JP6806973B2 - クロム化合物、これを利用した触媒システムおよびエチレンオリゴマーの製造方法 - Google Patents
クロム化合物、これを利用した触媒システムおよびエチレンオリゴマーの製造方法 Download PDFInfo
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Description
[X2CrLn]+[AY4]−
[(L∩L)CrX2Lm]+[AY4]−
(R1)2P−Z−P(R1)2
(R3)3Al
[X2CrLn]+[AY4]−
[(L∩L)CrX2Lm]+[AY4]−
(R1)2P−Z−P(R1)2
(R3)3Al
以下、本発明の好ましい実施例を通じて本発明の構成および作用をより詳細に説明することとする。ただし、これは、本発明の好ましい例示として提示されたものであり、いかなる意味でもこれによって本発明が制限されると解すべきものではない。
ペンタトリアコンタン−18−アミン(0.505g、0.994mmol)が溶解しているジクロロメタン(5mL)溶液をクロロジフェニルホスフィン(0.482mg、2.19mmol)とトリエチルアミン(1.00g、9.94mmol)が溶解しているジクロロメタン(5mL)溶液に0℃でゆっくり投入した。0℃で30分間撹拌後、温度をゆっくり常温に上げた。14時間反応後、減圧して、溶媒を除去し、ヘキサン(10mL)を投入した。不溶性の固体化合物を濾過して除去した。真空減圧して溶媒を除去し、残余物をジクロロメタンに溶解した後、アセトニトリルをゆっくり拡散させて、再結晶して、純粋な二座リガンド化合物N−(ジフェニルホスフィノ)−N−(ペンタトリアコンタン−18−イル)−1,1−ジフェニルホスフィノアミンを得た(0.593g、68%)。1H NMR(C6D6,400MHz)7.452−7.790(8H,br,ArH),7.080−7.163(12H,m,ArH),3.512−3.635(1H,m,NCH),2.110−2.115(2H,m,NCHCH2),1.179−1.186(2H,m,NCHCH2),1.361−1.202(60H,m,−CH2−),0.926(6H、t,JHH=6.4Hz,CH2CH3)
合成方法が文献(J.AM.CHEM.SOC.2004,126,14712−1471)に報告された化合物であって、原料の需給が容易なN−(ジフェニルホスフィノ)−N−イソプロピル−1,1−ジフェニルホスフィノアミンを準備した。
[CrCl2(CH3CN)4]+[B(C6F5)4]−
[CrCl2(THF)4]+[B(C6F5)4]−
[{(iPr)N(PPh2)2}CrCl2(CH3CN)2]+[B(C6F5)4]−
[{[(CH3)(CH2)16]2C(H)N(PPh2)2}CrCl2(NCCH3)2]+[B(C6F5)4]−
[{[(CH3)(CH2)16]2C(H)N(PPh2)2}Cr(CH2C6H4NMe2)2]+[B(C6F5)4]−
ドライボックス内で高圧反応器にクロロベンゼン(19mL)とMe3Al(10.8 mg、0.150mmol)を投入した後、ドライボックスの外に取り出して温度を60℃に上げた。前記実施例3で製造した化学式2Aのクロム化合物(2.0mg、0.0015mmol)をクロロベンゼン(0.5mL)に溶解させた後、Me3Al(22mg、0.300mmol)を添加し、全体溶液が1mLになるように、触媒溶液を製造した。5分間クロム化合物とアルミニウム化合物Me3Alを反応させて活性化した触媒種を生成した後、これを注射器で取って反応器に注入した後、30barの圧力でエチレンを注入して、75℃で30分間重合した。氷を使用して反応器の温度を低減した後、エチレンガスを開弁して除去し、エタノール(2mL)と10%塩酸水溶液(2mL)を入れて反応を終結した。気体クロマトグラフィー分析のために、ノナンをスタンダードで定量して(〜700mg)投入した後、一部のサンプルを取って、GC分析を通じて生成物を定量分析した。また、形成された高分子は、濾過を通じて分離して、真空オーブンで乾燥して質量を測定した。オリゴマー化結果を下記表1および表2に整理して示した。
Me3Alの代わりにEt3Alを使用し、触媒活性化(化学式2Aの化合物とEt3Alの反応)時間を1時間に増やしたことを除いて、実施例6と同じ方法および条件で行った。
Me3Alの代わりに(iBu)3Alを使用し、触媒活性化(化学式2Aの化合物と(iBu)3Alの反応)時間を1時間に増やしたことを除いて、実施例6と同じ方法および条件で行った。
化学式2Aで表されるクロム化合物の代わりに、化学式2Bで表されるクロム化合物を使用したことを除いて、実施例6と同じ方法および条件で行った。
ドライボックス内で高圧反応器にメチルシクロヘキサン(19mL)とiBu3Al(20mg、0.100mmol)を投入した後、ドライボックスの外に取り出して温度を40℃に上げた。前記実施例4で製造した化学式2Bのクロム化合物(2.6mg、0.0015mmol)をメチルシクロヘキサン(1mL)に分散させた後、注射器で取って反応器に注入した後、30barの圧力でエチレンを注入して、45℃で30分間重合した。実施例6と同じ方法で反応を終結し、生成物を分析した。
(iBu)3Alの代わりにEt3Alを使用したことを除いて、実施例10と同じ方法および条件で行った。
(iBu)3Alの代わりに(Octyl)3Alを使用したことを除いて、実施例10と同じ方法および条件で行った。
化学式2Bで表される化合物の代わりに化学式2Cで表される化合物を使用したことを除いて、実施例10と同じ方法および条件で行った。
(iBu)3Alの量を0.10mmolから0.45mmolに増加させ、エチレン圧力を30barから45barに増加させ、反応温度を45℃から35℃に下げたことを除いて、実施例10と同じ方法および条件で行った。
具体的に、ドライボックス内で高圧反応器にシクロヘキセン(C6H10)(19mL)とEt3Al(170mg、0.450mmol)を投入した後、ドライボックスの外に取り出して温度を35℃に上げた。実施例4で製造した[{[(CH3)(CH2)16]2C(H)N(PPh2)2}CrCl2(NCCH3)2]+[B(C6F5)4]−をシクロヘキセン(C6H10)(1mL)に分散させて、注射器で取って反応器に注入した後、45barの圧力でエチレンを注入して、45℃で30分間重合した。実施例1と同じ方法で反応を終結し、生成物を分析した。氷を使用して反応器の温度を下げた後、エチレンガスを開弁して除去し、エタノール(2mL)と10%塩酸水溶液(2mL)を入れて反応を終結した。気体クロマトグラフィー分析のために、ノナンをスタンダードで定量して(〜700mg)投入した後、一部のサンプルを取って、GC分析を通じて生成物を定量分析した。また、形成された高分子は、濾過を通じて分離して、真空オーブンで乾燥して質量を測定した。
具体的に、反応時間を1時間に増やしたことを除いて、実施例15と同じ方法で行った。
具体的に、Et3Alの代わりに(iBu)3Alを使用したことを除いて、実施例15と同じ方法で行った。
ドライボックス内で高圧反応器にクロロベンゼン(19mL)とMAO(modified−MAO、Akzo−Nobel社製品、7wt%−Al、170mg、0.450mmol)を投入した後、ドライボックスの外に取り出して温度を60℃に上げた。(iPrN(PPh2)2)CrCl3(2.0mg、0.0015mmol)をクロロベンゼン(1mL)に溶解させて、注射器で取って反応器に注入した後、30barの圧力でエチレンを注入して、75℃で30分間重合した。実施例1と同じ方法で反応を終結し、生成物を分析した。
反応溶媒としてクロロベンゼンの代わりにメチルシクロヘキサンを使用することを除いて、比較例1と同じ方法および条件で行った。
反応溶媒としてクロロベンゼンの代わりにメチルシクロヘキサンを使用し、(iPrN(PPh2)2)CrCl3の代わりにiPrN(PPh2)2(0.0015mmol)とCr(acac)3(0.0015mmol)の混合物を反応器に投入したことを除いて、比較例1と同じ方法および条件で行った。
b)メチルシクロペンタン+メチレンシクロペンタン
c)Organometallics 2007,26,1108:非特許文献7
Claims (11)
- 下記化学式1で表されるクロム化合物:
[化学式1]
[X2CrLn]+[AY4]−
前記化学式1で、Xは、それぞれ独立して、ハロゲン、またはオルト−(N,N−ジメチルアミノ)ベンジルであり;Lは、それぞれ独立して、炭素数2〜30のニトリル、炭素数2〜30のエーテル、またはH2Oリガンドであり;nは、0〜4の整数であり;Aは、ボロンであり;Yは、炭素数6〜20のフッ素が置換されたアリール、炭素数6〜20のフッ素が置換されたアリールオキシまたは炭素数1〜20のフッ素が置換されたアルコキシである。 - Xは、塩素であり、[AY4]−が、[B(C6F5)4]−、または[B((3,5−(CF3)2C6H3)4]−である、請求項1に記載のクロム化合物。
- Xは、オルト−(N,N−ジメチルアミノ)ベンジルであり、[AY4]−が、[B(C6F5)4]−、または[B((3,5−(CF3)2C6H3)4]−である、請求項1に記載のクロム化合物。
- 下記化学式2で表されるクロム化合物:
[化学式2]
[(L∩L)CrX2Lm]+[AY4]−
前記化学式2で、(L∩L)は、二座(bidentate)キレートリガンドであり、Xは、それぞれ独立して、ハロゲン、炭素数2〜30のカルボキシレート、アセチルアセトネート、またはエーテル基およびアミン基のうち1種以上を含むかまたは含まない炭素数1〜30のヒドロカルビルであり;Lは、それぞれ独立して、炭素数2〜30のニトリル、炭素数2〜30のエーテル、またはH2Oリガンドであり;mは、0〜2の整数であり;Aは、ボロンであり;Yは、炭素数6〜20のフッ素が置換されたアリール、炭素数6〜20のフッ素が置換されたアリールオキシまたは炭素数1〜20のフッ素が置換されたアルコキシである。 - 前記二座(bidentate)キレートリガンド(L∩L)が、下記化学式3で表される化合物である、請求項4に記載のクロム化合物:
[化学式3]
(R1)2P−Z−P(R1)2
前記化学式3で、R1は、それぞれ独立して、炭素数1〜50のアルキル基または炭素数6〜50のアリール基であり;Zは、二つのリン(P)原子を連結する炭素数2〜50のアルキレン基、炭素数6〜50のアリレン基、または−N(R2)−であり、前記R2は、炭素数1〜50のアルキルまたは炭素数6〜50のアリールである。 - 前記化学式3のR1は、フェニルであり;Zは、−N(R2)−、前記R2は、炭素数1〜50のアルキルまたは炭素数6〜50のアリールである、請求項5に記載のクロム化合物。
- 下記化学式2で表されるクロム化合物;および
下記化学式4で表される有機アルミニウム化合物を含むエチレンオリゴマー化触媒システム:
[化学式2]
[(L∩L)CrX2Lm]+[AY4]−
前記化学式2で、(L∩L)は、二座(bidentate)キレートリガンドであり、Xは、それぞれ独立して、ハロゲン、炭素数2〜30のカルボキシレート、アセチルアセトネート、またはエーテル基およびアミン基のうち1種以上を含むかまたは含まない炭素数1〜30のヒドロカルビルであり;Lは、それぞれ独立して、炭素数2〜30のニトリル、炭素数2〜30のエーテル、またはH2Oリガンドであり;mは、0〜2の整数であり;Aは、ボロンであり;Yは、炭素数6〜20のフッ素が置換されたアリール、炭素数6〜20のフッ素が置換されたアリールオキシまたは炭素数1〜20のフッ素が置換されたアルコキシである;
[化学式4]
(R3)3Al
前記化学式4でR3は、炭素数1〜20のアルキル基である。 - 前記化学式4のR3は、エチルまたはイソブチルである、請求項7に記載のエチレンオリゴマー化触媒システム。
- 前記触媒システムは、投入される前記化学式2で表されるクロム化合物と前記化学式4で表されるアルミニウム化合物のモル比が1:50〜1:500である、請求項7に記載のエチレンオリゴマー化触媒システム。
- 請求項7〜9のいずれかに記載の触媒システムとエチレン単量体を接触させて、1−ヘキセンおよび1−オクテンを選択的に製造する段階を含むエチレンオリゴマーの製造方法。
- 前記触媒システムとエチレン単量体は、シクロヘキセン(cyclohexene)溶媒で接触する、請求項10に記載のエチレンオリゴマーの製造方法。
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