JP3859302B2 - Process for producing branched polyene compounds - Google Patents

Description

【００１４】
（式中、ｆは１〜５の整数を示し、R¹及びR²はそれぞれ独立に水素原子又は炭素数１〜５のアルキル基を示し、R³は水素原子又は炭素数１〜５のアルキル基又は一般式（II）
【００１５】
【化７】

【００１６】
（式中、ｎは１〜５の整数を示し、R⁴、R⁵及びR⁶はそれぞれ独立に水素原子または炭素数１〜５のアルキル基を示す。但し、R⁴、R⁵及びR⁶は同時に水素原子であることはない。）
で表わされるアルケニル基を示す。但し、R¹、R²及びR³は同時に水素原子であることはない。）
で表わされる共役ジエン化合物とを遷移金属触媒の存在下に反応させて、一般式（III)
【００１７】
【化８】

【００１８】
（式中、ｆ、R¹、R²及びR³は前記と同じである。）
で表わされる分岐鎖状ポリエン化合物を製造する方法において、反応終了後、生成した分岐鎖状ポリエン化合物を含む反応混合物を水と酸化剤にて処理して、上記遷移金属触媒を失活させた後、反応混合物から上記分岐鎖状ポリエン化合物を蒸留によって分離することを特徴とする分岐鎖状ポリエン化合物の製造方法が提供される。
【００１９】
特に、本発明によれば、前記一般式（Ｉ）で表わされる共役ジエン化合物において、R³が前記一般式（II）で表わされるアルケニル基であるときは、エチレンと一般式（Ｉ')
【００２０】
【化９】

【００２１】
（式中、ｆは１〜５の整数を示し、ｎ１〜５の整数を示し、R¹、R²、R⁴、R⁵及びR⁶はそれぞれ独立に水素原子又は炭素数１〜５のアルキル基を示す。但し、R⁴、R⁵及びR⁶は同時に水素原子であることはない。）
で表わされる共役ジエン化合物を遷移金属触媒の存在下に反応させることによって、一般式（III')
【００２２】
【化１０】

【００２３】
（式中、ｆ、ｎ、R¹、R²、R⁴、R⁵及びR⁶は前記と同じである。）
で表わされる分岐鎖状ポリエン化合物の製造方法が提供される。
【００２４】
【発明の実施の形態】
本発明の方法において用いる共役ジエン化合物は、前記一般式（Ｉ）
【００２５】
【化１１】

【００２６】
（式中、ｆは１〜５の整数を示し、R¹及びR²はそれぞれ独立に水素原子又は炭素数１〜５のアルキル基を示し、R³は水素原子又は炭素数１〜５のアルキル基又は一般式（II）
【００２７】
【化１２】

【００２８】
（式中、ｎは１〜５の整数を示し、R⁴、R⁵及びR⁶はそれぞれ独立に水素原子又は炭素数１〜５のアルキル基を示す。但し、R⁴、R⁵及びR⁶は同時に水素原子であることはない。）
で表わされるアルケニル基を示す。但し、R¹、R²及びR³は同時に水素原子であることはない。）
で表わされる。
【００２９】
上記一般式（Ｉ）において、R¹、R²又はR³が炭素数１〜５のアルキル基であるとき、そのようなアルキル基として、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基等を挙げることができる。本発明においては、R¹、R²又はR³がアルキル基であるとき、そのようなアルキル基としては、特に、炭素数１〜３であることが好ましく、特に、メチル基又はエチル基であることが好ましい。
【００３０】
特に、本発明において、前記一般式（Ｉ）で表される共役ジエン化合物において、R³が前記一般式（II）で表されるアルケニル基であるときは、共役ジエン化合物は、前記一般式（I'）で表わされ、R¹、R²、R⁴、R⁵又はR⁶が炭素数１〜５のアルキル基であるとき、そのようなアルキル基としても、上述したような具体例を挙げることができ、特に、炭素数１〜３のアルキル基であることが好ましく、なかでも、メチル基であることが好ましい。
【００３１】
このような一般式（Ｉ）で表わされる共役ジエン化合物の具体例として、例えば、次のような化合物を挙げることができる。
【００３２】
【化１３】

【００３３】
【化１４】

【００３４】
【化１５】

【００３５】
【化１６】

【００３６】
これらのなかでは、特に、次式
【００３７】
【化１７】

【００３８】
で表わされる７−メチル−３−メチレン−1,６−オクタジエン（β−ミルセン）や、次式
【００３９】
【化１８】

【００４０】
で表される7,11−ジメチル−３−メチレン−1,6,10−ドデカトリエン（β−ファルネセン）等が実用上、好ましく用いられる。
本発明の方法によるエチレンと共役ジエン化合物との反応は、次式で示すことができる。
【００４１】
【化１９】

【００４２】
本発明によれば、エチレンと前記共役ジエン化合物との反応は、遷移金属化合物と有機アルミニウム化合物とからなる遷移金属触媒の存在下に行なわれる。
上記遷移金属化合物としては、具体的には、鉄、ルテニウム等の鉄族、コバルト、ロジウム、イリジウム等のコバルト族、ニッケル、パラジウム等のニッケル族から選ばれる遷移金属の塩化物、臭化物、ヨウ化物、炭酸塩、硫酸塩、硝酸塩、リン酸塩、酢酸塩、チオシアン酸塩、アセチルアセトナート等を挙げることができる。これらのなかでは、塩化コバルト(II)又は塩化ニッケル(II)等が好ましく、特に、塩化コバルト(II)が好ましく用いられる。
【００４３】
このような遷移金属化合物は、そのままでも、遷移金属触媒の調製に用いることができる。しかし、本発明によれば、触媒の調製のためには、遷移金属化合物は、これに有機配位子が配位した遷移金属錯体として用いることが有利である。即ち、遷移金属化合物と共に、上記遷移金属の配位子となり得る有機化合物、即ち、配位化合物を反応系に共存させるか、又は予め遷移金属化合物と上記配位化合物とから遷移金属錯体を調製して、触媒の調製に用いることが好ましい。
【００４４】
このような配位子となり得る化合物としては、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、テトラヒドロフラン、アセチルアセトン等の含酸素有機化合物、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、シクロヘキシルアミン、ジシクロヘキシルアミン、アニリン、ジフェニルアミン、ピリジン、ピコリン、2,2'−ビピリジン、1,10−フェナントロリン等の含窒素有機化合物、トリエチルホスフィン、トリプロピルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、ビス（ジフェニルホスフィノ）メタン、1,２−ビス（ジフェニルホスフィノ）エタン、1,３−ビス（ジフェニルホスフィノ）プロパン、1,４−ビス（ジフェニルホスフィノ）ブタン、トリエチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、トリフェニルホスファイト、トリフェニルホスフィンオキサイド、トリフェニルホスフェート等の含リン有機化合物を挙げることができる。これらのなかでは、含リン有機化合物が好ましく、特に、1,２−ビス（ジフェニルホスフィノ）エタンが好ましく用いられる。
【００４５】
また、予め遷移金属化合物に有機配位子を配位させた遷移金属錯体としては、例えば、1,２−ビス（ジフェニルホスフィノ）エタンコバルト(II)塩化物
（φ₂ ＰＣＨ₂ ＣＨ₂ Ｐφ₂ ）ＣｏＣｌ₂
（式中、φはフェニル基を示す。）
等を挙げることができる。
【００４６】
有機アルミニウム化合物としては、例えば、トリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリイソブチルアルミニウム等のトリアルキルアルミニウム、ジイソブチルアルミニウムヒドリド等のジアルキルアルミニウムヒドリド、イソブチルアルミニウムジヒドリド等のアルキルアルミニウムジヒドリド、塩化ジメチルアルミニウム、塩化ジエチルアルミニウム、塩化ジプロピルアルミニウム、塩化ジイソブチルアルミニウム等の塩化ジアルキルアルミニウム、エチルアルミニウムセスキクロライド等のアルキルアルミニウムセスキクロライド、二塩化エチルアルミニウム等の二塩化アルキルアルミニウム、臭化ジメチルアルミニウム、臭化ジエチルアルミニウム、臭化ジプロピルアルミニウム、臭化ジイソブチルアルミニウム等の臭化ジアルキルアルミニウム、エチルアルミニウムセスキブロマイド等のアルキルアルミニウムセスキブロマイド、二臭化エチルアルミニウム等の二臭化アルキルアルミニウム、ヨウ化ジメチルアルミニウム、ヨウ化ジエチルアルミニウム、ヨウ化ジプロピルアルミニウム、ヨウ化ジイソブチルアルミニウム等のヨウ化ジアルキルアルミニウム、エチルアルミニウムセスキヨーダイド等のアルキルアルミニウムセスキヨーダイド、二ヨウ化エチルアルミニウム等の二ヨウ化アルキルアルミニウム、ジメチルアルミニウムメトキシド、ジエチルアルミニウムエトキシド等のジアルキルアルミニウムアルコキシド等を挙げることができる。
【００４７】
本発明においては、これらのなかでも、特に、トリエチルアルミニウムのようなトリアルキルアルミニウムや塩化ジエチルアルミニウムのような塩化ジアルキルアルミニウムが好ましく用いられる。これらの有機アルミニウム化合物は、そのまま用いることができるが、また、トルエン溶液やヘキサン溶液として用いることもできる。また、これらの有機アルミニウム化合物は、１種のみを用いてもよいし、２種以上を併用してもよい。
【００４８】
本発明の方法において、用いる遷移金属触媒の量は、通常、遷移金属化合物が共役ジエン化合物に対して、0.００１〜１０モル％、好ましくは、0.０１〜１モル％の範囲になるように用いられる。また、配位化合物は、遷移金属化合物に対して、通常、２０倍モル以下、好ましくは、0.１〜１０倍モル量の範囲で用いられる。他方、有機アルミニウム化合物は、遷移金属化合物に対して、通常、１〜２００倍モル、好ましくは、３〜１００倍モルの範囲で用いられる。
【００４９】
予め調製した遷移金属錯体を用いる場合、遷移金属錯体は、共役ジエン化合物に対して、0.００１〜１０モル％、好ましくは、0.０１〜１モル％の範囲となるように用いられる。
【００５０】
本発明において用いる触媒は、好ましくは、遷移金属化合物と有機アルミニウム化合物とを反応させることによって得ることができる。このような触媒は、エチレンと共役ジエンとを含む反応系において、遷移金属化合物と有機アルミニウム化合物とをその場で反応させて調製してもよく、また、予め、遷移金属化合物と有機アルミニウム化合物とを反応させ、得られた反応生成物を触媒として、エチレンと共役ジエンとを含む反応系に供給して、反応を行なってもよい。
【００５１】
本発明の方法において、エチレンと共役ジエン化合物との反応は、共役ジエン化合物の種類によっても異なるが、遷移金属化合物と有機アルミニウム化合物とからなる遷移金属触媒の存在下に、通常、３０〜２００℃、好ましくは、５０〜１５０℃の範囲の温度で、エチレン圧0.５〜１００kg／cm² 、好ましくは、２〜７０kg／cm² の圧力下に行われる。反応時間は、特に限定されるものではないが、通常、0.５〜３時間の範囲である。但し、反応雰囲気は、エチレン単独の雰囲気でもよく、また、エチレンと共に窒素やアルゴン等の不活性ガスを含む雰囲気でもよい。 上記エチレンと共役ジエン化合物との反応において、反応溶媒は、特に用いる必要はないが、しかし、用いてもよい。この場合、反応溶媒としては、例えば、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、トリデカン、トルエン、キシレン等の炭化水素系溶媒を好ましく用いることができる。しかし、これらに限定されるものではない。
【００５２】
本発明の方法によれば、以上のようにして、エチレンと共役ジエン化合物とを遷移金属触媒の存在下に反応させた後、得られた反応混合物を水と酸化剤とによって処理することによって、反応混合物中に含まれる遷移金属触媒を完全に失活させる。
【００５３】
ここに、本発明によれば、反応混合物の水による処理と酸化剤による処理とは、いずれを先に反応混合物に加えて、反応混合物の処理を行なってもよく、また、反応混合物に水と酸化剤とを同時に加えて、同時に処理してもよい。しかし、反応混合物に先に酸化剤を加えて、酸化処理を行なえば、酸化剤が反応混合物に含まれる有機アルミニウム化合物の酸化に消費されるので、これを防ぐために、先に水を反応混合物に添加して水処理し、この後に、酸化剤を添加して、酸化処理するのが好ましい。
【００５４】
本発明の方法において、反応混合物に添加する水の量は、通常、反応混合物に対して0.１〜５重量倍、好ましくは、0.２〜１重量倍の範囲である。この水の添加に際しては、水を単独で添加してもよいが、有機アルミニウム化合物が加水分解されて生成する水酸化アルミニウムを水相に溶解させるために、酸又はアルカリを同時に添加することが好ましい。ここに、酸又はアルカリは、通常、有機アルミニウム化合物１モルに対して、0.１〜１００モルの範囲で添加すればよい。
【００５５】
また、遷移金属化合物の一部が加水分解されて生成する遷移金属水酸化物等を水層に溶解させるために、エチレンジアミン四酢酸（ＥＤＴＡ）等の所謂キレート配位性化合物を同時に添加することが好ましい。このキレート配位性化合物は、反応混合物中の遷移金属化合物に対して、通常、等モル以上添加するのが好ましい。特に、本発明によれば、上述した酸又はアルカリと共に、このキレート配位性化合物を反応混合物に添加するのが最も好ましい。
【００５６】
このようにして、反応終了後、水と、好ましくは、酸又はアルカリとキレート配位性化合物を反応混合物に添加して、反応混合物を水処理（水洗処理）するに際して、反応混合物と水との接触効率を高めるために、必要に応じて、加熱下に、反応混合物を攪拌するのが好ましい。このような攪拌は、通常、０〜９０℃、好ましくは１０〜５０℃の範囲の温度で行なわれる。攪拌時間は、特に限定されるものではないが、通常、0.１〜１時間の範囲である。
【００５７】
次に、本発明において用いる酸化剤としては、空気、酸素、オゾン、酸化窒素等の酸化性ガス、過酸化水素、ｔ−ブチルペルオキシド、クメンヒドロペルオキシド、ｍ−クロロ過安息香酸等の過酸化物、硝酸塩、亜硝酸塩等の無機窒素化合物、クロム酸、過マンガン酸等の金属酸化物酸、ピリジン−Ｎ−オキシド等のＮ−オキシド類、ジメチルスルホキシド等のスルホキシド類等を挙げることができる。これらのなかでは、空気、酸素又は過酸化水素が好ましく用いられる。
【００５８】
これらの酸化剤は、遷移金属化合物及び配位化合物の合計量に対して、通常、１〜２０モル倍、好ましくは、１〜５モル倍である。酸化剤をこのような範囲で用いることによって、遷移金属触媒を効果的に失活させることができ、しかも、目的とする分岐鎖状ポリエン化合物が過酸化物に転化する等の不都合も少ない。
【００５９】
上述した酸化剤は、そのまま用いることができるが、酸化剤が酸化性ガスであるとき、窒素やアルゴン等の不活性ガスで希釈して用いてもよく、また、酸化剤が液体又は固体であるとき、水、トルエン、ヘキサン等、適宜の溶剤で希釈して用いてもよい。
【００６０】
反応混合物に酸化剤を添加した後に、通常、反応混合物を攪拌する。この攪拌も、通常、０〜９０℃、好ましくは、１０〜５０℃の範囲の温度で行なわれる。攪拌時間は、特に限定されるものではないが、通常、0.１〜１０時間の範囲である。
【００６１】
このようにして、本発明の方法によれば、エチレンと共役ジエン化合物とを遷移金属化合物と有機アルミニウムとからなる遷移金属触媒の存在下て反応させた後、得られた反応混合物を水と酸化剤とで処理して、反応混合物に含まれる遷移金属触媒を失活させることによって、この後、この反応混合物から、通常の蒸留精製によって、目的生成物である分岐鎖状ポリエン化合物を、内部オレフィン化合物への異性化を抑えて、高収率にて得ることができる。
【００６２】
特に、本発明に従って、反応終了後、反応混合物を水処理した後、酸化処理する場合、具体的には、反応混合物に水、好ましくは、酸又はアルカリと共にキレート配位性化合物を含む水溶液を加え、攪拌して、水洗した後、水層を除き、かくして、得られた油相を酸化剤で酸化処理すればよい。このようにして、最終的に得られた油相を蒸留すれば、目的とする分岐鎖状ポリエン化合物が内部オレフィン化合物への異性化を起こさないので、目的とする分岐鎖状ポリエン化合物を高収率にて得ることができる。
【００６３】
しかしながら、本発明においては、反応終了後、得られた反応混合物から目的とする分岐鎖状ポリエン化合物を蒸留によって分離するとは、目的とする分岐鎖状ポリエン化合物を反応混合物から分離するに際して、蒸留を含む分離操作によって、目的とする分岐鎖状ポリエン化合物を反応混合物から分離することを意味する。従って、本発明においては、反応終了後、得られた反応混合物から目的とする分岐鎖状ポリエン化合物を蒸留によって分離するとは、反応混合物から目的とする分岐鎖状ポリエン化合物自体を留分として蒸留して分離する場合のほか、反応混合物から反応溶剤等を留去して、目的とする分岐鎖状ポリエン化合物を反応混合物から分離する場合をも含み、更に、これらの複数の蒸留操作を行なって、目的とする分岐鎖状ポリエン化合物を反応混合物から分離する場合をも含むものとする。
【００６４】
本発明によれば、原料として用いる共役ジエン化合物を適宜に選択することによって、次のような種々の分岐鎖状ポリエン化合物を得ることができる。
【００６５】
【化２０】

【００６６】
【化２１】

【００６７】
【化２２】

【００６８】
【化２３】

【００６９】
【化２４】

【００７０】
【化２５】

【００７１】
【化２６】

【００７２】
【化２７】

【００７３】
【化２８】

【００７４】
【化２９】

【００７５】
【化３０】

【００７６】
【化３１】

【００７７】
【化３２】

【００７８】
【化３３】

【００７９】
【化３４】

【００８０】
【化３５】

【００８１】
【化３６】

【００８２】
【化３７】

【００８３】
【化３８】

【００８４】
【化３９】

【００８５】
特に、本発明によれば、エチレンと前述した７−メチル−３−メチレン−1,６−オクタジエン（β−ミルセン）とを反応させることによって、４−エチリデン−８−メチル−1,７−ノナジエンを得ることができ、また、エチレンと前述した7,11−ジメチル−３−メチレン−1,6,10−ドデカトリエン（β−ファルネセン）とを反応させることによって、４−エチリデン−8,12−ジメチル−1,7,11−トリデカトリエンを得ることができる。
【００８６】
本発明の方法によって得ることができる分岐鎖状ポリエン化合物は、これをエチレン、プロピレン等のα−オレフィンと共重合させることによって、高速加硫が可能であるのみならず、耐候性、耐熱性、耐オゾン性等にもすぐれているエチレン性不飽和共重合体を得ることができる。
【００８７】
【発明の効果】
本発明によれば、遷移金属化合物と有機アルミニウム化合物とからなる遷移金属触媒の存在下に、エチレンと前記共役ジエン化合物とを反応させた後、得られた反応混合物を水と酸化剤とで処理して、上記遷移金属触媒を完全に失活させるので、この後、反応混合物から蒸留精製によって、目的とする分岐鎖状ポリエン化合物を分離する際に、分岐鎖状ポリエン化合物の異性化による重合に関与しない内部オレフィン化合物への転化を抑えることができ、かくして、高収率にて目的とする分岐鎖状ポリエン化合物を得ることができる。このようにして得られる分岐鎖状ポリエン化合物は、これをエチレン、プロピレン等のα−オレフィンと共重合させることによって、耐候性、耐熱性、耐オゾン性にすぐれ、しかも、加硫速度の速いエチレン性不飽和共重合体を得ることができる。
【００８８】
【実施例】
以下に実施例を比較例と共に挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。実施例及び比較例において、目的物の収率は、目的とする生成物のモル数をｐ、反応に用いた原料共役ジエンの仕込みモル数をｃ₀ とするとき、（ｐ／ｃ₀ ）×１００（％）にて求めた。また、原料である共役ジエンの転化率は、反応後の共役ジエンのモル数をｃとするとき、〔（ｃ₀ −ｃ）／ｃ₀ 〕×１００（％）にて求めた。
【００８９】
実施例１
（４−エチリデン−８−メチル−1,７−ノナジエンの合成）
窒素雰囲気下、１５００ｍｌ容量のステンレス（ＳＵＳ３１６）製オートクレーブに、２−ビス（ジフェニルホスフィノ）エタンコバルト（II）塩化物2.８６ｇ（5.４２ミリモル）と無水トルエン７０ｇと及び７−メチル−３−メチレン−1,６−オクタジエン（β−ミルセン）５９３ｇ（4.０２モル）とを仕込み、室温で１時間攪拌した。次に、トリエチルアルミニウムのトルエン溶液（0.９１モル／Ｌ）７0.５ｍＬ（６4.２ミリモル）を加えて、オートクレーブを密閉した。
【００９０】
この後、オートクレーブにエチレンボンベを直結して、エチレンを導入し、オートクレーブ内を５ｋｇ／ｃｍ² まで加圧し、８０℃に加熱した。消費されたエチレンを間欠的に追加しながら、エチレン圧を４〜５ｋｇ／ｃｍ² に維持し、８０℃で４時間反応を行なった。
【００９１】
反応終了後、オートクレーブを冷却した後、開放し、得られた反応混合物の一部を採取し、ガスクロマトグラフで分析して、生成物とその収率を求めた。その結果、β−ミルセンの転化率は９９％であり、目的物である４−エチリデン−８−メチル−1,７−ノナジエンの収量は４６１ｇ（収率７０％）であった。また、反応副生物である5,９−ジメチル−1,4,８−デカトリエンの収量は１１９ｇ（収率１８％）であった。
【００９２】
次いで、窒素雰囲気下、１０００ｍＬ容量の攪拌翼付きガラス製セパラブルフラスコに、上記反応混合物２００ｇを仕込み、続いて、これに５％水酸化ナトリウムと２％エチレンジアミン四酢酸二ナトリウムとを含む水溶液６７ｇを加え、室温で２０分間攪拌した後、２０分間静置した。水層を抜き出した後、油相に水６７ｇを加え、更に、室温で２０分間攪拌した後、２０分間静置して、水層を抜き出した（反応混合物の水処理）。この後、セパラブルフラスコの気相部に空気（酸化剤）を２００ｍり／分の割合で流通させながら、油相を３０分間攪拌した（油相の空気酸化処理）。
【００９３】
このように処理した油相１６０ｇ（４−エチリデン−８−メチル−1,７−ノナジエン７９ｇを含む。）を３００ｍＬ容量のフラスコに移し、１４０℃に加熱し、１４０℃で５時間加熱した。加熱終了後、油相の一部を採取して、ガスクロマトグラフで分析し、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンからの反応生成物を調べた。その結果、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンの転化率はいずれも０％であって、重合に関与しない内部オレフィン化合物への異性化は認められなかった。
【００９４】
実施例２
窒素雰囲気下、１０００ｍＬ容量の攪拌翼付きガラス製セパラブルフラスコに、実施例１にて得られた反応混合物２００ｇを仕込み、続いて、５％水酸化ナトリウムと２％エチレンジアミン四酢酸二ナトリウムとを含む水溶液６７ｇを加え、室温で２０分間攪拌した後、２０分間静置した。水層を抜き出した後、油相に水６７ｇを加え、更に、室温で２０分間攪拌した後、２０分間静置して、水層を抜き出した。この後、油相に0.１％過酸化水素水溶液６３ｇを加え、室温で２０分間攪拌した後、２０分間静置して、水層を抜き出した。
【００９５】
このようにして得られた油相１６０ｇ（４−エチリデン−８−メチル−1,７−ノナジエンを７９ｇ含む。）を、３００ｍＬ容量のフラスコに移し、１４０℃に加熱し、１４０℃で５時間加熱した。加熱終了後、油相の一部を採取して、ガスクロマトグラフで分析し、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンからの反応生成物を調べた。その結果、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンの転化率はいずれも０％であって、重合に関与しない内部オレフィン化合物への異性化は認められなかった。
【００９６】
比較例１
実施例１において、エチレンと７−メチル−３−メチレン−1,６−オクタジエン（β−ミルセン）との反応終了後、得られた反応混合物に空気酸化処理を行なわなかった以外は、実施例１と同様に処理して、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンからの反応生成物を調べた。その結果、４−エチリデン−８−メチル−1,７−ノナジエンの３４％が４−エチリデン−８−メチル−2,７−ノナジエンに異性化しており、また、5,９−ジメチル−1,4,８−デカトリエンの９３％が5,９−ジメチル−2,4,８−デカトリエンに異性化したことが確認された。
【００９７】
比較例２
実施例１において、反応混合物の水洗処理と油相の空気酸化処理を行なわなかった以外は、実施例１と同様に処理して、４−エチリデン−８−メチル−1,７−ノナジエンと5,９−ジメチル−1,4,８−デカトリエンからの反応生成物を調べた。その結果、４−エチリデン−８−メチル−1,７−ノナジエンの５％が４−エチリデン−８−メチル−2,７−ノナジエンに異性化しており、また、5,９−ジメチル−1,4,８−デカトリエンの４０％が5,９−ジメチル−2,4,８−デカトリエンに異性化したことが確認された。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a branched polyene compound, and more specifically, after reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst, the transition metal catalyst in the obtained reaction mixture is deactivated. To obtain the desired branched polyene compound in high yield by distillation from the reaction mixture while suppressing undesirable isomerization reaction of the obtained branched polyene compound to the internal olefin compound About.
[0002]
[Prior art]
In general, a polyene compound refers to a hydrocarbon compound having two or more carbon-carbon double bonds in one molecule, and many compounds are conventionally known. As such a polyene compound, for example, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, ethylidene-2-norbornene, dicyclopentadiene and the like are known.
[0003]
By copolymerizing such a polyene compound and an α-olefin such as ethylene or propylene, a vulcanizable unsaturated copolymer can be obtained, and such an ethylenically unsaturated copolymer can be obtained. The coalescence is excellent in weather resistance, heat resistance, ozone resistance, etc., as rubber products such as automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering materials, rubberized fabrics, polypropylene, It is widely used as a material for polymer blends to polystyrene and the like.
[0004]
Among such ethylenically unsaturated copolymers, the ethylene / propylene / 5-ethylidene-2-norbornene copolymer has a faster vulcanization rate than other ethylenically unsaturated copolymers. Especially widely used.
[0005]
However, conventionally known ethylenically unsaturated copolymers include, for example, the above-mentioned ethylene / propylene / 5-ethylidene-2-norbornene copolymers, natural rubber, styrene / butadiene rubber, isoprene rubber, butadiene Compared with normal diene rubbers such as rubber and nitrile rubber, the vulcanization speed is low and the co-vulcanizability with diene rubber is inferior.
[0006]
In addition, since conventional ethylenically unsaturated copolymers have a low vulcanization rate, the vulcanization rubber is reduced by shortening the vulcanization time or by lowering the vulcanization temperature and reducing the amount of energy consumed during vulcanization. It is difficult to manufacture with high productivity.
[0007]
Therefore, the present inventors have already described the branched polyene compound represented by the general formula (III) and an α-olefin such as ethylene and propylene as described in JP-A-8-325170. It has been found that an ethylenically unsaturated copolymer obtained by polymerization has a higher vulcanization rate than an ethylene / propylene / 5-ethylidene-2-norbornene copolymer. According to the above publication, the branched polyene compound represented by the general formula (III) includes ethylene and a conjugated diene compound in the presence of a transition metal catalyst obtained by reacting a transition metal compound with an organoaluminum compound. Can be obtained by reacting.
[0008]
However, according to such a method, after completion of the reaction between ethylene and the conjugated diene, when the desired branched polyene compound was separated from the obtained reaction mixture by distillation, it was used for the reaction in the reaction mixture. When the transition metal catalyst remains, a part of the obtained branched polyene compound is isomerized into an internal olefin compound not involved in the polymerization by heating during distillation, resulting in a product (branched polyene). Compound), and further adversely affects the quality of the product (branched polyene compound), so that the desired branched polyene compound is separated from the reaction mixture by distillation. It is necessary to deactivate the transition metal catalyst. That is, the non-polymerizable internal olefin compound does not have a copolymerizability with an α-olefin such as ethylene or propylene, and is therefore used as a raw material for producing the vulcanizable ethylenically unsaturated copolymer as described above. I can't.
[0009]
As a method for deactivating such a transition metal catalyst, conventionally, various methods are known, and one of them is a method using water as a deactivator. In this method, after the reaction is completed, water is added to the obtained reaction mixture, the transition metal catalyst is hydrolyzed, and the transition metal catalyst is converted into an inactive transition metal hydroxide, thereby deactivating it. Is. However, according to this method, depending on the type of the transition metal compound used as the catalyst, it is difficult to undergo hydrolysis, and therefore there is a problem that the transition metal catalyst cannot be sufficiently deactivated.
[0010]
In addition to the water described above, a method using alcohol, amine or the like as a deactivator is also known. According to this method, the transition metal catalyst can be deactivated relatively easily. However, since the deactivator such as alcohol or amine is dissolved in the reaction mixture, the deactivator is separated from the reaction mixture. There is a problem that special equipment is required for recovery.
[0011]
[Problems to be solved by the invention]
The present invention has been made to solve the above-described problems, and comprises reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst to represent a branched polyene compound represented by the general formula (III). When the above-mentioned transition metal catalyst in the obtained reaction mixture is deactivated after the completion of the reaction and the desired branched polyene compound is separated from the reaction mixture by distillation, the branched chain polyene compound is produced. It is an object of the present invention to provide a method for producing a branched polyene compound, which can suppress the isomerization of the compound into an internal olefin compound and obtain a target branched polyene compound in a high yield.
[0012]
[Means for Solving the Problems]
According to the invention, ethylene and the general formula (I)
[0013]
[Chemical 6]

[0014]
(In the formula, f represents an integer of 1 to 5, R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R^ThreeIs a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a general formula (II)
[0015]
[Chemical 7]

[0016]
(In the formula, n represents an integer of 1 to 5, R^Four, R^FiveAnd R⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R^Four, R^FiveAnd R⁶Are not simultaneously hydrogen atoms. )
The alkenyl group represented by these is shown. However, R¹, R²And R^ThreeAre not simultaneously hydrogen atoms. )
Is reacted with a conjugated diene compound represented by the general formula (III)
[0017]
[Chemical 8]

[0018]
(Where, f, R¹, R²And R^ThreeIs the same as above. )
In the method for producing a branched polyene compound represented by: After the reaction is completed, the reaction mixture containing the generated branched polyene compound is treated with water and an oxidizing agent to deactivate the transition metal catalyst. There is provided a method for producing a branched polyene compound, wherein the branched polyene compound is separated from the reaction mixture by distillation.
[0019]
In particular, according to the present invention, in the conjugated diene compound represented by the general formula (I), R^ThreeIs an alkenyl group represented by the general formula (II), ethylene and the general formula (I ′)
[0020]
[Chemical 9]

[0021]
(In the formula, f represents an integer of 1 to 5, represents an integer of n1 to 5, R¹, R², R^Four, R^FiveAnd R⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R^Four, R^FiveAnd R⁶Are not simultaneously hydrogen atoms. )
By reacting a conjugated diene compound represented by the formula (III ') with a transition metal catalyst:
[0022]
[Chemical Formula 10]

[0023]
(Where f, n, R¹, R², R^Four, R^FiveAnd R⁶Is the same as above. )
The manufacturing method of the branched polyene compound represented by these is provided.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
The conjugated diene compound used in the method of the present invention is the above general formula (I).
[0025]
Embedded image

[0026]
(In the formula, f represents an integer of 1 to 5, R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R^ThreeIs a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a general formula (II)
[0027]
Embedded image

[0028]
(In the formula, n represents an integer of 1 to 5, R^Four, R^FiveAnd R⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R^Four, R^FiveAnd R⁶Are not simultaneously hydrogen atoms. )
The alkenyl group represented by these is shown. However, R¹, R²And R^ThreeAre not simultaneously hydrogen atoms. )
It is represented by
[0029]
In the above general formula (I), R¹, R²Or R^ThreeIs an alkyl group having 1 to 5 carbon atoms, examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, t -A butyl group, n-pentyl group, isopentyl group, etc. can be mentioned. In the present invention, R¹, R²Or R^ThreeWhen is an alkyl group, such an alkyl group preferably has 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group.
[0030]
In particular, in the present invention, in the conjugated diene compound represented by the general formula (I), R^ThreeIs an alkenyl group represented by the general formula (II), the conjugated diene compound is represented by the general formula (I ′), and R¹, R², R^Four, R^FiveOr R⁶Is an alkyl group having 1 to 5 carbon atoms, examples of such an alkyl group can include the specific examples described above, and in particular, an alkyl group having 1 to 3 carbon atoms is preferable. However, it is preferably a methyl group.
[0031]
Specific examples of the conjugated diene compound represented by the general formula (I) include the following compounds.
[0032]
Embedded image

[0033]
Embedded image

[0034]
Embedded image

[0035]
Embedded image

[0036]
Among these, in particular:
[0037]
Embedded image

[0038]
7-methyl-3-methylene-1,6-octadiene (β-myrcene) represented by the following formula:
[0039]
Embedded image

[0040]
7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene) represented by the formula is preferably used in practice.
The reaction of ethylene and a conjugated diene compound by the method of the present invention can be represented by the following formula.
[0041]
Embedded image

[0042]
According to the present invention, the reaction between ethylene and the conjugated diene compound is carried out in the presence of a transition metal catalyst comprising a transition metal compound and an organoaluminum compound.
Specific examples of the transition metal compound include chlorides, bromides, and iodides of transition metals selected from iron groups such as iron and ruthenium, cobalt groups such as cobalt, rhodium and iridium, and nickel groups such as nickel and palladium. , Carbonate, sulfate, nitrate, phosphate, acetate, thiocyanate, acetylacetonate and the like. Among these, cobalt (II) chloride or nickel (II) chloride is preferable, and cobalt (II) chloride is particularly preferably used.
[0043]
Such a transition metal compound can be used as it is for the preparation of a transition metal catalyst. However, according to the present invention, for the preparation of the catalyst, the transition metal compound is advantageously used as a transition metal complex in which an organic ligand is coordinated. That is, together with the transition metal compound, an organic compound that can be a ligand of the transition metal, that is, a coordination compound coexists in the reaction system, or a transition metal complex is prepared in advance from the transition metal compound and the coordination compound. Thus, it is preferably used for preparing the catalyst.
[0044]
Compounds that can be such ligands include oxygenated organic compounds such as dimethyl ether, diethyl ether, dipropyl ether, tetrahydrofuran, acetylacetone, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, cyclohexylamine, dicyclohexylamine. Nitrogen-containing organic compounds such as aniline, diphenylamine, pyridine, picoline, 2,2′-bipyridine, 1,10-phenanthroline, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, trie Le phosphine, tributyl phosphine, triphenyl phosphine, triphenyl phosphite, triphenyl phosphine oxide, may be mentioned phosphorus-containing organic compounds such as triphenyl phosphate. Of these, phosphorus-containing organic compounds are preferable, and 1,2-bis (diphenylphosphino) ethane is particularly preferably used.
[0045]
Examples of the transition metal complex in which an organic ligand is coordinated with a transition metal compound in advance include, for example, 1,2-bis (diphenylphosphino) ethane cobalt (II) chloride.
(Φ₂PCH₂CH₂Pφ₂) CoCl₂
(In the formula, φ represents a phenyl group.)
Etc.
[0046]
Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, alkylaluminum dihydride such as isobutylaluminum dihydride, and dimethylaluminum chloride. Dialkylaluminum chloride such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, alkylaluminum dichloride such as ethylaluminum dichloride, dimethylaluminum bromide, diethylaluminum bromide , Dipropylaluminum bromide, dii bromide Dialkylaluminum bromide such as butylaluminum, alkylaluminum sesquibromide such as ethylaluminum sesquibromide, alkylaluminum bromide such as ethylaluminum dibromide, dimethylaluminum iodide, diethylaluminum iodide, dipropylaluminum iodide, iodine Dialkylaluminum iodide such as diisobutylaluminum iodide, alkylaluminum sesquiiodide such as ethylaluminum sesquiiodide, alkylaluminum diiodide such as ethylaluminum diiodide, dialkylaluminum alkoxide such as dimethylaluminum methoxide and diethylaluminum ethoxide Etc.
[0047]
In the present invention, among these, a trialkylaluminum such as triethylaluminum and a dialkylaluminum chloride such as diethylaluminum chloride are preferably used. These organoaluminum compounds can be used as they are, but can also be used as a toluene solution or a hexane solution. Moreover, these organoaluminum compounds may use only 1 type and may use 2 or more types together.
[0048]
In the method of the present invention, the amount of the transition metal catalyst used is usually such that the transition metal compound is in the range of 0.001 to 10 mol%, preferably 0.01 to 1 mol%, based on the conjugated diene compound. Used for. The coordination compound is usually used in an amount of 20 times or less, preferably 0.1 to 10 times the molar amount of the transition metal compound. On the other hand, the organoaluminum compound is generally used in an amount of 1 to 200 times mol, preferably 3 to 100 times mol for the transition metal compound.
[0049]
When a transition metal complex prepared in advance is used, the transition metal complex is used in an amount of 0.001 to 10 mol%, preferably 0.01 to 1 mol%, based on the conjugated diene compound.
[0050]
The catalyst used in the present invention can be preferably obtained by reacting a transition metal compound with an organoaluminum compound. Such a catalyst may be prepared by reacting a transition metal compound and an organoaluminum compound in situ in a reaction system containing ethylene and a conjugated diene. The reaction product obtained may be supplied to a reaction system containing ethylene and conjugated diene as a catalyst to carry out the reaction.
[0051]
In the method of the present invention, the reaction between ethylene and the conjugated diene compound varies depending on the kind of the conjugated diene compound, but is usually 30 to 200 ° C. in the presence of a transition metal catalyst composed of a transition metal compound and an organoaluminum compound. Preferably, at a temperature in the range of 50 to 150 ° C., the ethylene pressure is 0.5 to 100 kg / cm.², Preferably 2 to 70 kg / cm²Under pressure. Although reaction time is not specifically limited, Usually, it is the range of 0.5 to 3 hours. However, the reaction atmosphere may be an atmosphere of ethylene alone or an atmosphere containing an inert gas such as nitrogen or argon together with ethylene. In the reaction of ethylene with the conjugated diene compound, a reaction solvent is not particularly required, but may be used. In this case, as the reaction solvent, for example, a hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, undecane, tridecane, toluene, xylene and the like can be preferably used. However, it is not limited to these.
[0052]
According to the method of the present invention, after reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst as described above, the resulting reaction mixture is treated with water and an oxidizing agent, The transition metal catalyst contained in the reaction mixture is completely deactivated.
[0053]
Here, according to the present invention, any of the treatment of the reaction mixture with water and the treatment with the oxidizing agent may be carried out by first adding the reaction mixture to the reaction mixture, and treating the reaction mixture with water and An oxidizing agent may be added at the same time and treated simultaneously. However, if an oxidizing agent is first added to the reaction mixture and the oxidation treatment is performed, the oxidizing agent is consumed for the oxidation of the organoaluminum compound contained in the reaction mixture. To prevent this, water is first added to the reaction mixture. It is preferable to add and treat with water, and thereafter add an oxidizing agent to oxidize.
[0054]
In the method of the present invention, the amount of water added to the reaction mixture is usually in the range of 0.1 to 5 times by weight, preferably 0.2 to 1 times by weight with respect to the reaction mixture. When adding this water, water may be added alone, but it is preferable to add an acid or an alkali at the same time in order to dissolve the aluminum hydroxide produced by hydrolysis of the organoaluminum compound in the aqueous phase. . Here, the acid or alkali may be usually added in the range of 0.1 to 100 mol with respect to 1 mol of the organoaluminum compound.
[0055]
In addition, so-called chelate coordination compounds such as ethylenediaminetetraacetic acid (EDTA) may be added at the same time in order to dissolve transition metal hydroxide and the like produced by hydrolysis of part of the transition metal compound in the aqueous layer. preferable. This chelate coordination compound is usually preferably added in an equimolar amount or more with respect to the transition metal compound in the reaction mixture. In particular, according to the present invention, it is most preferable to add this chelate coordination compound to the reaction mixture together with the acid or alkali described above.
[0056]
Thus, after completion of the reaction, water, preferably an acid or alkali and a chelate coordination compound are added to the reaction mixture, and the reaction mixture is subjected to water treatment (water washing treatment). In order to increase the contact efficiency, it is preferable to stir the reaction mixture under heating, if necessary. Such stirring is usually performed at a temperature in the range of 0 to 90 ° C, preferably 10 to 50 ° C. The stirring time is not particularly limited, but is usually in the range of 0.1 to 1 hour.
[0057]
Next, examples of the oxidizing agent used in the present invention include oxidizing gases such as air, oxygen, ozone, and nitrogen oxide, and peroxides such as hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, and m-chloroperbenzoic acid. Inorganic nitrogen compounds such as nitrates and nitrites, metal oxide acids such as chromic acid and permanganic acid, N-oxides such as pyridine-N-oxide, and sulfoxides such as dimethyl sulfoxide. Of these, air, oxygen or hydrogen peroxide is preferably used.
[0058]
These oxidizing agents are usually 1 to 20 mol times, preferably 1 to 5 mol times based on the total amount of the transition metal compound and the coordination compound. By using the oxidizing agent in such a range, the transition metal catalyst can be effectively deactivated, and there are few inconveniences such as conversion of the target branched polyene compound into a peroxide.
[0059]
The above-mentioned oxidizing agent can be used as it is, but when the oxidizing agent is an oxidizing gas, it may be diluted with an inert gas such as nitrogen or argon, and the oxidizing agent is liquid or solid. Sometimes, it may be diluted with an appropriate solvent such as water, toluene or hexane.
[0060]
After adding the oxidizing agent to the reaction mixture, the reaction mixture is usually stirred. This stirring is also generally performed at a temperature in the range of 0 to 90 ° C, preferably 10 to 50 ° C. Although stirring time is not specifically limited, Usually, it is the range of 0.1 to 10 hours.
[0061]
Thus, according to the method of the present invention, ethylene and a conjugated diene compound are reacted in the presence of a transition metal catalyst composed of a transition metal compound and organoaluminum, and then the resulting reaction mixture is oxidized with water. Then, the transition metal catalyst contained in the reaction mixture is deactivated by treatment with an agent, and thereafter, the branched polyene compound as the target product is converted from the reaction mixture into an internal olefin by ordinary distillation purification. It can be obtained in a high yield while suppressing isomerization to the compound.
[0062]
In particular, according to the present invention, when the reaction mixture is treated with water after completion of the reaction and then oxidized, specifically, water, preferably an aqueous solution containing a chelate-coordinating compound together with an acid or alkali is added to the reaction mixture. After stirring and washing with water, the aqueous layer is removed, and the oil phase thus obtained may be oxidized with an oxidizing agent. In this way, if the oil phase finally obtained is distilled, the target branched polyene compound will not undergo isomerization to the internal olefin compound. At a rate.
[0063]
However, in the present invention, after the reaction is completed, to separate the target branched polyene compound from the obtained reaction mixture by distillation means that when the target branched polyene compound is separated from the reaction mixture, distillation is performed. It means that the target branched polyene compound is separated from the reaction mixture by the separating operation. Therefore, in the present invention, after the completion of the reaction, to separate the target branched polyene compound from the obtained reaction mixture by distillation, the target branched polyene compound itself is distilled from the reaction mixture as a fraction. In addition to the case where the reaction solvent is distilled off from the reaction mixture, the target branched polyene compound is separated from the reaction mixture, and further, a plurality of these distillation operations are performed, The case where the target branched polyene compound is separated from the reaction mixture is also included.
[0064]
According to the present invention, the following various branched polyene compounds can be obtained by appropriately selecting a conjugated diene compound used as a raw material.
[0065]
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[0066]
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[0067]
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[0068]
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[0069]
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[0070]
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[0071]
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[0072]
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[0073]
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[0074]
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[0075]
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[0076]
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[0077]
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[0078]
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[0079]
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[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
In particular, according to the present invention, 4-ethylidene-8-methyl-1,7-nonadiene is obtained by reacting ethylene with the aforementioned 7-methyl-3-methylene-1,6-octadiene (β-myrcene). In addition, by reacting ethylene with the aforementioned 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene), 4-ethylidene-8,12- Dimethyl-1,7,11-tridecatriene can be obtained.
[0086]
The branched polyene compound obtainable by the method of the present invention is not only capable of high-speed vulcanization by copolymerizing with an α-olefin such as ethylene and propylene, but also has weather resistance, heat resistance, An ethylenically unsaturated copolymer having excellent ozone resistance and the like can be obtained.
[0087]
【The invention's effect】
According to the present invention, after reacting ethylene and the conjugated diene compound in the presence of a transition metal catalyst comprising a transition metal compound and an organoaluminum compound, the resulting reaction mixture is treated with water and an oxidizing agent. Then, the transition metal catalyst is completely deactivated. Thereafter, when the target branched polyene compound is separated from the reaction mixture by distillation purification, polymerization is performed by isomerization of the branched polyene compound. Conversion to an unaffected internal olefin compound can be suppressed, and thus the desired branched polyene compound can be obtained in high yield. The branched polyene compound thus obtained is copolymerized with an α-olefin such as ethylene or propylene to give excellent weather resistance, heat resistance, ozone resistance, and high vulcanization speed. An unsaturated copolymer can be obtained.
[0088]
【Example】
EXAMPLES The present invention will be described below with reference to comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, the yield of the target product is p in the number of moles of the target product, and c₀(P / c₀) × 100 (%). The conversion rate of the conjugated diene as a raw material is [(c₀-C) / c₀] X 100 (%).
[0089]
Example 1
(Synthesis of 4-ethylidene-8-methyl-1,7-nonadiene)
Under a nitrogen atmosphere, a stainless steel (SUS316) autoclave with a capacity of 1500 ml was charged with 2.86 g (5.42 mmol) of 2-bis (diphenylphosphino) ethanecobalt (II) chloride, 70 g of anhydrous toluene, and 7-methyl-3. -593 g (4.02 mol) of methylene-1,6-octadiene (β-myrcene) was charged and stirred at room temperature for 1 hour. Next, 70.5 mL (64.2 mmol) of a toluene solution of triethylaluminum (0.91 mol / L) was added and the autoclave was sealed.
[0090]
Thereafter, an ethylene cylinder is directly connected to the autoclave, ethylene is introduced, and the inside of the autoclave is 5 kg / cm.²And heated to 80 ° C. While intermittently adding consumed ethylene, ethylene pressure is 4-5kg / cm²The reaction was carried out at 80 ° C. for 4 hours.
[0091]
After completion of the reaction, the autoclave was cooled and then opened, and a part of the obtained reaction mixture was collected and analyzed by gas chromatography to determine the product and its yield. As a result, the conversion rate of β-myrcene was 99%, and the yield of the target 4-ethylidene-8-methyl-1,7-nonadiene was 461 g (yield 70%). The yield of 5,9-dimethyl-1,4,8-decatriene, which is a reaction byproduct, was 119 g (yield 18%).
[0092]
Next, 200 g of the above reaction mixture was charged into a 1000 mL capacity glass separable flask with a stirring blade under a nitrogen atmosphere, and then 67 g of an aqueous solution containing 5% sodium hydroxide and 2% ethylenediaminetetraacetic acid disodium was added thereto. In addition, the mixture was stirred at room temperature for 20 minutes and then allowed to stand for 20 minutes. After extracting the aqueous layer, 67 g of water was added to the oil phase, and the mixture was further stirred at room temperature for 20 minutes and then allowed to stand for 20 minutes to extract the aqueous layer (water treatment of the reaction mixture). Thereafter, the oil phase was stirred for 30 minutes while circulating air (oxidant) through the separable flask at a rate of 200 m / min (oil phase air oxidation treatment).
[0093]
160 g of oil phase thus treated (containing 79 g of 4-ethylidene-8-methyl-1,7-nonadiene) was transferred to a 300 mL flask, heated to 140 ° C., and heated at 140 ° C. for 5 hours. After completion of heating, a part of the oil phase was collected and analyzed by gas chromatography, and the reaction from 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene The product was examined. As a result, the conversion rates of 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene were both 0%, leading to an internal olefin compound not involved in polymerization. Isomerization of was not observed.
[0094]
Example 2
Under a nitrogen atmosphere, 200 g of the reaction mixture obtained in Example 1 was charged in a 1000 mL capacity glass separable flask with a stirring blade, and subsequently 5% sodium hydroxide and 2% ethylenediaminetetraacetate disodium. After adding 67 g of an aqueous solution and stirring at room temperature for 20 minutes, it was allowed to stand for 20 minutes. After extracting the aqueous layer, 67 g of water was added to the oil phase, and the mixture was further stirred at room temperature for 20 minutes and then allowed to stand for 20 minutes to extract the aqueous layer. Thereafter, 63 g of a 0.1% aqueous hydrogen peroxide solution was added to the oil phase, and the mixture was stirred at room temperature for 20 minutes.
[0095]
160 g of the oil phase thus obtained (containing 79 g of 4-ethylidene-8-methyl-1,7-nonadiene) is transferred to a 300 mL flask, heated to 140 ° C., and heated at 140 ° C. for 5 hours. did. After completion of heating, a part of the oil phase was collected and analyzed by gas chromatography, and the reaction from 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene The product was examined. As a result, the conversion rates of 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene were both 0%, leading to an internal olefin compound not involved in polymerization. Isomerization of was not observed.
[0096]
Comparative Example 1
In Example 1, Example 1 was carried out except that after the reaction of ethylene and 7-methyl-3-methylene-1,6-octadiene (β-myrcene) was completed, the resulting reaction mixture was not subjected to air oxidation treatment. The reaction product from 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene was investigated. As a result, 34% of 4-ethylidene-8-methyl-1,7-nonadiene was isomerized to 4-ethylidene-8-methyl-2,7-nonadiene, and 5,9-dimethyl-1,4 It was confirmed that 93% of 1,8-decatriene was isomerized to 5,9-dimethyl-2,4,8-decatriene.
[0097]
Comparative Example 2
The same treatment as in Example 1 was carried out except that the reaction mixture was not washed with water and the oil phase was subjected to air oxidation treatment in Example 1, and 4-ethylidene-8-methyl-1,7-nonadiene and 5, The reaction product from 9-dimethyl-1,4,8-decatriene was investigated. As a result, 5% of 4-ethylidene-8-methyl-1,7-nonadiene was isomerized to 4-ethylidene-8-methyl-2,7-nonadiene, and 5,9-dimethyl-1,4 , 8-decatriene was confirmed to be isomerized to 5,9-dimethyl-2,4,8-decatriene.

Claims (9)

Ethylene and general formula (I)

(In the formula, f represents an integer of 1 to 5, R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Group or general formula (II)

(In the formula, n represents an integer of 1 to ^5, and R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ⁴ , R ⁵ and R ⁶ Are not hydrogen atoms at the same time.)
The alkenyl group represented by these is shown. However, R ¹ , R ² and R ³ are not simultaneously hydrogen atoms. )
Is reacted with a conjugated diene compound represented by the general formula (III)

(In the formula, f, R ¹ , R ² and R ³ are the same as described above.)
In the method for producing a branched polyene compound represented by the formula: A method for producing a branched polyene compound, wherein the branched polyene compound is separated from the reaction mixture by distillation. Ethylene and general formula (I ')

(In the formula, f represents an integer of 1 to 5, n represents an integer of 1 to 5, and R ¹ , R ² , R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or carbon number 1 to 5. (However, R ⁴ , R ^5, and R ⁶ are not hydrogen atoms at the same time.)
Is reacted with a conjugated diene compound represented by the general formula (III ′)

(In the formula, f, n, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are the same as described above.)
In the method for producing a branched polyene compound represented by the formula: A method for producing a branched polyene compound, wherein the branched polyene compound is separated from the reaction mixture by distillation. The method for producing a branched polyene compound according to claim 1, wherein the conjugated diene compound is 7-methyl-3-methylene-1,6-octadiene. The method for producing a branched polyene compound according to claim 2, wherein the conjugated diene compound is 7,11-dimethyl-3-methylene-1,6,10-dodecatriene. The method for producing a branched polyene compound according to claim 1 or 2, wherein the transition metal catalyst is a catalyst obtained by a reaction of a transition metal compound selected from iron, cobalt, nickel, rhodium or palladium with an organoaluminum compound. The branch according to claim 1 or 2, wherein the transition metal compound is a complex of a transition metal selected from iron, cobalt, nickel, rhodium or palladium having 1,2-bis (diphenylphosphino) ethane as a ligand. A method for producing a chain polyene compound. The method for producing a branched polyene compound according to claim 1 or 2, wherein the oxidizing agent is oxygen. The method for producing a branched polyene compound according to claim 1 or 2, wherein the oxidizing agent is hydrogen peroxide. The method for producing a branched polyene compound according to any one of claims 1 to 8, wherein after completion of the reaction between ethylene and the conjugated diene, the resulting reaction mixture is treated with water and then treated with an oxidizing agent.