JP4020540B2 - Process for producing olefin polymer - Google Patents

Description

【００４４】
上記一般式（２）および一般式（３）において、Ｒ²¹はＣ_1-8 のアルキル基であり、ｒは０以上の整数である。
これら［ａ３］成分は、１種類のトリアルキルアルミニウム、または２種類以上のトリアルキルアルミニウムと水との反応により得られる生成物である。具体的には１種類のトリアルキルアルミニウムの場合は、メチルアルモキサン、エチルアルモキサン、ブチルアルモキサン、イソブチルアルモキサン等が挙げられ、２種類以上のトリアルキルアルミニウムを用いる場合は、メチルエチルアルモキサン、メチルブチルアルモキサン、メチルイソブチルアルモキサン等が例示される。
【００４５】
これらの中で好ましいものはメチルアルモキサン、イソブチルアルモキサン、メチルイソブチルアルモキサン、およびこれらの混合物である。特に好ましいのは、メチルアルモキサン、およびメチルイソブチルアルモキサンである。
また、これらの有機アルミニウムオキシ化合物はシリカゲルやアルミナに担持させて使用することもでき、特にメチルアルモキサンをシリカゲルに担持させたものが好ましい。
これらのアルモキサンは公知の様々な条件下に調製することができる。具体的には以下の方法が例示できる。
【００４６】
（イ）トリアルキルアルミニウムをトルエン、ベンゼン、エーテル等の適当な有機溶剤を用いて直接水と反応させる方法。
（ロ）トリアルキルアルミニウムと結晶水を有する塩水和物、例えば硫酸銅、硫酸アルミニウムの水和物と反応させる方法。
（ハ）トリアルキルアルミニウムとシリカゲル等に含浸させた水分とを反応させる方法。
（ニ）トリメチルアルミニウムとトリイソブチルアルミニウムを混合し、トルエン、ベンゼン、エーテル等の適当な有機溶剤を用いて直接水と反応させる方法。
（ホ）トリメチルアルミニウムとトリイソブチルアルミニウムを混合し、結晶水を有する塩水和物、例えば硫酸銅、硫酸アルミニウムの水和物と加熱反応させる方法。
（ヘ）シリカゲル等に水分を含浸させ、トリイソブチルアルミニウムで処理した後、トリメチルアルミニウムで追加処理する方法。
【００４７】
［ａ４］ホウ素アニオン系化合物
次に、［ａ４］ホウ素アニオン系化合物を使用した場合について説明する。ホウ素アニオン系化合物を使用した場合、メタロセン系遷移金属触媒は［ａ１］成分と［ａ４］成分をあわせて下記一般式（４）で表される。
【００４８】
【化６】
［Ｒ¹¹ _i(ＣｐＲ¹² _j)(ＣｐＲ¹² _j)ＭＲ¹³Ｒ¹⁴］⁺ Ｒ^15- ・・・一般式(４）
【００４９】
ここでＲ¹¹ _i(ＣｐＲ¹² _j)、Ｍ、Ｒ¹³は一般式（１）で表されるものと同等である。即ち、Ｒ¹¹は、炭素、ケイ素、ゲルマニウム等の長周期律表の第１４または１５族元素を含む共有結合架橋基であり、Ｒ¹²は、同一または異なってもよい、水素、ハロゲン、ケイ素含有基、ハロゲン置換基を有しても良い炭素数が１〜２０の炭化水素基、アルコキシ基またはアリールオキシ基で、Ｒ¹³は、同一または異なっても良い、水素、ハロゲン、炭素数１〜２０の炭化水素基、ハロゲン含有炭化水素基、珪素含有基、アルコキシ基またはアリールオキシ基であり、Ｍは長周期律表第４，５，６族の金属であり、ｉは０または１、ｊはｉ＋ｊ＝５となる整数である。
【００５０】
さらにＲ¹⁴はＭに配位するテトラヒドロフラン等中性の配位子である。Ｒ¹⁵は一般式（４）の金属カチオンを安定化させることのできる対アニオンであり、テトラフェニルボレート、テトラ（ｐ−トリル）ボレート、カルバドデカボレート、ジカルバウンデカボレート等の［ａ４］成分、即ちホウ素アニオン系化合物である。
【００５１】
具体的に一般式（４）に相当するものを例示すると、イソプロピリデン−ビス（インデニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン−ビス（インデニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン−ビス（インデニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン（シクロペンタジエニル）（フルオレニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン（シクロペンタジエニル）（フルオレニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン（シクロペンタジエニル）（フルオレニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、メチレン−ビス（シクロペンタジエニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、エチレン−ビス（シクロペンタジエニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン−ビス（シクロペンタジエニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、ジメチルシリル−ビス（シクロペンタジエニル）ジルコニウム（クロライド）（テトラフェニルボレート）テトラヒドロフラン錯体、メチレン−ビス（シクロペンタジエニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、エチレン−ビス（シクロペンタジエニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン−ビス（シクロペンタジエニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、ジメチルシリル−ビス（シクロペンタジエニル）ジルコニウム（メチル）（テトラフェニルボレート）テトラヒドロフラン錯体、メチレン−ビス（シクロペンタジエニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、エチレン−ビス（シクロペンタジエニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、イソプロピリデン−ビス（シクロペンタジエニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、ジメチルシリル−ビス（シクロペンタジエニル）ジルコニウム（ヒドリド）（テトラフェニルボレート）テトラヒドロフラン錯体、等が挙げられる。
また、これらのホウ素アニオン系化合物はシリカゲルやアルミナに担持させて使用することもできる。
【００５２】
［ａ５］有機アルミニウム化合物
本発明においては［ａ５］成分として用いられる有機アルミニウム化合物は、下記一般式（５）で示されるアルミニウム化合物である。
【００５３】
【化７】
Ｒ³ _mＡｌ（Ｘ_3-m) ・・・一般式（５）
【００５４】
（式中、Ｒ³ はＣ_1-20のアルキル基、Ｘは水素、ハロゲン、アルコキシ基、アルキルシリル基、アルキルシロキシ基、アルキルアミノ基またはアルキルアミド基を表す。ｍは０＜ｍ＜３から選ばれる数。）
【００５５】
［ａ５］成分の具体例としては、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ｎ−ブチルアルミニウム、トリｔｅｒｔ−ブチルアルミニウム、トリペンチルアルミニウム、トリオクチルアルミニウム、トリデシルアルミニウム、トリシクロヘキシルアルミニウム、トリシクロオクチルアルミニウムなどのトリアルキルアルミニウム、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジエチルアルミニウムブロミド、ジイソブチルアルミニウムクロリドなどのジアルキルアルミニウムハライド、ジエチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどのジアルキルアルミニウムハイドライドであり、このうち特にトリアルキルアルミニウムが好ましく、その中でも特にトリエチルアルミニウムとトリイソブチルアルミニウムが好ましい。
【００５６】
上記において、Ｘがアルコキシ基の場合は［Ｂ］成分と同一になるが、運転安定化のために加える［Ｂ］成分とは別に加える。従って、［Ｂ］成分の供給量が反応器から排出される製品ポリマー１ｇに対して０.０００１ナノｍｏｌ〜１００００ナノｍｏｌ、好ましくは０.００１ナノｍｏｌ〜５０００ナノｍｏｌ、さらに好ましくは０.０１ナノｍｏｌ〜１０００ナノｍｏｌの量を添加するのに加え、さらに［ａ５］成分を添加することになる。
【００５７】
［ａ５］成分の供給方法は、通常、事前に触媒に接触させる方法と重合中に循環ラインへ供給する２つの方法をあわせて用いるが、その供給方法は特に限定されるものではなく、以下の供給方法でもよい。
▲１▼ 循環ラインに成分［ａ５］をフィードする。
▲２▼ 原料供給ラインに成分［ａ５］をフィードする。
▲３▼ メタロセン系遷移金属触媒を供給しているラインに成分［ａ５］をフィードする。
▲４▼ 触媒成分として、予めメタロセン系遷移金属触媒に成分［ａ５］を加えておく。
▲５▼ 上記▲１▼〜▲５▼の方法をあわせて行なう。
【００５８】
［Ｂ］有機アルミニウム化合物（アルコキシ基含有）
成分［Ｂ］として用いられる有機アルミニウム化合物は、下記一般式（６）で示されるアルコキシ基含有アルミニウムである。
【００５９】
【化８】
Ｒ¹ _nＡｌ(ＯＲ²)_3-n ・・・一般式（６）
【００６０】
（式中、Ｒ¹ はＣ_1-20のアルキル基、アリール基、水素またはハロゲンを表す。Ｒ² はＣ_1-20のアルキル基またはアリール基を表す。ｎは０≦ｎ＜３から選ばれる数。）
【００６１】
［Ｂ］成分の具体例を挙げると、
(1) 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、ジ（イソプロピル）アルミニウム（イソプロポキシド）、ジエチルアルミニウム（イソプロポキシド）、ジエチルアルミニウム（フェノキシド）等のモノアルコキシ基含有、またはモノアリールオキシ基含有アルミニウムや、
(2) メチルアルミニウムジ（メトキシド）、エチルアルミニウムジ（エトキシド）、イソプロピルアルミニウムジ（イソプロポキシド）、エチルアルミニウムジ（イソプロポキシド）、エチルアルミニウムジ（フェノキシド）等のジアルコキシ基含有、またはジアリールオキシ基含有アルミニウム、あるいはこれらと、ジアルキルアルミニウム（アルコキシド）、ジアリールアルミニウム（アルコキシド）、ジアルキルアルミニウム（アリールオキシド）、ジアリールアルミニウム（アリールオキシド）等のアルミニウムモノアルコキシドとの混合物や、
(3) アルミニウムトリ（メトキシド）、アルミニウムトリ（エトキシド）、アルミニウムトリ（イソプロポキシド）等のトリアルコキシアルミニウム、またはアルミニウムトリ（フェノキシド）等のトリアリールオキシアルミニウム化合物、またはこれらと、ジアルキルアルミニウム（アルコキシド）、ジアリールアルミニウム（アルコキシド）、ジアルキルアルミニウム（アリールオキシド）、ジアリールアルミニウム（アリールオキシド）、アルキルアルミニウムジ（アルコキシド）、アリールアルミニウムジ（アルコキシド）、アルキルアルミニウムジ（アリールオキシド）、アリールアルミニウムジ（アリールオキシド）等との混合物、等が挙げられる。
これらの中ではジエチルアルミニウムエトキシドが特に好ましい。これらアルコキシ基含有アルミニウム化合物は単独で用いても２種以上を混合しても良い。
【００６２】
さらにはこれらのアルミニウムはトリメチルアルミニウム、トリエチルアルミニウム、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との任意の混合物として使用できる。
特にトリアルキルアルミニウムとジアルキルアルミニウム（アルコキシド）の組み合わせが好ましく、特にはトリエチルアルミニウムとジエチルアルミニウムエトキシドの組み合わせが好ましい。
成分［Ｂ］の供給量は、反応器から排出される製品ポリマー１ｇに対して、０.０００１ナノｍｏｌ〜１００００ナノｍｏｌ、好ましくは０.００１ナノｍｏｌ〜５０００ナノｍｏｌ、さらに好ましくは０.０１ナノｍｏｌ〜１０００ナノｍｏｌの範囲である。
【００６３】
成分［ａ５］として有機アルミニウム化合物を供給する場合、成分［Ｂ］の供給量は成分［ａ５］に対して特に限定されるものではないが、成分［ａ５］１ｍｏｌに対して、０.００１〜１００ｍｏｌ、好ましくは０.０１〜１０ｍｏｌの範囲で供給されることが望ましい。
また、成分［Ｂ］の供給量は成分［ａ１］として反応系に供給されるメタロセン遷移金属化合物に対して特に限定されるものではないが、成分［ａ１］１ｍｏｌに対して、０.０１〜１００００ｍｏｌ、好ましくは０.１〜１０００ｍｏｌの範囲で供給されることが望ましい。
【００６４】
反応器への成分［Ｂ］の供給は、通常重合を行なっている反応器付帯の循環ラインへ供給するが、供給点は特に限定されるものではなく、以下の供給方法を採用することができる。
（１）反応器の循環ラインに成分［Ｂ］をフィードする。
（２）反応器の原料ラインに成分［Ｂ］をフィードする。
（３）メタロセン系遷移金属触媒を供給しているラインに成分［Ｂ］をフィードする。
（４）（１）〜（３）の方法をあわせて行なう。
【００６５】
《予備重合》
なお、本発明で用いられるメタロセン系触媒は上記成分の他にエチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン等のα−オレフィン、またはこれらの混合したオレフィン混合物が予備的に重合されていても良い。予備重合は予備重合前の触媒１ｇあたり０.０１〜１０００ｇの重合体が生成するようにすることが好ましい。
【００６６】
《重合》
本発明に係わるオレフィンの重合方法は、前述のオレフィン重合触媒の存在下にオレフィンを重合させるものであり、気相重合、バルク重合、スラリー重合等が挙げられ、媒体が液体、または超臨界流体の場合はバルク重合、もしくはスラリー重合となり、気体の場合には気相重合となる。これらの重合方法のうち、特に好ましいのは気相重合法である。
上記重合を行なうとこにおこるトラブルとして、重合ポリマーや微粉が静電気力等により反応器壁や攪拌翼に付着滞留し、さらに触媒が存在することにより、器壁や攪拌翼表面でポリマーが溶融し、シート状ポリマーや塊状ポリマーが生成するトラブルが挙げられる。これらのシート状ポリマーや塊状ポリマーは抜き出しラインを閉塞せしめ、重合ポリマーを抜き出せなくなるため、長期に安定して製品を供給する上では大きな障害となる。
【００６７】
シート状ポリマーや塊状ポリマーが生成する条件として、器壁や攪拌翼表面に重合ポリマーや微粉が付着滞留することが挙げられる。器壁に付着滞留しているかどうかは、器壁表面を測定する壁面温度計を設置し、壁面温度と重合温度の差を見ることにより監視できる。すなわち、付着滞留が多い場合は、重合ポリマーが厚く付着するために温度降下を生じ、重合温度と器壁温度の差は大きくなる。逆に付着滞留が少ない場合は温度降下が小さいため、重合温度と器壁温度の差は小さくなる。従って、この温度差を監視することにより、シート状ポリマーや塊状ポリマーが生成する条件を早期に検知することができる。
【００６８】
また、実際にシート状ポリマーや塊状ポリマーが生成した場合は、壁面温度が上昇するため、トラブルが生じた目安となる。
反応器は外部に熱が逃げていくため、通常、壁面温度（ｔｗと記す。単位：℃）は重合温度（ｔｒと記す。単位：℃）より低くなる。安定に運転を継続するためには壁面温度と重合温度の差が０.５＜ｔｒ−ｔｗ＜１０となるように保つ必要があり、好ましくは１.０＜ｔｒ−ｔｗ＜７．０の範囲に保つのが良い。
【００６９】
《流動床反応器》
以下、本発明の一例として、循環媒体が気体の場合のオレフィン重合方法（気相重合方法）を、図２を参照しながら詳細に説明する。
前述の［Ａ］成分を、図２中に示す、触媒供給ライン１より攪拌式流動床反応器２に供給する。また、重合時は循環ガスライン３中に、原料供給ライン４より原料モノマー、または窒素等の不活性ガスを供給し、成分［Ｂ］を供給ライン５より供給し、循環ガス圧送機７を駆動させこれらのガスを循環させる。最終的に循環ガスは再度、攪拌式流動床反応器に再供給される。
【００７０】
また、製品、および余剰ガスは抜出しライン９より製品分離器１０に導かれる。この分離器下部の製品抜き出しライン１２により製品を連続的、または間欠的に抜出し、上部パージライン１１より余分なガスを系外にパージする。反応器の圧力はパージライン１１に設置した圧力制御弁の開度を調整して一定に保つ。 反応器内は事前に投入した粒子、または重合により生じるポリマー粒子と原料モノマー、不活性ガス等からなる流動ガス、および機械的に攪拌する攪拌翼６により流動床を形成する。この攪拌翼６はモーター１４により強制的に攪拌する。
【００７１】
また、反応器には器壁の温度を測定するために壁面温度計１３を設置し、重合温度と器壁温度の差を監視する。器壁温度を測定する温度計は、器壁より０．５〜１０.０ｍｍの範囲で設置することが好ましい。
この場合、流動ガスは不活性ガスが５ｖｏｌ％〜９０ｖｏｌ％の範囲、原料モノマーであるエチレン、α−オレフィン等が１０ｖｏｌ％〜９５ｖｏｌ％の範囲で操作される。
また、反応によって生じる重合熱は、循環ガスライン中に設置した熱交換器８によって除去される。
【００７２】
使用ガスの圧力は１ｋｇ／ｃｍ² 〜１００ｋｇ／ｃｍ² の範囲、好ましくは５ｋｇ／ｃｍ² 〜５０ｋｇ／ｃｍ² の範囲で使用し、温度は１０℃〜１００℃の範囲、好ましくは３０℃〜１００℃の範囲、さらに好ましくは５０℃〜１００℃の範囲で使用する。
攪拌翼としては、リボン型攪拌翼機、錨型攪拌機、スクリュウ型攪拌機等の攪拌翼を用いて行なうことができる。さらに図２に示すような重合反応器を２段以上直列に接続し、多段重合運転で行なうこともできる。
【００７３】
本発明では流動床反応部２として攪拌式流動床以外の流動床を用いることができる。この流動床としては循環ガスを反応系に導く際に、分散板を使用する気相流動層が例示できる。
本発明で用いられるオレフィンとしては、炭素数２〜１８のα−オレフィンが好ましく、例としてはエチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセンなどが挙げられる。
【００７４】
さらにシクロペンテン、シクロヘプテン、ノルボルネン、５−メチル−２−ノルボルネン、スチレン、ビニルシクロヘキサンなども挙げられる。
本重合においてはこれらのオレフィンを重合あるいは共重合させるわけであるが、これらとともにブタジエン、イソプレン、１，４−ヘキサジエン、ジシクロペンタジエン、５−エチリデン−２−ノルボルネンなどのポリエン類を共重合させることもできる。
【００７５】
本発明ではこれらのうちエチレンの単独重合、またはエチレンと炭素数３〜１８のα−オレフィンと共重合させることが好ましく、特にエチレンと炭素数３〜１８のα−オレフィンと共重合体させること、またはプロピレンの単独重合、またはプロピレンとエチレンおよび／または炭素数４〜１８のα−オレフィンとの共重合することが好ましい。
また重合モノマーとして例を挙げたエチレン、α−オレフィン等の他に窒素、飽和炭化水素等の不活性ガスも同時に用いることができる。
露点の高いα−オレフィンあるいは不飽和炭化水素を用いる場合は熱交換器８で除熱され凝縮する場合もあるが、流動床反応器２の重合温度はこれ等のα−オレフィン、不飽和炭化水素が気体となる条件が選ばれる。
【００７６】
本発明においてメルトインデックス（ＭＩ）の測定はＪＩＳ規格Ｋ７２１０、密度の測定はＫ７１１２に準拠して測定を行なった。また系内ガス濃度はガスクロマトグラフィーを使用し、エチレン、１−ヘキセンの測定は日立製作所１６３型を使用、水素濃度の測定は島津製作所４Ｃ型（検出器ＴＣＤ方式）と日立製作所２６３−３０型（検出器ＰＩＤ方式）を使用し水素濃度により使い分けた。
【００７７】
【実施例】
以下、本発明を実施例によって説明するが、本発明はこれら実施例に限定されるものではない。
〔実施例１〕
（１）粘土鉱物の化学処理
市販の膨潤性合性雲母（コープケミカル社製、「ソマシフＭＥ−１００」）４００ｇと市販の親水性スメクタイト（コープケミカル社製、「ＳＷＮ」）１００ｇを混合し、これを２．０重量％硝酸クロム（III)水溶液２．８リットル中に分散させ、常温で２時間攪拌した。これを脱塩水にて濾過、洗浄した。得られた固体部に水を添加して、２０．０重量％水スラリーを調製し、噴霧乾燥処理を行なった。この結果、平均粒径５４μｍの粒子が４５０ｇ得られた。平均粒径１０μｍ以下の粒子の数は全粒子の４％であり、圧壊強度は２．０ＭＰａ、嵩密度は０．７５ｇ／ｃｃであった。この粒子をさらに２００℃で２時間減圧乾燥した。
【００７８】
（２）触媒調製
容量１０リットルの誘導攪拌装置付き反応器にｎ−ヘプタン４．４リットル、上記（１）で得られた合成雲母の粒子８０ｇを導入した。これに６００ミリリットルのトルエンに溶解したビス（ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド６．４ｍｍｏｌの溶液を添加し、室温で１０分間攪拌した。
【００７９】
（３）予備重合
上記攪拌混合物に、引き続きトリエチルアルミニウム７１．５ｍｍｏｌを添加し、系の温度を６０℃とした。１０分後エチレンガスを導入し、２．５時間反応を続けた。この間に生成したポリエチレンは５４７ｇであった。
【００８０】
（４）気相重合
上記（３）の予備重合触媒を用いて気相重合を行なった。図２に示すような連続気相重合反応装置において重合を行なった。予めシードポリマーを１．１ｋｇ計量して反応器内に充填し、上記で調製した触媒をｎ−ヘキサンでスラリー状にし、予備重合触媒あたりに換算して３００ｍｇ／ｈｒで反応器に供給した。同様にｎ−ヘキサンに希釈したトリエチルアルミニウムを２７０ｍｇ／ｈｒで反応器に供給した。さらにｎ−ヘキサンで希釈したジエチルアルミニウムエトキシドを３０ｍｇ／ｈｒで間欠的にフィードした。また、重合反応器は条件を、圧力２０ｋｇ／ｃｍ² 、重合反応温度８３℃、平均滞留時間は３．７時間、攪拌翼回転数１５０ｒｐｍとして行なった。系内のガス濃度を定期的にガスクロマトグラフィーを用いて分析し、都度、反応器内のエチレン濃度が８４．０〜８７．０ｖｏｌ％、１−ヘキセン濃度が３．３〜３．５ｖｏｌ％、水素濃度１８０〜２１０ｐｐｍの範囲に保たれるようにフィードガス量を調整した。生産量がほぼ一定となった定常状態ではエチレンガスフィード量は５．５ｋｇ／ｈｒ、１−ヘキセンフィード量は０．６ｋｇ／ｈｒであった。この条件下で３日間運転を行なったが、抜出し部ラインでのトラブルもなく、安定に運転することが可能であった。３日間の重合で、重合温度（ｔｒ）と器壁温度（ｔｗ）の差は３．０〜５．０℃の範囲であった。また、重合終了後に反応器を開放して内部点検を行なったが、シート状ポリマー、塊状ポリマーの生成は認められなく、壁へのポリマー付着もなかった。
重合体の密度は０．９２６ｇ／ｃｃ、メルトインデックス（ＭＩ）は１．６ｇ／１０分、平均粒径は７９０μｍ、嵩密度は０．３８ｇ／ｃｃであった。
【００８１】
〔比較例１〕
実施例１で得られた予備重合触媒を用いて、ジエチルアルミニウムエトキシドを使用しないで重合を実施した。系内ガス濃度、重合圧力、重合温度、攪拌翼回転数等の重合条件は実施例１と同じ条件になるようにした。触媒を添加する直前の重合温度と器壁温度との差は３．５℃であった。重合開始より半日経た時点で重合温度と器壁温度との温度差が大きくなり始め、１日経た時間で１１．５℃となった。さらに運転を継続すると、器壁温度が時々跳ね上がる現象を観察し最大８７℃までの上昇を観察した。また、抜出しポリマー中に小さい溶融ポリマーも観察された。そこで触媒供給をストップし、器壁温度が跳ね上がる現象が無くなるまで待ち、安定したところで再供給をしたが、その都度、器壁温度が上昇し、最終的に抜出しトラブルにより運転停止を余儀なくされた。運転停止後に反応器を開放して内部を点検すると、塊状ポリマーが確認された。また、反応器壁には薄膜状のポリマーの付着が大量に観察された。
【００８２】
〔実施例２〕
〈触媒調製と予備重合〉
独国Ｗｉｔｃｏ社製のＭ−ＳｉＯ₂(メチルアルモキサンをＳｉＯ₂ 上に担持したもの、Ａｌ濃度＝２２．３ｗｔ％）２０ｇを、ｎ−ヘプタン１リットルでスラリー状とし、ここにビス（ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリドをＡｌに対して１／２５０モル比、トリイソブチルアルミニウム（ＴｉＢＡ）をメチルアルモキサンのＡｌに対して１／６モル比加え、４０℃で１０分間攪拌した。その後、４０℃に保ちつつエチレンを導入し、１時間反応を続けた。エチレンの供給量はＭ−ＳｉＯ₂ に対して８倍重量であった。その後、室温で窒素にて１２時間パージした後、同じく室温にて２時間減圧乾燥を行った。
【００８３】
〈気相重合〉
上記の予備重合触媒を用いて連続気相重合を行った。実施例１と同様にシードポリマー高さになるように、予めシードポリマーを１．２kg計量して反応器内に充填し、上記で調整した触媒をｎ−ヘキサンでスラリー状にし、予備重合触媒あたりに換算して２１０mg／hrで反応器に供給した。同様にｎ−ヘキサンに希釈したトリエチルアルミニウムを１００mg／hrで反応器に供給した。また、運転条件を、圧力２０kg／cm² 、温度８０℃、平均滞留時間は４．１時間、攪拌翼回転数１５０rpm として重合を行った。系内のガス濃度を定期的にガスクロマトグラフィーを用いて分析し、都度、反応器内のエチレン濃度が８４.０〜８７.０ vol％、１−ブテン濃度が３.０〜３.５ vol％、水素濃度２１０〜２４０ppm の範囲に保たれるようにフィードガス量を調整した。
【００８４】
触媒フィード前の重合温度と反応器壁温度の差は３．５℃であった。触媒フィードを開始してから徐々に重合温度と反応器壁温度の差は広がり、１日を経た時点で１０℃以上となった。さらに半日を経ると、時々、反応器壁温度が跳ね上がり、重合温度は８０℃に保っているにもかかわらず、反応器壁温度は８０℃を超える現象が見られるようになった。そのためｎ−ヘキサンで希釈したジエチルアルミニウムエトキシドを３４mg／hrで間欠的にフィードした。すると、反応器壁温度が跳ね上がる現象はおさまり、ジエチルアルミニウムエトキシドを間欠フィードし始めてから約１日を経た時点で重合温度と反応器壁温度の差は３．９℃まで戻った。トータル５日間の運転の後、停止操作を行い、反応器内部の確認を行ったところ、溶融ポリマーの生成は認められなかった。
【００８５】
〔比較例２〕
〈気相重合〉
実施例１と同じようにして調整した触媒を用いて、連続気相重合反応器を用いて重合を行った。実施例１でジエチルアルミニウムエトキシドを供給する代わりに、エタノールを供給する以外は同じ条件で重合を行った。
触媒フィード前は重合温度と反応器壁温度の差は３．４℃であった。重合を開始してから徐々に温度差が広がり始めたため、エタノールを供給開始した。エタノールは、２５℃、重合圧力＋２kg／cm² の条件下で金属製のポット内にエタノールを入れ、このエタノール中を窒素ガスをバブリングして通過させた後、重合系に供給した。バブリングで通過した窒素ガス中のエタノールが飽和状態であると仮定して、２０mg／hrのエタノール供給量となった。
【００８６】
この状態で運転を継続していると、約２日後には徐々に重合温度と反応器壁温度との差は小さくなり始めたが、さらに運転を継続すると、突然、反応器壁温度が上昇し、最大９８℃までの上昇を観察した。反応器内部のポリマーの抜き出しができなくなったため、運転を停止した。停止後に反応器を開放して内部を点検すると塊状ポリマーが確認された。
【００８７】
【発明の効果】
本発明によれば、流動床反応器においてオレフィンの重合を行なう際に、シート状ポリマー、塊状ポリマーの生成によるトラブルがなく、長期に渡り安定に運転が可能であり、工業的に極めて有用である。
【図面の簡単な説明】
【図１】本発明の理解を助けるためのフローチャート図。
【図２】本発明に使用される流動床反応器を示すフローチャート図。
【符号の説明】
１ 触媒供給ライン
２ 攪拌式流動床反応器
３ 循環ガスライン
４ 原料供給ライン
５ 供給ライン
６ 攪拌翼
７ 循環ガス圧送機
８ 熱交換器
９ 抜出しライン
１０ 製品分離器
１１ パージライン
１２ 製品抜き出しライン
１３ 壁面温度計
１４ モーター[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an olefin polymer. More specifically, when an olefin is polymerized in the presence of a metallocene catalyst, there is no adhesion to a product wall or formation of a bulk polymer, and stable operation can be performed for a long period of time. The present invention relates to a method for producing an olefin polymer.
[0002]
[Prior art]
Olefin polymers such as ethylene polymer or linear low density polyethylene (LLDPE), which is a copolymer of ethylene and α-olefin, are widely used as film molding materials and injection molding materials. Yes.
Conventionally, such olefin polymers are polymerized or copolymerized in the presence of so-called Ziegler-based catalysts mainly composed of titanium, magnesium and halogen by solution polymerization, suspension polymerization, bulk polymerization or gas phase polymerization. It is manufactured by letting.
[0003]
In particular, in the production of olefins in gas phase polymerization, bulk polymerization, and slurry polymerization, the product polymer adheres to the wall surface and the stirring blade during long-term operation, and sometimes the adhering polymer melts to form a sheet polymer or bulk polymer. The product extraction line may be blocked and operation may be hindered.
[0004]
In order to prevent such operation inhibition, a method of adding alcohols, ketones, etc. into the system (JP-A-1-230607), a method of adding water (JP-B-7-5665), alcohol phosphate A method of adding a substance composed of a mixture of a fetal salt and a quaternary ammonium salt (Japanese Patent Laid-Open No. 6-17212), a method of starting the reaction by filling water-containing particles in the reactor in advance (Japanese Patent Laid-Open No. 4-85307) ), A method of starting the reaction by filling particles containing oxygen in advance into the reactor (Japanese Patent Laid-Open No. 4-85308), and the like are known.
[0005]
In addition to the above Ziegler catalyst system, a catalyst system comprising a catalyst component including a metallocene compound of a Group 4 metal of a long periodic table such as zirconium or titanium has been developed in recent years (Japanese Patent Publication No. 4). -12283 publication etc.). Polymers obtained using these methods have characteristics that are not found in products obtained using conventional Ziegler-based catalysts, such as low crystallinity, good blocking properties, and long-chain branching to control processed physical properties. It has attracted attention in recent years because it is.
[0006]
Even when olefins are vapor-phase polymerized, bulk polymerized or slurry polymerized in the presence of these metallocene catalysts, adhesion of product polymer to walls and stirring blades, and generation of sheet polymers and bulk polymers are conventional Ziegler systems. This is similar to the case of using this catalyst, and is a common problem from the viewpoint of stable operation.
[0007]
As for the metallocene catalyst, there is known a method for improving the fluidity of a polymer by adding at least one compound selected from water, alcohols and ketones (JP-A-7-76604). However, even when these substances are added, operation inhibition due to the formation of sheet-like polymers and bulk polymers has been frequently confirmed, and the appearance of further operation stabilization techniques has been desired.
The present inventors have completed the present invention by finding a method for stable operation over a long period of time in the production of olefin polymers using such metallocene-based transition metal catalysts without the formation of sheet-like polymers or bulk polymers. It came.
[0008]
[Problems to be solved by the invention]
In the present invention, when an olefin is polymerized in the presence of a metallocene-based transition metal catalyst, there is no adhesion of the polymer to the reactor wall, generation of a sheet-like polymer or a bulk polymer, and the like, and stable operation over a long period of time, that is, The purpose is to stabilize operation.
[0009]
[Means for Solving the Problems]
The present invention has been made as a result of intensive studies in order to achieve such an object.
[A] a metallocene-based transition metal catalyst and [B] a general formula
[0010]
[Chemical 3]
R¹ _nAl (OR²)_3-n
[0011]
An organoaluminum compound represented by the formula:¹Is C_1-20The alkylGroupTo express. R²Is C_1-20The alkylGroupTo express. n isRepresents 2) And [C] trialkylaluminum to the reactor, and the component [B] is in a range of 0.0001 nanomol to 10000 nanomol with respect to 1 g of the product polymer discharged from the reactor. [B] is supplied, water and alcohol under the condition that the temperature tw (° C.) of the wall of the polymerization reactor and the polymerization reaction temperature tr (° C.) satisfy the relationship of the following formula 1.Le,And ketoOrThe present invention provides a method for producing an olefin polymer, which comprises polymerizing an olefin without adding at least one compound selected from the group consisting of
[0012]
[Expression 2]
0.5 <tr-tw <10 Formula 1
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The olefin polymerization method according to the present invention will be specifically described below. In this case, the term “polymerization” is used not only in the case of using only one kind of monomer but also in the meaning including copolymerization using two or more kinds of monomers. Furthermore, when describing as "polymer", it includes not only a polymer using one type of monomer but also a meaning of a copolymer using two or more types of monomers.
In addition, “stabilization of operation” means not only the generation of a sheet-like polymer or a bulk polymer when polymerizing olefins, but also the conditions under which a molten polymer such as a sheet-like polymer or a bulk polymer is formed, that is, the polymer reacts. Used to mean long-term operation without adhering to the vessel wall or stirring blade.
[0014]
"catalyst"
[A] Metallocene transition metal catalyst
In the present invention, the metallocene transition metal catalyst used as component [A] is a catalyst composed of [a1] metallocene compound and [a2] clay, clay mineral, ion-exchange layered compound, or [a2] component instead of [A3] An organoaluminum oxy compound supported on a carrier, or [a4] a boron anion compound supported on a carrier. Hereinafter, components [a1], [a2], [a3], and [a4] will be described.
[A1] Metallocene compound
The [a1] metallocene compound used in the present invention is a metallocene transition metal compound containing a metal of Groups 4, 5, and 6 of the Long Periodic Table, and is a compound represented by the following general formula (1).
[0015]
[Formula 4]
R¹¹ _i(CpR¹² _j) (CpR¹² _jMR¹³ ₂    ... General formula (1)
[0016]
However, in general formula (1), each (CpR¹² _j) Represents a cyclopentadienyl group or a substituted cyclopentadienyl group which may be the same or different, and R¹¹Is a covalent bond bridging group containing a group 14 or 15 element of the long periodic table such as carbon, silicon, germanium, etc.¹²Are the same or different, hydrogen, halogen, silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group or an aryloxy group, and two R¹²Are present on the two adjacent carbon atoms of the cyclopentadienyl ring, the C_Four~ C₇The ring may be formed. R¹³Are the same or different, hydrogen, halogen, hydrocarbon group having 1 to 20 carbon atoms, halogen-containing hydrocarbon group, silicon-containing group, alkoxy group, aryloxy group, and i is 0 or 1 , Each j is an integer such that i + j = 5, and M is a metal of Groups 4, 5, and 6 of the Long Periodic Table.
[0017]
In the general formula (1), R¹¹Is a covalent bridging group containing a group 14 or 15 element of the long periodic table such as carbon, silicon, germanium, etc., and CpR¹² _jAnd two cyclopentadienyl ring-containing groups represented by Specifically, alkylene groups such as methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, alkylidene group such as phenylmethylidene group, diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropyl Silicon-containing bridging groups such as silylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgermylene group, diisopropylgermylene group Germanium-containing crosslinking groups such as diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t-butylgermylene group, alkylphosphine, amine And the like. Of these, an alkylene group, an alkylidene group, and a silicon-containing crosslinking group are particularly preferably used.
[0018]
Each CpR¹² _jAre the same or different cyclopentadienyl groups or substituted cyclopentadienyl groups. Where R¹²May be the same or different, halogens such as hydrogen, fluorine, chlorine, bromine, iodine, silicon-containing groups such as trimethylsilyl, triethylsilyl, triphenylsilyl groups, methyl, ethyl, propyl, butyl, isobutyl, pentyl, C1-C20 hydrocarbon group which may have a halogen group such as isopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, chloromethyl, chloroethyl group, methoxy, ethoxy, propoxy, butoxy group, etc. An alkoxy group or an aryloxy group such as phenoxy, methylphenoxy, pentamethylphenoxy group.
[0019]
Here, two R¹²Are present on two adjacent carbon atoms of the cyclopentadienyl ring, they are bonded to each other to form C_Four~ C₇And may be an indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, azulenyl, hexahydroazurenyl group or the like. R of these¹²Particularly preferred as hydrogen, methyl group, and two R¹²Are bonded to each other to form an indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, azulenyl or hexahydroazurenyl group.
[0020]
R¹³May be the same or different, halogens such as hydrogen, fluorine, chlorine, bromine, iodine, silicon-containing groups such as trimethylsilyl, triethylsilyl, triphenylsilyl groups, methyl, ethyl, propyl, butyl, isobutyl, pentyl, C1-C20 hydrocarbon group which may have a halogen group such as isopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, chloromethyl, chloroethyl group, methoxy, ethoxy, propoxy, butoxy group, etc. An alkoxy group or an aryloxy group such as phenoxy, methylphenoxy, pentamethylphenoxy group, etc., particularly preferably hydrogen, chlorine or methyl group.
[0021]
i represents two cyclopentadienyl ring-containing groups as R¹¹If it is not bonded, it is 0, and if it is bonded, it is 1. Each j is 4 when i is 1 and 5 when i is 0. M is a metal of Group 4, 5, 6 of the long periodic table such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, etc., and titanium, zirconium, and hafnium are particularly preferable.
[0022]
The above-mentioned metallocene-based transition metal compound, specifically taking zirconium as an example, includes isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium as those corresponding to the general formula (1). Dimethyl, isopropylidene-bis (indenyl) zirconium dihydride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylsilyl (cyclopentadienyl) (Fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dihydride, methylene-bis (cyclopentadienyl) zirconium dichloride Methylene-bis (tetramethylcyclopentadienyl) zirconium dichloride, ethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (cyclopentadienyl) zirconium Dichloride, methylene-bis (cyclopentadienyl) zirconium dimethyl, methylene-bis (tetramethylcyclopentadienyl) zirconium dimethyl, ethylene-bis (cyclopentadienyl) zirconium dimethyl, isopropylidene-bis (cyclopentadienyl) Zirconium dimethyl, dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, methylene-bis (cyclopentadienyl) zirconium dihydrogen , Ethylene-bis (cyclopentadienyl) zirconium dihydride, isopropylidene-bis (cyclopentadienyl) zirconium dihydride, dimethylsilyl-bis (cyclopentadienyl) zirconium dihydride, bis (n- Butylcyclopentadienyl) zirconium dichloride, bis (n-butylmethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (4-methyl-4-hydro-azulenyl) Zirconium dichloride, dimethylsilylenebis (2,4-dimethyl-4-hydro-azulenyl) zirconium dichloride, dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4-hydro-azule Nyl}] zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydro-azulenyl)} zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methyl-4-) Phenyl-4-hydro-azulenyl)} hafnium dichloride and the like.
[0023]
The same compounds as those described above can be used for other Group 4, 5, and 6 metal compounds of the Long Periodic Table such as titanium compounds and hafnium compounds. Moreover, the [a1] component represented by General formula (1) may be used independently, and may be used in combination of 2 or more types. Furthermore, it can be used simultaneously with a known solid catalyst mainly composed of titanium trichloride and a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components.
[0024]
[A2] Clay, clay mineral or ionic layered compound
The [a1] component is usually used together with [a2] clay, clay mineral, or ion-exchangeable layered compound. Here, clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force, and means that the contained ions can be exchanged. The clay, clay mineral, and ion-exchangeable layered compound are not limited to natural products, and may be artificial synthetic products.
[0025]
Specific examples of the [a2] component include kaolins such as dickite, nacrite, kaolinite, anorokite, metahalloysite, halloysite, serpentine groups such as chrysotile, lizardite, antigolite, montmorillonite, zauconite, beidellite, non Smectites such as tronite, saponite, theonite, hectorite, stevensite, vermiculite such as vermiculite, mica, illite, sericite, mica such as sea green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, Examples include talc and chlorite. These may form a mixed layer. Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, theonite, and the like are preferred, smectite group, vermiculite group and mica group.
[0026]
The [a2] component is preferably subjected to chemical treatment. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment affecting the crystal structure of the clay can be used. Specific examples include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
[0027]
In the salt treatment and the organic treatment, an ionic complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed. It is also possible to obtain a layered substance in a state in which the interlayer is expanded by replacing the exchangeable ions between the layers with another large and bulky ion by utilizing ion exchange. Here, bulky ions play a role of supporting pillars to support the layered structure, which is called a pillar.
[0028]
Introducing another substance between layered substances is called intercalation, but as a guest compound to intercalate, TiCl_Four, ZrCl_FourCationic inorganic compounds such as Ti (OR)_Four, Zr (OR)_Four, PO (OR)_Four, B (OR)_Four, (R is an alkyl group or an aryl group) and the like, [Al₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(OH)₁₄]²⁺, [Fe_ThreeO (OCOCH_Three)₆]⁺And metal hydroxide ions. These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, Si (OR)_Four, AL (OR)_Three, Ge (OR)_FourPolymer obtained by hydrolyzing metal alcoholates, etc., SiO₂Colloidal inorganic compounds such as can also be present together. Examples of pillars include oxides generated by heat dehydration after intercalation of the hydroxide ions between layers.
[0029]
Among the chemical treatments, particularly preferred chemical treatments are salt treatment and / or acid treatment. The acid strength of the solid can be changed by salt treatment and / or acid treatment. Further, the salt treatment can change the surface area and the interlayer distance by forming an ion complex, a molecular complex, an organic derivative and the like. That is, by utilizing ion exchange properties and replacing exchangeable ions between layers with other large and bulky ions, a layered material with the layers expanded can be obtained. In the present invention, 30% or more, preferably 40% or more, particularly preferably 60% of exchangeable cations contained in at least one compound selected from the group consisting of ion-exchangeable layered compounds before being treated with salts. % Or more is preferably ion exchanged with cations dissociated from the salts shown below. The salt used in the salt treatment of the present invention for such ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of groups 2 to 14.
[0030]
In particular,
(1) CaCl₂, CaSO_Four, CaC₂O_Four, Ca (NO_Three)₂, Ca_Three(C₆H_FiveO₇)₂,
(2) MgCl₂, MgBr₂, MgSO_Four, Mg (PO_Four)₂, Mg (ClO_Four)₂, MgC₂O_Four, Mg (NO_Three)₂, Mg (OOCCH_Three)₂, MgC_FourH_FourO_Four,
(3) Sc (OOCCH_Three)₂, Sc (CO_Three)_Three, Sc₂(C₂O_Four)_Three, Sc (NO_Three)_Three, Sc₂(SO_Four)_Three, ScF_Three, ScCl_Three, ScBr_Three, ScI_Three,
(4) Y (OOCCH_Three)_Three, Y (CH_ThreeCOCHCOCH_Three)_Three, Y₂(CO_Three)_Three, Y₂(C₂O_Four)_Three, Y (NO_Three)_Three, Y (ClO_Four)_Three, YPO_Four, Y₂(CO_Four)_Three, YF_Three, YCl_Three,
(5) La (OOCCH_Three)_Three, La (CH_ThreeCOCHCOCH_Three)_Three, La₂(CO_Three)_Three, La (NO_Three)_Three, La (ClO_Four)_Three, La₂(C₂O_Four)_Three, LaPO_Four, La₂(SO_Four)_Three, LaF_Three, LaCl_Three, LaBr_Three, LaI_Three,
[0031]
(6) Sm (OOCCH_Three)_Three, Sm (CH_ThreeCOCHCOCH_Three)_Three, Sm₂(CO_Three)_Three, Sm (NO_Three)_Three, Sm (ClO_Four)_Three, Sm₂(C₂O_Four)_Three, Sm₂(SO_Four)_Three, SmF_Three, SmCl_Three, SmI_Three,
(7) Yb (OOCCH_Three)_Three, Yb (NO_Three)_Three, Yb (ClO_Four)_Three, Yb (C₂O_Four)_Three, Yb₂(SO_Four)_Three, YbF_ThreeYbCl_Three,
(8) TiF_FourTiCl_Four, TiBr_Four, TiI_FourTiOCl₂, Ti (SO_Four)₂, Ti (NO_Three)_Four, TiO (NO_Three)₂, Ti_Three(PO_Four)_Four, Ti (ClO_Four)_Four, Ti (CO_Three)₂, Ti (OCOH)_Four, Ti (OCOCH_Three)_Four, Ti (OCOC₂H_Five)_Four, Ti (OCOC_ThreeH₇)_Four, Ti ((COO)₂)₂, Ti (CH₂(COO)₂)₂TiBrCl_ThreeTiF_ThreeTiCl_Three, TiBr_Three, TiI_Three, Ti (NO_Three)_Three, Ti (ClO_Four)_Three,
(9) Zr (OOCCH_Three)_Four, Zr (CO_Three)₂, Zr (NO_Three)_Four, Zr (SO_Four)₂, ZrF_Four, ZrCl_Four, ZrBr_Four, ZrI_Four, ZrOCl₂, ZrO (NO_Three)₂, ZrO (ClO_Four)₂, ZrO (SO_Four),
(10) Hf (OOCCH_Three)_Four, Hf (CO_Three)₂, Hf (NO_Three)_Four, Hf (SO_Four)₂, HfOCl₂, HfF_Four, HfCl_Four, HfBr_Four, HfI_Four,
[0032]
(11) V (CH_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VOCl_Three, VCl_Three, VBr_Three,
(12) Nb (CH_ThreeCOCHCOCH_Three)_Five, Nb₂(CO_Three)_Five, Nb (NO_Three)_Five, Nb₂(SO_Four)_Five, NbF_Five, NbCl_Five, NbBr_Five, NbI_Five,
(13) Ta (OOCCH_Three)_Five, Ta₂(CO_Three)_Five, Ta (NO_Three)_Five, Ta₂(SO_Four)_Five, TaF_Five, TaCl_Five, TaBr_Five, TaI_Five,
(14) Cr (CH_ThreeCOCHCOCH_Three)_Three, Cr (OOCH)₂OH, Cr (NO_Three)_Three, Cr (ClO_Four)_Three, CrPO_Four, Cr₂(SO_Four)_Three, CrO₂Cl₂, CrF_Three, CrCl_Three, CrBr_Three, CrI_Three,
(15) MoOCl_Four, MoCl_Three, MoCl_Four, MoCl_Five, MoF₆, MoI₂,
[0033]
(16) WCl_Four, WCl₆, WF₆, WBr₆,
(17) Mn (OOCCH_Three)₂, Mn (CH_ThreeCOCHCOCH_Three)₂, MnCO_Three, Mn (NO_Three)₂, MnO, Mn (ClO_Four)₂, MnF₂, MnCl₂, MnBr₂, MnI₂,
(18) Fe (OOCCH_Three)₂, Fe (CH_ThreeCOCHCOCH_Three)_Three, FeCO_Three, Fe (NO_Three)_Three, Fe (ClO_Four)_Three, FePO_Four, FeSO_Four, Fe₂(SO_Four)_Three, FeF_Three, FeCl_Three, FeBr_Three, FeI_Three, FeC₆H_FiveO₇,
(19) Co (OOCCH_Three)₂, Co (CH_ThreeCOCHCOCH_Three)_Three, CoCO_Three, Co (NO_Three)₂, CoC₂O_Four, Co (ClO_Four)₂, Co_Three(PO_Four)₂, CoSO_Four, CoF₂CoCl₂, CoBr₂CoI₂,
(20) NiCO_Three, Ni (NO_Three)₂, NiC₂O_Four, Ni (ClO_Four)₂, NiSO_FourNiCl₂, NiBr₂,
[0034]
(21) Pb (OOCCH_Three)₂, PbCO_Three, Pb (NO_Three)₂, PbHPO_Four, PbSO_Four, Pb (ClO_Four)₂, PbF₂, PbCl₂, PbBr₂, PbI₂,
(22) CuCl₂, CuBr₂, Cu (NO_Three)₂, CuC₂O_Four, Cu (ClO_Four)₂, CuSO_Four, Cu (OOCCH_Three)₂,
(23) Zn (OOCCH_Three)₂, Zn (CH_ThreeCOCHCOCH_Three)₂, Zn (OOCH)₂ZnCO_Three, Zn (NO_Three)₂Zn (ClO_Four)₂, Zn_Three(PO_Four)₂ZnSO_FourZnF₂ZnCl₂ZnBr₂, ZnI₂,
(24) Cd (OOCCH_Three)₂, Cd (CH_ThreeCOCHCOCH_Three)₂, Cd (OCOCH₂CH_Three)₂, Cd (NO_Three)₂, Cd (ClO_Four)₂, CdSO_Four, CdF₂, CdCl₂, CdBr₂, CdI₂,
(25) AlF_ThreeAlCl_Three, AlBr_Three, AlI_Three, Al₂(SO_Four)_Three, Al₂(C₂O_Four)_Three, Al (CH_ThreeCOCHCOCH_Three)_Three, Al (NO_Three)_Three, AlPO_Four,
(26) GeCl_Four, GeBr_Four, GeI_Four,
(27) Sn (OOCCH_Three)_Four, Sn (SO_Four)₂, SnF_Four, SnCl_Four, SnBr_Four, SnI_Four,
(28) Pb (OOCCH_Three)_Four, PbCO_Three, Pb (NO_Three)₂, PbHPO_Four, Pb (ClO_Four)₂, PbSO_Four, PbF₂, PbCl₂, PbBr₂, PbI₂,
Etc.
[0035]
Preferably, a cation of the periodic table 4, 5, 6 transition metal, ie Ti²⁺, Ti³⁺, Ti⁴⁺, Zr²⁺, Zr³⁺, Zr⁴⁺, Hf²⁺, Hf³⁺, Hf⁴⁺, V²⁺, V³⁺, V⁴⁺, V⁵⁺, Nb²⁺, Nb³⁺, Nb⁴⁺, Nb⁵⁺, Ta²⁺, Ta³⁺, Ta⁴⁺, Ta⁵⁺, Cr²⁺, Cr³⁺, Cr⁴⁺, Cr⁵⁺, Cr⁶⁺, Mo²⁺, Mo³⁺, Mo⁴⁺, Mo⁵⁺, Mo⁶⁺, W²⁺, W³⁺, W⁴⁺, W⁵⁺, W⁶⁺Is a salt containing These salts may be used alone or two or more of them may be used simultaneously and / or continuously.
[0036]
In addition to removing impurities on the surface, the acid treatment elutes some or all of the cations such as Al, Fe, and Mg in the crystal structure. The acid used in the acid treatment here is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. Two or more kinds of salts and acids used in the treatment may be used. When the salt treatment and the acid treatment are combined, there are a method in which the salt treatment is performed and then the acid treatment is performed, a method in which the acid treatment is performed and then the salt treatment is performed, and a method in which the salt treatment and the acid treatment are simultaneously performed.
[0037]
The conditions for treatment with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 30% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Thus, it is preferable to carry out the reaction under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered compounds is eluted. In addition, salts and acids are generally used in an aqueous solution, but are not particularly limited thereto.
[0038]
The component [a2] obtained as described above can provide a catalyst having good fluidity by satisfying the following condition (a), and has a high bulk density with few fine particles and coarse particles. It is preferable in that a polymer can be obtained, and it is particularly preferable that the conditions (a), (b) and (c) are satisfied at the same time.
(A) The average particle size is 20 μm or more and 1,000 μm or less, and the number of particles having a particle size of 10 μm or less is 20% or less of all particles.
(B) The particle crushing strength measured with a micro compression tester is 0.5 MPa or more.
(C) The bulk density of the particles is 0.6 g / cm^ThreeThat's it.
[0039]
Here, the condition (A) relates to the average particle diameter of the component [a2] and the abundance ratio of the particle diameter of 10 μm or less, specifically, the average particle diameter is 20 μm or more and 1,000 μm or less, And the number of particles having a particle size of 10 μm or less is 20% or less of all particles. Those having an average particle size of 20 μm or more and 500 μm or less, particularly 20 μm or more and 100 μm or less are preferred, and particles having a particle size of 10 μm or less are preferably 15% or less, particularly preferably 10% or less.
Accordingly, it is preferable that the condition (A) satisfies either one or both of the above preferable conditions regarding the average particle diameter and the abundance of the particle diameter of 10 μm or less.
Specifically, the particle measurement is performed by a laser diffraction method particle size distribution measuring apparatus (“LMS024”, light source: semiconductor laser (wavelength 670 nm)) manufactured by Seishin Enterprise Co., Ltd.
Can be used. In the measurement, ethanol was used as a dispersion medium, and the particle size distribution and average particle size were calculated with a refractive index of 1.33 and a shape factor of 1.0.
[0040]
The condition (b) relates to the strength of the component [a2]. Specifically, the crushing strength of the particles measured with a micro compression tester is 0.5 MPa or more. The crushing strength is preferably 1.0 MPa or more. The upper limit is 40 MPa. Here, the crushing strength was specifically measured by using a micro compression tester “MCTM-500” manufactured by Shimadzu Corporation to measure the compressive strength of any 10 or more particles, and the average value was obtained as the crushing strength. Is.
The condition (c) relates to the bulk density of the component [a2], and specifically the value is 0.6 g / cm.^ThreeThat's it. The upper limit is 1.5 g / cm
^ThreeIt is.
[0041]
Specifically, the component [a2] satisfying the conditions (a), (b), and (c) is obtained by subjecting the above-described salt treatment and / or acid treatment to the clay, clay mineral, or ion-exchange layered compound exemplified above. When performing, it can manufacture by controlling a particle | grain property by grinding | pulverization, granulation, sizing, fractionation, etc. before a process, between processes, and after a process. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method, Examples thereof include an emulsification granulation method and a submerged granulation method. Particularly preferred granulation methods are the spray granulation method, the tumbling granulation method, and the compression granulation method. The clay, clay mineral, and ion-exchange layered compound may be used alone or in combination of two or more.
[0042]
[A3] Organoaluminum oxy compound
Next, [a3] the organoaluminum oxy compound will be described. The organoaluminum oxy compound here is a compound represented by the following general formula (2) or general formula (3).
[0043]
[Chemical formula 5]

[0044]
In the above general formula (2) and general formula (3), R^{twenty one}Is C_1-8And r is an integer of 0 or more.
These [a3] components are products obtained by the reaction of one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, in the case of one kind of trialkylaluminum, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane and the like can be mentioned. When two or more kinds of trialkylaluminum are used, methylethylalumoxane is used. , Methylbutylalumoxane, methylisobutylalumoxane and the like.
[0045]
Preferred among these are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, and mixtures thereof. Particularly preferred are methylalumoxane and methylisobutylalumoxane.
These organoaluminum oxy compounds can also be used by being supported on silica gel or alumina, and those in which methylalumoxane is supported on silica gel are particularly preferable.
These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified.
[0046]
(A) A method in which trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene, ether or the like.
(B) A method of reacting with a salt hydrate containing trialkylaluminum and crystal water, for example, copper sulfate or aluminum sulfate hydrate.
(C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like.
(D) A method in which trimethylaluminum and triisobutylaluminum are mixed and reacted directly with water using an appropriate organic solvent such as toluene, benzene, or ether.
(E) A method in which trimethylaluminum and triisobutylaluminum are mixed and heated with a salt hydrate having crystal water, for example, copper sulfate or aluminum sulfate hydrate.
(F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then further treated with trimethylaluminum.
[0047]
[A4] Boron anion compound
Next, the case where the [a4] boron anion compound is used will be described. When a boron anion-based compound is used, the metallocene-based transition metal catalyst is represented by the following general formula (4) by combining the [a1] component and the [a4] component.
[0048]
[Chemical 6]
[R¹¹ _i(CpR¹² _j) (CpR¹² _jMR¹³R¹⁴]⁺R^15-... General formula (4)
[0049]
Where R¹¹ _i(CpR¹² _j), M, R¹³Is equivalent to that represented by the general formula (1). That is, R¹¹Is a covalent bond bridging group containing a group 14 or 15 element of the long periodic table such as carbon, silicon, germanium, etc., and R¹²Are the same or different, hydrogen, halogen, silicon-containing group, C 1-20 hydrocarbon group, alkoxy group or aryloxy group which may have a halogen substituent, and R¹³Are the same or different, hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group, a silicon-containing group, an alkoxy group or an aryloxy group; , 5 and 6 metals, i is 0 or 1, and j is an integer such that i + j = 5.
[0050]
R¹⁴Is a neutral ligand such as tetrahydrofuran coordinated to M. R¹⁵Is a counter anion that can stabilize the metal cation of the general formula (4), and [a4] component such as tetraphenylborate, tetra (p-tolyl) borate, carbadodecaborate, dicarbaoundecaborate, ie boron An anionic compound.
[0051]
Specific examples corresponding to the general formula (4) include isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (methyl) (tetraphenylborate) ) Tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclohexane) Pentadienyl) (fluorenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopente) Dienyl) (fluorenyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) Tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahi Lofuran complex, ethylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (Cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium ( Hydrido) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl) zirconium (hydrido) (tetrapheni And dimethylsilyl-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex.
Further, these boron anion compounds can be used by being supported on silica gel or alumina.
[0052]
[A5] Organoaluminum compound
In the present invention, the organoaluminum compound used as the component [a5] is an aluminum compound represented by the following general formula (5).
[0053]
[Chemical 7]
R^Three _mAl (X_3-m) General formula (5)
[0054]
(Wherein R^ThreeIs C_1-20And X represents hydrogen, halogen, alkoxy group, alkylsilyl group, alkylsiloxy group, alkylamino group or alkylamide group. m is a number selected from 0 <m <3. )
[0055]
Specific examples of the component [a5] include, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tritert-butylaluminum, tripentylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, Trialkylaluminums such as tricyclooctylaluminum, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, diethylaluminum hydride and diisobutylaluminum hydride. Alkyl aluminum is preferred , Particularly triethylaluminum and triisobutylaluminum Among them are preferable.
[0056]
In the above, when X is an alkoxy group, it is the same as the component [B], but is added separately from the component [B] added for operational stability. Therefore, the supply amount of the component [B] is 0.0001 nanomol to 10000 nanomol, preferably 0.001 nanomol to 5000 nanomol, and more preferably 0.01 to 1 g of the product polymer discharged from the reactor. In addition to adding an amount of nanomol to 1000 nanomol, the [a5] component is further added.
[0057]
The method for supplying the component [a5] is usually used in combination with a method of contacting the catalyst in advance and two methods of supplying to the circulation line during the polymerization. However, the supply method is not particularly limited, and the following method is used. The supply method may be used.
(1) Feed component [a5] to the circulation line.
(2) Feed component [a5] to the raw material supply line.
(3) The component [a5] is fed to the line supplying the metallocene transition metal catalyst.
(4) The component [a5] is added to the metallocene transition metal catalyst in advance as a catalyst component.
(5) Perform the above methods (1) to (5) together.
[0058]
[B] Organoaluminum compound (containing alkoxy group)
The organoaluminum compound used as the component [B] is an alkoxy group-containing aluminum represented by the following general formula (6).
[0059]
[Chemical 8]
R¹ _nAl (OR²)_3-n          ... General formula (6)
[0060]
(Wherein R¹Is C_1-20Represents an alkyl group, an aryl group, hydrogen or halogen. R²Is C_1-20Represents an alkyl group or an aryl group. n is a number selected from 0 ≦ n <3. )
[0061]
Specific examples of the component [B] are as follows:
(1) Contains monoalkoxy groups such as dimethylaluminum methoxide, diethylaluminum ethoxide, di (isopropyl) aluminum (isopropoxide), diethylaluminum (isopropoxide), diethylaluminum (phenoxide), or monoaryloxy groups Aluminum,
(2) Dialkoxy group containing methylaluminum di (methoxide), ethylaluminum di (ethoxide), isopropylaluminum di (isopropoxide), ethylaluminum di (isopropoxide), ethylaluminum di (phenoxide), or diaryl An oxy group-containing aluminum, or a mixture thereof with a dialkylaluminum (alkoxide), a diarylaluminum (alkoxide), an aluminum monoalkoxide such as a dialkylaluminum (aryloxide), a diarylaluminum (aryloxide),
(3) Trialkoxyaluminum compounds such as aluminum tri (methoxide), aluminum tri (ethoxide) and aluminum tri (isopropoxide), or triaryloxyaluminum compounds such as aluminum tri (phenoxide), and these and dialkylaluminum (alkoxide) ), Diaryl aluminum (alkoxide), dialkyl aluminum (aryl oxide), diaryl aluminum (aryl oxide), alkyl aluminum di (alkoxide), aryl aluminum di (alkoxide), alkyl aluminum di (aryl oxide), aryl aluminum di (aryl oxide) ) And the like.
Of these, diethylaluminum ethoxide is particularly preferred. These alkoxy group-containing aluminum compounds may be used alone or in admixture of two or more.
[0062]
Furthermore, these aluminums can be used in any mixture with trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum.
In particular, a combination of trialkylaluminum and dialkylaluminum (alkoxide) is preferable, and a combination of triethylaluminum and diethylaluminum ethoxide is particularly preferable.
Component [B] is supplied in an amount of 0.0001 nanomol to 10,000 nanomol, preferably 0.001 nanomol to 5000 nanomol, and more preferably 0.01 to 1 g of the product polymer discharged from the reactor. The range is from nano mol to 1000 nano mol.
[0063]
When the organoaluminum compound is supplied as the component [a5], the supply amount of the component [B] is not particularly limited with respect to the component [a5], but is 0.001 to 1 mol of the component [a5]. It is desirable to supply in the range of 100 mol, preferably 0.01 to 10 mol.
The amount of component [B] supplied is not particularly limited with respect to the metallocene transition metal compound supplied to the reaction system as component [a1], but is 0.01 to 0.1 mol per component [a1]. It is desirable to supply in the range of 10,000 mol, preferably 0.1 to 1000 mol.
[0064]
  The component [B] is supplied to the reactor to the circulation line attached to the reactor that is usually performing polymerization, but the supply point is not particularly limited, and the following supply method can be adopted. .
(1)Ingredient [B] is fed to the circulation line of the reactor.
(2)Ingredient [B] is fed to the raw material line of the reactor.
(3)Feed component [B] to the line supplying the metallocene transition metal catalystThe
(4) (1)-(3)Follow the same procedure.
[0065]
<Preliminary polymerization>
In addition to the above components, the metallocene catalyst used in the present invention is an α-olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, or a mixture thereof. The olefin mixture may be preliminarily polymerized. The prepolymerization is preferably performed so that 0.01 to 1000 g of a polymer is produced per 1 g of the catalyst before the prepolymerization.
[0066]
"polymerization"
The olefin polymerization method according to the present invention is a method in which an olefin is polymerized in the presence of the above-mentioned olefin polymerization catalyst, and examples thereof include gas phase polymerization, bulk polymerization, slurry polymerization, etc., and the medium is a liquid or a supercritical fluid. In the case, it becomes bulk polymerization or slurry polymerization, and in the case of gas, it becomes gas phase polymerization. Of these polymerization methods, the gas phase polymerization method is particularly preferable.
As a trouble that occurs when performing the above polymerization, polymerized polymer and fine powder adhere to and stay on the reactor wall and stirring blade due to electrostatic force, etc., and the presence of the catalyst causes the polymer to melt on the vessel wall and stirring blade surface, The trouble which a sheet-like polymer and a block polymer produce | generate is mentioned. Since these sheet-like polymers and block polymers block the extraction line and the polymerized polymer cannot be extracted, this is a great obstacle to supplying products stably over a long period of time.
[0067]
As a condition for generating a sheet polymer or a bulk polymer, a polymerized polymer or fine powder adheres and stays on the vessel wall or the surface of the stirring blade. It can be monitored whether the wall stays attached to the vessel wall by installing a wall thermometer for measuring the vessel wall surface and observing the difference between the wall surface temperature and the polymerization temperature. That is, when there is a large amount of adhesion and retention, the polymerized polymer adheres thickly, causing a temperature drop, and the difference between the polymerization temperature and the vessel wall temperature increases. Conversely, when there is little adhesion and retention, the temperature drop is small, so the difference between the polymerization temperature and the vessel wall temperature is small. Therefore, by monitoring this temperature difference, the conditions under which the sheet-like polymer and the bulk polymer are generated can be detected at an early stage.
[0068]
Further, when a sheet-like polymer or a block polymer is actually produced, the wall surface temperature rises, which is a measure of trouble.
Since heat escapes from the reactor, the wall surface temperature (denoted as tw. Unit: ° C) is usually lower than the polymerization temperature (denoted as tr. Unit: ° C). In order to continue the operation stably, it is necessary to keep the difference between the wall surface temperature and the polymerization temperature such that 0.5 <tr-tw <10, preferably 1.0 <tr-tw <7.0. Good to keep on.
[0069]
《Fluidized bed reactor》
Hereinafter, as an example of the present invention, an olefin polymerization method (gas phase polymerization method) when the circulating medium is a gas will be described in detail with reference to FIG.
The aforementioned component [A] is supplied to the stirring fluidized bed reactor 2 from the catalyst supply line 1 shown in FIG. Further, during polymerization, an inert gas such as raw material monomer or nitrogen is supplied from the raw material supply line 4 into the circulating gas line 3, the component [B] is supplied from the supply line 5, and the circulating gas pressure feeder 7 is driven. These gases are circulated. Finally, the circulating gas is again fed back to the stirred fluidized bed reactor.
[0070]
Further, the product and surplus gas are led to the product separator 10 from the extraction line 9. The product is continuously or intermittently extracted by the product extraction line 12 at the lower part of the separator, and excess gas is purged out of the system from the upper purge line 11. The pressure in the reactor is kept constant by adjusting the opening of the pressure control valve installed in the purge line 11. In the reactor, a fluidized bed is formed by particles charged in advance, or a polymer gas generated by polymerization and a raw material monomer, a fluid gas composed of an inert gas, and a stirring blade 6 that is mechanically stirred. The stirring blade 6 is forcibly stirred by the motor 14.
[0071]
A wall thermometer 13 is installed in the reactor to measure the temperature of the vessel wall, and the difference between the polymerization temperature and the vessel wall temperature is monitored. The thermometer for measuring the vessel wall temperature is preferably installed within a range of 0.5 to 10.0 mm from the vessel wall.
In this case, the flowing gas is operated in the range of 5 vol% to 90 vol% of the inert gas, and in the range of 10 vol% to 95 vol% of the raw material monomers such as ethylene and α-olefin.
The polymerization heat generated by the reaction is removed by the heat exchanger 8 installed in the circulation gas line.
[0072]
The pressure of the gas used is 1 kg / cm²~ 100kg / cm²Range, preferably 5 kg / cm²~ 50kg / cm²The temperature is in the range of 10 ° C to 100 ° C, preferably in the range of 30 ° C to 100 ° C, more preferably in the range of 50 ° C to 100 ° C.
As a stirring blade, it can carry out using stirring blades, such as a ribbon type stirring blade machine, a vertical stirring machine, a screw type stirring machine. Furthermore, two or more stages of polymerization reactors as shown in FIG. 2 can be connected in series to carry out the multistage polymerization operation.
[0073]
In the present invention, a fluidized bed other than the stirring fluidized bed can be used as the fluidized bed reaction section 2. An example of the fluidized bed is a gas phase fluidized bed using a dispersion plate when introducing the circulating gas to the reaction system.
The olefin used in the present invention is preferably an α-olefin having 2 to 18 carbon atoms. Examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
[0074]
Furthermore, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, styrene, vinylcyclohexane and the like can be mentioned.
In the main polymerization, these olefins are polymerized or copolymerized, and with these, polyenes such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene are copolymerized. You can also.
[0075]
In the present invention, ethylene is preferably homopolymerized or copolymerized with ethylene and an α-olefin having 3 to 18 carbon atoms, and particularly preferably copolymerized with ethylene and an α-olefin having 3 to 18 carbon atoms. Alternatively, homopolymerization of propylene, or copolymerization of propylene with ethylene and / or an α-olefin having 4 to 18 carbon atoms is preferable.
Further, in addition to ethylene, α-olefin and the like mentioned as examples of polymerization monomers, inert gases such as nitrogen and saturated hydrocarbons can be used at the same time.
When α-olefins or unsaturated hydrocarbons having a high dew point are used, heat may be removed by the heat exchanger 8 to condense, but the polymerization temperature of the fluidized bed reactor 2 may be those α-olefins and unsaturated hydrocarbons. The conditions under which gas becomes gas are selected.
[0076]
In the present invention, the melt index (MI) was measured according to JIS standard K7210, and the density was measured according to K7112. The gas concentration in the system uses gas chromatography, the measurement of ethylene and 1-hexene uses Hitachi 163 type, and the measurement of hydrogen concentration uses Shimadzu 4C type (detector TCD method) and Hitachi 263-30 type. (Detector PID method) was used, and was properly used depending on the hydrogen concentration.
[0077]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
(1) Chemical treatment of clay minerals
400 g of commercially available swellable synthetic mica (manufactured by Corp Chemical Co., “Somasif ME-100”) and 100 g of commercially available hydrophilic smectite (Corp Chemical Co., “SWN”) were mixed, and this was mixed with 2.0 wt% nitric acid. The mixture was dispersed in 2.8 liters of an aqueous chromium (III) solution and stirred at room temperature for 2 hours. This was filtered and washed with demineralized water. Water was added to the obtained solid part to prepare a 20.0 wt% water slurry, and spray drying treatment was performed. As a result, 450 g of particles having an average particle diameter of 54 μm were obtained. The number of particles having an average particle size of 10 μm or less was 4% of the total particles, the crushing strength was 2.0 MPa, and the bulk density was 0.75 g / cc. The particles were further dried under reduced pressure at 200 ° C. for 2 hours.
[0078]
(2) Catalyst preparation
4.4 liters of n-heptane and 80 g of the synthetic mica particles obtained in the above (1) were introduced into a reactor equipped with an induction stirrer having a capacity of 10 liters. To this was added a solution of 6.4 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride dissolved in 600 ml of toluene, and the mixture was stirred at room temperature for 10 minutes.
[0079]
(3) Prepolymerization
Subsequently, 71.5 mmol of triethylaluminum was added to the stirred mixture, and the temperature of the system was adjusted to 60 ° C. Ten minutes later, ethylene gas was introduced and the reaction was continued for 2.5 hours. The amount of polyethylene produced during this period was 547 g.
[0080]
(4) Gas phase polymerization
Gas phase polymerization was carried out using the prepolymerization catalyst (3). Polymerization was carried out in a continuous gas phase polymerization reactor as shown in FIG. 1.1 kg of seed polymer was weighed in advance and charged into the reactor, the catalyst prepared above was slurried with n-hexane, and converted into a prepolymerized catalyst and supplied to the reactor at 300 mg / hr. Similarly, triethylaluminum diluted in n-hexane was supplied to the reactor at 270 mg / hr. Furthermore, diethylaluminum ethoxide diluted with n-hexane was fed intermittently at 30 mg / hr. In addition, the polymerization reactor is operated under a pressure of 20 kg / cm.²The polymerization reaction temperature was 83 ° C., the average residence time was 3.7 hours, and the stirring blade speed was 150 rpm. The gas concentration in the system was periodically analyzed using gas chromatography. Each time, the ethylene concentration in the reactor was 84.0-87.0 vol%, the 1-hexene concentration was 3.3-3.5 vol%, The amount of feed gas was adjusted so that the hydrogen concentration was maintained in the range of 180 to 210 ppm. In a steady state where the production amount was almost constant, the ethylene gas feed amount was 5.5 kg / hr, and the 1-hexene feed amount was 0.6 kg / hr. Although the operation was performed for 3 days under these conditions, it was possible to operate stably without any trouble in the extraction line. In the polymerization for 3 days, the difference between the polymerization temperature (tr) and the vessel wall temperature (tw) was in the range of 3.0 to 5.0 ° C. Further, after the polymerization was completed, the reactor was opened and the inside was inspected. However, formation of a sheet-like polymer and a bulk polymer was not observed, and no polymer was adhered to the wall.
The density of the polymer was 0.926 g / cc, the melt index (MI) was 1.6 g / 10 min, the average particle size was 790 μm, and the bulk density was 0.38 g / cc.
[0081]
[Comparative Example 1]
Polymerization was carried out using the prepolymerized catalyst obtained in Example 1 without using diethylaluminum ethoxide. The polymerization conditions such as the gas concentration in the system, the polymerization pressure, the polymerization temperature, and the stirring blade rotation speed were the same as those in Example 1. The difference between the polymerization temperature immediately before the addition of the catalyst and the vessel wall temperature was 3.5 ° C. The temperature difference between the polymerization temperature and the vessel wall temperature began to increase when half a day had elapsed from the start of the polymerization, and reached 11.5 ° C. after 1 day. When the operation was further continued, the phenomenon that the wall temperature jumped from time to time was observed, and the increase to a maximum of 87 ° C was observed. A small molten polymer was also observed in the extracted polymer. Therefore, the catalyst supply was stopped and waited until the phenomenon that the wall temperature jumped was eliminated, and then the supply was resumed when it was stable. When the reactor was opened after the operation was stopped and the inside was inspected, bulk polymer was confirmed. A large amount of thin film polymer was observed on the reactor wall.
[0082]
[Example 2]
<Catalyst preparation and prepolymerization>
M-SiO manufactured by Witco, Germany₂(Methylalumoxane is SiO₂1 g of n-heptane was slurried with 20 g of the one supported above, Al concentration = 22.3 wt%, and bis (n-butylcyclopentadienyl) zirconium dichloride was 1/250 mol with respect to Al. Ratio, triisobutylaluminum (TiBA) was added at 1/6 molar ratio to Al of methylalumoxane, and stirred at 40 ° C. for 10 minutes. Thereafter, ethylene was introduced while maintaining the temperature at 40 ° C., and the reaction was continued for 1 hour. Ethylene supply is M-SiO₂The weight was 8 times. After purging with nitrogen at room temperature for 12 hours, vacuum drying was performed at room temperature for 2 hours.
[0083]
<Gas phase polymerization>
Continuous gas phase polymerization was carried out using the above prepolymerization catalyst. In the same manner as in Example 1, 1.2 kg of the seed polymer was previously weighed and charged into the reactor, and the catalyst prepared above was slurried with n-hexane, and the amount of the prepolymerized catalyst was reduced. Was converted into, and fed to the reactor at 210 mg / hr. Similarly, triethylaluminum diluted in n-hexane was supplied to the reactor at 100 mg / hr. Also, the operating conditions are pressure 20kg / cm²Polymerization was carried out at a temperature of 80 ° C., an average residence time of 4.1 hours, and a stirring blade speed of 150 rpm. The gas concentration in the system was periodically analyzed using gas chromatography, and the ethylene concentration in the reactor was 84.0-87.0 vol% and the 1-butene concentration was 3.0-3.5 vol each time. %, And the feed gas amount was adjusted so that the hydrogen concentration was maintained in the range of 210 to 240 ppm.
[0084]
The difference between the polymerization temperature before the catalyst feed and the reactor wall temperature was 3.5 ° C. The difference between the polymerization temperature and the reactor wall temperature gradually increased after the catalyst feed was started, and became 10 ° C. or higher after 1 day. After a further half day, the reactor wall temperature jumped from time to time, and even though the polymerization temperature was kept at 80 ° C., a phenomenon in which the reactor wall temperature exceeded 80 ° C. was observed. Therefore, diethyl aluminum ethoxide diluted with n-hexane was fed intermittently at 34 mg / hr. Then, the phenomenon in which the reactor wall temperature jumped up was stopped, and the difference between the polymerization temperature and the reactor wall temperature returned to 3.9 ° C. after about 1 day from the start of intermittent feeding of diethylaluminum ethoxide. After a total of 5 days of operation, a stop operation was performed and the inside of the reactor was checked. As a result, formation of molten polymer was not observed.
[0085]
[Comparative Example 2]
<Gas phase polymerization>
Polymerization was carried out using a catalyst prepared in the same manner as in Example 1, using a continuous gas phase polymerization reactor. Instead of supplying diethylaluminum ethoxide in Example 1, polymerization was carried out under the same conditions except that ethanol was supplied.
Before the catalyst feed, the difference between the polymerization temperature and the reactor wall temperature was 3.4 ° C. Since the temperature difference gradually started to widen after the start of polymerization, ethanol supply was started. Ethanol is 25 ° C, polymerization pressure + 2 kg / cm²Ethanol was placed in a metal pot under the conditions described above, and nitrogen gas was bubbled through the ethanol and then supplied to the polymerization system. Assuming that the ethanol in the nitrogen gas passed by bubbling was saturated, the ethanol supply amount was 20 mg / hr.
[0086]
If the operation was continued in this state, the difference between the polymerization temperature and the reactor wall temperature began to decrease gradually after about 2 days, but if the operation was continued further, the reactor wall temperature suddenly increased. An increase up to 98 ° C. was observed. The operation was stopped because the polymer inside the reactor could not be extracted. When the reactor was opened after the shutdown and the inside was inspected, bulk polymer was confirmed.
[0087]
【The invention's effect】
According to the present invention, when performing olefin polymerization in a fluidized bed reactor, there is no trouble due to the formation of sheet polymer and bulk polymer, and stable operation is possible for a long period of time, which is extremely useful industrially. .
[Brief description of the drawings]
FIG. 1 is a flowchart for helping understanding of the present invention.
FIG. 2 is a flow chart showing a fluidized bed reactor used in the present invention.
[Explanation of symbols]
1 Catalyst supply line
2 Stirring fluidized bed reactor
3 Circulating gas line
4 Raw material supply line
5 Supply line
6 Stirring blade
7 Circulating gas pressure feeder
8 Heat exchanger
9 Extraction line
10 Product separator
11 Purge line
12 Product extraction line
13 Wall thermometer
14 Motor

Claims (7)

[A] a metallocene-based transition metal catalyst and [B] a general formula
R ¹ _n Al (OR ² ) _3-n
(In the general formula, R ¹ represents a C _1-20 alkyl group, R ² represents a C _1-20 alkyl group, n represents 2 ), and [C] tri The alkyl aluminum is supplied to the reactor, and the component [B] is supplied so that the component [B] is in the range of 0.0001 nanomol to 10000 nanomol with respect to 1 g of the product polymer discharged from the reactor. at a temperature tw of the polymerization reactor vessel wall and (℃) polymerization temperature tr (℃) and is fully to condition the relation of the formula 1, water, alcohol, and ketone or al least one compound selected A process for producing an olefin polymer, characterized in that olefin is polymerized without adding.
[Expression 1]
0.5 <tr-tw <10 Formula 1   The process for producing an olefin polymer according to claim 1, wherein the component [A] metallocene transition metal catalyst comprises [a1] metallocene transition metal compound and [a2] clay, clay mineral or ion-exchangeable layered compound.   The method for producing an olefin polymer according to claim 1, wherein the component [A] metallocene transition metal catalyst comprises [a1] a metallocene transition metal compound and [a3] an organoaluminum oxy compound supported on a carrier.   The method for producing an olefin polymer according to claim 1, wherein the component [A] metallocene transition metal catalyst comprises [a1] metallocene transition metal compound and [a4] boron anion compound supported on a carrier.   Component [B] The organoaluminum compound is diethylaluminum ethoxide, The method for producing an olefin polymer according to any one of claims 1 to 4. The method for producing an olefin polymer according to any one of claims 1 to 5 , wherein the component [A] metallocene-based transition metal catalyst is subjected to a prepolymerization treatment of an α-olefin. The method for producing an olefin polymer according to any one of claims 1 to 6 , wherein the olefin is a gas in the polymerization.

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