 100 % tvoria látky živičnatého charakteru·A 250 cm 3-necked flask equipped with a stirrer, an in-line cooler, and a thermometer was charged with 6.7 g of cocoychemic dioyclopentadiene (purity of 88.5% by weight) and 98 g of maleic anhydride so that the molar ratio of dioyclopentadiene: maleic anhydride = 0.5: The mixture is heated to 170 ° C with constant stirring at this temperature and pressure equal to the laboratory air pressure, i. The product is cooled, weighed and analyzed. 171.3 β of a dark brown solid product of the following composition (% by weight) is obtained: 0.67 maleic anhydride; 5-Norbomene-2,3-dicarboxylic acid anhydride (exo stereospecific form); 16,93 5-norbornene-2,3-dicarboxylic anhydride (endo stereospecific form) · The remainder up to 100% consists of bituminous substances ·
Dosiahne sa tak konverzia maleínanhydridu 98,9 % a prakticky úplná konverzia dioyklopentadiénu· Získaný produkt má bromové číslo 90,21 g Br/100 g, číslo kyslosti 3él,2 mg K0H/g a číslo zmydelnenia 640,8 mg KOH/g·The product obtained has a bromine number of 90.21 g Br / 100 g, an acid number of 3el, 2 mg KOH / g and a saponification number of 640.8 mg KOH / g ·
Příklad 4Example 4
224 809224 809
Do rotačného autoklávu o objeme 1 dur sa naváži 100 g dicyklo pentadiónu, 149 8 maleínanhydridu a 1Q0 g xylénu, takže molový poměr dicyklopentadién : maleínanhydrid = 0,5 : 1« Po uzavretí sa autokláv prefúka dusikom a dotlačí dusíkom na celkový tlak v autokláve 4 MPa. Obsah autoklávu sa za neustálej rotáoie vyhřeje na teplotu 240 °C. Tlak v autokláve stúpne na 7,4 MPa. Po 5 h sa obsah autoklávu ochladí, odplyní a produkt sa po vybrati a oddělení kvapalnej fázy od pevnej fázy zváží a analyzuje· Získá sa 217 6 kvapalného produktu a 121,6 g pevného produktu hnedej farby· Pevný produkt má toto zloženie (% hmot·): 0,31 maleínanhydrid;100 g of dicyclo pentadione, 149 8 maleic anhydride and 10 g of xylene are weighed into a 1 major rotary autoclave so that the molar ratio of dicyclopentadiene: maleic anhydride = 0.5: 1. After closing, the autoclave is purged with nitrogen and pressurized with nitrogen to the total autoclave pressure. bar. The contents of the autoclave are heated to 240 ° C with constant rotation. The pressure in the autoclave rises to 7.4 MPa. After 5 h, the contents of the autoclave were cooled, degassed and the product was weighed and analyzed after removal and separation of the liquid phase from the solid phase. ): 0.31 maleic anhydride;
55,1 anhydrid 5-norbornón-2,3-dikarboxylove j kyseliny (exo stereošpecifloká forma); 11,9 anhydrid 5-norbornén-2,3-dikarboxylove j kyseliny (endo stereoSpecifleká forma).5-norbornone-2,3-dicarboxylic acid anhydride (exo stereospecific form); 5-Norbornene-2,3-dicarboxylic acid anhydride (endo stereospecific form).
Kvapalný produkt má toto zloženie (% hmot·): 45,6 xylén;The liquid product has the following composition (% by weight): 45.6 xylene;
0,85 maleínanhydrid} 16,7 anhydrid 5-norbomón-2,3-dikarboxylovej kyseliny; 12,5 anhydrid 5-norbomén-2,3-dikarboxylove j kyseliny· Zvyšok do 100 % v obidvoch častiach produktu tvoria látky živičnatého charakteru· Konverzia maleínanhydridu dosiahne 9θ,5 % a prakticky úplná konverzia dicyklopentadiénu·0.85 maleic anhydride} 16.7 5-norbomone-2,3-dicarboxylic anhydride; 12.5-5-norbomene-2,3-dicarboxylic acid anhydride · The residue up to 100% in both parts of the product consists of bituminous substances · Maleic anhydride conversion reaches 9θ, 5% and virtually complete dicyclopentadiene conversion ·
Získaný pevný produkt má brómové číslo 75,17 6 Br/100 g, číslo kyslosti 317,2 mg K0H/g, číslo zmydelnenia 581,7 mg KOH/g a kvapalný produkt má číslo kyslosti 202,o mg KOH/g a číslo zmydelnenia 407,5 mg KOH/g.The obtained solid product has a bromine number of 75.17 6 Br / 100 g, an acid number of 317.2 mg KOH / g, a saponification number of 581.7 mg KOH / g and the liquid product has an acid number of 202.0 mg KOH / g and a saponification number of 407, 5 mg KOH / g.
Příklad 5Example 5
Postupuje sa podobné ako v příklade 4, len miesto 149 6 maleínanhydridu sa použije 176,4 g kyseliny maleínovej, pričom konverzia kyseliny maleínovej dosiahne 9θ % pri úplnéj konverzii dicyklopentadiénu; výťažok 5-norbornén-2,3-dikarboxylových kyselin je podobný ako ioh anhydridov v přiklade 4·The procedure is similar to that of Example 4 except that 176.4 g of maleic acid is used in place of 149 6 maleic anhydride, whereby the conversion of maleic acid reaches 9% by complete conversion of dicyclopentadiene; the yield of 5-norbornene-2,3-dicarboxylic acids is similar to the ioh anhydrides in Example 4;
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS165582A CS224809B1 (en) | 1982-03-11 | 1982-03-11 | Manufacturing process of 5-norbornen-2,3-dikarboxyl acidand/or its anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS165582A CS224809B1 (en) | 1982-03-11 | 1982-03-11 | Manufacturing process of 5-norbornen-2,3-dikarboxyl acidand/or its anhydride |
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| Publication Number | Publication Date |
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| CS224809B1 true CS224809B1 (en) | 1984-01-16 |
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|---|---|---|---|
| CS165582A CS224809B1 (en) | 1982-03-11 | 1982-03-11 | Manufacturing process of 5-norbornen-2,3-dikarboxyl acidand/or its anhydride |
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| CS (1) | CS224809B1 (en) |
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1982
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