JPH03215480A - Production of 1,2,3,6-tetrahydrophthalic anhydride - Google Patents
Production of 1,2,3,6-tetrahydrophthalic anhydrideInfo
- Publication number
- JPH03215480A JPH03215480A JP574890A JP574890A JPH03215480A JP H03215480 A JPH03215480 A JP H03215480A JP 574890 A JP574890 A JP 574890A JP 574890 A JP574890 A JP 574890A JP H03215480 A JPH03215480 A JP H03215480A
- Authority
- JP
- Japan
- Prior art keywords
- butadiene
- reaction
- butene
- fraction
- crude
- 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
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 38
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 241000219495 Betulaceae Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- -1 hydroquinone Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- PMYYGAMMFAQAGL-UHFFFAOYSA-N 4-tert-butylcyclohexa-1,5-diene-1,4-diol Chemical compound CC(C)(C)C1(O)CC=C(O)C=C1 PMYYGAMMFAQAGL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリエステル樹脂の原料やエボキシ樹脂硬化
剤として有用な１，２，３．６−テトラヒド口無水フタ
ル酸《以下、ｒ Ｔ Ｈ Ｐ Ａ Ｊと称する）の製造
方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention provides 1,2,3,6-tetrahydrophthalic anhydride (r T H P A.J.).
（従来技術）
Ｔ Ｈ Ｐ Ａが無水マレイン酸と１，３−ブタジエン
とのディールス・アルダー反応により得られることは既
に良く知られている．原料の一方である１．３−ブタジ
エンは、主に石油化学プラントでのＣ４留分（以下、［
粗製Ｃ４留分）」と称する）から抽出等の操作で得られ
、精留等で高純度化した後，種々の用途に使用されてい
る．
従来においては、ＴＨＰＡは無水マレイン酸と高純度の
１，３−ブタジエンを用い、必要な場合には適当な重合
禁止剤及び／又はベンゼン、トルエン、キシレン等の溶
媒を用いて、ディ・−ルス・アルダー反応により製造さ
れていた．
即ち、粗製Ｃ４留分中に存在する１．３−ブタジエン以
外の不純物を除去した高純度の１．３−ブタジエンを用
いて該反応をすることが必要とされていた。これはＣ４
留分中に含まれるブテン１、インブチレン、１・ランス
ーブテン−２（以下［ｔ−ブテン−２」と称ず）、シス
ーブテン−２〈以下、「Ｃ−ブテン−２」と称す）．
１． ２ブタジエン、アセチレン化合物が、ホモボリマ
ーもしくはコボリマーを副成し、又は無水マレイン酸と
の重合によりコボリマーを副成し、その結果生成したＴ
Ｈ Ｉ） Ａの純度を低下せしめる。これらの重合物
を含むＴＨＰΔをポリエステル原初として、あるいはエ
ボキシ樹脂硬化剤として用いた場合、不溶成分として析
出したり、粘度」一昇をきたすなど、製品設計上、様々
な欠点や特性低下の原因となっていた。(Prior Art) It is already well known that THPA can be obtained by a Diels-Alder reaction between maleic anhydride and 1,3-butadiene. One of the raw materials, 1,3-butadiene, is mainly produced as a C4 fraction (hereinafter referred to as [
It is obtained from the crude C4 fraction (referred to as "crude C4 fraction") through operations such as extraction, and is used for various purposes after being highly purified through rectification. Conventionally, THPA is produced using maleic anhydride and high-purity 1,3-butadiene, and if necessary, a suitable polymerization inhibitor and/or a solvent such as benzene, toluene, or xylene.・Produced by Alder reaction. That is, it has been necessary to carry out the reaction using highly purified 1,3-butadiene from which impurities other than 1,3-butadiene present in the crude C4 fraction have been removed. This is C4
Butene-1, inbutylene, 1-lan-butene-2 (hereinafter not referred to as [t-butene-2]), cis-butene-2 (hereinafter referred to as "C-butene-2") contained in the fraction.
1. 2 Butadiene and acetylene compounds sub-produce homobolymers or cobolymers, or copolymer by-produces by polymerization with maleic anhydride, resulting in T
H I) Decrease the purity of A. When THPΔ containing these polymers is used as a polyester base material or as an epoxy resin curing agent, it may precipitate as an insoluble component or cause a sudden increase in viscosity, resulting in various defects and property deterioration in product design. It had become.
該重合物は通常ゲル状を呈しており、その生成は、一般
的には温度因子が大きく関与している。The polymer is usually in the form of a gel, and its formation is generally largely influenced by temperature factors.
重合物の生成を抑制するためには反応温度はより低温側
の方が好ましいとされているが、無水マレイ〉′酸自体
の融点が約５２℃、生成する］’ Ｈ Ｐ Ａの融点が
１０２℃のため、反応温度には自ずと制限があった。In order to suppress the formation of polymers, it is said that a lower reaction temperature is preferable; ℃, there was naturally a limit to the reaction temperature.
従って註重合物の生成を避けるための手段としては、高
純度の１．３−ブタジエン、具体的には純度９８重量％
以上の１．３−＝ブタジエンを用いて、ディールス・ア
ルダー反応を行っているのが実情であった。しかし、高
純度１．３−ブタジエンを用いることは、租製Ｃ４留分
から抽出・精留等の操作を必要し、コスｔ・高になるた
め、粗製Ｃ４留分と無水マレイン酸を直接ディールス・
アルダー反応して、ＴＨＰＡを得る方法の開発が望まれ
ていた。Therefore, as a means to avoid the formation of polymerized products, use high-purity 1,3-butadiene, specifically, 98% pure
The actual situation was that the Diels-Alder reaction was carried out using the above 1.3-=butadiene. However, using high-purity 1,3-butadiene requires operations such as extraction and rectification from the crude C4 fraction, which increases costs.
It has been desired to develop a method for obtaining THPA through Alder reaction.
（問題を解決するための手段》
本発明者らは、ＴＨＰＡを工業的に製造するに際し、粗
製Ｃ４留分を用いても重合物の荏成が認められず、従来
の品質と同等以上の目的物を得る容易な方法について鋭
意検討した結果、特定組成の粗製Ｃ４留分を用いれば、
重合物を生成することなく、高純度の１’ Ｈ Ｐ Ａ
を得ることを見い出し、この知見に基づいて本発明を完
成するに至った。(Means for Solving the Problem) The present inventors have found that when producing THPA industrially, even when using a crude C4 fraction, no formation of polymer products was observed, and the objective of As a result of intensive studies on easy methods to obtain the product, we found that if a crude C4 fraction with a specific composition is used,
High purity 1'HPA without producing polymers
Based on this knowledge, the present invention was completed.
即ち、本発明は抽出・猜留等により精製された１．３−
ブタジエンを用いることなく、１，３ブタジエンが５重
菫％以上、かつインブチレンとブテン−１の合計含量が
２５重景％以上である粗製Ｃ４留分を原料として、無水
マレイン酸と反応させれば、重合物を生成することなく
、目的とする高純度のＴ’ Ｈ Ｐ Ａを製造し得るこ
とを特徴とする。That is, the present invention provides 1.3- purified by extraction, distillation, etc.
A crude C4 fraction containing 5% or more of 1,3-butadiene and a total content of imbutylene and butene-1 of 25% or more is reacted with maleic anhydride without using butadiene. For example, the method is characterized in that the desired high-purity T'HPA can be produced without producing a polymer.
１．３−ブタジエンが５重量％以上、かつインブナレン
とブテン−１の合計含社が２５重１％以上である粗製Ｃ
４留分を用いれば、重合物の生成か抑制される理由につ
いては明確ではないが、例えはインブチレンは分岐のメ
チル基を存ずるため、池のＣ４留分と比較して重合しに
くいものと推定される。1. Crude C containing 5% by weight or more of 3-butadiene and a total content of inbunalene and butene-1 of 25% by weight or more
It is not clear why the formation of polymer products is suppressed when using the C4 fraction, but for example, imbutylene has a branched methyl group, so it is difficult to polymerize compared to the C4 fraction from the pond. Presumed.
反応に際しては、組成中の１．３−ブタジエンの純度が
高いほど好ましいが、高純度であると精製のためコスト
高になり、また逆に５１ｆＬ量％以下の低純度になると
、ディールス・アルダー反応の結果生成するＴＨＰＡの
製造量が減少することになり好ましくない。また、イン
ブチレンとブテン１の合計含量が２５重量％以下になる
と、ｌ３−ブタジエン以外の重合性の他のＣ４留分が増
加し、重合物が生成しやすくなる。During the reaction, the higher the purity of 1,3-butadiene in the composition, the better; however, if the purity is high, the cost for purification will be high, and conversely, if the purity is lower than 51 fL amount%, the Diels-Alder reaction will occur. As a result, the amount of THPA produced decreases, which is undesirable. Furthermore, when the total content of inbutylene and butene 1 is less than 25% by weight, the amount of polymerizable C4 fractions other than 13-butadiene increases, making it easier to form polymers.
本発明に係るＴ ｔｌ Ｐ Ａ製造のための具体的な反
応条件を以下に掲げる。即ち、１．３−ブタジエンを５
重菫％以上かつ、インブチレンとブテン−１の合計含量
が２５重量％以上であるｆｌｌ製Ｃ４留分を無水マレイ
ン酸に対し、当量以」ユ、好ましくは１〜１．５倍当量
仕込み、反応温度５０〜１５０℃、好ましくは１００〜
１４０℃で、０．３時間〜２０時間、好ましくは０．５
時問〜１０時間反応せしめる。Specific reaction conditions for producing T tl PA according to the present invention are listed below. That is, 1,3-butadiene is
% or more of violet % and the total content of inbutylene and butene-1 is 25% by weight or more, an equivalent amount or more, preferably 1 to 1.5 times equivalent amount, of maleic anhydride is charged, Reaction temperature: 50-150°C, preferably 100-150°C
At 140°C, 0.3 hours to 20 hours, preferably 0.5 hours
Allow to react for up to 10 hours.
必要に応じて重合禁止剤を用いることで、重合物の生成
をより抑制することができ、本発明の効果をさらに向上
せしめることができる．重合禁止剤は重合物の生成を有
効に抑制できるものであればよく，その添加量は通常無
水マレイン酸に対し０〜３重量％、好ましくはＯ〜１重
菫％の範囲で、単独又は２種以上を混合して使用される
。重合禁止剤の具体例としては、以下の（Ａ）〜（Ｄ）
が例示される。By using a polymerization inhibitor as necessary, the formation of polymers can be further suppressed, and the effects of the present invention can be further improved. Any polymerization inhibitor may be used as long as it can effectively inhibit the formation of polymers, and the amount added is usually 0 to 3% by weight, preferably 0 to 1% by weight, based on maleic anhydride, and may be used alone or in the range of 2% by weight. It is used by mixing more than one species. Specific examples of polymerization inhibitors include the following (A) to (D).
is exemplified.
（Ａ）２．６−ジターシャリーブチル−４−メチルフェ
ノール５２，６−ジシクロベンチル−４メチルフェノー
ル、２．２−メチレンビス（４エチル−６−ターシＡ・
リーブチルフェノール）、４，４−メチレンビス（２，
６−ジターシャリープチルフェノール）、４．４−チオ
ビス（３−メチル−６−ターシャリーブチルフェノール
》等のフェノール類。(A) 2,6-ditertiarybutyl-4-methylphenol 52,6-dicyclobentyl-4methylphenol, 2,2-methylenebis(4ethyl-6-tertiaryA.
butylphenol), 4,4-methylenebis(2,
Phenols such as 6-ditertiarybutylphenol) and 4,4-thiobis(3-methyl-6-tertiarybutylphenol).
（Ｉ３）フエノナアジン、ペンゾフエノチアジン、アセ
ｌ・アミドフェノナアジン等のフエノナアジン類。(I3) Phenonaazines such as phenonaazine, penzophenothiazine, and aceramidephenonaazine.
（Ｃ）ヒドロキノン、ペンジルヒドロキノン、ジターシ
ャリープチルヒドロキノン，カテコール、ｐ一ターシャ
リーブチル力テコール、ビロガロール等のキノン類。(C) Quinones such as hydroquinone, penzylhydroquinone, ditertiarybutylhydroquinone, catechol, p-tertiarybutylhydroquinone, birogallol, and the like.
（Ｄ）Ｎ−ニトロソジフエニルアミン、Ｎ一二トロンジ
メチルアミン等のＮ−二１・ロソアミン類。(D) N-21.rosoamines such as N-nitrosodiphenylamine and N1-dithronedimethylamine.
また、”ｒ” Ｈ Ｐ Ａ又は無水マレイン酸と非反応
性の溶剤を用いることで、反応系が希釈され重合物の生
成を抑制することができる．
ＴＨＰＡ又は無水マレイン酸と非反応性の溶剤とは、具
体的には以下の（Ｎ〜（ＩＶ）が例示され、無水マレイ
ン酸に対し、０〜１００重１％の範囲で、単独又は２種
以上を混合して使用される。Furthermore, by using a solvent that is non-reactive with "r" HPA or maleic anhydride, the reaction system is diluted and the formation of a polymer can be suppressed. Examples of solvents that are non-reactive with THPA or maleic anhydride include the following (N to (IV)), which may be used alone or in combination in a range of 0 to 100% by weight based on maleic anhydride. A mixture of the above is used.
（１）炭素数６〜１６の脂肪族炭化水素、脂環式炭化水
素及び芳香族炭化水素等の炭化水素。(1) Hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons having 6 to 16 carbon atoms.
具体的にはヘキサン、ヘプタン、オクタン、デカン、ド
デカン，シクロヘキサン、デカリン、テトラリン、トル
エン、キシレン、エチルベンゼン、ブチルベンゼン及び
石油精製の際に得られる混合炭化水素．
（Ｉｔ）鎖状及び環状エーテル類．
具体的にはジエチルエーテル、ジイソグ口ビルエーテル
、ジブチルエーテル、テトラヒド口フラン、ジオキサン
等。Specifically, hexane, heptane, octane, decane, dodecane, cyclohexane, decalin, tetralin, toluene, xylene, ethylbenzene, butylbenzene, and mixed hydrocarbons obtained during petroleum refining. (It) Chain and cyclic ethers. Specifically, diethyl ether, diisobutyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc.
（ＩＩ１＞鎖状及び環状ゲトン類。(II1> Chain and cyclic getons.
具体的にはアセｌ・ン、メチルエチルケトン、ジエチル
ケトン、メチルイソブチルケトン、シクロペンタノン、
シクロヘキサノン等。Specifically, acel, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone,
Cyclohexanone etc.
（ＴＶ）その他の非反応性有機溶剤としてアセトニ１・
リル等の二ｌ・リル類、酢酸エチル、酢酸１口ピル、酢
酸ブチル等のエステル類、エチルセロゾルブ、ブナルセ
ロゾルブ等のポリエーテル類。(TV) As other non-reactive organic solvents, acetoni
Diliters such as ril, esters such as ethyl acetate, one-mouth pill acetate, butyl acetate, and polyethers such as ethyl cellosolve and bunal cellosolve.
これらの非反応性有機溶剤の添加量は、特に限定される
ものではないが、添加量が多いと目的物であるＴ ｌ−
Ｉ Ｐ Ａの製造菫が減少するため、Ｔ Ｈ ＰＡに対
し、Ｏ〜５００重藍％の範囲内、好ましくは０〜２００
重１％で用いられる。The amount of these non-reactive organic solvents added is not particularly limited, but if the amount added is large, the target product T l-
In order to reduce the production violet of IPA, it is within the range of 0 to 500 violet%, preferably 0 to 200% of THPA.
Used at 1% by weight.
１１１製Ｃ４留分は溶融した無水マレイン酸中へ液状で
仕込んで良く、また、ガス状で仕込んでもよい。必要に
応じて適宜遷択できる。The C4 fraction manufactured by No. 111 may be charged into the molten maleic anhydride in liquid form or in gas form. You can change the selection as needed.
イソブチレン、ブテン−１などの非重合性成分並びに未
反応１．３−ブタジエンは、反応と共に連続的に回収除
去するのが好ましいが、反応終了？麦にまとめて、常圧
又は減圧下で反応系より、全１を回収する工程をとって
も何等支障はない。It is preferable that non-polymerizable components such as isobutylene and butene-1 and unreacted 1,3-butadiene be continuously collected and removed along with the reaction. There is no problem in taking the step of collecting all 1 in wheat and collecting it from the reaction system under normal pressure or reduced pressure.
また、係る回分式の方法に限定されることなく、連続的
に製造することができる。Further, the present invention is not limited to such a batch method, and can be produced continuously.
（実施例》 以下に、実施例をもって本発明を説明する。(Example" The present invention will be explained below with reference to Examples.
実施例ｌ
撹拌器、温度計、冷却器の付いた２５０ｍｌの四ツロフ
ラスコに所定量の原料を仕込み、表１に示す反応条件に
従って、ディールス・アルダー反応を行った．反応終了
後、残存するＣ４留分を減圧で除去し、Ｔ １１ Ｐ
Ａを得た。Example 1 A predetermined amount of raw materials was charged into a 250 ml four-way flask equipped with a stirrer, a thermometer, and a condenser, and a Diels-Alder reaction was carried out according to the reaction conditions shown in Table 1. After the reaction, the remaining C4 fraction was removed under reduced pressure and T 11 P
I got an A.
Ｔ Ｈ Ｐ Ａの外観が透明で濁りがないときは、重合
物の含量は０．１ｗｔ％以下であることが判明している
ため、得られた′ｒＨ Ｐ Ａのベンゼンｌ＼の溶解し
たときの外観を目視することにより、生成した重合物の
量を判定した。得られたＴ Ｈ Ｐ Ａの収率及び外観
その結果を表１に示す。When the appearance of T H P A is transparent and there is no turbidity, the content of the polymer is known to be less than 0.1 wt%, so when the benzene l\ of the obtained 'rH P A is dissolved. The amount of produced polymer was determined by visually observing the appearance. The yield and appearance of the obtained T H P A and the results are shown in Table 1.
実施例２〜８
原料組成、反応条件をかえた以外は、実施例１と同様に
ディールス・アルダー反応をおこなった。Examples 2 to 8 Diels-Alder reactions were carried out in the same manner as in Example 1, except that the raw material composition and reaction conditions were changed.
その結果を表１に示す．
比較例１．
１．３−ブタジエン及び／・′又はインブチレンとブテ
ン〜１の合計含量をかえた以外は、実施例６と同様にデ
ィールス・アルダー反応を行い、Ｔ ＨＰＡを得た。そ
の結果を表１に示す。The results are shown in Table 1. Comparative example 1. THPA was obtained by carrying out the Diels-Alder reaction in the same manner as in Example 6, except that the total content of 1,3-butadiene and/·' or inbutylene and butene ~1 was changed. The results are shown in Table 1.
比較例２．
１．３−ブタジエン及び／又はインブチレンとブテン−
１の合計含量をかえた以外は、実施例６と同様にディー
ルス・アルダー反応を行い、ＴＨＰＡを得た。その結果
を表１に示す。Comparative example 2. 1.3-Butadiene and/or imbutylene and butene-
Diels-Alder reaction was carried out in the same manner as in Example 6 except that the total content of 1 was changed to obtain THPA. The results are shown in Table 1.
比較例３．
１．３−ブタジエン及び／又はインブチレンとプテンー
ｌの合計含量をかえた以外は、実施（ｆ４４と同様にデ
ィールス・アルダー反応を行い、］゛■ＩＰＡを得た。Comparative example 3. 1. Diels-Alder reaction was carried out in the same manner as in f44, except that the total content of 3-butadiene and/or imbutylene and butene-1 was changed, and IPA was obtained.
その結果を表１に示す。The results are shown in Table 1.
（発明の効果）(Effect of the invention)
Claims (2)
ス・アルダー反応せしめて１，２，３，６−テトラヒド
ロ無水フタル酸を製造するに際し、溶媒の存在下又は非
存在下、１，３−ブタジエンが５重量％以上かつ、イソ
ブチレンとブテン−１の合計含量が２５重量％以上であ
る粗製Ｃ４留分を用いることを特徴とする方法。(1) When producing 1,2,3,6-tetrahydrophthalic anhydride by subjecting maleic anhydride and 1,3-butadiene to a Diels-Alder reaction, 1,3-butadiene is produced in the presence or absence of a solvent. is 5% by weight or more and the total content of isobutylene and butene-1 is 25% by weight or more.
める際に、重合禁止剤を添加することを特徴とする方法
。(2) A method characterized in that a polymerization inhibitor is added when causing the Diels-Alder reaction according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP574890A JPH03215480A (en) | 1990-01-12 | 1990-01-12 | Production of 1,2,3,6-tetrahydrophthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP574890A JPH03215480A (en) | 1990-01-12 | 1990-01-12 | Production of 1,2,3,6-tetrahydrophthalic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03215480A true JPH03215480A (en) | 1991-09-20 |
Family
ID=11619731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP574890A Pending JPH03215480A (en) | 1990-01-12 | 1990-01-12 | Production of 1,2,3,6-tetrahydrophthalic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03215480A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400530C (en) * | 2004-02-24 | 2008-07-09 | 河南省科学院化学研究所 | New method for producing liquid tetrahydrophthalic anhydride |
| JPWO2015125734A1 (en) * | 2014-02-24 | 2017-03-30 | マナック株式会社 | Halohexahydrophthalic acid derivatives |
-
1990
- 1990-01-12 JP JP574890A patent/JPH03215480A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400530C (en) * | 2004-02-24 | 2008-07-09 | 河南省科学院化学研究所 | New method for producing liquid tetrahydrophthalic anhydride |
| JPWO2015125734A1 (en) * | 2014-02-24 | 2017-03-30 | マナック株式会社 | Halohexahydrophthalic acid derivatives |
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