JPH0311040A - Method for purifying aromatic dicarboxylic acid diaryl ester - Google Patents
Method for purifying aromatic dicarboxylic acid diaryl esterInfo
- Publication number
- JPH0311040A JPH0311040A JP14331789A JP14331789A JPH0311040A JP H0311040 A JPH0311040 A JP H0311040A JP 14331789 A JP14331789 A JP 14331789A JP 14331789 A JP14331789 A JP 14331789A JP H0311040 A JPH0311040 A JP H0311040A
- Authority
- JP
- Japan
- Prior art keywords
- dicarboxylic acid
- ester
- aromatic dicarboxylic
- diaryl ester
- aromatic
- 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.)
- Pending
Links
- -1 aromatic dicarboxylic acid diaryl ester Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 17
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000001953 recrystallisation Methods 0.000 claims description 28
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 22
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 abstract description 16
- 125000003118 aryl group Chemical group 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 abstract description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 abstract description 3
- 229940094933 n-dodecane Drugs 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 30
- 238000000746 purification Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 241001550224 Apha Species 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-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
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- PLPFTLXIQQYOMW-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(Cl)=CC(C(O)=O)=C1 PLPFTLXIQQYOMW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GRCSTCVUPHAXQK-UHFFFAOYSA-N bis(2-methylphenyl) benzene-1,4-dicarboxylate Chemical compound CC1=CC=CC=C1OC(=O)C1=CC=C(C(=O)OC=2C(=CC=CC=2)C)C=C1 GRCSTCVUPHAXQK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- JSKSILUXAHIKNP-UHFFFAOYSA-N naphthalene-1,7-dicarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=CC(C(=O)O)=CC=C21 JSKSILUXAHIKNP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、芳香族ジカルボン酸ジアリールエステルの精
製方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for purifying aromatic dicarboxylic acid diaryl ester.
芳香族ポリエステルは１強度、ヤング率、耐薬品性など
に優れているため、高性能の樹脂や繊維などに使用され
ているが、色相の優れた芳香族ポリエステルを製造する
には、原料となる芳香族カルボン酸アリールエステル自
体にも色相の優れた高純度のものが要求される。Aromatic polyester has excellent strength, Young's modulus, and chemical resistance, so it is used in high-performance resins and fibers, but in order to manufacture aromatic polyester with excellent color, it is necessary to use it as a raw material. The aromatic carboxylic acid aryl ester itself is also required to be highly pure and have an excellent hue.
従来、芳香族ポリエステルの原料となる芳香族ジカルボ
ン酸ジアリールエステルなどの芳香族カルボン酸アリー
ルエステルは、通常対応するカルボン酸と過剰量の芳香
族モノヒドロキシ化合物とのエステル化反応によって製
造される。Conventionally, aromatic carboxylic acid aryl esters such as aromatic dicarboxylic acid diaryl esters, which are raw materials for aromatic polyesters, are usually produced by an esterification reaction between a corresponding carboxylic acid and an excess amount of an aromatic monohydroxy compound.
しかし上記のようなエステル化反応の反応生成物は、通
常着色が著しいため、そのままでは芳香族ポリエステル
の原料として使用するには適さない。このため、いくつ
かの芳香族カルボン酸アリールエステルの精製方法が提
案されている。However, the reaction product of the above-mentioned esterification reaction is usually markedly colored and is therefore unsuitable for use as a raw material for aromatic polyester. For this reason, several methods for purifying aromatic carboxylic acid aryl esters have been proposed.
芳香族カルボン酸アリールエステルの精製方法としては
、例えば再結晶溶剤として炭素数９〜１゜のアルキル置
換ベンゼンおよびモノクロルベンゼンよりなる群から選
ばれた１種または２種以上あるいはこれらの少なくとも
１種を主成分とする混合物を用いるテレフタル酸ジアリ
ールエステルの精製方法（特公昭５５−４７０２７号）
、再結晶溶剤として式ＲＯ（ＣＨ２Ｃｔ１２０）ｎＨ（
Ｒは炭素数１〜ｌＯの有機残基であり、ｎは１〜２の数
を表わす）で示されるアルコール類を用いるテレフタル
酸ジアリールエステルの精製方法（特公昭４６−３７５
７４号）、再結晶溶剤として沸点１００〜２５０’（、
融点２０℃以下の芳香族炭化水素および活性水素を分子
内に持たない含窒素塩基性化合物を用いる芳香族カルボ
ン酸アリールエステルの精製方法（特開昭５９−３６６
４４号）などが提案されている。As a method for purifying aromatic carboxylic acid aryl esters, for example, one or more selected from the group consisting of alkyl-substituted benzenes having 9 to 1° carbon atoms and monochlorobenzene, or at least one of these may be used as a recrystallization solvent. Method for purifying terephthalic acid diaryl ester using a mixture containing the main components (Japanese Patent Publication No. 55-47027)
, the formula RO(CH2Ct120)nH(
R is an organic residue having 1 to 10 carbon atoms, and n represents a number of 1 to 2.
No. 74), boiling point 100-250' (,
Method for purifying aromatic carboxylic acid aryl ester using an aromatic hydrocarbon having a melting point of 20°C or less and a nitrogen-containing basic compound having no active hydrogen in the molecule (Japanese Patent Application Laid-Open No. 59-366
No. 44) have been proposed.
しかし、上記従来の精製方法では被精製物の溶解温度が
被精製物の融点より低いため、従来の精製方法を芳香族
ジカルボン酸ジアリールエステルの精製に適用した場合
、下記のような問題点がある。However, in the conventional purification method described above, the melting temperature of the product to be purified is lower than the melting point of the product, so when the conventional purification method is applied to the purification of aromatic dicarboxylic acid diaryl ester, there are the following problems. .
（イ）多量の再結晶溶剤を必要とする。(b) Requires a large amount of recrystallization solvent.
（０）再結晶溶剤を多量に用いるので、母液中に失われ
る被精製物の量が多くなり、回収率が低下する。(0) Since a large amount of recrystallization solvent is used, the amount of the purified product lost in the mother liquor increases and the recovery rate decreases.
（ハ）再結晶溶剤を多量に用いるので１例えば溶剤とし
てプソイドクメンを用いて、テレフタル酸ジフェニルエ
ステルとイソフタル酸ジフェニルエステルとの混合物を
晶析して精製した場合、イソフタル酸ジフェニルエステ
ルの溶解度がテレフタル酸ジフェニルエステルの溶解度
よりも約１０倍大きいため、精製前の混合物の組成比と
精製後の混合物の組成比が大きく違ってくる。(c) Since a large amount of recrystallization solvent is used, 1. For example, when a mixture of diphenyl terephthalate and diphenyl isophthalate is crystallized and purified using pseudocumene as a solvent, the solubility of diphenyl isophthalate is lower than that of terephthalate. Since the solubility is about 10 times greater than that of diphenyl ester, the composition ratio of the mixture before purification and the composition ratio of the mixture after purification are greatly different.
（ニ）溶解に長時間を要する。(d) It takes a long time to dissolve.
本発明の目的は、上記のような問題点を解決するため、
少量の再結晶溶剤を使用して短時間に溶解を行い、高純
度で色相の優れた芳香族ジカルボン酸ジアリールエステ
ルを高回収率で得ることができる芳香族ジカルボン酸ジ
アリールエステルの精製方法を提案することである。The purpose of the present invention is to solve the above problems,
We propose a method for purifying aromatic diaryl ester of dicarboxylic acid that can be dissolved in a short time using a small amount of recrystallization solvent and obtain diaryl ester of aromatic dicarboxylic acid with high purity and excellent color at a high recovery rate. That's true.
本発明は、芳香族ジカルボン酸ジアリールエステルを再
結晶溶剤に溶解した後、再結晶させて芳香族ジカルボン
酸ジアリールエステルを精製する方法において、芳香族
ジカルボン酸ジアリールエステル１００重量部に対して
再結晶溶剤を１〜２００重量部の割合で使用し、前記芳
香族ジカルボン酸ジアリールエステルの融点以上の温度
で前記芳香族ジカルボン酸ジアリールエステルを前記再
結晶溶剤に溶解した後、冷却して芳香族ジカルボン酸ジ
アリールエステルを析出させることを特徴とする芳香族
ジカルボン酸ジアリールエステルの精製方法である。The present invention provides a method for purifying aromatic diaryl ester of dicarboxylic acid by dissolving the diaryl ester of aromatic dicarboxylic acid in a recrystallization solvent and then recrystallizing the diaryl ester of aromatic dicarboxylic acid. is used in an amount of 1 to 200 parts by weight, and after dissolving the aromatic diaryl ester in the recrystallization solvent at a temperature higher than the melting point of the aromatic diaryl ester, the diaryl aromatic dicarboxylate is cooled to form the diaryl aromatic dicarboxylate. This is a method for purifying aromatic dicarboxylic acid diaryl ester, which is characterized by precipitating the ester.
本発明において精製の対象となる芳香族ジカルボン酸ジ
アリールエステル（以下、精製原料と呼ぶ場合がある）
としては、特に制限はないが、下記芳香族ジカルボン酸
と下記芳香族モノヒドロキシ化合物とのエステルを例示
できる。Aromatic dicarboxylic acid diaryl ester to be purified in the present invention (hereinafter sometimes referred to as purified raw material)
There are no particular limitations on the ester, but examples include esters of the following aromatic dicarboxylic acids and the following aromatic monohydroxy compounds.
上記芳香族ジカルボン酸としては１例えばテレフタル酸
、イソフタル酸、フタル酸、ナフタレン−２，６−ジカ
ルボン酸、ナフタレン−２，７−ジカルボン酸、ナフタ
レン−１，４−カルボン酸、ナフタレン−１゜５−ジカ
ルボン酸、ナフタレン−１，６−ジカルボン酸。Examples of the above aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,4-carboxylic acid, naphthalene-1.5 -dicarboxylic acid, naphthalene-1,6-dicarboxylic acid.
ナフタレン−１，７−ジカルボン酸、４．４′−ジフェ
ニルジカルボン酸、３，３′−ジフェニルジカルボン酸
、３．４′−ジフェニルジカルボン
ルジカルボン酸， ４．４’−ジフェニルケトンジカ
ルボン酸、３，３′−ジフェニルケトンジカルボン酸、
３、４′−ジフェニルケトンジカルボン酸、２，２′−
ジフェニルケトンジカルボン酸， ４．４’−ジフェ
ニルスルホンジカルボン酸、３，４′−ジフェニルスル
ホンジカルボン酸、３．３′−ジフェニルスルホンジカ
ルボン酸、４，４′−スチルベンジカルボン酸、４．４
′−ジフェノキシエタンジカルボン酸，およびこれらの
ハロゲンもしくは低級アルキル基等による置換体などを
あげることができる．ハロゲンとしては、例えば塩素、
臭素などをあげることができる。低級アルキル基として
は、例えば炭素数１〜４のアルキル基，具体的にはメチ
ル基、エチル基、プロピル基、ブチル基などをあげるこ
とができる。置換体の具体的なものとして、例えばクロ
ルテレフタル酸、５−クロルイソフタル酸、メチルテレ
フタル酸などをあげることができる。naphthalene-1,7-dicarboxylic acid, 4.4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 3.4'-diphenyldicarboxylic acid, 4.4'-diphenylketonedicarboxylic acid, 3, 3'-diphenylketone dicarboxylic acid,
3,4'-diphenylketonedicarboxylic acid, 2,2'-
Diphenylketonedicarboxylic acid, 4.4'-diphenylsulfonedicarboxylic acid, 3,4'-diphenylsulfonedicarboxylic acid, 3.3'-diphenylsulfonedicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 4.4
Examples include '-diphenoxyethanedicarboxylic acid and substituted products thereof with halogen or lower alkyl groups. Examples of halogens include chlorine,
Examples include bromine. Examples of the lower alkyl group include an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Specific examples of the substituent include chlorterephthalic acid, 5-chloroisophthalic acid, methylterephthalic acid, and the like.
前記芳香族モノヒドロキシ化合物としては、例えばフェ
ノール、オルトクレゾール、パラクレゾール、オルトク
ロロフェノール、メタクロロフェノール、パラクロロフ
ェノールなどをあげることができる。Examples of the aromatic monohydroxy compound include phenol, ortho-cresol, para-cresol, ortho-chlorophenol, meta-chlorophenol, and para-chlorophenol.
芳香族ジカルボン酸ジアリールエステルの具体的なもの
として、例えばテレフタル酸ジフェニルエステル（ＤＰ
Ｔ）、イソフタル酸ジフェニルエステル（叶■）、テレ
フタル酸ジ（メチルフェニル）エステルなどをあげるこ
とができる。これらの中では、ＤＰＴ、 ＤＰＩ、およ
びこれらの混合物が好ましい。本発明の精製方法は、上
記精製原料をそれぞれ屯独で回収する場合のほか、混合
物例えばＤＰＴとＤＰＩとの混合物を混合物の形で回収
する場合にも好適に採用できる。Specific examples of the aromatic dicarboxylic acid diaryl ester include terephthalic acid diphenyl ester (DP
T), isophthalic acid diphenyl ester (Kano), terephthalic acid di(methylphenyl) ester, etc. Among these, DPT, DPI, and mixtures thereof are preferred. The purification method of the present invention can be suitably employed not only when recovering each of the above-mentioned purified raw materials individually, but also when recovering a mixture, for example, a mixture of DPT and DPI, in the form of a mixture.
精製原料としては、前記芳香族ジカルボン酸と前記芳香
族モノヒドロキシ化合物とのエステル化反応により得ら
れる反応混合液をそのまま使用してもよいが、これをあ
らかじめ蒸留、特に減圧蒸留により予備精製したものを
使用するのが好ましい。As the raw material for purification, the reaction mixture obtained by the esterification reaction of the aromatic dicarboxylic acid and the aromatic monohydroxy compound may be used as it is, but it may be pre-purified by distillation, especially vacuum distillation. It is preferable to use
本発明においては、前記精製原料を、精製原料の融点以
上の温度で再結晶溶剤に溶解した後、晶析して芳香族ジ
カルボン酸ジアリールエステルを精製する。In the present invention, the purified raw material is dissolved in a recrystallization solvent at a temperature higher than the melting point of the purified raw material, and then crystallized to purify the aromatic dicarboxylic acid diaryl ester.
本発明で使用される再結晶溶剤としては、例えば１，２
．４−トリメチルベンゼン（プソイドクメン）等のアル
キル置換ベンゼン７モノクロルベンゼン等のハロゲン化
ベンゼン；ブチルエーテル、アニソール等のエーテル類
；フェノール、クレゾール等のフェノール類；ヘキサン
、ヘプタン、ドデカン等の脂肪族炭化水素などがあげら
れる。The recrystallization solvent used in the present invention includes, for example, 1,2
．． Alkyl-substituted benzenes such as 4-trimethylbenzene (pseudocumene); halogenated benzenes such as 7-monochlorobenzene; ethers such as butyl ether and anisole; phenols such as phenol and cresol; aliphatic hydrocarbons such as hexane, heptane, and dodecane; can give.
これらの中ではアルキル置換ベンゼン、特に経済性の点
でプソイドクメンが好ましい。再結晶溶剤としては、上
記化合物を１種単独で使用してもよいし、２種以上を混
合して使用してもよい。Among these, alkyl-substituted benzene is preferred, especially pseudocumene from the economic point of view. As the recrystallization solvent, one type of the above compounds may be used alone, or two or more types may be used in combination.
再結晶溶剤の使用割合は、溶剤の種類、温度、精製原料
の純度などにより異なるが、通常精製原料１００重量部
に対して１〜２００重量部、好ましくは１０〜１００重
量部である。The proportion of the recrystallization solvent used varies depending on the type of solvent, temperature, purity of the purified raw material, etc., but is usually 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the purified raw material.
本発明においては、精製原料を、精製原料の融点以上の
温度、好ましくは融点以上ないし再結晶溶剤の沸点以下
の温度で、再結晶溶剤に溶解する。In the present invention, a purified raw material is dissolved in a recrystallization solvent at a temperature above the melting point of the purified raw material, preferably at a temperature between above the melting point and below the boiling point of the recrystallization solvent.
このときの温度は重要であり、精製原料の融点以上の温
度で再結晶溶剤に溶解することにより、精製原料を溶融
状態で再結晶溶剤中に溶解することができ、これにより
従来の方法に較べて再結晶溶剤の使用液を少なくして、
短時間で完全に溶解することができる。The temperature at this time is important; by dissolving the refined raw material in the recrystallization solvent at a temperature higher than its melting point, the refined raw material can be dissolved in the recrystallization solvent in a molten state, which makes it possible to dissolve the refined raw material in a molten state in the recrystallization solvent, which makes it possible to dissolve the refined raw material in a molten state in the recrystallization solvent. to reduce the amount of recrystallization solvent used.
Can be completely dissolved in a short time.
上記加熱溶解の圧力は常圧〜１ｏｏｋ４／ｃｄＧ、好ま
しくは常圧〜］Ｏｋｇ／ ａｊＧ、時間は０．１〜８時
間、好ましくは０．２〜２時間が好ましい。The pressure of the heating and melting is normal pressure to 1 ook4/cdG, preferably normal pressure to ]Okg/ajG, and the time is 0.1 to 8 hours, preferably 0.2 to 2 hours.
加熱溶解後、冷却して芳香族ジカルボン酸ジアリールエ
ステルの結晶を析出させるが、冷却温度は加熱溶解温度
より低い温度５通常Ｏ〜５０℃が好ましい２
析出した芳香族ジカルボン酸ジアリールエステルの結晶
は、ろ過、遠心分離などの方法により固液分離できる。After heating and dissolving, it is cooled to precipitate crystals of aromatic diaryl ester of diaryl dicarboxylic acid, and the cooling temperature is lower than the temperature of heating and dissolution5, usually preferably from 0 to 50°C. Solid-liquid separation can be performed by methods such as filtration and centrifugation.
加熱溶解時または冷却時に活性白土または活性炭を共存
させることもできる。Activated clay or activated carbon can also be present during heating and melting or cooling.
上記再結晶精製は２度以上繰返して行うことができる。The above recrystallization purification can be repeated two or more times.
また、再結晶精製の前および／または後に蒸留、特に減
圧蒸留を行うことにより、より好ましい純度で精製芳香
族ジカルボン酸ジアリールエステルを得ることができる
。Further, by performing distillation, particularly vacuum distillation, before and/or after recrystallization purification, purified aromatic dicarboxylic acid diaryl ester can be obtained with more preferable purity.
以上のようにして精製された芳香族ジカルボン酸ジアリ
ールエステルは、高純度で色相が優れているため、芳香
族ポリエステルの製造原料、プロピレン・エチレン・テ
レフタレート樹脂の改質材などとして好適に使用できる
。The aromatic dicarboxylic acid diaryl ester purified as described above has high purity and excellent hue, so it can be suitably used as a raw material for producing aromatic polyester, a modifying material for propylene/ethylene/terephthalate resin, etc.
本発明によれば、精製原料を、精！１に原料の融点以」
二の温度で再結晶溶剤に溶解した後、冷却して芳香族ジ
カルボン酸ジアリールエステルを析出させるようにした
ので、少量の再結晶溶剤を使用して短時間に溶解を行い
、高純度で色相の優れた芳香族ジカルボン酸ジアリール
エステルを高回収率で得られる。According to the present invention, refined raw materials can be refined! 1. Above the melting point of the raw material
After dissolving in the recrystallization solvent at the second temperature, the aromatic dicarboxylic acid diaryl ester is precipitated by cooling, so the dissolution can be carried out in a short time using a small amount of recrystallization solvent, and the color can be obtained with high purity. Excellent aromatic dicarboxylic acid diaryl ester can be obtained with high recovery rate.
さらに１本発明の精製方法では、精製原料として溶解度
の異なる芳香族ジカルボン酸ジアリールエステルの混合
物、例えばテレフタル酸ジフェニルエステルとイソフタ
ル酸ジフェニルエステルとの混合物を用いる場合、精製
による混合物の組成変化を小さくすることができる。Furthermore, in the purification method of the present invention, when a mixture of aromatic dicarboxylic acid diaryl esters having different solubility, such as a mixture of terephthalic acid diphenyl ester and isophthalic acid diphenyl ester, is used as a raw material for purification, the change in composition of the mixture due to purification is minimized. be able to.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１
反応器にテレフタル酸１モル、イソフタル酸１モル、フ
ェノール１６モルおよび触媒として酸化第−スズ０．０
０４モルを仕込み、撹拌下、１０ｋｇ／ｆｆ１Ｇの圧力
下、２８０℃の温度で生成する水を留去しながら５時間
反応させた。その結果３．１６モルの水が留出した。こ
のことから、ジカルボン酸のカルボキシル基のうち７９
％が反応したことがわかった。Example 1 In a reactor, 1 mol of terephthalic acid, 1 mol of isophthalic acid, 16 mol of phenol, and 0.0 stannous oxide as a catalyst were added.
04 mol was charged, and the reaction was carried out for 5 hours while stirring, under a pressure of 10 kg/ff1G, and at a temperature of 280° C. while distilling off the produced water. As a result, 3.16 mol of water was distilled out. From this, 79 of the carboxyl groups of dicarboxylic acid
It was found that % responded.
次に反応器を室温まで冷却した後開放し、炭酸ジフェニ
ル０．６３モルを加えた。この混合物を２５０℃で２時
間反応させてカルボキシル基を完全にフェニルエステル
に変換した。次に反応混合物から減圧蒸留によりフェノ
ールを除いた。The reactor was then cooled to room temperature and then opened, and 0.63 mol of diphenyl carbonate was added. This mixture was reacted at 250° C. for 2 hours to completely convert the carboxyl groups into phenyl esters. Next, phenol was removed from the reaction mixture by vacuum distillation.
このようにして得られた混合物の組成は、フェノール２
重量％、炭酸ジフェニル６重量％、ＤＰ７４６重量％、
ＤＰＩ４６重量％であった。この粗ＤＰＴ／ＤＰＩ混合
物の溶融色相（ハーゼン色、以下ＡＰＩＩＡと呼ぶ）は
３００以上、結晶色ｇｂ値は８．Ｏ，融点は約１３０℃
であった。The composition of the mixture thus obtained was phenol 2
weight%, diphenyl carbonate 6% by weight, DP746% by weight,
DPI was 46% by weight. The melt hue (Hazen color, hereinafter referred to as APIIA) of this crude DPT/DPI mixture is 300 or more, and the crystal color gb value is 8. O, melting point is approximately 130℃
Met.
上記粗ＤＰＴ／ＤＰＩ混合物２００ｇに再結晶溶剤とし
てプソイドクメン２００ｇを加えて、常圧下、１４０°
Ｃで１０分間撹拌した。１０分後加熱を止め室温になる
まで放置した１次に析出した結晶をろ過により分取した
後、乾燥して精製ＤＰＴ／叶■混合物１８０ｇを得た。200 g of pseudocumene was added as a recrystallization solvent to 200 g of the above crude DPT/DPI mixture, and the mixture was heated at 140° under normal pressure.
The mixture was stirred at C for 10 minutes. After 10 minutes, the heating was stopped and the mixture was allowed to cool to room temperature. The primary precipitated crystals were collected by filtration and dried to obtain 180 g of a purified DPT/leaf mixture.
この精製ＤＰＴ／ＤＰＩ混合物のＡＰＨＡは１００、結
晶色調す値は５．０であった。なお精製ＤＰＴ ／叶■
混合物のＤＰＴとＤＰＩとの割合はＤＰＴ ／叶■の重
量比で５０１５０であった。The purified DPT/DPI mixture had an APHA of 100 and a crystal color value of 5.0. In addition, purified DPT / Kano ■
The ratio of DPT to DPI in the mixture was 50,150 in DPT/leaf weight ratio.
実施例２
実施例１の晶析において、再結晶溶剤としてのプソイド
クメンの代りにブチルエーテルを用いて実施例１と同様
の操作を行った。得られた精製ＤＰＴ／ＤＰＩ混合物の
ＤＰＴとＤＰＩとの割合はＤＩ’Ｔ／ＤＩ）Ｉの重量比
で５０１５０であり、 ＡＰＨＡは１００であった。Example 2 In the crystallization of Example 1, the same operation as in Example 1 was carried out using butyl ether instead of pseudocumene as a recrystallization solvent. The ratio of DPT to DPI in the obtained purified DPT/DPI mixture was 50,150 in terms of weight ratio of DI'T/DI)I, and APHA was 100.
実施例３
ＤＰＴ／ＤＰＩの重量比を３０１５０に調製したもの（
ＡＰＨＡ ２７０、融点約１３０℃）を精製原料に用い
て実施例１の晶析操作と同様の操作を行った。得られた
精製ＤＰＴ／ＤＰＩ混合物のＤＰＴとＤＰＩとの割合は
叶Ｔ／ＤＰＩ（７）重量比テコ０１５０テあり、ＡＰＨ
Ａはｌｏｆテあった。Example 3 DPT/DPI weight ratio adjusted to 30150 (
The same crystallization operation as in Example 1 was carried out using APHA 270 (melting point: about 130° C.) as a purified raw material. The ratio of DPT and DPI in the purified DPT/DPI mixture obtained is 0.150% by weight (7), and APH
A was lofte.
実施例４
実施例１の晶析において、再結晶溶剤としてのプソイド
クメンの代りにｎ−ドデカンを用いて実施例１と同様の
操作を行った。得られた精製ＤＰＴ／ＤＰＩ混合物のＤ
ＰＴとＤＰＩとの割合はＤＰＴ／ＤＰＩの重量比テ５０
１５０テあり、ＡＰＨＡは２００ ｔ’あった。Example 4 In the crystallization of Example 1, the same operation as in Example 1 was performed using n-dodecane instead of pseudocumene as a recrystallization solvent. D of the obtained purified DPT/DPI mixture
The ratio of PT to DPI is the weight ratio of DPT/DPI te50
There were 150 te, and APHA had 200 t'.
比較例Ｉ
ＤＰＴ／ＤＰＩの重量比を５０１５０に調製したもの（
ＡＰＨＡ ２７０、融点約１３０℃）１６部ニｌｏｏ’
ｃ １？ （７）溶解量分のプソイドクメン８４部を加
えて１００℃で溶解し。Comparative Example I DPT/DPI weight ratio was adjusted to 50150 (
APHA 270, melting point approximately 130°C) 16 parts
c1? (7) Add 84 parts of pseudocumene to dissolve at 100°C.
１０分間撹拌した。１０分後加熱を止め室温になるまで
放置した。次に析出した結晶をろ過により分取した後、
乾燥した。得られた精製１）ＰＴ／ＤＰＩ混合物のＤＰ
ＴとＤＰＩとの割合はＤＰＴ／ＤＰＩの重量比で６１／
３９であり、Ａ Ｐ １１ Ａは１００であった。Stir for 10 minutes. After 10 minutes, heating was stopped and the mixture was left to stand until it reached room temperature. Next, after separating the precipitated crystals by filtration,
Dry. Purification obtained 1) DP of PT/DPI mixture
The ratio of T to DPI is the weight ratio of DPT/DPI of 61/
39, and A P 11 A was 100.
Claims (1)
溶剤に溶解した後、再結晶させて芳香族ジカルボン酸ジ
アリールエステルを精製する方法において、芳香族ジカ
ルボン酸ジアリールエステル１００重量部に対して再結
晶溶剤を１〜２００重量部の割合で使用し、前記芳香族
ジカルボン酸ジアリールエステルの融点以上の温度で前
記芳香族ジカルボン酸ジアリールエステルを前記再結晶
溶剤に溶解した後、冷却して芳香族ジカルボン酸ジアリ
ールエステルを析出させることを特徴とする芳香族ジカ
ルボン酸ジアリールエステルの精製方法。(1) In a method of dissolving aromatic dicarboxylic acid diaryl ester in a recrystallization solvent and then recrystallizing it to purify aromatic dicarboxylic acid diaryl ester, the recrystallization solvent is added to 100 parts by weight of aromatic dicarboxylic acid diaryl ester. The aromatic diaryl ester is dissolved in the recrystallization solvent at a temperature higher than the melting point of the aromatic diaryl ester, and then cooled to form the aromatic diaryl ester. A method for purifying an aromatic dicarboxylic acid diaryl ester, the method comprising precipitating the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14331789A JPH0311040A (en) | 1989-06-06 | 1989-06-06 | Method for purifying aromatic dicarboxylic acid diaryl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14331789A JPH0311040A (en) | 1989-06-06 | 1989-06-06 | Method for purifying aromatic dicarboxylic acid diaryl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0311040A true JPH0311040A (en) | 1991-01-18 |
Family
ID=15335968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14331789A Pending JPH0311040A (en) | 1989-06-06 | 1989-06-06 | Method for purifying aromatic dicarboxylic acid diaryl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0311040A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074954A (en) * | 2006-09-21 | 2008-04-03 | Nitto Denko Corp | Double-sided adhesive tape |
-
1989
- 1989-06-06 JP JP14331789A patent/JPH0311040A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074954A (en) * | 2006-09-21 | 2008-04-03 | Nitto Denko Corp | Double-sided adhesive tape |
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