JPH0123465B2 - - Google Patents
Info
- Publication number
- JPH0123465B2 JPH0123465B2 JP4920382A JP4920382A JPH0123465B2 JP H0123465 B2 JPH0123465 B2 JP H0123465B2 JP 4920382 A JP4920382 A JP 4920382A JP 4920382 A JP4920382 A JP 4920382A JP H0123465 B2 JPH0123465 B2 JP H0123465B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- trimellitic
- trimellitic anhydride
- trichloride
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 claims description 23
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000012320 chlorinating reagent Substances 0.000 claims description 13
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- -1 chloroformyl group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NPCLRBQYESMUPD-UHFFFAOYSA-N 2-methylpropanethioamide Chemical compound CC(C)C(N)=S NPCLRBQYESMUPD-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
- MJNHIYILRDOOTC-UHFFFAOYSA-N tetrachlorophosphanium Chemical compound Cl[P+](Cl)(Cl)Cl MJNHIYILRDOOTC-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical group 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Description
本発明は高分子原料に適した高純度無水トリメ
リツト酸モノクロリドを経済的に製造する方法に
関するものであり、特に再結晶精製工程を経るこ
となく、高純度の無水トリメリツト酸モノクロリ
ドを製造することを目的としたものである。
近年、合成高分子研究の発展に伴い、すぐれた
性質をもつ高分子物質が多く知られるようになつ
た、無水トリメリツト酸モノクロリドは、それら
の高分子物質製造用の原料として極めて有用なも
のの一つであり、特にポリアミドイミド、ポリエ
ステルイミドなどの耐熱性高分子製造にとつて欠
くことのできない原料の一つとなつている。
従来から無水トリメリツト酸に対して過剰モル
の塩素化剤を作用させて酸クロリド化反応を行な
わせ無水トリメリツト酸モノクロリドを製造する
方法はよく知られている（たとえば、J.Chem.
Soc.，3475〜７（1965）、J.Prakt.Chem.，27，
152〜170（1965）、特公昭47−49570号公報、特開
昭50−5346号公報、特開昭51−6934号公報、特公
昭53−19571号公報など）。しかし、これらの公知
の方法で製造される無水トリメリツト酸モノクロ
リドには、副反応生成物であるトリメリツト酸ト
リクロリドが比較的多量に混入してくる。２官能
性としての無水トリメリツト酸モノクロリドを高
分子原料として利用する場合には、３官能性とし
て作用するトリメリツト酸トリクロリドの混入は
重合体のゲル化原因につながつて実用性を半減さ
せる。そのため無水トリメリツト酸モノクロリド
からトリメリツト酸トリクロリドを厳密に、たと
えば混入量を１重量％、好ましくは0.5重量％以
下まで排除しておく必要がある。ところが、無水
トリメリツト酸モノクロリド中にトリメリツト酸
トリクロリドが混入すると両者の沸点が接近して
いることおよび両者がある程度共沸傾向を示すこ
とから蒸留精製によつて両者を分別することは極
めて困難である。そこで両者を分離するためには
再結晶精製操作を適用する必要がある。しかし無
水トリメリツト酸モノクロリドの再結晶精製に
は、生産性のよい効果的再結晶溶媒の選定がむず
かしいこと、再結晶／ロ過／乾燥の多段単位操作
における製品の劣化、収率低下、環境汚染などの
難問が山積しており、経済的かつ工業的に実施す
ることは極めて困難である。そこで本発明者ら
は、再結晶操作を経ることなく、トリメリツト酸
トリクロリドの混入を許容範囲以下におさえた高
純度無水トリメリツト酸モノクロリドを製造する
方法について鋭意検討した結果、蒸留製精工程に
先立つて特定の化合物類を作用させることにより
トリメリツト酸トリクロリドを顕著に減失させる
ことができることを見出し本発明に到達した。す
なわち本発明は、(1)無水トリメリツト酸に対して
過剰モルの塩素化剤を作用させて酸クロリド化反
応を行なう第１工程、(2)過剰残留する塩素化剤を
除去する第２工程、(3)水、有機カルボン酸、その
無水物および有機スルホン酸から選ばれた少なく
とも１種を、第１工程で副生したトリメリツト酸
トリクロリドの隣接するクロロホルミル基を減失
させるに十分な量添加して反応させる第３工程お
よび(4)生成物を蒸留精製して無水トリメリツト酸
モノクロリドを分離回収する第４工程を順次経由
することを特徴とする高純度無水トリメリツト酸
モノクロリドの製造方法を提供するものである。
本発明は第１工程において無水トリメリツト酸
１モルに対して過剰モルたとえば1.01〜20モル
（好ましくは1.1〜５モル）の塩素化剤を作用させ
て酸クロリド化反応を行なわせる。塩素化剤とし
ては、無水トリメリツト酸から無水トリメリツト
酸モノクロリドを合成することに関してよく知ら
れている塩素化剤を巾広く使用することができ
る。その塩素化剤の例として、塩化チオニル、ホ
スゲン、三塩化リン／塩素併用、五塩化リン、
ａ，ａ，ａ−トリクロルトルエン、ａ，ａ，ａ，
a′，a′，a′−ヘキサクロルキシレンなどをあげる
ことができる。
これらの塩素化剤の使用量が無水トリメリツト
酸に対して等モル以下の場合、反応収率が単純に
低下するだけでなく、残留無水トリメリツト酸と
生成無水トリメリツト酸モノクロリドとの反応に
よる２量化副反応が起こりやすく、反応系の融点
が上昇してトラブルの原因となり好ましくない。
また塩素化剤の使用量はあまり過大にすることは
経済的に好ましくなく、20倍モル以下とすること
が適当である。この反応には溶媒の使用は必らず
しも必要でないが、場合によつては、ベンゼン、
トルエン、クロルベンゼン、ニトロベンゼン、キ
シレン、ｏ−ジクロルベンゼン、ヘキサクロロエ
タン、四塩化炭素、オキシ塩化リンなどの溶媒を
使用することができる。また、反応促進剤として
ジメチルホルムアミド、ジメチルアセトアミド、
Ｎ−メチルピロリドンなどの第３級アミド類、ジ
メチルアセトチオアミド、ジメチルホルムチオア
ミドなどの第３級チオアミド類、第４級アンモニ
ウム塩、ホスホニウム塩、テトラアルキルチオ尿
素などの触媒を利用することができる。反応温度
は常温〜200℃が一般的であり、特に塩化チオニ
ルを利用する場合70〜90℃が効果的である。反応
時間は通常１〜30時間である。
本発明においては、酸クロリド化反応終了後、
過剰残留する塩素化剤を反応系外に除去する第２
工程に移る。この塩素化剤除去方法には特に制限
がないが、塩化チオニル、三塩化リン、四塩化リ
ン、ａ，ａ，ａ−トリクロルトルエンの場合、た
とえば、70〜200℃の条件下、常圧または減圧蒸
留することにより留去される。またホスゲン、塩
素の場合、たとえば70〜200℃の条件下窒素ガス
を流通させることにより同伴除去することができ
る。本発明の第１工程においては通常無水トリメ
リツト酸モノクロリドとトリメリツト酸トリクロ
リドが概略90〜99／10〜１モル比の比率で生成す
る。本発明の第３工程では反応系へ水、有機カル
ボン酸、その無水物および有機スルホン酸から選
ばれた少なくとも１種（以下トリクロリド減失剤
と総称する）を添加、反応させて、上記第１工程
で副生したトリメリツト酸トリクロリドの隣接ク
ロロホルミル基を減失、閉環せしめ、無水トリメ
リツト酸モノクロリドに変質させる操作を行な
う。
本発明の第３工程におけるトリクロリド減失剤
の添加量は副生したトリメリツト酸トリクロリド
の隣接クロロホルミル基を減失・閉環せしめるに
十分な量であり、トリクロリド減失剤の種類によ
り相違するが、概略トリメリツト酸トリクロリド
に対し0.2〜５倍モル（好ましくは0.5〜２倍モ
ル）である。減失反応は常温〜200℃（好ましく
は70〜160℃）の温度で、常圧または減圧下に0.1
時間以上（好ましくは0.5時間以上）反応させる
ことにより行なわれる。
ここでいうトリクロリド減失剤は水、一般式Ｒ
−COOHで表わされる有機カルボン酸類、その
無水物類および一般式Ｒ−SO3Hで表わされる有
機スルホン酸類〔Ｒは、C1〜C20の脂肪族基、C6
〜C20の芳香族基またはC7〜C20のアラルキル基を
示し、それらにクロル基、ニトロ基、カルボキシ
ル基、酸無水物基、スルホン酸基などの非妨害性
置換基が置換されたものも含む〕から選ばれた１
種または２種以上の混合物であり、たとえば水、
酢酸、プロピオン酸、酪酸、アクリル酸、メタク
リル酸、アジピン酸、安息香酸、トルイル酸、フ
タル酸、イソフタル酸、テレフタル酸、トリメリ
ツト酸、ピロメリツト酸およびそれらの酸無水
物、メタンスルホン酸、エタンスルホン酸、プロ
パンスルホン酸、ベンゼンスルホン酸、ｐ−トル
エンスルホン酸などがあげられる。これらの化合
物は、加熱条件下にトリメリツト酸トリクロリド
と反応して、次のような反応を起こし、トリメリ
ツト酸トリクロリドの減失が起こると考えられ
る。
この第３工程終了後の反応物には、生成した無
水トリメリツト酸モノクロリドと共に第１工程で
副生したトリメリツト酸トリクロリド以外の不純
物および第３工程で副生した酸クロリド類が含有
されているので、本発明の第４工程では蒸留精製
によつて主成分たる無水トリメリツト酸モノクロ
リドを分離回収する。本発明の第４工程は通常反
応物を精留管（塔）を備えた蒸留装置に採り、減
圧度0.1〜20mmHg、温度100〜250℃の条件で減圧
蒸留することにより行なわれ、高純度無水トリメ
リツト酸モノクロリドを高収率で容易に回収する
ことができる。
以下、実施例によつて本発明をさらに詳述す
る。なお生成物の分析はサンプルをアルコールで
エステル化し、次いでガスクロマトグラフイーに
供する方法により行なつた。
実施例 １
〔第１工程〕
コンデンサーおよび撹拌機を備えた内容積３
の丸底フラスコに無水トリメリツト酸1000ｇ
（5.2モル）、塩化チオニル1000ｇ（8.4モル）およ
びジメチルホルムアミド５ｇ（0.068モル）を仕
込んで、外温を80〜90℃にセツトし、塩化チオニ
ルの還流条件下に６時間反応させた。この間、多
量の塩化水素ガスおよび亜硫酸ガスが発生したの
で、５重量％のカセイソーダ−水溶液で吸収処理
した。
〔第２工程〕
次にコンデンサーをとりはずし、水流アスピレ
ーター（減圧度40〜60mmHg）で吸引し、内温を
80℃から150℃まで徐々に上昇させながら残留塩
化チオニルをほぼ完全に流出させた。ここで生成
物のサンプルを採取して酸クロリド成分の分析を
行なつたところ無水トリメリツト酸モノクロリド
93.7重量％、トリメリツト酸トリクロリド3.8重
量％、テレフタル酸ジクロリド／イソフタル酸ジ
クロリド混合物2.2重量％およびその他0.3重量％
であつた。
〔第３工程〕
次にトリクロリド減失剤として酢酸15.6ｇ
（0.26モル）を添加して110℃で１時間反応させ、
さらに150℃で30分間、水流アスピレーター（減
圧度40〜60mmHg）で減圧処理を行なつた。
〔第４工程〕
続いて精留管を取りつけて減圧蒸留を行ない、
約100ｇの初留をカツトして減圧度２mmHgで150
〜155℃の留分を995ｇ得た。この留分の仕込み無
水トリメリツト酸に対する収率は91モル％という
高いものであつた。また、この留分の純度分析結
果は次のようであり、高分子原料用として十分な
高純度を有するものであつた。
〔純度分析結果〕
無水トリメリツト酸モノクロリド99.0重量％、
テレフタル酸ジクロリド／イソフタル酸ジクロリ
ド混合物0.6重量％、トリメリツト酸トリクロリ
ド0.3重量％およびその他0.1重量％。
比較例 １
上記実施例１の第３工程を行なわず、第２工程
生成品を直接第４工程にかけて減圧蒸留を行なつ
たところ、初留約100ｇカツト後に減圧度２mmHg
で150〜155℃の留分を990ｇ得た。この留分の純
度分析結果は下記のようであり、トリメリツト酸
トリクロリドが比較的多量に含まれ高分子原料と
して不適当であつた。ちなみにこの留分と４，
4′−ジアミノジフエニルメタンを等モル比でジメ
チルアセトアミド中で重合反応させたところ、重
合途中でゲル化反応が起こり、実用性のないもの
であつた。
無水トリメリツト酸モノクロリド94.9重量％、
テレフタル酸ジクロリド／イソフタル酸ジクロリ
ド混合物0.7重量％、トリメリツト酸トリクロリ
ド2.9重量％およびその他1.5重量％。
実施例 ２〜７
実施例１の第３工程のトリクロリド減失剤とし
て第１表のような化合物を用いる以外すべて実施
例１と同様にして減圧度２mmHg、留出温度150〜
155℃の留分（主留分）を得た。その留分の分析
結果は第１表のとおりであり、いずれもトリメリ
ツト酸トリクロリド含量の少ない高純度品であつ
た。
The present invention relates to a method for economically producing high-purity trimellitic anhydride monochloride suitable as a polymer raw material, and in particular, a method for producing high-purity trimellitic anhydride monochloride without going through a recrystallization purification process. The purpose is to In recent years, with the development of synthetic polymer research, many polymeric substances with excellent properties have become known. Trimellitic anhydride monochloride is one of the extremely useful raw materials for the production of these polymeric substances. In particular, it is one of the essential raw materials for the production of heat-resistant polymers such as polyamideimide and polyesterimide. A method for producing trimellitic anhydride monochloride by reacting an excess molar amount of a chlorinating agent with trimellitic anhydride to carry out an acid chloridation reaction is well known (for example, J.Chem.
Soc., 3475-7 (1965), J.Prakt.Chem., 27,
152-170 (1965), Japanese Patent Publication No. 47-49570, Japanese Patent Application Publication No. 5346-1980, Japanese Patent Application Publication No. 6934-1982, Japanese Patent Publication No. 1957-1971, etc.). However, trimellitic anhydride monochloride produced by these known methods is contaminated with a relatively large amount of trimellitic acid trichloride, which is a side reaction product. When using trimellitic anhydride monochloride as a difunctional polymer as a raw material for a polymer, the incorporation of trimellitic acid trichloride, which acts as a trifunctional polymer, causes gelation of the polymer and reduces its practicality by half. Therefore, it is necessary to strictly exclude trimellitic acid trichloride from trimellitic acid anhydride monochloride, for example, to an amount of 1% by weight or less, preferably 0.5% by weight or less. However, when trimellitic acid trichloride is mixed into trimellitic acid monochloride anhydride, it is extremely difficult to separate the two by distillation purification because the boiling points of the two are close to each other and both exhibit a certain degree of azeotropic tendency. . Therefore, in order to separate the two, it is necessary to apply a recrystallization purification operation. However, in the recrystallization purification of trimellitic anhydride monochloride, it is difficult to select an effective recrystallization solvent with good productivity, product deterioration in multi-stage unit operations of recrystallization/filtration/drying, yield reduction, and environmental pollution. There are many difficult problems such as these, and it is extremely difficult to implement it economically and industrially. Therefore, the present inventors have conducted intensive studies on a method for producing high-purity trimellitic anhydride monochloride in which the contamination of trimellitic acid trichloride is kept below the permissible range without going through a recrystallization operation. The present invention was achieved by discovering that trimellitic acid trichloride can be significantly reduced by applying specific compounds. That is, the present invention comprises (1) a first step in which an excess molar amount of a chlorinating agent acts on trimellitic anhydride to perform an acid chloridation reaction; (2) a second step in which the excess remaining chlorinating agent is removed; (3) Addition of at least one selected from water, organic carboxylic acids, their anhydrides, and organic sulfonic acids in an amount sufficient to eliminate the adjacent chloroformyl group of trimellitic acid trichloride produced as a by-product in the first step. and (4) a fourth step of separating and recovering trimellitic anhydride monochloride by distilling and purifying the product. This is what we provide. In the first step of the present invention, an excess mole of chlorinating agent, for example 1.01 to 20 moles (preferably 1.1 to 5 moles), is applied to 1 mole of trimellitic anhydride to carry out the acid chloridation reaction. As the chlorinating agent, a wide variety of chlorinating agents can be used which are well known for the synthesis of trimellitic anhydride monochloride from trimellitic anhydride. Examples of chlorinating agents include thionyl chloride, phosgene, phosphorus trichloride/chlorine combination, phosphorus pentachloride,
a, a, a-trichlorotoluene, a, a, a,
Examples include a', a', a'-hexachloroxylene. If the amount of these chlorinating agents used is less than equimolar to trimellitic anhydride, the reaction yield will not only simply decrease, but also dimerization will occur due to the reaction between the residual trimellitic anhydride and the produced trimellitic anhydride monochloride. This is undesirable because side reactions tend to occur and the melting point of the reaction system increases, causing trouble.
Furthermore, it is economically undesirable to use too much of the chlorinating agent, and it is appropriate to use 20 times the mole or less. This reaction does not necessarily require the use of a solvent, but in some cases benzene,
Solvents such as toluene, chlorobenzene, nitrobenzene, xylene, o-dichlorobenzene, hexachloroethane, carbon tetrachloride, phosphorus oxychloride, etc. can be used. In addition, dimethylformamide, dimethylacetamide,
Catalysts such as tertiary amides such as N-methylpyrrolidone, tertiary thioamides such as dimethylacetothioamide and dimethylformthioamide, quaternary ammonium salts, phosphonium salts, and tetraalkylthioureas can be used. The reaction temperature is generally room temperature to 200°C, and 70 to 90°C is particularly effective when thionyl chloride is used. The reaction time is usually 1 to 30 hours. In the present invention, after completion of the acid chloridation reaction,
The second step is to remove excess residual chlorinating agent from the reaction system.
Let's move on to the process. There are no particular limitations on this method for removing the chlorinating agent, but in the case of thionyl chloride, phosphorus trichloride, phosphorus tetrachloride, a,a,a-trichlorotoluene, for example, under conditions of 70 to 200°C, normal pressure or reduced pressure. It is removed by distillation. Further, in the case of phosgene and chlorine, they can be removed together by flowing nitrogen gas under conditions of, for example, 70 to 200°C. In the first step of the present invention, trimellitic anhydride monochloride and trimellitic acid trichloride are usually produced in a molar ratio of about 90 to 99/10 to 1. In the third step of the present invention, at least one selected from water, organic carboxylic acids, their anhydrides, and organic sulfonic acids (hereinafter collectively referred to as trichloride reducing agent) is added to the reaction system and reacted with the first The adjacent chloroformyl groups of trimellitic acid trichloride produced as a by-product in the process are removed, ring-closed, and modified into trimellitic anhydride monochloride. The amount of the trichloride-reducing agent added in the third step of the present invention is sufficient to reduce and close the adjacent chloroformyl groups of the by-produced trimellitic acid trichloride, and varies depending on the type of the trichloride-reducing agent. The amount is approximately 0.2 to 5 times the mole (preferably 0.5 to 2 times the mole) relative to trimellitic acid trichloride. The reduction reaction is carried out at a temperature of room temperature to 200℃ (preferably 70 to 160℃) under normal pressure or reduced pressure.
This is carried out by reacting for a period of time or more (preferably 0.5 hours or more). The trichloride reducing agent mentioned here is water, general formula R
Organic carboxylic acids represented by -COOH, their anhydrides, and organic sulfonic acids represented by the general formula R-SO 3 H [R is a C 1 to C 20 aliphatic group, C 6
~ C20 aromatic group or C7 - C20 aralkyl group substituted with non-interfering substituents such as chloro group, nitro group, carboxyl group, acid anhydride group, sulfonic acid group, etc. 1 selected from
species or a mixture of two or more species, such as water,
Acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, adipic acid, benzoic acid, toluic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and their acid anhydrides, methanesulfonic acid, ethanesulfonic acid , propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like. It is thought that these compounds react with trimellitic acid trichloride under heating conditions to cause the following reaction, resulting in loss and loss of trimellitic acid trichloride. The reaction product after the third step contains the produced trimellitic anhydride monochloride as well as impurities other than the trimellitic acid trichloride produced as a by-product in the first step and acid chlorides produced as a by-product in the third step. In the fourth step of the present invention, the main component, trimellitic anhydride monochloride, is separated and recovered by distillation purification. The fourth step of the present invention is usually carried out by taking the reactant into a distillation apparatus equipped with a rectification tube (column) and distilling it under reduced pressure at a reduced pressure of 0.1 to 20 mmHg and a temperature of 100 to 250°C. Trimellitic acid monochloride can be easily recovered in high yield. Hereinafter, the present invention will be explained in further detail with reference to Examples. The product was analyzed by esterifying the sample with alcohol and then subjecting it to gas chromatography. Example 1 [First step] Internal volume 3 with condenser and stirrer
1000 g of trimellitic anhydride in a round bottom flask.
(5.2 mol), 1000 g (8.4 mol) of thionyl chloride, and 5 g (0.068 mol) of dimethylformamide were charged, the external temperature was set at 80 to 90°C, and the reaction was carried out for 6 hours under reflux conditions of thionyl chloride. During this time, a large amount of hydrogen chloride gas and sulfur dioxide gas was generated, so they were absorbed with a 5% by weight aqueous caustic soda solution. [Second step] Next, remove the condenser and use a water aspirator (degree of vacuum 40 to 60 mmHg) to aspirate and check the internal temperature.
While gradually raising the temperature from 80°C to 150°C, the residual thionyl chloride was almost completely flowed out. A sample of the product was taken here and analyzed for acid chloride components, and it was found that trimellitic anhydride monochloride
93.7% by weight, 3.8% by weight of trimellitic acid trichloride, 2.2% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture and 0.3% by weight of others.
It was hot. [3rd step] Next, add 15.6 g of acetic acid as a trichloride reducing agent.
(0.26 mol) was added and reacted at 110°C for 1 hour.
Further, vacuum treatment was performed at 150° C. for 30 minutes using a water aspirator (degree of vacuum: 40 to 60 mmHg). [Fourth step] Next, a rectification tube is attached and vacuum distillation is performed.
Cut the first distillate of about 100g and reduce the pressure to 150 with a degree of vacuum of 2mmHg.
995g of a fraction of ~155°C was obtained. The yield of this fraction based on the charged trimellitic anhydride was as high as 91 mol%. Further, the purity analysis results of this fraction were as follows, and it was found to have a high enough purity to be used as a raw material for polymers. [Purity analysis results] Trimellitic anhydride monochloride 99.0% by weight,
0.6% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture, 0.3% by weight of trimellitic acid trichloride and 0.1% by weight of others. Comparative Example 1 When the third step of Example 1 was not carried out and the product of the second step was directly subjected to the fourth step for vacuum distillation, the degree of vacuum was 2 mmHg after cutting about 100 g of the initial distillate.
990g of a fraction with a temperature of 150 to 155°C was obtained. The purity analysis results of this fraction are as follows, and it was found that it contained a relatively large amount of trimellitic acid trichloride and was unsuitable as a polymer raw material. By the way, this fraction and 4,
When 4'-diaminodiphenylmethane was polymerized in dimethylacetamide in an equimolar ratio, a gelation reaction occurred during the polymerization, making it impractical. Trimellitic anhydride monochloride 94.9% by weight,
0.7% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture, 2.9% by weight of trimellitic acid trichloride and 1.5% by weight of others. Examples 2 to 7 All procedures were carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the trichloride reducing agent in the third step of Example 1, the degree of vacuum was 2 mmHg, the distillation temperature was 150~
A fraction at 155°C (main fraction) was obtained. The analysis results of the fractions are shown in Table 1, and all were high purity products with a low content of trimellitic acid trichloride.
無水トリメリツト酸モノクロリド99.3重量％、
テレフタル酸ジクロリド／イソフタル酸ジクロリ
ド混合物0.5重量％、トリメリツト酸トリクロリ
ド0.1重量％およびその他0.1重量％。
実施例 ９
コンデンサーおよび撹拌機を備えた内容積１
の丸底フラスコに無水トリメリツト酸192ｇ（１
モル）、三塩化リン151ｇ（1.1モル）および１，
１，２−トリクロルエタン400ｇを仕込み70℃で
激しくかきまぜながら塩素ガスを細流として85ｇ
（1.2モル）を３時間かけて通気した。続いて反応
液に90℃で窒素ガスを50／hrの速さで約２時間
流通させ、過剰の塩素および三塩化リンをほぼ完
全に除去した。この反応液から水流アスピレータ
ーにより減圧蒸留して溶媒のトリクロルエタンお
よび生成したオキシ塩化リンを留去した。この時
点で生成物のサンプルを採取して酸クロリド成分
の分析を行なつたところ、無水トリメリツト酸モ
ノクロリド93.5重量％、トリメリツト酸トリクロ
リド1.8重量％、テレフタル酸ジクロリド／イソ
フタル酸ジクロリド混合物2.2重量％およびその
他2.5重量％であつた。
次にトリクロリド減失剤として無水酢酸３ｇ
（0.03モル）を添加して130℃で１時間反応させ、
さらに150℃で30分間水流アスピレーター（減圧
度40〜60mmHg）で減圧処理を行なつた。続いて
精留管を取りつけて減圧蒸留を行ない約20ｇの初
留をカツトして減圧度１mmHgで138〜143℃の留
分を185ｇ得た。この留分の仕込み無水トリメリ
ツト酸に対する収率は88モル％という高いもので
あつた。また、この留分の純度分析結果は次のよ
うであり、高分子原料用として十分な高純度を有
するものであつた。
〔純度分析結果〕
無水トリメリツト酸モノクロリド99.0重量％、
テレフタル酸ジクロリド／イソフタル酸ジクロリ
ド混合物0.6重量％、トリメリツト酸トリクロリ
ド0.2重量％およびその他0.2重量％。
Trimellitic anhydride monochloride 99.3% by weight,
0.5% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture, 0.1% by weight of trimellitic acid trichloride and 0.1% by weight of others. Example 9 Internal volume 1 with condenser and stirrer
192 g of trimellitic anhydride (1
mol), 151 g (1.1 mol) of phosphorus trichloride and 1,
Prepare 400g of 1,2-trichloroethane and stir vigorously at 70°C, adding 85g of chlorine gas as a trickle.
(1.2 mol) was bubbled through the solution over a period of 3 hours. Subsequently, nitrogen gas was passed through the reaction solution at 90° C. at a rate of 50/hr for about 2 hours to almost completely remove excess chlorine and phosphorus trichloride. This reaction solution was distilled under reduced pressure using a water aspirator to remove the solvent trichloroethane and the produced phosphorus oxychloride. At this point, a sample of the product was taken and analyzed for acid chloride components; 93.5% by weight of trimellitic anhydride monochloride, 1.8% by weight of trimellitic acid trichloride, 2.2% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture, and Others were 2.5% by weight. Next, 3 g of acetic anhydride as a trichloride reducer.
(0.03 mol) was added and reacted at 130°C for 1 hour.
Further, a vacuum treatment was performed at 150° C. for 30 minutes using a water aspirator (degree of vacuum: 40 to 60 mmHg). Subsequently, a rectifying tube was attached and vacuum distillation was carried out to cut off about 20 g of the first distillate, yielding 185 g of a fraction having a temperature of 138 to 143° C. at a vacuum degree of 1 mmHg. The yield of this fraction based on the charged trimellitic anhydride was as high as 88 mol%. Further, the purity analysis results of this fraction were as follows, and it was found to have a high enough purity to be used as a raw material for polymers. [Purity analysis results] Trimellitic anhydride monochloride 99.0% by weight,
0.6% by weight of terephthalic acid dichloride/isophthalic acid dichloride mixture, 0.2% by weight of trimellitic acid trichloride and 0.2% by weight of others.
Claims (1)
素化剤を作用させて酸クロリド化反応を行なう第
１工程、(2)過剰残留する塩素化剤を除去する第２
工程、(3)水、有機カルボン酸、その無水物および
有機スルホン酸から選ばれた少なくとも１種を、
第１工程で副生したトリメリツト酸トリクロリド
の隣接するクロロホルミル基を減失させるに十分
な量添加して反応させる第３工程および(4)生成物
を蒸留精製して無水トリメリツト酸モノクロリド
を分離回収する第４工程を順次経由することを特
徴とする高純度無水トリメリツト酸モノクロリド
の製造方法。1 (1) A first step in which an excess molar amount of chlorinating agent acts on trimellitic anhydride to perform an acid chloridation reaction, (2) a second step in which the excess remaining chlorinating agent is removed.
step (3) at least one selected from water, organic carboxylic acids, their anhydrides, and organic sulfonic acids;
A third step in which a sufficient amount of trimellitic acid trichloride produced as a by-product in the first step is removed and reacted to eliminate the adjacent chloroformyl group, and (4) the product is purified by distillation to separate trimellitic anhydride monochloride. A method for producing high-purity trimellitic anhydride monochloride, the method comprising sequentially passing through a fourth step of recovering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4920382A JPS58167580A (en) | 1982-03-29 | 1982-03-29 | Production of high-purity trimellitic anhydride monochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4920382A JPS58167580A (en) | 1982-03-29 | 1982-03-29 | Production of high-purity trimellitic anhydride monochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58167580A JPS58167580A (en) | 1983-10-03 |
| JPH0123465B2 true JPH0123465B2 (en) | 1989-05-02 |
Family
ID=12824428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4920382A Granted JPS58167580A (en) | 1982-03-29 | 1982-03-29 | Production of high-purity trimellitic anhydride monochloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58167580A (en) |
-
1982
- 1982-03-29 JP JP4920382A patent/JPS58167580A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58167580A (en) | 1983-10-03 |
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