JPS62190164A - Production of aryl imidodicarboxylate - Google Patents
Production of aryl imidodicarboxylateInfo
- Publication number
- JPS62190164A JPS62190164A JP61030945A JP3094586A JPS62190164A JP S62190164 A JPS62190164 A JP S62190164A JP 61030945 A JP61030945 A JP 61030945A JP 3094586 A JP3094586 A JP 3094586A JP S62190164 A JPS62190164 A JP S62190164A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- alkylenediamine
- formula
- water
- acid anhydride
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000003118 aryl group Chemical group 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 125000005263 alkylenediamine group Chemical group 0.000 claims abstract description 13
- -1 phenol Chemical class 0.000 claims abstract description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000003756 stirring Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004985 diamines 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
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- 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
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 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
- 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
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 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 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000276 sedentary effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
ｔａｌ 座業上のオＵ用分野
本発明はイミドジカルボン酸アリールエステルの製造方
法に閣するものであり、更に詳しくはアルキレンジアミ
ン、トリメリント酸無水物および芳：ｅｆａ七ノナノオ
キシ化合物らそのアリールエステルを装造する方法に関
するものである。[Detailed description of the invention] tal Field of sedentary use The present invention is directed to a method for producing imidodicarboxylic acid aryl esters, and more specifically, alkylene diamines, trimellitic acid anhydride, and aromatic: efa heptanonanooxy. The present invention relates to a method for preparing compounds and their aryl esters.
ｌｂ） 従来技術
下記式（ｆｆ）
・・・・・・（■）
で表わされるイミドジカルボン酸の７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。lb) Prior Art Regarding the heptadyl ester of imidodicarboxylic acid represented by the following formula (ff) (■), almost no examples of its production have been known.
（ｅ） 発明の目的
そこで、本発明者らは、上記イミドジカルボン酸の７リ
ールエステルの製造方法について鋭意研究した結果、ア
ルキレンジアミン、トリメリット酸無水物および芳査族
七ノオ−？７化合物を直接加熱反応させることにより、
目的とするアリールエステルか極めて短時間で容易に、
安価にかつ嶋収率で得られることな見い出し本発明に到
達した。(e) Purpose of the Invention The inventors of the present invention conducted intensive research on a method for producing the heptadyl ester of imidodicarboxylic acid, and found that alkylene diamine, trimellitic anhydride, and aromatic heptano-? By directly heating and reacting the 7 compounds,
You can easily obtain the desired aryl ester in an extremely short time.
We have arrived at the present invention, a finding that can be obtained at low cost and with a high yield.
ｔｄｌ 発明の構成および効果
すなわち、本発明は１−記式（１）
％式％（１）
で示されるアルキレンジアミンと、該アルキレンジアミ
ンに対し、１．９〜２．１１ｉモルのトリメリット酸無
水物および２倍モル以上の芳香族モノオキシ化合物とを
１加熱反応することを特徴とす０イミドジカルボンａ１
７１ｊ−ルエステルの製造方法である。tdl Structure and effect of the invention That is, the present invention provides an alkylene diamine represented by the formula (1) % formula % (1) and 1.9 to 2.11 imoles of trimellitic anhydride to the alkylene diamine. and an aromatic monooxy compound in an amount of 2 times the mole or more.0 imidodicarbon a1
This is a method for producing 71j-lester.
以下、本発明について更に詳細ＶＣ説明する。Hereinafter, the present invention will be explained in more detail.
式（１）で示されるアルキレンジアミンにおいて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、史に好
ましくは６のヘキサメチレンジアミンである。In the alkylene diamine represented by formula (1), n is 2
Represents an integer between ~12. Among these, n is preferably an even number, more preferably 2°6.12, and most preferably 6 hexamethylene diamine.
次に、践フル千レンジアミンに対し、１．９〜２．１倍
モルのトリメリント２無水物を用いる。Next, trimelin dianhydride is used in an amount of 1.9 to 2.1 times the mole of 1.9 to 2.1 times the mole of 100% diamine.
トリメリント酸無水物の使用量が１．９倍セル未満およ
び２．１倍モルより多い場合には得られるイミドジカル
ボン酸アリールエステルの取置、純度が低下し好ましく
ない。トリメリット酸無水物はアルキレンジアミンに対
し１．９５〜２．０５５倍モル用することが特に好まし
い。If the amount of trimellitic acid anhydride used is less than 1.9 times the cell and more than 2.1 times the mole, the retention and purity of the resulting imidodicarboxylic acid aryl ester will decrease, which is not preferable. It is particularly preferable to use trimellitic anhydride in a molar amount of 1.95 to 2.055 times the amount of alkylene diamine.
また、本発明に用いる芳香原子ノオキン化合物としては
、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−クロルフェン−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り、特にフェノールが好ま
しい。In addition, the aromatic atom compound used in the present invention includes phenol, m-cresol, p-cresol, m-
Examples include chlorophenol, p-octylphenol, p-nonylphenol, p-chlorfenol, 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量は、上記アルキレンジ
アミンに対して２倍モル以上必安である。便用意が２倍
モル未満の場合には、化学鰍論的に目的とする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倍モル以上が特に好ヱしい。上限は％に規定されない
が２０倍モル以）が好ましい。The amount of the aromatic monooxy compound to be used is necessarily at least twice the mole of the alkylene diamine. If the amount of the preparation is less than 2 times the mole, it is impossible to obtain the desired heptadyl ester with high purity from a chemical theory. The amount of the aromatic monooxy compound used is preferably 3 times the mole or more,
Particularly preferred is 4 times the mole or more. Although the upper limit is not specified as a percentage, it is preferably 20 times the mole or more.
本発明では上記の原料混合物を加熱反応することにより
イミドジカルボン酸アリールエステルを製造す０が、以
下反応条件について述べる。In the present invention, imidodicarboxylic acid aryl ester is produced by heating the above raw material mixture, and the reaction conditions will be described below.
反応は好ましくは１００〜３２Ｕ’Ｃ％特に好ましくは
１２０〜３００’Ｃの一足温度条件で実施してもよいが
、反応の進何に従い、反応温度を徐々に上昇させること
が好ましい。その際の反応の初期温度は好ましくはＩＩ
ＪＵ〜２２０℃、より好ましくは１１０〜２１０℃、更
に好ましくは１２０〜２００℃であり、また最終反応温
度は好ましくは２００〜３２０℃、より好ましくは２１
０〜３１０℃、更に好ましくは２２０〜３００℃である
。The reaction may be carried out at a temperature of preferably 100 to 32 U'C%, particularly preferably 120 to 300'C, but it is preferable to gradually increase the reaction temperature according to the progress of the reaction. In this case, the initial temperature of the reaction is preferably II
JU~220°C, more preferably 110~210°C, even more preferably 120~200°C, and the final reaction temperature is preferably 200~320°C, more preferably 21°C.
The temperature is 0 to 310°C, more preferably 220 to 300°C.
反応は常圧下または加圧下で実施できるが、反応温度が
芳香族モノオキシ化合物の常圧での沸点以上の場合には
必要に応じて加圧条件下とすることが好ましい。The reaction can be carried out under normal pressure or under increased pressure, but if the reaction temperature is higher than the boiling point of the aromatic monooxy compound at normal pressure, it is preferable to carry out under increased pressure as necessary.
反応の雰囲気としτ、！！累、フルゴン寺の不活性ガス
娠流中が好ましい。The atmosphere of reaction is τ,! ! It is preferable to use an inert gas stream at Fulgon Temple.
また、反応時に化成する水は速やかに反応糸外へ除去す
ることが好工しい。反応は平伽反応であり、生成する水
を系外へ除去丁Φことにより、反応速度か上がり、叉に
瞥云した水の菫より反応の進行状況を知ることもできる
。水を留去する際、水と共那混合物を形成する有機溶媒
を用いて共沸により水を除去することにより好ましく実
施できる。該有機溶媒としてはそれ自身反応条件下で分
解することなく、また反応原料および生成物と反応せず
、かつ水と共沸するものであればよいが、具体的にはト
ルエン、キシレン、エチルベンゼン等の芳香族系炭化水
素が好ましく使用できる。Further, it is preferable that the water that is chemically converted during the reaction is quickly removed to the outside of the reaction yarn. The reaction is a Heika reaction, and by removing the water produced from the system, the reaction rate increases, and the progress of the reaction can also be determined by looking at the violet of water. When water is distilled off, water can be preferably removed by azeotropic distillation using an organic solvent that forms a synergistic mixture with water. The organic solvent may be one that does not decompose itself under the reaction conditions, does not react with the reaction raw materials and products, and is azeotropic with water; specific examples include toluene, xylene, ethylbenzene, etc. aromatic hydrocarbons can be preferably used.
反応時間は特に制限はなく、反応が十分に進行するに足
る必責な時間であればよく、また、この時間は反応条件
によっても異なるか、好ましくは３０分〜３０時間、よ
り好ましくは１〜２５時間、史に好ましくは２〜２０時
間程度である。There is no particular restriction on the reaction time, and it may be any time necessary for the reaction to proceed sufficiently, and this time may vary depending on the reaction conditions, preferably 30 minutes to 30 hours, more preferably 1 to 30 hours. 25 hours, preferably about 2 to 20 hours.
本発明によればよ６ｄの方法により目的とするイミドジ
カルボン眩ジアリールニスデルを得ることができるが、
特に好ましい態様としてはまず反応温度１２０〜２００
℃で王としてイミド化反応によって生成する水な留去し
、仄いて反応温度を２２０〜３ＵＵ’Ｃに上げ、引き就
き王としてエステル化反ＫＣ）＆′ｃよって生成すりボ
ケ留去させる方法が挙げられ心。これにより、他めて再
現性よく目的物を１粂的に有利に得ることができる。According to the present invention, the desired imidodicarbonate diarylnisdel can be obtained by the method of 6d.
In a particularly preferred embodiment, first, the reaction temperature is 120 to 200.
℃ to distill off the water produced by the imidization reaction, raise the reaction temperature to 220~3UU'C, and then distill off the esterified anti-KC)&'c produced. Heart raised. Thereby, the desired product can be advantageously obtained in one kettle with good reproducibility.
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、特に反応速度を向上させるためＩｃ触媒を
少象添加することが好ましい。Although the 7-reel ester of the present invention can be obtained by the above-mentioned method, it is particularly preferable to add a small amount of Ic catalyst to improve the reaction rate.
触媒としては、スズ（Ｓｎ） 、チタン（Ｔｉ）、７ン
チ七ン（Ｓｂ） 、 マンガン（Ｍｎ） 、Ｉｌｌ鉛（
Ｚｎ） 、ナトリウム（Ｎａ）、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
いる化合物か例示できる。これらは−鴇あるいは二株以
上を併用してσいることができる。触媒の使用黛はフル
ヤレンジ７ミンｅこ対し−（０，００５〜５モル％、好
ましくは０．Ｕ１〜３モル％程度である。As catalysts, tin (Sn), titanium (Ti), 7-inch (Sb), manganese (Mn), Ill lead (
Examples include compounds used as transesterification catalysts such as Zn), sodium (Na), potassium (K) and their compounds. These can be used together or in combination of two or more. The amount of catalyst used is about 0.005 to 5 mol %, preferably about 0.01 to 3 mol %, based on the total amount of diamine.
本発明の方法によれは、イミドジヵルホン酸アリールエ
ステルを極めて谷わかつ安価に４％ にとができる。得
られたアリールエステルは純度が幼く、特に署肯製する
ことなく、Ｉ−＆原料として使用することも可能である
。According to the method of the present invention, imidodicarphonic acid aryl ester can be reduced to 4% in a very low cost and at low cost. The obtained aryl ester has a low purity and can be used as an I-& raw material without any special approval.
以Ｆ％実施例？：４げて不発明の祝＃４をするが、これ
らは本発明な例示するだめのものであって、これに限定
されるものではない。また、実施例中１部」は「ＩＬ童
金部を意味する。またジアリールエステルの−ｃｏｏＨ
価は反応生成物をよく水洗いおよびメタノール洗浄し、
過剰の芳香族七ノオ千シ化合智を除去したものについて
Ａ、Ｃｏｎ１ｘの方法（Ｍａｅｒｏｍｏｌ 、 Ｃｈｅ
ｍ、２６ ２２６（１９５８）参照〕に準じて測定した
。Is this an example of F%? I would like to express my congratulations on non-invention #4, but these are merely examples of the present invention and are not intended to be limiting. In addition, "1 part" in Examples means "IL dokin part. Also, -cooH of diaryl ester
To determine the value, thoroughly wash the reaction product with water and methanol.
A, Con1x method (Maeromol, Che
m, 26 226 (1958)].
実施例１〜５
ヘキサメチレンジアミン１１６！Ｂ、）リメリット醒無
水物３８４部、所定にの７エノールおよび触媒を攪拌装
置および留出系を備えたＪ圧反応器に入れ、１４１Ｊ〜
１８０Ｃで３時間冨圧下Ｕ嵩気流中反応し、生成する本
釣３５部を留去させた。次いで反応糸を３ ｋ＆／ｃＩ
ｉのＳ１累加比とし、＠ｌに示した反応条件で反応させ
、生成する水？：ｗ去させた。この加圧反応時、圧力は
３ ｋｇ／ｄから１に９／−まで途去に低下させた。Examples 1-5 Hexamethylene diamine 116! B.) Put 384 parts of Limerit awakened anhydride, the specified 7 enol and catalyst into a J-pressure reactor equipped with a stirring device and a distillation system, and add 141 J~
The reaction was carried out at 180C for 3 hours under a high pressure in a bulk air flow, and 35 parts of the resulting honsuri were distilled off. Then the reaction thread was 3 k&/cI
The water produced by reacting under the reaction conditions shown in @l with the S1 cumulative ratio of i? :w I made him leave. During this pressurized reaction, the pressure was gradually lowered from 3 kg/d to 1 to 9/-.
反応終了後、得られた反応物を水洗し、夾にメタノール
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１７４〜１８３℃であり、また赤外線吸収スペクトル
により１７ ］ Ｕ ｃｙｐｒ−’。After the reaction was completed, the obtained reaction product was washed with water and then with methanol. All of the obtained diaryl esters had a melting point of 174 to 183°C, and their infrared absorption spectra revealed that they were 17] U cypr-'.
１７７０譚−１に特徴的ピークがみもれ、Ｎ、Ｎ’ −
ヘキサメチレンビストリメリットイミドジカルボン故ジ
フェニルｔステルであることを確認した。衣ＩＫ収装置
よび純度を示した本発明の方法により、目的とする生成
物が誦収単かつ高純度で得られりことがわかる。A characteristic peak is observed in 1770tan-1, N, N'-
It was confirmed that it was hexamethylene bistrimeritimidodicarbonate late diphenyl t-ster. It can be seen that the desired product can be obtained easily and with high purity by the method of the present invention, which shows the IK collection device and the purity.
実施例６
へ千すメチレンジアミン １１６ｇ、トリメリント酸無
水物３８４部、ｐ−クレゾール５４Ｌ１部およびｉ”
ｉ （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入れ、に比下室木気流中、１４
０℃より１８０℃まで保々に反応温度を上げ生成する水
を留去させた。次いで反応水を３ Ｋ９／ｃｄの窒素加
圧とし、反応温度を２６０′Ｃに上げ４時間反応させた
。反応の進打に従い、系の圧力な約１ ｉｗ／ａｄまで
徐々に低下させ、また生成する水を留去させた。反応終
了後、反応物を冷却し水およびメタノールで洗浄して−
ＣｏＯＨ価７５当ＩＩ＃／１０’ Ｊｏ）Ｎ、Ｎ’−ヘ
’Ｐすｌチレンビストリメリットイミドジクレジルエス
テル５７８倍を得た。向、赤外線吸収スペクトルにより
］ ７１０ｃｔｒ−’ 、 １７７０ｃｍ−’ ｉＣ
％徴的ビークがみられ、生成物す確認した。Example 6 116 g of hesylmethylenediamine, 384 parts of trimeltic anhydride, 1 part of p-cresol 54L, and i''
i (OB u ) 40, 1 part was placed in a pressurized reactor equipped with a stirring device and a distillation system, and 14
The reaction temperature was steadily raised from 0°C to 180°C to distill off the produced water. Next, the reaction water was pressurized with nitrogen at 3 K9/cd, the reaction temperature was raised to 260'C, and the reaction was carried out for 4 hours. As the reaction progressed, the system pressure was gradually lowered to about 1 iw/ad, and the water produced was distilled off. After the reaction is complete, the reaction product is cooled and washed with water and methanol.
A CoOH value of 75 equivalent II#/10' Jo) N,N'-he'Psl tyrene bistrimeritimid dicresyl ester 578 times was obtained. direction, according to infrared absorption spectrum] 710 ctr-', 1770 cm-' iC
A characteristic peak was observed, confirming the presence of the product.
実施例７
ヘキサメチンンジ７ミン １１６ｆ５．）リメリ７トｔ
ｌ１ｍ水物３８４部、フェノール６５０ ｉｌ。Example 7 Hexamethindi7mine 116f5. ) Limeri 7t
l1m water 384 parts, phenol 650 il.
’ｒ ＋ （ＯＢｕ ）４ ＬＪ 、１ ｍ ｉｏよび
ｚ ｆ ルーヘンセンＢ ＬＪ Ｕ 部を攪拌装置およ
び留出系′／を備えた反応器に仕込んだ。尚、この反応
装置は留出するエチルベンセンおよび水を分液してエチ
ルベンゼンだけを反応器ヘオーバーフー−できる循環系
な備えている。反応はまず、常圧下輩業気流中、１５０
℃に３Ｑ間加熱し、生成する水を留去させた。'r + (OBu)4 LJ , 1 m io and z f Luhensen B LJ U parts were charged into a reactor equipped with a stirring device and a distillation system '/. This reactor is equipped with a circulation system that separates the distilled ethylbenzene and water and allows only ethylbenzene to be overflowed to the reactor. The reaction first begins with 150
C. for 3Q to distill off the water produced.
次いで反応系を４ ｋ＆／ｃＩｄの′Ｉｉ１素加圧状感
とし、反応温度を２６０℃に上げて５時間反応した。Then, the reaction system was brought to a pressure of 4 k&/cId, and the reaction temperature was raised to 260°C, and the reaction was carried out for 5 hours.
この際、圧力を約２に９７６ｄまで徐々に低下させた。At this time, the pressure was gradually lowered to about 2.976 d.
反応終了後、反応物をメタノール次いで水でＶＣ浄し生
成物５７８ｍを得た。−ＣＯＯＨ価は２３２当重／ｌ（
Ｊ＠ｇであり、赤外線吸収スペクトルにより１７ ］
Ｏｃｍ−’ 、 １７７０ｃｍ−’に％徴的ピークが
みられ、裕遺を確認した。After the reaction was completed, the reaction product was VC-purified with methanol and then water to obtain 578m of product. -COOH value is 232 equivalent weight/l (
J@g, and according to the infrared absorption spectrum 17 ]
A characteristic peak was observed at 1,770 cm-' and 1,770 cm-', confirming Yuki.
％針山願人 帝人株式会社% Hariyama Ganjin Teijin Ltd.
Claims (1)
）においてｎは２〜１２の整数を表わす。］ で示されるアルキレンジアミンと、該アルキレンジアミ
ンに対し、１．９〜２．１倍モルのトリメリット酸無水
物および２倍モル以上の芳香族モノオキシ化合物とを、
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) H_2N(CH_2)nNH_2...(I) [Formula (I
), n represents an integer from 2 to 12. ] An alkylene diamine represented by the following, and 1.9 to 2.1 times the mole of trimellitic acid anhydride and 2 times the mole or more of an aromatic monooxy compound relative to the alkylene diamine,
A method for producing an imidodicarboxylic acid aryl ester, which is characterized by carrying out a heating reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61030945A JPS62190164A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61030945A JPS62190164A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62190164A true JPS62190164A (en) | 1987-08-20 |
Family
ID=12317814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61030945A Pending JPS62190164A (en) | 1986-02-17 | 1986-02-17 | Production of aryl imidodicarboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62190164A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01317444A (en) * | 1988-06-17 | 1989-12-22 | Nippon Zeon Co Ltd | Novel deodorant composition |
| WO2019225166A1 (en) * | 2018-05-24 | 2019-11-28 | 積水化学工業株式会社 | Active ester compound, curable resin composition, adhesive, adhesive film, circuit substrate, interlayer insulation material, and multilayer printed wiring board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414498A (en) * | 1977-07-05 | 1979-02-02 | Mitsubishi Electric Corp | Heat resistant epoxy resin composition |
| JPS55139358A (en) * | 1979-04-13 | 1980-10-31 | Hitachi Ltd | Bisimide-ether compound and its preparation |
-
1986
- 1986-02-17 JP JP61030945A patent/JPS62190164A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414498A (en) * | 1977-07-05 | 1979-02-02 | Mitsubishi Electric Corp | Heat resistant epoxy resin composition |
| JPS55139358A (en) * | 1979-04-13 | 1980-10-31 | Hitachi Ltd | Bisimide-ether compound and its preparation |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01317444A (en) * | 1988-06-17 | 1989-12-22 | Nippon Zeon Co Ltd | Novel deodorant composition |
| WO2019225166A1 (en) * | 2018-05-24 | 2019-11-28 | 積水化学工業株式会社 | Active ester compound, curable resin composition, adhesive, adhesive film, circuit substrate, interlayer insulation material, and multilayer printed wiring board |
| CN111971267A (en) * | 2018-05-24 | 2020-11-20 | 积水化学工业株式会社 | Active ester compound, curable resin composition, adhesive film, circuit board, interlayer insulating material, and multilayer printed wiring board |
| JPWO2019225166A1 (en) * | 2018-05-24 | 2021-04-22 | 積水化学工業株式会社 | Active ester compounds, curable resin compositions, adhesives, adhesive films, circuit boards, interlayer insulating materials, and multilayer printed wiring boards |
| CN111971267B (en) * | 2018-05-24 | 2023-09-19 | 积水化学工业株式会社 | Active ester compound, curable resin composition, adhesive film, circuit board, interlayer insulating material, and multilayer printed wiring board |
| TWI828675B (en) * | 2018-05-24 | 2024-01-11 | 日商積水化學工業股份有限公司 | Active ester compounds, curable resin compositions, adhesives, adhesive films, circuit boards, interlayer insulating materials, and multilayer printed wiring boards |
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