JPS62190163A - Production of aryl imidodicarboxylate - Google Patents
Production of aryl imidodicarboxylateInfo
- Publication number
- JPS62190163A JPS62190163A JP61030944A JP3094486A JPS62190163A JP S62190163 A JPS62190163 A JP S62190163A JP 61030944 A JP61030944 A JP 61030944A JP 3094486 A JP3094486 A JP 3094486A JP S62190163 A JPS62190163 A JP S62190163A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- compound
- acid
- imidodicarboxylic
- imidodicarboxylic acid
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000003118 aryl group Chemical group 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 20
- -1 phenol Chemical class 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005263 alkylenediamine group Chemical group 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-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
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
ｌａ） 産業上の利用分野
本発明１ゴイミドンカルボン酸７リールエステルの製造
方法に関し、更に詳しくはイミドジカルボン酸と芳香族
モノオキシ化合物とからその７リールエステルを製造す
る方法に関するものである。Detailed Description of the Invention la) Industrial Field of Application The present invention 1 relates to a method for producing a heptadyl ester of goimidonecarboxylic acid, more specifically a method for producing the heptadyl ester from imidodicarboxylic acid and an aromatic monooxy compound. It is related to.
（ｂｌ 従来技術
下記式（１）
〔式ｍにおいてｎ Ｇヨ２〜１２の整数を表わす。〕で
示されるイミドジカルボン酸は各社ポリマー、具体的に
はポリエステル、ポリアミド郷のジカルボン酸成分とし
て知られているが、例えばポリエステルの場合の原料と
して極めて有用な該ジカルボン酸のジアリールエステル
については、従来その製造例がほとんど知られていなか
った。(bl Prior art) Imidodicarboxylic acid represented by the following formula (1) [In the formula m, n G represents an integer from 2 to 12] is known as a dicarboxylic acid component of various polymers, specifically polyesters and polyamides. However, with regard to the diaryl ester of dicarboxylic acid, which is extremely useful as a raw material for making polyester, for example, few examples of its production have been known.
（ｃｌ 発明の目的
本発明者は、上記イミドジカルボン酸の７リールールエ
ステルの製造方法について鋭意研究した結果、イミドジ
カルボン酸と芳香族モノオキシ化合物とを特定条件下で
反応させることにより、目的とするジアリールエステル
が極めて短時間で容易に、安価に、かつ高収率で得られ
ることな見出し本発明に到達した。(cl) Purpose of the Invention As a result of intensive research into the method for producing the above-mentioned 7-reel ester of imidodicarboxylic acid, the present inventor has discovered that the object of the invention can be achieved by reacting imidodicarboxylic acid and an aromatic monooxy compound under specific conditions. The present invention was made based on the discovery that diaryl esters can be obtained easily, inexpensively, and in high yields in an extremely short period of time.
（ｄｉ 発明の構成および効果
すなわち１本発明は下記式＋１）
〔式（１）において、ｎは２〜１２の整数を表わす。〕
で示されるイミドジカルボン酸と該ジカルボン酸に対し
て２倍モル以上の芳香族モノオキシ化合物とを２００〜
３２０℃の温度で加熱反応することを特徴とするイミド
ジカルボン酸７リールエステルの製造方法である。(di Structure and Effects of the Invention, ie 1 The present invention is expressed by the following formula +1) [In formula (1), n represents an integer from 2 to 12. ]
An imidodicarboxylic acid represented by
This is a method for producing imidodicarboxylic acid 7-aryl ester, which is characterized by carrying out a heating reaction at a temperature of 320°C.
以下１本発明について更に詳しく説明する。The present invention will be explained in more detail below.
下記式＋１１
においてｎは２〜１２の整数を表わす。これらのうち好
ましくはｎは偶数であり、より好ましくは２，６．１２
であり、更に好ましくは６である。イミドジカルボン酸
は無水トリメリット酸と対応するフルキレンジアミンと
の反応により極めて容易に得ることができる。In the following formula +11, n represents an integer from 2 to 12. Among these, preferably n is an even number, more preferably 2,6.12
and more preferably 6. Imidodicarboxylic acid can be obtained very easily by reaction of trimellitic anhydride with the corresponding fullkylene diamine.
次に、本発明に用いる芳香族モノオキシ化合物としては
、フェノール、ｍ−クレゾール、Ｐ−クレゾール、ｍ−
クロルフェノール、Ｐ−オクチルフェノール、Ｐ−ノニ
ルフェノール、Ｐ−クロルフェノール、α−ナフトール
、β−ナフトール等が挙げられる。これらのうち、フェ
ノール、クレゾールが好ましく、特にフェノールが好ま
しい。Next, the aromatic monooxy compounds used in the present invention include phenol, m-cresol, P-cresol, m-
Examples include chlorophenol, P-octylphenol, P-nonylphenol, P-chlorophenol, α-naphthol, β-naphthol, and the like. Among these, phenol and cresol are preferred, and phenol is particularly preferred.
芳香族モノオキシ化合物の使用ｔは上記イミドジカルボ
ン酸に対して２倍モル以上必要である。使用量が２倍モ
ル未満の場合には化学量論的に目的とする７リールエス
テルを高純度で得ることはできない。芳香族モノオキシ
化合物の使用量としては３倍モル以上が好ましく、４倍
モル以上が％に好ましい。上限は特に規定さ第１ないが
２０倍モル以下が好ましい。The amount of the aromatic monooxy compound used must be at least twice the amount of the imidodicarboxylic acid. When the amount used is less than 2 times the mole, it is impossible to obtain the desired 7-aryl ester with high purity stoichiometrically. The amount of the aromatic monooxy compound used is preferably 3 times the mole or more, and preferably 4 times the mole or more. The upper limit is not particularly specified, but is preferably 20 times the mole or less.
反応温度は２００〜３２０℃の範囲である。反応温度が
２００℃以下では反応速度が遅く、また３２０℃以上で
は反応生成物の着色が多く純度が低い。反応温度は好ま
しくは２１０〜３１０℃。The reaction temperature is in the range of 200-320°C. When the reaction temperature is below 200°C, the reaction rate is slow, and when the reaction temperature is above 320°C, the reaction product is often colored and has low purity. The reaction temperature is preferably 210 to 310°C.
特に好ましくは２２０〜３００℃である。反応は常圧〜
加圧下で行うことができるが芳香族モノオキシ化合物の
常圧における沸点が反応温度以下の場合には、加圧条件
下で反応することが好ましい。また反応系は窒素、アル
ゴン等の不活性ガス雰囲気下とすることが好ましい。Particularly preferably, the temperature is 220 to 300°C. Reaction takes place at normal pressure
Although the reaction can be carried out under pressure, if the boiling point of the aromatic monooxy compound at normal pressure is lower than the reaction temperature, it is preferable to carry out the reaction under pressure. Further, the reaction system is preferably under an inert gas atmosphere such as nitrogen or argon.
反応時間は、上記エステル反応が十分に進行するに足る
時間であればよ（、またこの時間は反応温度１反応スケ
ール等によっても異るが３０分〜２０時間、好ましくは
１〜ｌＯ時間程度である。The reaction time should be long enough for the above ester reaction to proceed sufficiently (although this time varies depending on the reaction temperature, reaction scale, etc., it is 30 minutes to 20 hours, preferably about 1 to 10 hours). be.
上記反応に際しては、エステル化により発生する水を反
応系外に除去せしめることが好ましい。エステル化反応
は平衡反応であり、生成する水を糸外に除去することに
より１反応が速くなり、生成物の収率、純度が向上する
。生成した水は、芳香族モノオキシ化合物との沸点差に
より１反応系外に除去することができるが、水と共沸混
合物を形成する有機溶媒を用いて共沸により１反応系外
に除去することもで営る。該有機溶媒としては、それ自
身、反応条件で分解することなく、かつイミドジカルボ
ン酸、芳香族モノ・オキシ化合物と反応せず、水と共沸
するものであればよ（・。具体的にはトルエン、キシレ
ン、エチルベンゼン勢の芳香族炭化水素が好ましく使用
できる。In the above reaction, it is preferable to remove water generated by esterification from the reaction system. The esterification reaction is an equilibrium reaction, and by removing the produced water to the outside of the thread, one reaction becomes faster and the yield and purity of the product are improved. The generated water can be removed outside the reaction system due to the boiling point difference with the aromatic monooxy compound, but it can be removed outside the reaction system by azeotropy using an organic solvent that forms an azeotrope with water. I also run a business. The organic solvent may be one that does not decompose itself under the reaction conditions, does not react with imidodicarboxylic acid or aromatic mono-oxy compounds, and is azeotropic with water. Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene can be preferably used.
エステル化反応の反応率は８０％以上とすることが好ま
しい。このエステル化反応率は反応により生成する水の
ｆＫより知ることができるが、より正確に求めるために
は、反応生成物の未反応−〇 〇 〇 ）１価を測定す
ればよい。反応物の−ＣＯＯＨ価をＣ（当ｔ／１０’＆
）、原料であるイミドジカルボン酸の理論−ＣＯＯＨ価
をＣｏ（当量／ １０’１９ ）とするとエステル化反
応率は下式により求めることができる。The reaction rate of the esterification reaction is preferably 80% or more. This esterification reaction rate can be known from the fK of water produced by the reaction, but in order to more accurately determine it, it is sufficient to measure the unreacted -〇〇〇) monovalent value of the reaction product. -COOH value of the reactant is C(t/10'&
), and assuming that the theoretical -COOH value of imidodicarboxylic acid as a raw material is Co (equivalent/10'19), the esterification reaction rate can be determined by the following formula.
エステル化反応率＝−ｘ１ｏｏ（＠
Ｏ
ここでＣｏはイミドジカルボン酸の分子量をＭとすると
Ｃｏ ＝ ２ Ｘ １０’／ Ｍにより算出できる。例
えばイミドジカルボン酸がＮ ＋ ｌ’Ｊ’ ｌ ＋
６−ヘキサメチレンピストリメリツトイミド（Ｍ＝４
６４）の場合にはＣｏ＝４３ｔＯとなる。Esterification reaction rate = -x1oo (@O Here, Co can be calculated as Co = 2 X 10'/M, where M is the molecular weight of imidodicarboxylic acid. For example, if imidodicarboxylic acid is N + l'J' l +
6-hexamethylene pistrimellitimide (M=4
64), Co=43tO.
尚、Ｃｏは反応生成物をよく水洗いし、過剰の芳香族モ
ノオキシ化合物等を除去したものＫついて測定した。Incidentally, Co was measured after thoroughly washing the reaction product with water to remove excess aromatic monooxy compounds and the like.
本発明の７リールエステルは上記の方法により得ること
ができるが反応速度を向上させるために触媒を少量添加
することが好ましい。触媒としてはスズ（Ｓｎ）、チタ
ン（Ｔ＋）、アンチモン（Ｓｂ）。The 7-reel ester of the present invention can be obtained by the method described above, but it is preferable to add a small amount of a catalyst to improve the reaction rate. The catalysts are tin (Sn), titanium (T+), and antimony (Sb).
マンガン（Ｍｎ）、亜鉛（Ｚｎ）、ナトリウム（Ｎａ
） ｔカリウム（Ｋ）およびその化合物等の如きエステ
ル交換触媒として使用されている化合物が例示できる。Manganese (Mn), zinc (Zn), sodium (Na
) Examples include compounds used as transesterification catalysts such as potassium (K) and its compounds.
これらは一種あるいは二種以上を併用して用いることが
できる。触媒の使用量はイミドジカルボン酸に対してｏ
、ｏ ｏ ｓ〜５モルチ、好ましくは０．０１〜３モル
チ程度である。These can be used alone or in combination of two or more. The amount of catalyst used is o relative to imidodicarboxylic acid.
, o o s to 5 molti, preferably about 0.01 to 3 molti.
本発明の方法によれば、イミドジカルボン酸アリールエ
ステルを極めて容易かつ安価に得ることができる。得ら
れ、た７リールエステルは純度が高く、特ＫｗＩ製する
ことなく、重合原料として使用することも可能で））る
。According to the method of the present invention, imidodicarboxylic acid aryl esters can be obtained extremely easily and at low cost. The obtained 7-reel ester has a high purity and can be used as a polymerization raw material without special KwI production.
以下、実施例を単げて本発明を説明するが、これらは本
発明を例示するためのものであってこれに限定されるも
のではない。また、実施例中「部Ｊは「Ｎ金部」を意味
する。７リールエステルの純度は未反応−ＣＯＯＨ価よ
り引算により求めた。−ＣＯＯＨ価はＡ、Ｃｏｎ１ｘの
方法（Ｍａｅｒｏｍｏｌ、 Ｃｈｅｍ、 ２６ ２２６
（１９５Ｂ）＄照〕に準じて測定した。Hereinafter, the present invention will be explained using only Examples, but these are for illustrating the present invention and are not intended to limit the present invention. Further, in the examples, "part J" means "N gold part". The purity of the 7-reel ester was determined by subtraction from the unreacted -COOH value. -COOH value is A, Con1x method (Maeromol, Chem, 26 226
(195B) $Sho].
実施例１〜５
Ｎ、Ｎ’−へキサメチリ／ビストリメリントイミド４６
４部、所定蓋のフェノールおよび所定量の触媒を攪拌装
置および留出系を偏えた加圧反応器に仕込み、所定の温
度で反応させ住成する水を留去させた。この際反応系は
１〜５ ｋｇ／ ｅｒａの９累加圧の状態とした。反応
終了後冷却し、得られた反応物を水洗いし、更にメタノ
ールで洗浄した。得られたジアリールエステルはいずれ
も融点１７５〜１８３℃でありほとんど着色することな
く色調も良好であった。また、赤外線吸収スペクトルよ
り１１９５ｃｒ 、 ｊ７３５ｃ＊′に特徴的ピークが
みられ、ジフェニルエステルであることを確認した。収
ｉ、純度を表１に示したが本発明の製造決によりＮ、Ｎ
’−１，６−へキサメチレンビストリメリットイミドジ
カルボン酸ジフェニルエステルが高収率かつ高純度で得
られることがわかる。Examples 1-5 N,N'-hexamethylene/bistrimelin imide 46
4 parts, a predetermined amount of phenol, and a predetermined amount of catalyst were charged into a pressurized reactor equipped with a stirrer and a distillation system, and reacted at a predetermined temperature to distill off the water formed. At this time, the reaction system was kept under nine cumulative pressures of 1 to 5 kg/era. After the reaction was completed, the reaction product was cooled, washed with water, and further washed with methanol. All of the obtained diaryl esters had a melting point of 175 to 183°C, were hardly colored, and had a good color tone. In addition, characteristic peaks were observed at 1195cr and j735c*' in the infrared absorption spectrum, confirming that it was a diphenyl ester. The yield i and purity are shown in Table 1, but due to the manufacturing decision of the present invention, N, N
It can be seen that '-1,6-hexamethylenebistrimeritimidodicarboxylic acid diphenyl ester can be obtained in high yield and purity.
実施例６
Ｎ、Ｎ’ −１，２−エチレンビストリメリットイミド
４０８部、Ｐ−クレゾール５４０部およびＴｉ （ＯＢ
ｕ ）４０．１部を攪拌装置および留出系を備えた加圧
反応器に仕込み、温度２６０℃で４時間反応させた。こ
の際、反応系を窒素によりｌ〜４ｋｇ／ｃｗｔの加圧状
態とし、反応により生成する水を留去させた。反応混合
物を冷却後、水およびメタノールで洗浄したところ、取
計５８０部、純度９８．２％であった。Example 6 408 parts of N,N'-1,2-ethylene bistrimeritimide, 540 parts of P-cresol and Ti (OB
u) 40.1 parts were charged into a pressurized reactor equipped with a stirring device and a distillation system, and reacted at a temperature of 260° C. for 4 hours. At this time, the reaction system was pressurized with nitrogen at 1 to 4 kg/cwt, and water produced by the reaction was distilled off. After the reaction mixture was cooled, it was washed with water and methanol, and the total amount was 580 parts, with a purity of 98.2%.
実施例７
Ｎ、Ｎ’ −１，６−ヘキサメチレンピストリメリツト
イミド４６４％、Ｐ−オクチルフェノール９２７部、
Ｔｉ （ＯＢｕ ）ａ Ｏ，２ｉｔｓを攪拌装置およ
び留出系を備えた反応器に入れ、温度２７０℃の常圧ｔ
′Ａ気流中下で約４時間反応させた。反応終了抜冷却し
、メタノールおよび水で洗浄し、７３０部の７リールエ
ステルを得た。純度は９８．０％でほとんど着色してい
なかった。Example 7 N,N'-1,6-hexamethylene pistrimellit imide 464%, P-octylphenol 927 parts,
Ti(OBu)aO,2its was placed in a reactor equipped with a stirring device and a distillation system, and the temperature was 270°C and normal pressure t.
The reaction was carried out for about 4 hours under a stream of 'A' air. After the reaction was completed, the mixture was cooled and washed with methanol and water to obtain 730 parts of 7-reel ester. The purity was 98.0% and there was almost no coloration.
＋１１ 明細書第６頁第８行〜詔７頁第３行に「工手
続補正書
昭和６１年ぐ月−日+11 From page 6, line 8 of the specification to page 7 of the imperial decree, line 3:
Claims (1)
〕で示されるイミドジカルボン酸と該ジカルボン酸に対
して２倍モル以上の芳香族モノオキシ化合物とを２００
〜３２０℃の温度で加熱反応することを特徴とするイミ
ドジカルボン酸アリールエステルの製造方法。[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula (I), n represents an integer from 2 to 12.
] of the imidodicarboxylic acid and an aromatic monooxy compound in an amount of 2 times or more moles relative to the dicarboxylic acid.
A method for producing imidodicarboxylic acid aryl ester, characterized by carrying out a heating reaction at a temperature of ~320°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61030944A JPS62190163A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61030944A JPS62190163A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62190163A true JPS62190163A (en) | 1987-08-20 |
| JPH0513148B2 JPH0513148B2 (en) | 1993-02-19 |
Family
ID=12317785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61030944A Granted JPS62190163A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62190163A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272571A (en) * | 1987-07-28 | 1989-10-31 | Canon Inc | Optically active liquid crystal compound and liquid crystal composition containing the same compound |
| CN110835356A (en) * | 2019-11-14 | 2020-02-25 | 安徽金德润滑科技有限公司 | Anti-foaming agent and application thereof in road vehicle gear oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127067A (en) * | 1975-04-28 | 1976-11-05 | Nippon Telegr & Teleph Corp <Ntt> | Process for preparation of allylester compound containing imide ring |
| JPS5414498A (en) * | 1977-07-05 | 1979-02-02 | Mitsubishi Electric Corp | Heat resistant epoxy resin composition |
-
1986
- 1986-02-17 JP JP61030944A patent/JPS62190163A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127067A (en) * | 1975-04-28 | 1976-11-05 | Nippon Telegr & Teleph Corp <Ntt> | Process for preparation of allylester compound containing imide ring |
| JPS5414498A (en) * | 1977-07-05 | 1979-02-02 | Mitsubishi Electric Corp | Heat resistant epoxy resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272571A (en) * | 1987-07-28 | 1989-10-31 | Canon Inc | Optically active liquid crystal compound and liquid crystal composition containing the same compound |
| JPH0667913B2 (en) * | 1987-07-28 | 1994-08-31 | キヤノン株式会社 | Optically active liquid crystal compound and liquid crystal composition containing the same |
| CN110835356A (en) * | 2019-11-14 | 2020-02-25 | 安徽金德润滑科技有限公司 | Anti-foaming agent and application thereof in road vehicle gear oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0513148B2 (en) | 1993-02-19 |
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