JPH01157972A - Production of alkenylsuccinic acid anhydride - Google Patents
Production of alkenylsuccinic acid anhydrideInfo
- Publication number
- JPH01157972A JPH01157972A JP31585987A JP31585987A JPH01157972A JP H01157972 A JPH01157972 A JP H01157972A JP 31585987 A JP31585987 A JP 31585987A JP 31585987 A JP31585987 A JP 31585987A JP H01157972 A JPH01157972 A JP H01157972A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- maleic anhydride
- olefin
- temperature
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000008065 acid anhydrides Chemical class 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007259 addition reaction Methods 0.000 claims abstract description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000002421 anti-septic effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- -1 hydroxy aromatic compound Chemical class 0.000 description 5
- OOKDYUQHMDBHMB-UHFFFAOYSA-N 3,6-dichloro-2-methoxybenzoic acid;2-(2,4-dichlorophenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CNC.COC1=C(Cl)C=CC(Cl)=C1C(O)=O.OC(=O)COC1=CC=C(Cl)C=C1Cl OOKDYUQHMDBHMB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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〕 本発明はアルケニルコハク酸無水物の製造法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing alkenylsuccinic anhydrides.
詳しくは本発明は、オレフィンと無水マレイン酸とを熱
付加反応させる際、反応を特定の条件下で行なうことに
よシ、タール状副生物の生成を抑制して色相の良好なア
ルケニルコハク酸無水物を製造する方法に関する。Specifically, the present invention provides alkenylsuccinic anhydride with a good hue by suppressing the formation of tar-like by-products by carrying out a thermal addition reaction between an olefin and maleic anhydride under specific conditions. It relates to a method of manufacturing things.
アルケニルコハク酸無水物は、潤滑油添加剤、エポギシ
樹脂硬化剤、樹脂改質剤、可塑剤、分散剤、防錆剤等に
広い用−途をもっておシ、最近注目されている化合物で
ある。Alkenylsuccinic anhydride is a compound that has been attracting attention recently because it has a wide range of uses such as lubricating oil additives, epoxy resin curing agents, resin modifiers, plasticizers, dispersants, and rust preventives.
一般にアルケニルコハク酸無水物はオレフィンと無水マ
レイン酸とｆ／ｇＯ−２５０℃の加熱下に熱付加反応さ
せることてよシ製造されるが、この際、タール状物質や
高分子量重合体等の副生物が生成すると共に著しい着色
が生じ、製品の品質を劣化させ、製品の用途に制限を加
えることになっている。Generally, alkenylsuccinic anhydride is produced by carrying out a thermal addition reaction with an olefin and maleic anhydride under heating at f/gO -250°C. Significant coloring occurs as organisms form, degrading the quality of the product and limiting its uses.
上記した副生物の生成を抑制する種々の方法が提案され
ている。例えば、ヒドロキシ芳香族化合物あるいはアミ
ン芳香族化合物を添加する方法（米国特許筒ｓ、ｙｌｚ
ｉｉｉ号）、立体障害性フェノール化合物を添加する方
法（米国特許第こりり＆、 ７７１１号）、亜リン酸エ
ステルを添加する方法（特公昭！ｒＯ−３．７７２０号
）、リン含有有機金属イオン封鎖剤もしくは正リン酸を
添加する方法（特公昭ｑデーコロ２２７号）、有機塩素
化合物を添加する方法（特公昭５２−一３６６５号）、
ハロゲン又はハロゲン化合物を添加する方法（特公昭！
；２−３９Ａ７’１号）、有機亜リン酸エステルを添加
する方法（特開昭５６−７１２３１２号）等が報告され
ている。Various methods have been proposed to suppress the production of the above-mentioned byproducts. For example, a method of adding a hydroxy aromatic compound or an amine aromatic compound (U.S. Pat.
iii), a method of adding a sterically hindered phenol compound (US Patent No. 7711), a method of adding a phosphite ester (Special Publication Sho!rO-3.7720), a method of adding a phosphorus-containing organometallic ion A method of adding a sequestering agent or orthophosphoric acid (Special Publication No. 227 of the Japanese Patent Publication No. Shoq Decoro), a method of adding an organic chlorine compound (Special Publication No. 13665 of 1987),
Method of adding halogen or halogen compound (Tokukosho!
; 2-39A7'1), a method of adding an organic phosphite (Japanese Patent Application Laid-open No. 712312/1983), etc. have been reported.
これらの方法では上記副生物の生成を抑制する効果は認
められるが、その効果は必ずしも充分とは言えない。特
に反応温度が２０θ℃以上の場合には、有機塩素化合物
やハロゲン化合物を添加する方法においては、副生物の
生成を抑制する効果が小さくなシ、シかもハロゲン化合
物の使用は装置の腐蝕の原因となると共に毒性が強く、
作業管理上からも好ましいものとは言えない。また、リ
ン酸、リン酸エステルあるいは亜リン酸エステルはオレ
フィンと無水マレイン酸との反応を行なうような高温条
件下では強酸と同程度の腐食性を示すので、特殊な材質
の装置の使用を必要とする。Although these methods are effective in suppressing the production of the above-mentioned by-products, the effects cannot necessarily be said to be sufficient. Particularly when the reaction temperature is 20θ℃ or higher, methods that add organic chlorine compounds or halogen compounds may have little effect in suppressing by-product formation.The use of halogen compounds may cause corrosion of the equipment. It is also highly toxic,
This cannot be said to be desirable from a work management perspective. In addition, phosphoric acid, phosphate esters, or phosphite esters are as corrosive as strong acids under high-temperature conditions where olefins react with maleic anhydride, so it is necessary to use equipment made of special materials. shall be.
本発明者等は従来技術のかかる状況に鑑み、オレフィン
と無水マレイン酸との熱付加反応時におけるタール状物
質等の副生物の生成を抑制する方法を見出すべく鋭意検
討を重ねた結果、オレフィンと無水マレイン酸とを特定
の反応条件下で熱付加反応させることによシ、上記副生
物の生成を抑制することができ、着色による製品の色相
、品質の問題が改良されることを見出して、本発明に到
達した。In view of the state of the prior art, the present inventors have conducted intensive studies to find a method for suppressing the production of by-products such as tar-like substances during the thermal addition reaction between olefins and maleic anhydride. It has been discovered that by carrying out a thermal addition reaction with maleic anhydride under specific reaction conditions, the production of the above-mentioned by-products can be suppressed, and problems with coloring and quality of products can be improved, We have arrived at the present invention.
即ち本発明の要旨は、オレフィンと無水マレイン酸とを
熱付加反応させてアルケニルコノ・り酸無水物を製造す
る方法において、反応系中の無水マレイン酸濃度を仕込
みオレフィン及び無水マレイン酸の合計モル数に対して
３０モル係以下に維持し、かつ無水マレイン酸の反応率
が少なくとも３０％になるまで２１０℃以下の温度で反
応を行ない、ついで反応温度を少なくともｓ ’Ｃ上昇
させて反応を行なうこと全特徴とするアルケニルコハク
酸無水物の製造法、に存する。That is, the gist of the present invention is to provide a method for producing alkenylcono-phosphoric anhydride by subjecting an olefin to a thermal addition reaction with maleic anhydride. The reaction is carried out at a temperature below 210°C until the reaction rate of maleic anhydride is at least 30%, and then the reaction temperature is increased by at least s'C to carry out the reaction. The invention consists in a method for producing alkenylsuccinic anhydride, which is characterized by:
次に、本発明につき詳細に説明する。Next, the present invention will be explained in detail.
本発明方法における原料のオレフィンはエチレン性不飽
和二重結合を有する化合物であって、その炭素原子数は
通常コ〜ＳＯＯ，好ましくはｔＩ〜３００．さらに好ま
しくはｇ〜１００である。該オレフィンは、単品であっ
ても、異なる炭素原子数を有するものの混合物であって
もよい。例えば炭素原子数７２及び／ｌＩのα−オレフ
ィンの混合物（例えば、三菱化成工業株製”ダイヤレン
／λグ（登録商標））、炭素原子数／６及び７ｇのα
−オレフィンの混合物（同じく“ダイヤレン ／Ａｔ”
）、炭素原子数ＪＯ−２，？のα−オレフィン混合物（
同じく６ダイヤレン ２０ｇ″）、炭素原子数３θ〜６
θのα−オレフィン混合物（同じく１ダイヤレン３０”
）等が好適に用いられる。The olefin as a raw material in the method of the present invention is a compound having an ethylenically unsaturated double bond, and the number of carbon atoms thereof is usually co-SOO, preferably tI-300. More preferably, it is g to 100. The olefin may be a single product or a mixture of olefins having different numbers of carbon atoms. For example, a mixture of α-olefins having 72 carbon atoms and /lI (for example, “Dialen /λg (registered trademark) manufactured by Mitsubishi Chemical Corporation), α-olefins having 6 and 7 g carbon atoms,
-Mixtures of olefins (also “dialene/At”)
), number of carbon atoms JO-2, ? α-olefin mixture (
Similarly, 6-dialene 20g''), number of carbon atoms 3θ~6
α-olefin mixture of θ (also 1 diaryen 30”
) etc. are preferably used.
本発明においては、上記オレフィンと無水マレイン酸と
を熱付加反応させてアルケニルコノ・り酸無水物を製造
する際、まず、反応系中の無水マレイン酸濃度を原料の
仕込みオレフィン及び無水マレイン酸の合計モル数に対
して３０モルチ以下、好ましくは２ｇモルチ以下、さら
に好ましくはλ〜コＳモルチの範囲に維持し、かつ無水
マレイン酸の反応率が少なくとも３０チ、好ましくはｔ
ｔｏ−ｇｏｏ％、さらに好ましくは５０〜７５％になる
まで、反応温度をコ１０′Ｃ以下、好ましくＦｉ／７０
〜．２００℃、さらに好ましくは／り０−１９０℃の範
囲に維持して第一段の反応を行なう。In the present invention, when producing alkenylcono-phosphate anhydride by thermal addition reaction of the above-mentioned olefin and maleic anhydride, first, the maleic anhydride concentration in the reaction system is adjusted to The total number of moles is maintained in the range of 30 moles or less, preferably 2 g moles or less, more preferably λ to coS moles, and the reaction rate of maleic anhydride is at least 30 moles, preferably t
The reaction temperature is kept below 10'C, preferably Fi/70, until the temperature reaches to-goo%, more preferably 50 to 75%.
~． The first stage reaction is carried out while maintaining the temperature at 200°C, more preferably in the range of 0-190°C.
上記第一段反応において、反応系中の無水マレイン酸の
濃度が上記の上限値よシ高いと、上記タール状物質等の
副生物の生成が著しく増加し、また、無水マレイン酸の
反応率が上記の下限値未満で第二段の反応に移行すると
、該第二段の反応において、上記タール状物質等の副生
物が増加し、さらに第一段の反応における反応温度が上
記の上限値よシ高いと、上記タール状物質等の副生物が
著しく増加するので好ましくない。In the first stage reaction above, if the concentration of maleic anhydride in the reaction system is higher than the above upper limit, the production of by-products such as the above-mentioned tar-like substances will increase significantly, and the reaction rate of maleic anhydride will decrease. If the temperature moves to the second stage reaction below the above lower limit, by-products such as the above-mentioned tar-like substances will increase in the second stage reaction, and furthermore, the reaction temperature in the first stage reaction will rise below the above upper limit. If it is too high, by-products such as the above-mentioned tar-like substances will increase significantly, which is not preferable.
上記第一段反応の方式として、好ましくは反応器に予め
オレフィンを所定量仕込んでおき、所定温度下で無水マ
レイン酸を反応系中の無水マレイン酸濃度が上記範囲と
なるように連続的にまたは間欠的に添加して反応させる
方法が採用される。上記反応におけるオレフィン対無水
マレイン酸の仕込みモル比は、通常ｉ ： ｏ、ｓ〜／
：２、好ましくは／ ： ｏ、ｇ〜／：２、さらに好ま
しくは／：／〜／：２の範囲である。また、反応は通常
、無溶媒で行なわれる。さらに、反応は通常、大気圧下
で実施するのが好ましいが、加圧下あるいは減圧下でも
実施することができる。As for the method of the above-mentioned first stage reaction, preferably, a predetermined amount of olefin is charged into a reactor in advance, and maleic anhydride is continuously or A method of intermittently adding and reacting is adopted. The molar ratio of olefin to maleic anhydride in the above reaction is usually i: o, s~/
:2, preferably /:o,g~/:2, more preferably /:/~/:2. Further, the reaction is usually carried out without a solvent. Furthermore, although it is usually preferable to carry out the reaction under atmospheric pressure, it can also be carried out under increased pressure or reduced pressure.
上記第一段の反応液は次いで第二段の反応に供せられ、
反応温度を第一段反応の反応温度に対して左°Ｃ以上高
い温度、好ましくは＆−ＡＯ°Ｃ高い温度、さらに好ま
しくはｌ０〜１１０℃高い温度として反応を行なうこと
によシ、無水マレイン酸の反応率をｇｏ〜１００％まで
高めることができる。The first stage reaction solution is then subjected to a second stage reaction,
Maleic anhydride can be produced by carrying out the reaction at a temperature higher than the reaction temperature of the first stage reaction by at least 1°C, preferably at a temperature of &-AO°C higher, and more preferably at a temperature of 10 to 110°C higher. The acid reaction rate can be increased up to 100%.
なお、未反応の無水マレイン酸及びオレフィンは、必要
に応じて、減圧下に加熱して除去することができる。In addition, unreacted maleic anhydride and olefin can be removed by heating under reduced pressure, if necessary.
かくして得られるアルケニルコハク酸無水物はタール状
副生物の生成が殆どなく、色相も良好なものであシ、そ
の融点は通常−５０−９！；℃の範囲であシ、またｉｏ
ｏ℃における粘度は通常７０〜／ ０００ ｃｐである
。The alkenylsuccinic anhydride thus obtained has almost no formation of tar-like by-products, has a good color, and has a melting point of usually -50-9! ;℃ range, also io
The viscosity at 0° C. is usually between 70 and 1/000 cp.
次に本発明の実施の態様を実施例によシさらに具体的に
説明するが、本発明は、その要旨を超えない限シ、以下
の実施例によって限定されるものではない。Next, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお、以下の実施例における各物性の測定方法は次の通
シである。In addition, the method of measuring each physical property in the following examples is as follows.
融 点：自動融点測定装置（メトラーＦＰ）を用いて
測定した。Melting point: Measured using an automatic melting point measuring device (Mettler FP).
色 調：ＡＳＴＭ−Ｄ−／ｊ弘グに従い、１００℃に
て測定した。Color tone: Measured at 100°C in accordance with ASTM-D-/j hirogu.
針入度： ＡＳＴＭ−Ｄ−／ ３２ ／−乙／Ｔ に従
い、２！；０Ｃにて測定した。Penetration: 2 according to ASTM-D-/32/-Otsu/T! ; Measured at 0C.
ケン化価：ＪＩＳ ＫＯＯ７０に準拠して測定した。Saponification value: Measured according to JIS KOO70.
分子量：ＧＰＣによシ次の条件で測定した。Molecular weight: Measured by GPC under the following conditions.
装 置−東洋曹達工業１Ｌ ３０００＋１Ｉ０００）ＨＸＬ。Equipment - Toyo Soda Kogyo 1L 3000+1I000)HXL.
７、ｇ＋ＩＩ！ＩφＸ ３００？ｍ
溶離液−ＴＨＦ／ｄ／分
ス
検量線−ポリメチレン標準試料
実施例−／
炭素数／６〜ｉｔのα−オレフィン混合物（三菱化成工
業株？製、“ダイヤレン ｉｔ、ｇ”（登録商標） ）
２／、ｑ ｔｃｉ （デハｇモル）及びハイドロキノ
ンθ、０３７ ｋＱを５Ｏ８−３ｔ６製槽型槽型器に仕
込み、窒素ガスで十分置換した。その後、これに温度／
ｒ Ｏ’Ｃにおいて無水マレイン酸ヂ、θｋｇ（ｑ／
、ｇモル）を３時間かけて一定速度で連続的に滴下した
。無水マレイン酸滴下終了直後の反応液中の残存無水マ
レイン酸濃度は仕込みオレフィン及び無水マレイン酸の
合計モル数に対して／９．７モル俤であシ、かつ、無水
マレイン酸反応率はるへサチであった。7.g+II! IφX 300? m Eluent - THF/d/min Calibration curve - Polymethylene standard sample example - / α-olefin mixture with carbon number/6 to it (manufactured by Mitsubishi Chemical Industries, Ltd., "Dialen it, g" (registered trademark))
2/, q tci (dehag moles) and hydroquinone θ, 037 kQ were charged into a 5O8-3t6 tank type vessel, and the mixture was sufficiently purged with nitrogen gas. Then add this to the temperature/
r At O'C, maleic anhydride, θkg (q/
, g mol) were continuously added dropwise at a constant rate over 3 hours. The concentration of residual maleic anhydride in the reaction solution immediately after the dropwise addition of maleic anhydride was 9.7 mol based on the total number of moles of the charged olefin and maleic anhydride, and the maleic anhydride reaction rate was much higher. It was Sachi.
次いで、上記反応液を温度２００ ℃で６．２時間熟成
した。得られた反応液は無水マレイン酸の反応率が９３
．０ ％であった。Next, the reaction solution was aged at a temperature of 200° C. for 6.2 hours. The reaction solution obtained had a reaction rate of maleic anhydride of 93.
．． It was 0%.
その後、圧力！ｒｍＨＩ、温度／ｇ３℃において反応液
から未反応物を除去した。Then pressure! Unreacted materials were removed from the reaction solution at rmHI and temperature/g 3°C.
得られた反応液はタール状副生物が全くなく、かつ製品
色相も良好なものであった。The resulting reaction solution was completely free of tar-like by-products and had a good product color.
ケン化価：３３７
融 点： ９１７℃
色相（ガードナー腐）： １２〜／３
比較例−／
炭Ｘ数／Ａ〜／ｇのα−オレフィン混合物（”ダイヤレ
ン ／１．ｇ″）２？、、７に９（７２３モル）無水マ
レイン酸１２．／に９（７２３モル）及びハイドロキノ
ン０．ＯＩＩ／ｋＱを５ＵＳ−３／ｌ、人種型反応器に
仕込み、屋素ガスで十分置換した。ついで、これを温度
２００′Ｇに加熱し、７．７時間反応させたところ、無
水マレイン酸の反応率は９コ、クチであった。Saponification value: 337 Melting point: 917°C Hue (Gardner rot): 12~/3 Comparative example-/ α-olefin mixture (“Dialene/1.g”) with carbon X number/A~/g 2? , 7 to 9 (723 mol) maleic anhydride 12. /9 (723 mol) and hydroquinone 0. 5US-3/l of OII/kQ was charged into a racial reactor and thoroughly replaced with nitrogen gas. Then, this was heated to a temperature of 200'G and reacted for 7.7 hours, and the reaction rate of maleic anhydride was 9 units.
その後、圧カフＩＩＩＩＩＨｇ、温度２７０℃において
反応液から未反応物を除去した。Thereafter, unreacted substances were removed from the reaction solution using a pressure cuff IIIHg and a temperature of 270°C.
得られた反応液は、タール状副生物が下部に沈降して層
をなしていた。このタール状副生物を除去した後の製品
は下記のようなものであった。The resulting reaction solution had a layer of tar-like by-products that settled at the bottom. After removing this tar-like by-product, the product was as shown below.
ケン化価： ３９３
融 点＝ ３３℃
色相（ガードナーＡ６）： ｌＡ〜／７実施例−コ
炭素数３０〜６０のα−オレフィン混合物（三菱化成工
業株製、′ダイキレン３０”（登録商標））り＜＜９．
９（へ／コモル）及びハイドロキノンｏ、ｇ ｂ ｇ−
＠パイレックスガラス製反応器に仕込み、１００℃に加
熱して窒素ガスで十分置換した。その後、これに温度／
ざ０℃におい無水マレイン酸滴下終了直後の反応液中の
残存無水マレイン酸濃度は、仕込オレフィン及び無水マ
レイン酸の合計モル数に対して／ ’１．ｇモルチであ
シ、かつ、無水マレイン酸の反応率は７０、！チであっ
た。Saponification value: 393 Melting point = 33°C Hue (Gardner A6): lA~/7 Example-Co α-olefin mixture having 30 to 60 carbon atoms (manufactured by Mitsubishi Chemical Industries, Ltd., 'Daikiren 30'' (registered trademark)) ri<<9.
9 (h/comole) and hydroquinone o, g b g-
The mixture was placed in a Pyrex glass reactor, heated to 100°C, and thoroughly purged with nitrogen gas. Then add this to the temperature/
The concentration of residual maleic anhydride in the reaction solution immediately after the dropwise addition of maleic anhydride at 0° C. is 1/' with respect to the total number of moles of the charged olefin and maleic anhydride. The reaction rate of g molty acid and maleic anhydride is 70,! It was Chi.
次いで、上記反応液を温度２／θ℃で３．夕時間熟成し
た。得られた反応液は無水マレイン酸の反応率がｇ９．
３チであった。Next, the above reaction solution was heated at a temperature of 2/θ°C for 3. It matured in the evening. The reaction solution obtained had a reaction rate of maleic anhydride of g9.
It was 3 chi.
その後、圧力！；ｍＨ９，温度／ Ａ ／ ℃において
反応液から未反応物を除去した。Then pressure! Unreacted substances were removed from the reaction solution at mH9, temperature/A/°C.
得られた反応液は、タール状副生物の生成がごく僅かで
あった。The resulting reaction solution contained very little tar-like byproducts.
融 点＝ ７０ ’Ｃ
ケン化価： ざ１
分子量： ／７３０
針入度： り、！
実施例−３
炭素数、３０−４０のα−オレフィン混合物（″ダイキ
レン３０”）Ａ？Ａｇ（へ〇グモル）をパイレックスガ
ラス製反応器に仕込み、１００℃に加熱して窒素ガスで
十分置換した。その後これに温度ｉｇｏ℃において無水
マレモノ駿了直後の反応液中の残存無水マレイン酸濃度
は、仕込オレフィン及び無水マレイン酸の合計モル数に
対して、２ ／、９モルチであシ、かつ無水マレイン酸
の反応率は３６．２％であった。Melting point = 70'C Saponification value: 1 Molecular weight: /730 Penetration: ri! Example-3 α-olefin mixture having 30-40 carbon atoms (“Daikiren 30”) A? Ag (〇 gmol) was charged into a Pyrex glass reactor, heated to 100° C., and thoroughly purged with nitrogen gas. Thereafter, the concentration of residual maleic anhydride in the reaction solution immediately after the completion of the anhydrous maleic anhydride reaction at a temperature of 10° C. is 2/9 mol, based on the total number of moles of the charged olefin and maleic anhydride. The acid reaction rate was 36.2%.
次いで上記反応液を温度、２７０℃でｅ、ｏ時間熟成し
た。得られた反応液は、無水マレイン酸の反応率がｇ
９−０％であった。The reaction solution was then aged at a temperature of 270° C. for e and o hours. The reaction solution obtained had a reaction rate of maleic anhydride of g
It was 9-0%.
得られた反応液は、タール状副生物の生成がごく僅かで
あった。The resulting reaction solution contained very little tar-like byproducts.
融 点： ７５℃
ケン化価−／２１
分子量： 、２３７０
比較例−コ
炭素数３０〜６０のα−オレフィン混合物（″ダイキレ
ン３０”）Ｓり＜ｉ ｙ （ｏ、ざ７２モル）及び無水
マレイン酸り９．Ａ ｇ（Ｏ−ざ７２モル）をパイレッ
クスガラス製反応器に仕込み、１００°Ｃに加熱して窒
素ガスで十分置換した。ついで、これを温度２１０℃に
加熱し、？、０時間反応させたところ、無水マレイン酸
の反応率は９Ａ、０チであった。Melting point: 75°C Saponification number -/21 Molecular weight: , 2370 Comparative example - Alpha-olefin mixture having 30 to 60 carbon atoms ("Daikiren 30") S < i y (o, 72 mol) and maleic anhydride Acid9. Ag (72 moles of O-za) was charged into a Pyrex glass reactor, heated to 100°C, and thoroughly purged with nitrogen gas. Next, heat this to a temperature of 210°C and... When the reaction was carried out for 0 hours, the reaction rate of maleic anhydride was 9A, 0H.
その後、圧カフｔｍＨ９，温度１６θ０Ｃにおいて、反
応液から未反応物を除去した。Thereafter, unreacted substances were removed from the reaction solution under a pressure cuff of tmH9 and a temperature of 16θ0C.
得られた反応液は、タール状副生物が下部に沈降して層
をなしていた。このタール状副生物を除去した後の製品
は下記のようなものであった。The resulting reaction solution had a layer of tar-like by-products that settled at the bottom. After removing this tar-like by-product, the product was as shown below.
融 点：ｘ、ｒｏＣ
ケン化価：／／グ
分子量： ２Ａｉ！；０
針入度： ９．５
〔発明の効果〕
本発明方法によシ、オレフィンと無水マレイン酸とを熱
付加反応させてアルケニルコハク酸無水物を製造する際
の副生物の生成が抑制され、また製品の色相及び品質が
改善される。Melting point: x, roC Saponification value: //g Molecular weight: 2Ai! ;0 Penetration: 9.5 [Effects of the Invention] The method of the present invention suppresses the production of by-products when producing alkenylsuccinic anhydride by subjecting an olefin to a thermal addition reaction with maleic anhydride. , and the color and quality of the product is improved.
特許出願人 三菱化成工業株式会社 代 理 人 弁理士 良否用 − ほか／名Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative patent attorney - Others/names
Claims (1)
てアルケニルコハク酸無水物を製造する方法において、
反応系中の無水マレイン酸濃度を仕込みオレフィン及び
無水マレイン酸の合計モル数に対して３０モル％以下に
維持し、かつ無水マレイン酸の反応率が少なくとも３０
％になるまで２１０℃以下の温度で反応を行ない、つい
で反応温度を少なくとも５℃上昇させて反応を行なうこ
とを特徴とするアルケニルコハク酸無水物の製造法。(1) In a method for producing alkenylsuccinic anhydride by subjecting an olefin to a thermal addition reaction with maleic anhydride,
The concentration of maleic anhydride in the reaction system is maintained at 30 mol% or less based on the total number of moles of the charged olefin and maleic anhydride, and the reaction rate of maleic anhydride is at least 30%.
%, and then the reaction temperature is raised by at least 5°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315859A JP2584802B2 (en) | 1987-12-14 | 1987-12-14 | Process for producing alkenyl succinic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315859A JP2584802B2 (en) | 1987-12-14 | 1987-12-14 | Process for producing alkenyl succinic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01157972A true JPH01157972A (en) | 1989-06-21 |
| JP2584802B2 JP2584802B2 (en) | 1997-02-26 |
Family
ID=18070447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62315859A Expired - Fee Related JP2584802B2 (en) | 1987-12-14 | 1987-12-14 | Process for producing alkenyl succinic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2584802B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5454964A (en) * | 1993-05-04 | 1995-10-03 | Bp Chemicals Limited | Substituted acylating agents |
| JP2018524297A (en) * | 2015-06-12 | 2018-08-30 | テクノロギアン トゥトキムスケスクス ヴェーテーテー オイ | Method and apparatus for producing chemical compounds, chemical compounds and uses thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5476516A (en) * | 1977-11-21 | 1979-06-19 | Goi Kasei Kk | Manufacture of diisobutenylsuccinic anhydride |
| JPS55100374A (en) * | 1979-01-23 | 1980-07-31 | Goi Kasei Kk | Preparation of diisobutenylsuccinic anhydride |
| JPS56115783A (en) * | 1980-02-20 | 1981-09-11 | Goi Kasei Kk | Preparation of diisobutenylsuccinic anhydride |
| JPS61172866A (en) * | 1985-01-26 | 1986-08-04 | Mitsubishi Monsanto Chem Co | Production of alkenylsuccinic anhydride |
-
1987
- 1987-12-14 JP JP62315859A patent/JP2584802B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5476516A (en) * | 1977-11-21 | 1979-06-19 | Goi Kasei Kk | Manufacture of diisobutenylsuccinic anhydride |
| JPS55100374A (en) * | 1979-01-23 | 1980-07-31 | Goi Kasei Kk | Preparation of diisobutenylsuccinic anhydride |
| JPS56115783A (en) * | 1980-02-20 | 1981-09-11 | Goi Kasei Kk | Preparation of diisobutenylsuccinic anhydride |
| JPS61172866A (en) * | 1985-01-26 | 1986-08-04 | Mitsubishi Monsanto Chem Co | Production of alkenylsuccinic anhydride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5454964A (en) * | 1993-05-04 | 1995-10-03 | Bp Chemicals Limited | Substituted acylating agents |
| JP2018524297A (en) * | 2015-06-12 | 2018-08-30 | テクノロギアン トゥトキムスケスクス ヴェーテーテー オイ | Method and apparatus for producing chemical compounds, chemical compounds and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2584802B2 (en) | 1997-02-26 |
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