JP3873449B2 - Olefin (co) polymer composition and method for producing the same - Google Patents

Description

【００５４】
【化２】

【００５５】
ここで、Ｒ³ は炭素数１〜６、好ましくは、１〜４の炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基などのアルキル基、アリル基、２−メチルアリル基、プロペニル基、イソプロペニル基、２−メチル−１−プロペニル基、ブテニル基等のアルケニル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、およびアリール基などである化合物が挙げられる。これらのうち特に好ましいのは、アルキル基であり、各Ｒ³ は同一でも異なっていても良い。ｐは４〜３０の整数であるが、好ましくは６〜３０、特に好ましくは８〜３０である。
【００５６】
また、有機金属化合物（ＡＬ１）としての別の化合物として、ホウ素系有機金属化合物が挙げられる。このホウ素系有機金属化合物は、遷移金属化合物とホウ素原子を含むイオン性化合物と反応させることにより得られる。このとき用いられる遷移金属化合物としては、オレフィン（共）重合用予備活性化触媒を製造する際に使用する遷移金属化合物触媒成分と同様のものが使用可能であるが、好ましく用いられるのは、前述した通常メタロセンと称される少なくとも１個のπ電子共約配位子を有する遷移金属化合物触媒成分である。
【００５７】
ホウ素原子を含むイオン性化合物としては、具体的には、テトラキス（ペンタフルオロフェニル）硼酸トリエチルアンモニウム、テトラキス（ペンタフルオロフェニル）硼酸トリ−ｎ−ブチルアンモニウム、テトラキス（ペンタフルオロフェニル）硼酸トリフェニルアンモニウム、テトラキス（ペンタフルオロフェニル）硼酸メチルアンモニウム、テトラキス（ペンタフルオロフェニル）硼酸トリジメチルアンモニウム、テトラキス（ペンタフルオロフェニル）硼酸トリメチルアンモニウム等が挙げられる。
【００５８】
ホウ素系有機金蔵化合物は、また、遷移金属化合物とホウ素原子含有ルイス酸とを接触させることによっても得られる。このとき用いられる遷移金属化合物としては、オレフィン（共）重合用予備活性化触媒を製造する際に使用する遷移金属触媒成分と同様のものが使用可能であるが、好ましく用いられるのは、前述した通常メタロセンと称される少なくとも１個のπ電子共役配位子を有する遷移金属化合物触媒成分である。
【００５９】
ホウ素原子含有ルイス酸としては、下記の一般式（化３）で表される化合物が使用可能である。
【００６０】
【化３】
ＢＲ⁴Ｒ⁵Ｒ⁶
（式中、Ｒ４、Ｒ５、Ｒ６は、それぞれ独立してフッ素原子、メチル基、トリフルオロフェニル基などの置換基を有しても良いフェニル基、または、フッ素原子を示す。）
【００６１】
上記一般式で表される化合物として具体的には、トリ（ｎ−ブチル）ホウ素、トリフェニルホウ素、トリス［３，５−ビス（トリフルオロメチル）フェニル］ホウ素、トリス（４−フルオロメチルフェニル）ホウ素、トリス（３，５−ジフルオロフェニル）ホウ素、トリス（２，４，６−トリフルオロフェニル)ホウ素、トリス（ペンタフルオロフェニル）ホウ素等が挙げられ、トリス（ペンタフルオロフェニル）ホウ素が特に好ましい。
【００６２】
電子供与体（Ｅ１）は、ポリオレフィンの生成速度および／または立体規則性を制御することを目的として必要に応じて使用される。
電子供与体（Ｅ１）として、たとえば、エーテル類、アルコール類、エステル類、アルデヒド類、脂肪酸類、ケトン類、ニトリル類、アミン類、アミド類、尿素およびチオ尿素類、イソシアネート類、アゾ化合物、ホスフィン類、ホスファイト類、ホスフィナイト類、硫化水素およびチオエーテル類、ネオアルコール類、シラノール類などの分子中に酸素、窒素、硫黄、燐のいずれかの原子を有する有機化合物および分子中にＳｉ−Ｏ−Ｃ結合を有する有機ケイ素化合物などが挙げられる。
【００６３】
エーテル類としては、ジメチルエーテル、ジエチルエーテル、ジ−ｎ−プロピルエーテル、ジ−ｎ−ブチルエーテル、ジ−ｉ−アミルエーテル、ジ−ｎ−ペンチルエーテル、ジ−ｎ−ヘキシルエーテル、ジ−ｉ−ヘキシルエーテル、ジ−ｎオクチルエーテル、ジ−ｉ−オクチルエーテル、ジ−ｎ−ドデシルエーテル、ジフェニルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフラン等が、アルコール類としては、メタノール、エタノール、プロパノール、ブタノール、ぺントノール、ヘキサノール、オクタノール、２−エチルヘキサノール、アリルアルコール、ベンジルアルコール、エチレングリコール、グリセリン等が、またフェノール類として、フェノール、クレゾール、キシレノール、エチルフェノール、ナフトール等が挙げられる。
【００６４】
エステル類としては、メタクリル酸メチル、ギ酸メチル、酢酸メチル、酪酸メチル、酢酸エチル、酢酸ビニル、酢酸−ｎ−プロピル、酢酸−ｉ−プロピル、ギ酸ブチル、酢酸アミル、酢酸−ｎ−ブチル、酢酸オクチル、酢酸フェニル、プロピオン酸エチル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、安息香酸オクチル、安息香酸−２−エチルヘキシル、トルイル酸メチル、トルイル酸エチル、アニス酸メチル、アニス酸エチル、アニス酸プロピル、アニス酸フェニル、ケイ皮酸エチル、ナフトエ酸メチル、ナフトエ酸エチル、ナフトエ酸プロピル、ナフトエ酸ブチル、ナフトエ酸−２−エチルヘキシル、フェニル酢酸エチル等のモノカルボン酸エステル類、コハク酸ジエチル、メチルマロン酸ジエチル、ブチルマロン酸ジエチル、マレイン酸ジブチル、ブチルマレイン酸ジエチル等の脂肪族多価カルボン酸エステル類、フタル酸モノメチル、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジ−ｎ−プロピル、フタル酸モノ−ｎ−ブチル、フタル酸ジ−ｎ−ブチル、フタル酸ジ−ｉ−ブチル、フタル酸ジ−ｎ−ヘプチル、フタル酸ジ−２−エチルヘキシル、フタル酸ジ−ｎ−オクチル、ｉ−フタル酸ジエチル、ｉ−フタル酸ジプロピル、ｉ−フタル酸ジブチル、ｉ−フタル酸ジ−２−エチルヘキシル、テレフタル酸ジエチル、テレフタル酸ジプロピル、テレフタル酸ジブチル、ナフタレンジカルボン酸ジ−ｉ−ブチル等の芳香族多価カルボン酸エステル類が挙げられる。
【００６５】
アルデヒド類としては、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド等が、カルボン酸類として、ギ酸、酢酸、プロピオン酸、酪酸、修酸、コハク酸、アクリル酸、マレイン酸、吉草酸、安息香酸などのモノカルボン酸類および無水安息香酸、無水フタル酸、無水テトラヒドロフタル酸などの酸無水物が、けとん類として、アセトン、メチルエチルケトン、メチル−ｉ−ブチルケトン、ベンゾフェノン等が例示される。
【００６６】
窒素含有化合物としては、アセトニトリル、ベンゾニトリル等のニトリル類、メチルアミン、ジエチルアミン、トリブチルアミン、トリエタノールアミン、β（Ｎ，Ｎ−ジメチルアミノ）エタノール、ピリジン、キノリン、α−ピコリン、２，４，６−トリメチルピリジン、２，２，５，６−テトラメチルピペリジン、２，２，５，５，テトラメチルピロリジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、アニリン、ジメチルアニリン等のアミン類、ホルムアミド、ヘキサメチルリン酸トリアミド、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ”−ペンタメチル−Ｎ’−β−ジメチルアミノメチルリン酸トリアミド、オクタメチルピロホスホルアミド等のアミド類、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル尿素等の尿素類、フェニルイソシアネート、トルイルイソシアネート等のイソシアネート類、アゾベンゼン等のアゾ化合物類が例示される。
【００６７】
燐含有化合物としては、エチルホスフィン、トリエチルホスフィン、トリ−ｎ−オクチルホスフィン、トリフェニルホスフィン、トリフェニルホスフィンオキシド等のホスフィン類、ジメチルホスファイト、ジ−ｎ−オクチルホスフィン、トリフェニルホスフィン、トリフェニルホスフィンオキシド等のホスフィン類、ジメチルホスファイト、ジ−ｎ−オクチルホスファイト、トリエチルホスファイト、トリ−ｎ−ブチルホスファイト、トリフェニルホスファイト等のホスファイト類が例示される。
【００６８】
硫黄含有化合物としては、ジエチルチオエーテル、ジフェニルチオエーテル、メチルフェニルチオエーテル等のチオエーテル類、エチルチオアルコール、ｎ−プロピルチオアルコール、チオフェノール等のチオアルコール類が挙げられ、さらに、有機ケイ素化合物として、トリメチルシラノール、トリエチルシラノール、トリフェニルシラノール等のシラノール類、トリメチルメトキシシラン、ジメチルジメトキシシラン、メチルフェニルジメトキシシラン、ジフェニルジメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、フェニルトリメトキシシラン、トリメチルエトキシシラン、ジメチルジエトキシシラン、ジ−ｉ−プロピルジメトキシシラン、ジ−ｉ−ブチルジメトキシシラン、ジフェニルジエトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ビニルトリエトキシシラン、ブチルトリエトキシシラン、フェニルトリエトキシシラン、エチルトリイソプロポキシシラン、ビニルトリアセトキシシラン、シクロペンチルメチルジメトキシシラン、シクロペンチルトリメトキシシラン、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルトリメトキシシラン、ジシクロヘキシルジメトキシシラン、２−ノルボルニルメチルジメトキシシラン等の分子中にＳｉ−Ｏ−Ｃ結合を有する有機ケイ素化合物等が挙げられる。
これらの電子供与体は、１種の単独あるいは２種類以上を混合して使用することができる。
【００６９】
予備活性化触媒は、
遷移金属化合物触媒成分、および
遷移金属原子１モルに対し０．０１〜１，０００モルの周期表（１９９１年版）第１族、第２族、第１２族および第１３族に属する金属よりなる群から選択された金属の有機金属化合物（ＡＬ１）、および
遷移金属原子１モルに対し０〜５００モルの電子供与体（Ｅ１）、
の組み合わせからなるポリオレフィン製造用触媒、
ならびに、この触媒に担持した
遷移金属化合物成分１ｇ当たり０．０１〜１００ｇの１３５℃のテトラリン中で測定した固有粘度［η_D ］が１０dl／ｇより小さい本（共）重合目的のポリプロピレン、および
遷移金属化合物触媒成分１ｇ当たり０．０１〜５，０００ｇの１３５℃のテトラリン中で測定した固有粘度［η_A ］が１５〜１００dl／ｇであるポリエチレン（ａ）、および
遷移金属化合物触媒成分１ｇ当たり０．０１〜５，０００ｇの１３５℃のテトラリン中で測定した固有粘度［η_B ］が（ａ）の固有粘度［η_A ］よりも小さく、かつ１０〜５０dl／ｇであるポリエチレン（ｂ）、からなる。
【００７０】
予備活性化触媒において、ポリエチレン（ａ）は、１３５℃のテトラリン中で測定した固有粘度［η_A ］が１５〜１００dl／ｇ、好ましくは１７〜５０dl／ｇの範囲のエチレン単独重合体またはエチレン重合単位が５０重量％以上、好ましくは７０重量％以上、さらに好ましくは９０重量％以下であるエチレンと炭素数３〜１２のオレフィンとの共重合体である。
【００７１】
予備活性化触媒において、ポリエチレン（ｂ）は、１３５℃のテトラリン中で測定した固有粘度［η_B ］が（ａ）の固有粘度［η_A ］よりも小さく、かつ１０〜５０dl／ｇ、好ましくは１０〜２５dl／ｇの範囲のエチレン単独重合体またはエチレン重合単位が５０重量％以上、好ましくは７０重量％以上、さらに好ましくは９０重量％以下であるエチレンと炭素数３〜１２のオレフィンとの共重合体である。
【００７２】
ポリエチレン（ａ）および（ｂ）の遷移金属化合物触媒成分１ｇ当たりの担持量は０．０１〜５，０００ｇ、好ましくは０．０５〜２，０００ｇ、さらに好ましくは０．１〜１，０００ｇである。遷移金属化合物触媒成分１ｇ当たりの担持量が０．０１ｇ未満では、本（共）重合の後に得られるポリプロピレン組成物の溶融張力の向上効果が不十分であり、成形性への向上効果が不十分である。また５，０００ｇを越える場合にはそれらの効果の向上が顕著でなくなるばかりでなく、ポリプロピレン組成物の均質性が悪化する場合があるので好ましくない。
【００７３】
一方、ポリプロピレンは、１３５℃のテトラリン中で測定した固有粘度［η_B ］が１０dl／ｇより小さい本（共）重合目的の（ｃ）成分のポリプロピレンと同一組成のポリプロピレンであり、ポリプロピレン組成物の（ｃ）成分のポリプロピレンの一部として組み入られる。
【００７４】
一方、ポリプロピレンの遷移金属化合物触媒成分１ｇ当たりの担持量は０．０１〜１００ｇ、換言すればポリプロピレン組成物基準で０．００１〜１重量％の範囲が好適である。
【００７５】
予備活性化触媒は、遷移金属化合物触媒成分、有機金属化合物（ＡＬ１）および所望により使用される電子供与体（Ｅ１）の組み合わせからなるポリオレフィン製造用触媒の存在下に、本（共）重合目的のプロピレンまたはプロピレンとその他のオレフィンを予備（共）重合させてポリプロピレンを生成させ、次いでエチレンまたはエチレンとその他のオレフィンを予備活性化（共）重合させてポリエチレン（ａ）を生成させて、さらにエチレンまたはエチレンとその他のオレフィンを予備活性化（共）重合させてポリエチレン（ｂ）を生成させて、遷移金属化合物触媒成分にポリプロピレンおよびポリエチレン（ａ）およびポリエチレン（ｂ）を担持させる予備活性化処理により製造する。
【００７６】
この予備活性化処理において、遷移金属化合物触媒成分、触媒成分中の遷移金属１モルに対し０．０１〜１，０００モル、好ましくは０．０５〜５００モルの有機金属化合物（ＡＬ１）、および触媒成分中の遷移金属１モルに対し０〜５００モル、好ましくは０〜１００モルの電子供与体（Ｅ１）を組み合わせてポリオレフィン製造用触媒として使用する。
【００７７】
このポリオレフィン製造用触媒を、エチレンまたはエチレンとその他のオレフィンの（共）重合容積１リットル当たり、触媒成分中の遷移金属原子に換算して０．００１〜５，０００ミリモル、好ましくは０．０１〜１，０００ミリモル存在させ、溶媒の不存在下または遷移金属化合物触媒成分１ｇに対し１００リットルまでの溶媒中において、本（共）重合目的のプロピレンまたはプロピレンとその他のオレフィンとの混合物０．０１〜５００ｇを供給して予備（共）重合させて遷移金属化合物触媒成分１ｇに対し０．０１〜１００ｇのポリプロピレンを生成させ、次いでエチレンまたはエチレンとエチレンとその他のオレフィンとの混合物０．０１ｇ〜１０，０００ｇを供給して予備活性化（共）重合させて遷移金属化合物触媒成分１ｇに対し０．０１〜５，０００ｇのポリエチレン（ａ）を生成させ、次いでエチレンまたはエチレンとエチレンとその他のオレフィンとの混合物０．０１ｇ〜１０，０００ｇを供給して予備活性化（共）重合させて遷移金属化合物触媒成分１ｇに対し０．０１〜５，０００ｇのポリエチレン（ｂ）を生成させることにより、遷移金属化合物触媒成分にポリプロピレンおよびポリエチレン（ａ）およびポリエチレン（ｂ）が被覆担持される。
【００７８】
本明細書中において、「重合容積」の用語は、液層重合の場合には重合器内の液相部分の容積を、気相重合の場合には重合器内の気相部分の容積を意味する。
【００７９】
遷移金属化合物触媒成分の使用量は、プロピレンの効率的、かつ制御された（共）重合反応速度を維持する上で、前記範囲であることが好ましい。また、有機金属化合物（ＡＬ１）の使用量が、少なすぎると（共）重合反応速度が遅くなりすぎ、また大きくしても（共）重合反応速度のそれに見合う上昇が期待できないばかりか、ポリプロピレン組成物中に有機金属化合物（ＡＬ１）の残さが多くなるので好ましくない。さらに、電子供与体（Ｅ１）の使用量が大きすぎると、（共）重合反応速度が低下する。溶媒使用量が大きすぎると、大きな反応容器を必要とするばかりでなく、効率的な（共）重合反応速度の制御及び維持が困難となる。
【００８０】
予備活性化処理は、たとえば、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、イソオクタン、デカン、ドデカン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、他にガソリン留分や水素化ジーゼル油留分等の不活性溶媒、オレフィン自身を溶媒とした液相中で行いことができ、また溶媒を用いずに気相中で行うことも可能である。
【００８１】
予備活性化処理は水素の存在下においても実施してもよいが、固有粘度［η_A ］が１５〜１００dl／ｇの高分子量のポリエチレン（ａ）および固有粘度［η_B ］が１０〜５０dl／ｇの高分子量のポリエチレン（ｂ）を生成させるためには、水素は用いないほうが好適である。
【００８２】
予備活性化処理においては、本（共）重合目的のプロピレンまたはプロピレンとその他のオレフィンとの混合物の予備（共）重合条件は、ポリプロピレンが遷移金属化合物触媒成分１ｇ当たり０．０１ｇ〜１００ｇ生成する条件であればよく、通常、−４０℃〜１００℃の温度下、０．１ＭＰａ〜５ＭＰａの圧力下で、１分〜２４時間実施する。またエチレンまたはエチレンとその他のオレフィンとの混合物の予備活性化（共）重合条件は、ポリエチレン（ａ）および（ｂ）が遷移金属化合物触媒成分１ｇ当たり０．０１〜５，０００ｇ、好ましくは０．０５〜２，０００ｇ、さらに好ましくは０．１〜１，０００ｇの量で生成するような条件であれば特に制限はなく、通常、−４０℃〜４０℃、好ましくは−４０℃〜３０℃、さらに好ましくは−４０℃〜２０℃程度の比較的低温度下、０．１ＭＰａ〜５ＭＰａ、好ましくは０．２ＭＰａ〜５ＭＰａ、特に好ましくは０．３ＭＰａ〜５ＭＰａの圧力下で、１分〜２４時間、好ましくは５分〜１８時間、特に好ましくは１０分〜１２時間である。
【００８３】
また、前記予備活性化処理後に、予備活性化処理による本（共）重合活性の低下を抑制することを目的として、本（共）重合目的のプロピレンまたはプロピレンとその他のオレフィンとの混合物による付加重合を、遷移金属化合物触媒成分１ｇ当たり０．０１〜１００ｇのポリプロピレンの反応量で行ってもよい。この場合、有機金属化合物（ＡＬ１）、電子供与体（Ｅ１）、溶媒、およびプロピレンまたはプロピレンとその他のオレフィンとの混合物の使用量はエチレンまたはエチレンとその他のオレフィンとの混合物による予備活性化重合と同様な範囲で行うことができるが、遷移金属原子１モル当たり０．００５〜１０モル、好ましくは０．０１〜５モルの電子供与体の存在下に行うのが好ましい。また、反応条件については−４０〜１００℃の温度下、０．１〜５ＭＰａの圧力下で、１分から２４時間実施する。
【００８４】
付加重合に使用される有機金属化合物（ＡＬ１）、電子供与体（Ｅ１）、溶媒の種類については、エチレンまたはエチレンとその他のオレフィンとの混合物による予備活性化重合と同様なものを使用でき、プロピレンまたはプロピレンとその他のオレフィンとの混合物については本（共）重合目的と同様の組成のものを使用する。
【００８５】
予備活性化触媒は、そのまま、または追加の有機金属化合物（ＡＬ２）及び電子供与体（Ｅ２）をさらに含有させたオレフィン本（共）重合触媒として、ポリプロピレン組成物を得るための炭素数２〜１２のオレフィンの本（共）重合に用いることができる。
【００８６】
前記オレフィン本（共）重合用触媒は、前記予備活性化触媒、予備活性化触媒中の遷移金属原子１モルに対し有機金属化合物（ＡＬ２）を活性化触媒中の有機金属化合物（ＡＬ１）との合計（ＡＬ１＋ＡＬ２）で０．０５〜３，０００モル、好ましくは０．１〜１，０００モルおよび活性化触媒中の遷移金属原子１モルに対し電子供与体（Ｅ２）を予備活性化触媒中の電子供与体（Ｅ１）との合計（Ｅ１＋Ｅ２）で０〜５，０００モル、好ましくは０〜３，０００モルからなる。
【００８７】
有機金属化合物の含有量（ＡＬ１＋ＡＬ２）が小さすぎると、プロピレンまたはプロピレンとその他のオレフィンの本（共）重合における（共）重合反応速度が遅すぎ、一方過剰に大きくしても（共）重合反応速度の期待されるほどの上昇は認められず非効率的であるばかりではなく、最終的に得られるポリプロピレン組成物中に残留する有機金属化合物残さが多くなるので好ましくない。さらに電子供与体の含有量（Ｅ１＋Ｅ２）が過大になると（共）重合反応速度が著しく低下する。
【００８８】
オレフィン本（共）重合用触媒に必要に応じて追加使用される有機金属化合物（ＡＬ２）および電子供与体（Ｅ２）の種類については既述の有機金属化合物（ＡＬ１）および電子供与体（Ｅ１）と同様なものを使用することができる。また、１種の単独使用でもよく２種以上を混合使用してもよい。また予備活性化処理の際に使用したものと同種でも異なっていてもよい。
【００８９】
オレフィン本（共）重合用触媒は、前記予備活性化触媒中に存在する溶媒、未反応のオレフィン、有機金属化合物（ＡＬ１）、および電子供与体（Ｅ１）等を濾別またはデカンテーションして除去して得られた粉粒体またはこの粉粒体に溶媒を添加した懸濁液と、追加の有機金属化合物（ＡＬ２）および所望により電子供与体（Ｅ２）とを組み合わせてもよく、また、存在する溶媒および未反応のオレフィンを減圧蒸留または不活性ガス流等により蒸発させて除去して得た粉粒体または粉粒体に溶媒を添加した懸濁液と、所望により有機金属化合物（ＡＬ２）及び電子供与体（Ｅ２）とを組み合わせてもよい。
【００９０】
ポリプロピレン組成物の製造方法において、前記予備活性化触媒またはオレフィン本（共）重合用触媒の使用量は、重合容積１リットルあたり、予備活性化触媒中の遷移金属原子に換算して、０．００１〜１，０００ミリモル、好ましくは０．００５〜５００ミリモル使用する。遷移金属化合物触媒成分の使用量を上記範囲とすることにより、プロピレンまたはプロピレンと組成オレフィンとの混合物の効率的かつ制御された（共）重合反応速度を維持することができる。
【００９１】
ポリプロピレン組成物におけるプロピレンまたはプロピレンとその他のオレフィンとの混合物の本（共）重合は、その重合プロセスとして公知のオレフィン（共）重合プロセスが使用可能であり、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、イソオクタン、デカン、ドデカン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、他にガソリン留分や水素化ジーゼル油留分等の不活性溶媒中で、オレフィンの（共）重合を実施するスラリー重合法、オレフィン自身を溶媒として用いるバルク重合法、オレフィンの（共）重合を気相中で実施する気相重合法、さらに（共）重合して生成するポリオレフィンが液状である液相重合、あるいはこれらのプロセスの２以上を組み合わせた重合プロセスを使用することができる。
【００９２】
上記のいずれの重合プロセスを使用する場合も、重合条件として、重合温度は２０〜１２０℃、好ましくは３０〜１００℃、特に好ましくは４０〜１００℃の範囲、重合圧力は０．１〜５ＭＰａ、好ましくは０．３〜５ＭＰａの範囲において、連続的、半連続的、若しくはバッチ的に重合時間は５分間〜２４時間程度の範囲が採用される。上記の重合条件を採用することにより、（ｃ）成分のポリプロピレンを高効率かつ制御された反応速度で生成させることができる。
【００９３】
ポリプロピレン組成物の製造方法により好ましい態様においては、本（共）重合において生成する（ｃ）成分のポリプロピレン組成物の固有粘度［η_T ］が０．２〜１０dl／ｇ、好ましくは０．７〜５dl／ｇの範囲となり、かつ得られるポリプロピレン組成物中に、使用した予備活性化触媒に由来するポリエチレン（ａ）が０．０１〜５重量％の範囲およびポリエチレン（ｂ）が０．０１〜５重量％の範囲となるように重合条件を選定する。
【００９４】
本（共）重合の終了後、必要に応じて公知の触媒失活処理工程、触媒残さ除去工程、乾燥工程等の後処理工程を経てポリプロピレン組成物が得られる。
【００９５】
【実施例】
以下に、本発明を実施例および比較例によりさらに詳細に説明する。
実施例および比較例において使用する用語の定義および測定方法は以下の通りである。
固有粘度［η］：１３５℃のテトラリン中で測定した極限粘度を、オストヴァルト粘度計（三井東圧化学（株）製）により測定した値（単位：dl／ｇ）。
フィッシュアイ数：組成物を口径（直径）６５ｍｍ押出機及びＴダイを用いて溶融温度２５０℃で押出し、エアーチャンバー及び表面温度３０℃の冷却ロールで急冷して厚さ３０μｍのフィルムとし、そのフィルムの５００ｃｍ² 中の５０μｍ以上のフィッシュアイ数を目視にて定量し以下のように評価を行い、フィッシュアイ数とした（単位：ケ／５００ｃｍ² ）。
【００９６】
【実施例１】
（１）遷移金属化合物触媒成分の調製
撹拌機付きステンレス製反応器中において、デカン３７．５リットル、無水塩化マグネシウム７．１４ｋｇ、オルトチタン酸−ｎ−ブチル２８．３ｋｇ、および２−エチル−１−ヘキサノール３５．１リットルを混合し、撹拌しながら１４０℃に４時間加熱反応を行って均一な溶液とした。この均一溶液中に無水フタル酸１．６７ｋｇを添加し、さらに１３０℃にて１時間撹拌混合を行い、無水フタル酸をこの均一溶液に溶解した。
【００９７】
得られた均一溶液を室温（２３℃）に冷却した後、この均一溶液を−２０℃に保持した四塩化チタン２００リットル中に３時間かけて全量滴下した。滴下後、４時間かけて１１０℃に昇温し、１１０℃に達したところでフタル酸ジ−ｉ−ブチル５．０３リットルを添加し、２時間１１０℃にて撹拌保持して反応を行った。２時間の反応終了後、熱濾過して固体部を採取し、固体部を２７５リットルの四塩化チタンにより再懸濁させた後、再び１１０℃で２時間、反応を持続した。
【００９８】
反応終了後、再び熱濾過により固体部を採取し、ｎ−ヘキサンにて、洗浄液中に遊離のチタンが検出されなくなるまで充分洗浄した。続いて、濾過により溶媒を分離し、固体部を減圧乾燥してチタン２．４重量％を含有するチタン含有担持型触媒成分（遷移金属化合物触媒成分）を得た。
【００９９】
（２）予備活性化触媒の調製
内容積３０リットルの傾斜羽根付きステンレス製反応器を窒素ガスで置換後、ｎ−ヘキサン１８リットル、トリエチルアルミニウム（有機金属化合物（ＡＬ１））６０ミリモルおよび前項で調整したチタン含有担持型触媒成分１５０ｇ（チタン原子換算で７５．１６ミリモル）を添加した後、プロピレン５００ｇを供給し、−２℃で４０分間、予備重合を行った。
【０１００】
別途、同一の条件で行った予備重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、３．２ｇのポリプロピレン(Ｄ)が生成し、このポリプロピレン(Ｄ)の１３５℃のテトラリン中で測定した固有粘度［η_D ］が２．８dl／ｇであった。
【０１０１】
反応時間終了後、未反応のプロピレンを反応器外に放出し、反応器の気相部を１回、窒素置換した後、反応器内の温度を−１℃に保持しながら、反応器内の圧力を０．５９ＭＰａに維持するようにエチレンを反応器に連続的に５時間供給し、１段目の予備活性化重合を行った。
【０１０２】
別途、同一の条件で行った予備活性化重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、ポリマーが６５．３ｇ存在し、かつポリマーの１３５℃のテトラリン中で測定した固有粘度［η_T1］が３０．４dl／ｇであった。
【０１０３】
エチレンによる予備活性化重合で生成したチタン含有担持型触媒成分１ｇ当たりのポリエチレン（Ａ）量（Ｗ_A ）は、予備活性化処理後のチタン含有担持型触媒成分１ｇ当たりのポリマー生成量（Ｗ_T1）と予備重合後のチタン含有担持型触媒成分１ｇ当たりのポリプロピレン（Ｄ）生成量（Ｗ_D ）との差として次式で求められる。
Ｗ_A ＝Ｗ_T1−Ｗ_D
【０１０４】
また、エチレンによる予備活性化重合で生成したポリエチレン（Ａ）の固有粘度［η_A ］は、予備重合で生成したポリプロピレン（Ｄ）の固有粘度［η_D ］および予備活性化処理で生成したポリマーの固有粘度［η_T1］から次式により求められる。
［η_A ］＝（［η_T1］×Ｗ_T1−［η_D ］×Ｗ_D ）／（Ｗ_T1−Ｗ_D ）
上記式に従ってエチレンによる１段目の予備活性化重合で生成したポリエチレン(Ａ)量は、チタン含有担持型触媒成分１ｇ当たり６２．１ｇ、固有粘度［η_A ］は３１．８dl／ｇであった。
【０１０５】
反応時間終了後、未反応のエチレンを反応器外に放出し、反応器の気相部を１回、窒素置換した後、反応器内の温度を１０℃に保持しながら、反応器内の圧力を０．４９ＭＰａに維持するようにエチレンを反応器に連続的に３時間供給し、２段目の予備活性化重合を行った。
【０１０６】
別途、同一の条件で行った予備活性化重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、ポリマーが９７．５ｇ存在し、かつポリマーの１３５℃のテトラリン中で測定した固有粘度［η_T2］が２７．０dl／ｇであり、上記と同様にして算出した２段目の予備活性化重合により生成したポリエチレン（Ｂ）の生成量は、チタン含有担持型触媒成分１ｇ当たり３２．２ｇ、固有粘度［η_B ］は２０．１dl／ｇであった。
【０１０７】
反応時間終了後、未反応のエチレンを反応器外に放出し、反応器の気相部を１回、窒素置換し、本（共）重合用の予備活性化触媒スラリーとした。
【０１０８】
（３）ポリプロピレン組成物の製造（プロピレンの本（共）重合）
窒素置換された、内容積１１０リットルの撹拌機を備えた連続式横型気相重合器（長さ／直径＝３．７）に、ポリプロピレンパウダーを２５ｋｇ導入し、さらに予備活性化触媒スラリーをチタン含有担持型触媒成分として０．６１ｇ／ｈ、トリエチルアルミニウム（有機金属化合物（ＡＬ２））およびジイソプロピルジメトキシシラン（電子供与体（Ｅ２））の１５重量％ｎ−ヘキサン溶液をチタン含有担持型触媒成分中のチタン原子に対し、それぞれモル比が９０および１５となるように連続的に供給した。
【０１０９】
さらに、重合温度６０℃の条件下、重合器内のプロピレン濃度に対する水素濃度比が０．０８およびプロピレン濃度に対するエチレン濃度比が０．０２となるようにエチレンを、さらに重合器内の圧力が２．１５ＭＰａを保持するようにプロピレンをそれぞれ重合器内に供給して、プロピレン・エチレンの共重合を１５０時間連続して行った。
【０１１０】
重合期間中は重合器内の重合体の保有レベルが６０容積％に維持するように重合器からポリマーを１１．４ｋｇ／ｈの速度で抜き出した。
【０１１１】
抜き出したポリマーを、水蒸気を５容積％含む窒素ガスにより１００℃にて３０分間接触処理し、固有粘度［η_T ］が１．７５ｄｌ／ｇであるポリプロピレン組成物を得た。
【０１１２】
得られたポリマーは、（ａ）成分に該当する１段目に予備活性化処理により生成したポリエチレン含有率は０．３３重量％、および（ｂ）成分に該当する２段目に予備活性化処理により生成したポリエチレン含有率は０．１７重量％、および（ｃ）成分に該当するポリプロピレンの固有粘度［η_C ］は１．６２dl／ｇであった。
【０１１３】
得られたポリプロピレン組成物１００重量部に対して、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．１重量部、およびステアリン酸カルシウム０．１重量部混合し、混合物をスクリュー径４０ｍｍの押出し造粒機を用いて２３０℃にて造粒し、ペレットとした。ペレットについて各種物性を評価測定したところ、ＭＦＲは７．３ｇ／１０分、溶融張力（ＭＳ）は１．４ｃＮであった。フィッシュアイ数は１２ヶ／５００ｃｍ² であった。詳細な物性は表中にまとめて示す。
【０１１４】
【実施例２〜４】
実施例１において、１段目および２段目のエチレンによる予備活性化重合条件を変化させてポリエチレン（ａ）および（ｂ）の生成量または固有粘度を変えたことを除いては実施例１と同一の条件でポリプロピレン組成物を製造し、実施例２〜４の評価試料を調整した。
得られたポリプロピレン組成物の諸条件を表中に示す。
【０１１５】
【比較例１】
（１）遷移金属化合物触媒成分の調製
撹拌機付きステンレス製反応器中において、デカン０．３リットル、無水塩化マグネシウム４８ｇ、オルトチタン酸−ｎ−ブチル１７０ｇおよび２−エチル−１−ヘキサノール１９５ｇを混合し、撹拌しながら１３０℃に１時間加熱反応を行って均一な溶液とした。この均一溶液を７０℃に加温し、攪拌しながらフタル酸ジ−ｉ−ブチル１８ｇを加え１時間経過後、四塩化ケイ素５２０ｇを２．５時間加熱保持した。固体を溶液から分離し、ヘキサンで洗浄した固体生成物を得た。
【０１１６】
固体生成物の全量を１，２−ジクロルエタン１．５リットルに溶解した四塩化チタン１．５リットルと混合し、次いでフタル酸ジ−ｉ−ブチル３６ｇを加え、攪拌しながら１００℃で２時間反応させた後、同温度においてデカンテーションにより液相部を除き、再び、１，２−ジクロルエタン１．５リットルおよび四塩化チタン１．５リットルを加え、１００℃に２時間攪拌保持し、ヘキサンで洗浄し乾燥してチタン２．８重量％を含有するチタン含有担持型触媒成分（遷移金属化合物触媒成分）を得た。
【０１１７】
（２）予備活性化触媒の調製
内容積５リットルの傾斜羽根付きステンレス製反応器を窒素ガスで置換後、ｎ−ヘキサン２．８リットル、トリエチルアルミニウム（有機金属化合物（ＡＬ１））４ミリモルおよび前項で調整したチタン含有担持型触媒成分９．０ｇ（チタン原子換算で５．２６ミリモル）を添加した後、プロピレン２０ｇを供給し、−２℃で１０分間、予備重合を行った。
【０１１８】
別途、同一の条件で行った予備重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、１．８ｇのポリプロピレン(Ｄ)が生成し、このポリプロピレン(Ｄ)の１３５℃のテトラリン中で測定した固有粘度［η_D ］が２．７dl／ｇであった。
【０１１９】
反応時間終了後、未反応のプロピレンを反応器外に放出し、反応器の気相部を１回、窒素置換した後、反応器内の温度を−１℃に保持しながら、反応器内の圧力を０．５９ＭＰａに維持するようにエチレンを反応器に連続的に２時間供給し、１段目の予備活性化重合を行った。
【０１２０】
別途、同一の条件で行った予備活性化重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、ポリマーが２４．０ｇ存在し、かつポリマーの１３５℃のテトラリン中で測定した固有粘度［η_T1］が３１．４dl／ｇであった。
【０１２１】
これらの結果からエチレンによる１段目の予備活性化重合で生成したポリエチレン（Ａ）量は、チタン含有担持型触媒成分１ｇ当たり２２．２ｇ、固有粘度［η_A ］は３３．７dl／ｇであった。
【０１２２】
反応時間終了後、未反応のエチレンを反応器外に放出し、反応器の気相部を１回、窒素置換した後、反応器内にジイソプロピルジメトキシシラン（電子供与体（Ｅ１））１．６ミリモルを加えた後、プロピレン２０ｇを供給し、１℃で１０分間保持し、２段目の予備活性化重合を行った。
【０１２３】
別途、同一の条件で行った２段目の予備活性化重合後に生成したポリマーを分析した結果、チタン含有担持型触媒成分１ｇ当たり、ポリマーが２５．９ｇ存在し、かつポリマーの１３５℃のテトラリン中で測定した固有粘度［η_T2］が２９．３dl／ｇであり、上記と同様にして算出した２段目の予備活性化重合により生成したポリプロピレンの生成量は、チタン含有担持型触媒成分１ｇ当たり１．９ｇ、固有粘度［η_B ］は２．８dl／ｇであった。
【０１２４】
反応時間終了後、未反応のプロピレンを反応器外に放出し、反応器の気相部を１回、窒素置換し、本（共）重合用の予備活性化触媒スラリーとした。
【０１２５】
（３）ポリプロピレン組成物の製造（プロピレンの本（共）重合）
内容積５００リットルの撹拌機付き、ステンレス製重合器を窒素置換した後、２０℃においてｎ−ヘキサン２４０リットル、トリエチルアルミニウム（有機金属化合物（ＡＬ２））７８０ミリモル、ジイソプロピルジメトキシシラン（電子供与体（Ｅ２））７８ミリモルおよび前記で得た予備活性化触媒スラリー１／２量を重合器内に投入した。引き続いて、プロピレン濃度に対する水素濃度比およびエチレン濃度比を０．０２および０．０５になるように供給し、６０℃に昇温した後、重合器の気相部の圧力が０．７９ＭＰａを保持しながらプロピレン、水素およびエチレンを連続的に２時間、重合器内に供給しプロピレン・エチレンの共重合を実施した。
【０１２６】
重合時間経過後、引き続き未反応ガスを排出後、メタノール１リットルを重合器内に導入し、触媒失活反応を６０℃にて１５分間実施し、溶媒分離、重合体乾燥を行い、固有粘度［η_T ］が１．７０ｄｌ／ｇであるポリマーを４５．６ｋｇ得た。
【０１２７】
得られたポリマーは、（ａ）成分に該当する１段目に予備活性化処理により生成したポリエチレン含有率は０．２２重量％、および（ｃ）成分に該当するポリプロピレンの固有粘度［η_C ］は１．６３dl／ｇであった。
【０１２８】
引き続いて、実施例１と同様の条件で、押出造粒機にて造粒し、ポリマーペレットを得た。このペレットについての各種物性を測定した結果は、表中に示す。
【０１２９】
【比較例２】
２段目の予備活性化重合を省いた以外は、実施例１と同条件でポリプロピレン組成物を得た。このペレットについての各種物性を測定した結果は、表中に示す。
【０１３０】
【表１】

【０１３１】
【発明の効果】
以上説明した通り、本発明によれば、ポリオレフィン製造用触媒に少量の本（共）重合目的のポリプロピレンおよび特定の２種類以上の固有粘度を有するポリエチレンを担持させて予備活性化した触媒を使用してプロピレンを本（共）重合させた組成物は、溶融張力が高く、成形性が優れ、フィルム製膜時に発生するフィッシュアイが少ないオレフィン（共）重合体組成物を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an olefin (co) polymer composition and a method for producing the same, and more particularly, an olefin (co) polymer composition using a specific preactivation catalyst has high melt tension and moldability. The present invention relates to an olefin (co) polymer composition that is excellent and generates less fisheye during film formation, and a method for producing the same.
[0002]
[Prior art]
Polypropylene is widely used in various molding fields because it is excellent in mechanical properties, chemical resistance, etc., and extremely useful in balance with economy. However, since melt tension is small, it is inferior in moldability, such as thermoforming, such as vacuum and pressure forming, hollow molding, and foam molding.
[0003]
As a method for increasing the melt tension of polypropylene, a method in which an organic peroxide and a crosslinking aid are reacted with polypropylene in a molten state (JP 59-93711 A, JP 61-152754 A, etc.), A method of producing a polypropylene having free end long chain branching and free of gel by reacting crystalline polypropylene with a low decomposition temperature peroxide in the absence of oxygen is disclosed (JP-A-2-298536). ing.
[0004]
As other methods for improving melt viscoelasticity such as melt tension, a composition in which polyethylene or polypropylene having different intrinsic viscosities or molecular weights are blended, and a method for producing such a composition by multistage polymerization have been proposed.
[0005]
For example, 2 to 30 parts by weight of ultrahigh molecular weight polypropylene was added to 100 parts by weight of ordinary polypropylene, and extruded by a temperature range from the melting point to 210 ° C. (Japanese Patent Publication No. 61-28694), obtained by a multistage polymerization method. Extruded sheet made of two-component polypropylenes having different molecular weights with an intrinsic viscosity ratio of 2 or more (Japanese Patent Publication No. 1-1770), 3 types of polyethylene having a high viscosity average molecular weight of 1 to 10% by weight and having different viscosity average molecular weights A method for producing a polyethylene composition comprising polyethylene by a melt-kneading method or a multistage polymerization method (Japanese Patent Publication No. 62-61057), a multi-stage polymerization method using a highly active titanium / vanadium solid catalyst component, and an intrinsic viscosity of 20 dl. / G or more of ultra high molecular weight polyethylene polymerized to 0.05 to less than 1% by weight Polymerization of len (Japanese Patent Publication No. 5-79683), a multi-stage polymerization method using a highly active titanium catalyst component prepolymerized with 1-butene or 4-methyl-1-pentene by a polymerizer with a special arrangement In addition, a polyethylene polymerization method (Japanese Patent Publication No. 7-8890) in which 0.1 to 5% by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity of 15 dl / g or more is disclosed.
[0006]
Furthermore, a method for producing polypropylene having a high melt tension by polymerizing propylene using a prepolymerized catalyst in which ethylene and a polyene compound are prepolymerized on a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component ( Japanese Patent Laid-Open No. 5-222122) and ethylene having a high melt tension using an ethylene-containing prepolymerized catalyst containing polyethylene having an intrinsic viscosity of 20 dl / g or more by preliminarily polymerizing ethylene using a similar catalyst component A method for producing an olefin copolymer (Japanese Patent Laid-Open No. 4-55410) is disclosed.
[0007]
[Problems to be solved by the invention]
In the various proposed compositions and their production methods, although some improvement in the melt tension of the polyolefin is recognized, residual odor due to the crosslinking aid, moldability, and fish eyes are generated during film formation. There are still points to be improved.
[0008]
In addition, in the multistage polymerization method in which the production process of high molecular weight polyolefin is incorporated into the normal propylene (co) polymerization process in the main polymerization, a small amount of olefin (co) polymerization amount is required to produce a small amount of the high molecular weight polyolefin. Difficult to control and low polymerization temperatures may be required to produce sufficiently high molecular weight polyolefins, requiring process modifications and lowering the productivity of the polypropylene composition.
[0009]
In the method of prepolymerizing the polyene compound, it is necessary to prepare the polyene compound separately, and when propylene is polymerized based on the literature disclosing the method of prepolymerizing polyethylene, the final polypropylene composition is obtained. The prepolymerized polyethylene has a non-uniform dispersibility, and further improvement is required in terms of stability of the polypropylene composition.
[0010]
As described above, in the prior art, polypropylene is not sufficient for improving the melt tension, but also has a problem to be improved in terms of odor and moldability.
[0011]
Further, when an olefin copolymer in which polymer particles having greatly different fluidity coexist is processed into a film, fish eyes are generated and the film appearance is impaired.
[0012]
The present invention relates to an olefin (co) polymer composition using a specific pre-activated catalyst, an olefin (co) polymer having a high melt tension, excellent molding processability, and less fish eyes generated during film formation. It aims at providing a composition and its manufacturing method.
[0013]
As a result of diligent research to achieve the above object, the present inventors have carried out a preliminary activity by supporting a small amount of polypropylene for the purpose of this (co) polymerization and two or more specific types of polyethylene having different intrinsic viscosities on a catalyst for polyolefin production. It was found that a composition obtained by subjecting propylene to main (co) polymerization using a modified catalyst had excellent moldability and few fish eyes generated during film formation, leading to the present invention.
[0014]
[Means for Solving the Problems]
That is, the present invention is an olefin (co) polymer composition containing the following components (a) to (c), and the component (a) is 0.01 to 5 with respect to 100 parts by weight of the component (c). 0.0 part by weight and 0.01 to 5.0 parts by weight of component (b).
(A) Intrinsic viscosity measured with tetralin at 135 ° C. [η_A ] Is a high molecular weight polyethylene in the range of 15-100 dl / g.
(B) Intrinsic viscosity measured with tetralin at 135 ° C. [η_B ] In the range of 10 to 50 dl / g, and (a) the intrinsic viscosity [η_A ] Higher molecular weight polyethylene.
(C) Olefin (co) polymers other than the high molecular weight polyethylene (a) and (b).
[0015]
In the olefin (co) polymer composition, the intrinsic viscosity of the olefin (co) polymer measured with tetralin at 135 ° C. [η_T ] Is preferably in the range of 0.2 to 10 dl / g.
[0016]
In the olefin (co) polymer composition, the olefin (co) polymer of component (c) is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units. It is preferable that one or more types be selected.
[0017]
In the olefin (co) polymer composition, the olefin (co) polymer has an intrinsic viscosity [η] measured in melt tension (MS) at 230 ° C. and tetralin at 135 ° C._T ] Between
log (MS)> 4.24 × log [η_T ] -0.75
It is preferable to have a relationship represented by
log (MS)> 4.24 × log [η_T ]-0.72
Particularly preferably,
log (MS)> 4.24 × log [η_T ]-0.70
It has the relationship represented by.
[0018]
Moreover, in the said olefin (co) polymer composition, the olefin (co) polymer is a transition metal compound catalyst component, 0.01-1,000 mol periodic table with respect to 1 mol of transition metal atoms (1991 edition). An organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 and 0 to 500 moles of electron donor per mole of transition metal atoms ( In the presence of a polyolefin production catalyst comprising a combination of E1) and a pre-activated catalyst comprising polyethylene supported on this catalyst, propylene alone or propylene and other olefins having 2 to 12 carbon atoms are present ) It is preferably produced by polymerization.
[0019]
Further, in the olefin (co) polymer composition, the olefin (co) polymer is divided into a pre-activated catalyst, a periodic table (1991 edition), Group 1, Group 2, Group 12 and Group 13. 0.05 to 5,000 with respect to 1 mol of transition metal atoms in total of organometallic compound (AL2) of a metal selected from the group consisting of metals belonging to the organometallic compound (AL1) contained in the pre-activated catalyst And 0 to 3,000 moles per mole of transition metal atoms in the preactivated catalyst in total with the electron donor (E1) contained in the preactivated catalyst as well as the electron donor (E2). It is preferable to produce propylene alone or propylene and other olefins having 2 to 12 carbon atoms in the presence of the main olefin (co) polymerization catalyst.
[0020]
Further, in the olefin (co) polymer composition, the preactivation catalyst has an intrinsic viscosity [η measured in 135 ° C. tetralin per gram of the transition metal compound catalyst component._A ] Is 15 to 100 dl / g, and the intrinsic viscosity [η_B ] Is the intrinsic viscosity [η_A And polyethylene in the range of 10 to 50 dl / g preferably carries 0.01 to 5,000 g each.
[0021]
Further, in the olefin (co) polymer composition, the preactivation catalyst has an intrinsic viscosity [η measured in 135 ° C. tetralin per gram of the transition metal compound catalyst component._D ] Of 0.01 to 100 g of polypropylene with a viscosity of less than 10 dl / g and intrinsic viscosity [η measured in tetralin at 135 ° C._A ] Is 15 to 100 dl / g, and the intrinsic viscosity [η_B ] Is the intrinsic viscosity [η_A And polyethylene in the range of 10 to 50 dl / g preferably carries 0.01 to 5,000 g.
[0022]
Next, the manufacturing method of this invention is a manufacturing method of the olefin (co) polymer composition including the process of following (a)-(c), Comprising: The olefin (co) polymer 100 obtained at (c) process In the range of 0.01 to 5.0 parts by weight of the high molecular weight polyethylene obtained in the step (a) and 0.01 to 5.0 parts by weight of the high molecular weight polyethylene obtained in the step (b) with respect to parts by weight. It is characterized by polymerizing.
(A) Intrinsic viscosity measured with tetralin at 135 ° C. [η_A ] Is a prepolymerization step for polymerizing high molecular weight polyethylene having a range of 15 to 100 dl / g.
(B) Intrinsic viscosity measured with tetralin at 135 ° C. [η_B ] In the range of 10 to 50 dl / g, and (a) the intrinsic viscosity [η_A ] Is a prepolymerization step for polymerizing a smaller high molecular weight polyethylene.
(C) This (co) polymerization step of polymerizing an olefin (co) polymer other than the high molecular weight polyethylene (a) and (b).
[0023]
In the method, the order of the steps (a) and (b) is not limited, and either step may be performed first, but the step (b) is preferably performed after the step (a).
In the above method,(A) Process and (b) ProcessIn any process selected from the group consisting of the transition metal compound catalyst component and the transition metal atom, 0.01 to 1,000 moles of the periodic table (1991 edition), Group 1, Group 2, Group 12 and Group Using a pre-activated catalyst comprising a combination of an organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 13 and 0 to 500 moles of an electron donor (E1) per mole of transition metal atoms It is preferred to polymerize the polymer.
In the method, the propylene homopolymer or propylene polymerized unit is added in an amount of 50% by weight in the presence of a preactivated catalyst in which two or more kinds of polyethylenes having different intrinsic viscosities are supported using the preactivated catalyst. It is preferable to subject this (co) polymerization to at least one polymer selected from the propylene-olefin copolymer contained above.
In the above method,(A) Process and (b) ProcessIn any process selected from the group consisting of the transition metal compound catalyst component and the transition metal atom, 0.01 to 1,000 moles of the periodic table (1991 edition), Group 1, Group 2, Group 12 and Group Using a pre-activated catalyst comprising a combination of an organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 13 and 0 to 500 moles of an electron donor (E1) per mole of transition metal atoms It is preferred to polymerize the polymer.
In the method, the propylene homopolymer or propylene polymerized unit is added in an amount of 50% by weight in the presence of a preactivated catalyst in which two or more kinds of polyethylenes having different intrinsic viscosities are supported using the preactivated catalyst. It is preferable to subject this (co) polymerization to at least one polymer selected from the propylene-olefin copolymer contained above.
In the method, the olefin (co) polymer composition is selected from the group consisting of a pre-activated catalyst and a metal belonging to Group 1, Group 2, Group 12 and Group 13 of the Periodic Table (1991 edition). The total amount of organometallic compound (AL2) of the selected metal and organometallic compound (AL1) contained in the preactivated catalyst is 0.05 to 5,000 moles per mole of transition metal atom, and electron donor Olefin (co) further containing 0 to 3,000 moles per mole of transition metal atoms in the preactivated catalyst in total with (E2) and the electron donor (E1) contained in the preactivated catalyst In the presence of a polymerization catalyst, at least one polymer selected from propylene homopolymers or propylene-olefin copolymers containing 50% by weight or more of propylene polymerized units is subjected to main (co) polymerization. It is preferable to obtain.
Further, in the above method, the pre-activated catalyst has an intrinsic viscosity [η measured in 135 ° C. tetralin per gram of the transition metal compound catalyst component._A ] Is 15 to 100 dl / g, and the intrinsic viscosity [η_B ] Is the intrinsic viscosity [η_A And polyethylene in the range of 10 to 50 dl / g preferably carries 0.01 to 5,000 g.
Further, in the above method, the pre-activated catalyst has an intrinsic viscosity [η measured in 135 ° C. tetralin per gram of the transition metal compound catalyst component._D ] Of 0.01 to 100 g of polypropylene with a viscosity of less than 10 dl / g and intrinsic viscosity [η measured in tetralin at 135 ° C._A ] Is 15 to 100 dl / g, and the intrinsic viscosity [η_B ] Is the intrinsic viscosity [η_A And polyethylene in the range of 10 to 50 dl / g preferably carries 0.01 to 5,000 g.
Moreover, in the said method, 0.01-1,000 millimoles of olefin (co) polymer is converted into the transition metal atom in the catalyst per liter of (co) polymerization volume of propylene or propylene and other olefins. It is preferably produced in a catalytic amount.
The olefin (co) polymer composition can be preferably applied to a film.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term “polypropylene” means a propylene homopolymer and a propylene-olefin random copolymer and a propylene-olefin block copolymer containing 50% by weight or more of a propylene polymer unit, and “polyethylene”. Means an ethylene homopolymer and an ethylene-olefin random copolymer containing 50% by weight or more of ethylene polymerized units.
[0025]
The polyethylene constituting the component (a) of the polypropylene composition has an intrinsic viscosity [η measured in tetralin at 135 ° C._A ] Is 15 to 100 dl / g polyethylene, and is an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, preferably 70% by weight of ethylene homopolymer or ethylene polymerized units. % Of ethylene-olefin copolymer, particularly preferably ethylene homopolymer or ethylene-olefin copolymer containing 90% by weight or more of ethylene polymerized units, and these (co) polymers are one kind. In addition, two or more kinds may be mixed.
[0026]
(A) Intrinsic viscosity of component polyethylene [η_A ] Is less than 15 dl / g, the melt tension of the resulting polypropylene composition is lowered, and the effect of improving moldability becomes insufficient.
[0027]
(A) Intrinsic viscosity of component polyethylene [η_A ] Is in the range of 15-100 dl / g, preferably 17-50 dl / g. In addition, polyethylene (a) has an intrinsic viscosity [η measured in tetralin at 135 ° C._A ], It is necessary to increase the molecular weight to 15 dl / g, so that the ethylene polymerized unit is preferably 50% by weight or more from the viewpoint of efficiency of increasing the molecular weight.
[0028]
The polyethylene constituting the component (b) of the polypropylene composition has an intrinsic viscosity [η measured in tetralin at 135 ° C._B ] Is the intrinsic viscosity [η] of (a)_A And is an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of an ethylene polymerized unit, preferably an ethylene homopolymer or an ethylene polymerized polymer. An ethylene-olefin copolymer containing 70% by weight or more of units, particularly preferably an ethylene homopolymer or an ethylene-olefin copolymer containing 90% by weight or more of ethylene polymerized units is suitable. The combination may be not only one type but also two or more types.
[0029]
(B) Intrinsic viscosity of component polyethylene [η_B ] Is less than 10 dl / g, the melt tension of the resulting polypropylene composition is lowered, the effect of improving moldability is insufficient, and the intrinsic viscosity [η_B ] Is 50 dl / g or more, the intrinsic viscosity [η_A ] And intrinsic viscosity of the component (c) polypropylene [η_C ], The dispersion of the polyethylene of the component (a) in the polypropylene of the component (c) becomes poor, fish eyes are generated during film formation, and the film appearance is impaired.
[0030]
(B) Intrinsic viscosity of component polyethylene [η_B ] Is in the range of 10-50 dl / g, preferably 10-25 dl / g. The polyethylene of component (b) has an intrinsic viscosity [η measured in tetralin at 135 ° C._B ], It is necessary to increase the molecular weight to 10 dl / g. Therefore, it is preferable that the ethylene polymerized unit is 50% by weight or more from the viewpoint of increasing the molecular weight.
[0031]
Although it does not specifically limit as olefin other than ethylene copolymerized with ethylene which comprises the polyethylene of (a) and (b) component, A C3-C12 olefin is used preferably. Specific examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. May be not only one but also two or more.
(A) Intrinsic viscosity of component polyethylene [η_A ] And intrinsic viscosity of the component (b) polyethylene [η_B ] And intrinsic viscosity of the component (c) polypropylene [η_C ], When the relationship of the following formula (Equation 1) is further satisfied, the fish eye during film formation is preferably reduced.
[Expression 1]
[η_C] + {([η_A-[η_C]) / 2} -13 <[η_B] <[Η_C] + {([η_A-[η_C]) / 2} +13
More preferably, it satisfies the relationship of the following formula (Equation 2).
[Expression 2]
[η_C] + {([η_A-[η_C]) / 2} -10 <[η_B] <[Η_C] + {([η_A-[η_C]) / 2} +10
[0032]
The density of the polyethylenes (a) and (b) is not particularly limited, but specifically, a density of about 880 to 980 g / liter is preferable.
[0033]
The polypropylene as the component (c) constituting the polypropylene composition has an intrinsic viscosity [η measured in tetralin at 135 ° C._C ] Is a crystalline polypropylene of 0.2 to 10 dl / g, a propylene homopolymer or a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of a propylene polymer unit, A propylene homopolymer, a propylene-olefin random copolymer having a propylene polymer unit content of 90% by weight or more, or a propylene-olefin block copolymer having a propylene polymer unit content of 70% by weight or more is preferable. These (co) polymers may be not only one type but also a mixture of two or more types.
[0034]
(C) Intrinsic viscosity of component polypropylene [η_C ] Is 0.2 to 10 dl / g, preferably 0.5 to 8 dl / g. (C) Intrinsic viscosity of component polypropylene [η_C ] Is less than 0.2 dl / g, the mechanical properties of the resulting polypropylene composition are deteriorated, and if it exceeds 10 dl / g, the moldability of the obtained polypropylene composition is deteriorated.
[0035]
(C) Although it does not specifically limit as olefins other than the propylene copolymerized with the propylene which comprises the polypropylene of a component, A C2-C12 olefin is used preferably. Specific examples include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. May be not only one but also two or more.
[0036]
The stereoregularity of the component (c) polypropylene is not particularly limited and may be any polypropylene that achieves the object of the present invention as long as it is crystalline polypropylene. In particular¹³The isotactic pentad fraction (mmmm) measured by C-NMR (nuclear magnetic resonance spectrum) is 0.80 to 0.99, preferably 0.85 to 0.99, particularly preferably 0.90 to 0.00. Polypropylene having a crystallinity of 99 is used.
[0037]
Isotactic pentad fraction (mmmm) is measured by 13C-NMR proposed by A. Zambelli et al. (Macromolecules 6, 925 (1973)). This is an isotactic fraction, and the method for determining the attribution of a peak in the measurement of a spectrum is determined according to the attribution proposed by A. Zambelli et al. (Macromolecules 8, 687 (1975)). Specifically, it is determined by measuring at 67.20 MHz and 130 ° C. using a mixed solution of o-dichlorobenzene / benzene bromide = 8/2 weight ratio with a polymer concentration of 20% by weight. As the measuring device, for example, a JEOL-GX270 NMR measuring device (manufactured by JEOL Ltd.) is used.
[0038]
The melt tension of the polypropylene composition is determined by the melt tension (MS) at 230 ° C. and the intrinsic viscosity measured in tetralin at 135 ° C. [η_T ]
log (MS)> 4.24 × log [η_T ] -0.75
It is preferable that it is a relationship represented by these. The upper limit is not particularly limited, but if the melt tension is too high, the moldability of the composition deteriorates, preferably,
log (MS)> 4.24 × log [η_T ]-0.72
More preferably, log (MS)> 4.24 × log [η_T ] − 0.70 is satisfied.
[0039]
Here, the melt tension (MS) at 230 ° C. is obtained by heating the olefin (co) polymer composition to 230 ° C. in the apparatus using a melt tension tester type 2 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) When the molten olefin (co) polymer composition is extruded from a nozzle having a diameter of 2.095 mm into the atmosphere at 23 ° C. at a speed of 20 mm / min to form a strand, and the strand is drawn at a speed of 3.14 m / min. It is a value (unit: cN) obtained by measuring the tension of the composition.
[0040]
As used herein, the term “pre-activation” refers to pre-activating the high molecular weight activity of a polyolefin production catalyst prior to carrying out the (co) polymerization of propylene or propylene with other olefins. This means that ethylene or ethylene and other olefins are preactivated (co) polymerized and supported on the catalyst in the presence of a polyolefin production catalyst.
[0041]
The pre-activated catalyst for olefin (co) polymerization of the present invention is a catalyst for polyolefin production comprising a transition metal compound catalyst component, an organometallic compound, and an electron donor that are optionally used for the production of polyolefins. , A catalyst pre-activated by loading a small amount of a polyolefin for the purpose of (co) polymerization having a specific intrinsic viscosity and a small amount of a specific polyolefin having two or more specific intrinsic viscosities.
[0042]
In the pre-activated catalyst for olefin (co) polymerization of the present invention, any of the known catalyst components mainly composed of transition metal compound catalyst components proposed for polyolefin production is used as the transition metal compound catalyst component. In particular, a titanium-containing solid catalyst component is preferably used for industrial production.
[0043]
As the titanium-containing solid catalyst component, a titanium-containing solid catalyst component mainly composed of a titanium trichloride composition (Japanese Patent Publication No. 56-3356, Japanese Patent Publication No. 59-28573, Japanese Patent Publication No. 63-66323, etc.), Titanium-containing supported catalyst component comprising titanium, magnesium, halogen, and electron donor as essential components, in which titanium tetrachloride is supported on a magnesium compound (Japanese Patent Laid-Open Nos. 62-104810 and 62-104811, Japanese Patent Laid-Open Nos. 62-104812, 57-63310, 57-63311, 58-83006, 58-138712, etc. are proposed. Any of these can be used.
[0044]
As a transition metal compound catalyst component other than the above, a transition metal compound having at least one π-electron conjugated ligand usually referred to as metallocene can also be used. The transition metal at this time is preferably selected from Zr, Ti, Hf, V, Nb, Ta and Cr.
[0045]
Specific examples of the π-electron conjugated ligand include a ligand having a η-cyclopentadienyl structure, η-benzene structure, η-cyclopentatrienyl structure, or η-cyclooctatetraene structure. Particularly preferred are ligands having an η-cyclopentadienyl structure.
[0046]
Examples of the ligand having an η-cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a fluorenyl group, and the like. These groups include hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, silicon-substituted hydrocarbon groups such as trialkylsilyl groups, halogen atoms, alkoxy groups, aryloxy groups, chain and cyclic alkylene groups, etc. It may be replaced.
[0047]
When the transition metal compound contains two or more π-electron conjugated ligands, the two π-electron conjugated ligands are alkylene groups, substituted alkylene groups, cycloalkylene groups, substituted cycloalkylene groups, substituted alkylidenes. It may be crosslinked via a group, a phenyl group, a silylene group, a substituted dimethylsilylene group, a germyl group or the like. At this time, the transition metal catalyst component includes at least one π-electron ligand as described above, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and a silicon-substituted hydrocarbon group. , An alkoxy group, an aryloxy group, a substituted sulfonate group, an amidosilylene group, an amidoalkylene group, and the like. Note that a divalent group such as an amidesilylene group or an amidealkylene group may be bonded to a π-electron conjugated ligand.
[0048]
The transition metal compound catalyst component having at least one π-electron conjugated ligand usually called metallocene as described above can be used by being supported on a fine particle carrier. As such a fine particle carrier, a granular or spherical fine particle solid having a particle diameter of 5 to 300 μm, preferably 10 to 200 μm is used even if it is an inorganic or organic compound. Among these, as an inorganic compound used for a carrier, SiO₂ , Al₂O_Three , MgO, TiO₂ , ZnO, etc., or a mixture thereof. Among these, SiO₂ Or Al₂O_Three The thing which has as a main component is preferable. Moreover, as an organic compound used for a support | carrier, the polymer or copolymer of C2-C12 alpha olefins, such as ethylene, propylene, 1-butene, 4-methyl-1- pentene, Furthermore, styrene or styrene Derivative polymers or copolymers may be mentioned.
[0049]
As the organometallic compound (AL1), a compound having an organic group of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 of the periodic table (1991 edition), for example, organic Lithium compounds, organic sodium compounds, organic magnesium compounds, organic zinc compounds, organic aluminum compounds, and the like can be used in combination with the transition metal compound catalyst component.
[0050]
In particular, the general formula is AlR¹ _pR² _qX_{3- (p + q)}(Wherein R¹ And R²Are the same or different hydrocarbon groups and alkoxy groups such as alkyl, cycloalkyl, and aryl groups, X represents a halogen atom, and p and q represent a positive number of 0 <p + q ≦ 3) An organoaluminum compound represented by the formula can be preferably used.
[0051]
Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-hexylaluminum, Trialkylaluminum such as tri-n-octylaluminum, diethylaluminum chloride, di-n-propylaluminum chloride, di-i-butylaluminum chloride, diethylaluminum bromide, dialkylaluminum monohalide such as diethylaluminum iodide, diethylaluminum hydride Dialkylaluminum hydrides such as ethylaluminum sesquichloride, alkylaluminum sesquihalides, etc. Other examples include monoalkylaluminum dihalides such as rualuminum dichloride and alkoxyalkylaluminums such as diethoxymonoethylaluminum. Trialkylaluminum and dialkylaluminum monohalides are preferably used. These organoaluminum compounds can be used alone or in combination of two or more.
[0052]
Moreover, an aluminoxane compound can also be used as the organometallic compound (AL1). Aluminoxane is an organoaluminum compound represented by the following general formula (Formula 1) or the following general formula (Formula 2).
[0053]
[Chemical 1]

[0054]
[Chemical 2]

[0055]
Where R^Three Is a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, Allyl groups, 2-methylallyl groups, propenyl groups, isopropenyl groups, 2-methyl-1-propenyl groups, alkenyl groups such as butenyl groups, cycloalkyl groups such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, and The compound which is an aryl group etc. is mentioned. Of these, alkyl groups are particularly preferred, and each R^Three May be the same or different. Although p is an integer of 4-30, Preferably it is 6-30, Most preferably, it is 8-30.
[0056]
Moreover, a boron type | system | group organometallic compound is mentioned as another compound as an organometallic compound (AL1). This boron-based organometallic compound is obtained by reacting a transition metal compound with an ionic compound containing a boron atom. The transition metal compound used at this time can be the same as the transition metal compound catalyst component used when producing the pre-activated catalyst for olefin (co) polymerization, but is preferably used as described above. A transition metal compound catalyst component having at least one π-electron co-ligand, commonly referred to as metallocene.
[0057]
Specific examples of the ionic compound containing a boron atom include triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, Examples thereof include methylammonium tetrakis (pentafluorophenyl) borate, tridimethylammonium tetrakis (pentafluorophenyl) borate, and trimethylammonium tetrakis (pentafluorophenyl) borate.
[0058]
The boron-based organic gold compound can also be obtained by bringing a transition metal compound into contact with a boron atom-containing Lewis acid. The transition metal compound used at this time can be the same as the transition metal catalyst component used in the production of the pre-activated catalyst for olefin (co) polymerization, but is preferably used as described above. It is a transition metal compound catalyst component having at least one π-electron conjugated ligand usually referred to as metallocene.
[0059]
As the boron atom-containing Lewis acid, a compound represented by the following general formula (Formula 3) can be used.
[0060]
[Chemical Formula 3]
BR^FourR^FiveR⁶
(In the formula, R 4, R 5 and R 6 each independently represent a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluorophenyl group, or a fluorine atom.)
[0061]
Specific examples of the compound represented by the above general formula include tri (n-butyl) boron, triphenylboron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and tris (4-fluoromethylphenyl). Examples thereof include boron, tris (3,5-difluorophenyl) boron, tris (2,4,6-trifluorophenyl) boron, and tris (pentafluorophenyl) boron, and tris (pentafluorophenyl) boron is particularly preferable.
[0062]
The electron donor (E1) is used as needed for the purpose of controlling the production rate and / or stereoregularity of the polyolefin.
Examples of the electron donor (E1) include ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea and thioureas, isocyanates, azo compounds, phosphines , Phosphites, phosphinites, hydrogen sulfide and thioethers, neoalcohols, silanols and other organic compounds having oxygen, nitrogen, sulfur or phosphorus atoms in the molecule and Si-O- in the molecule Examples include organosilicon compounds having a C bond.
[0063]
Examples of ethers include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-i-amyl ether, di-n-pentyl ether, di-n-hexyl ether, di-i-hexyl ether. , Di-n octyl ether, di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like, and alcohols include methanol, ethanol, propanol, butanol, Tontool, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, etc. are also used as phenols, such as phenol, cresol, quinol. Renoru, ethylphenol, naphthol and the like.
[0064]
Esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, acetic acid-n-propyl, acetic acid-i-propyl, butyl formate, amyl acetate, acetic acid-n-butyl, octyl acetate , Phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate , Monocarboxylic acid esters such as propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoate-2-ethylhexyl, ethyl phenylacetate, succinic acid Diethyl, diethyl methylmalonate, butyl Aliphatic polycarboxylic esters such as diethyl ronate, dibutyl maleate, diethyl butyl maleate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate Di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl i-phthalate, i-phthalate Aromatic polycarboxylic acid esters such as dipropyl acid, dibutyl i-phthalate, di-2-ethylhexyl i-phthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, and di-i-butyl naphthalenedicarboxylate Can be mentioned.
[0065]
As aldehydes, acetaldehyde, propionaldehyde, benzaldehyde and the like, as carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid and other monocarboxylic acids and Acid anhydrides such as benzoic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and the like are exemplified by acetone, methyl ethyl ketone, methyl-i-butyl ketone, benzophenone, and the like.
[0066]
Nitrogen-containing compounds include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4, Amines such as 6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine, 2,2,5,5, tetramethylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline Amides such as formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, N, Ureas such as N, N ′, N′-tetramethylurea, phenyl isocyanate, tolu Isocyanates such as Le isocyanate, azo compounds such as azobenzene can be exemplified.
[0067]
Phosphorus-containing compounds include phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethyl phosphite, di-n-octylphosphine, triphenylphosphine, triphenylphosphine. Examples include phosphines such as oxides, dimethyl phosphites, di-n-octyl phosphites, triethyl phosphites, tri-n-butyl phosphites, triphenyl phosphites, and the like.
[0068]
Examples of the sulfur-containing compound include thioethers such as diethyl thioether, diphenyl thioether, and methylphenyl thioether, and thioalcohols such as ethyl thioalcohol, n-propyl thioalcohol, and thiophenol. Further, as the organosilicon compound, trimethylsilanol Silanols such as triethylsilanol and triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldi Ethoxysilane, di-i-propyldimethoxysilane, di-i-butyldimethoxysilane, diphenyldiethoxysilane, Titritriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltriacetoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane , Cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, 2-norbornylmethyldimethoxysilane, and the like, such as organosilicon compounds having a Si—O—C bond in the molecule.
These electron donors can be used singly or in combination of two or more.
[0069]
The pre-activated catalyst is
A transition metal compound catalyst component, and
Periodic table of 0.01 to 1,000 moles per mole of transition metal atom (1991 edition) Organic of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 A metal compound (AL1), and
0 to 500 moles of electron donor (E1) per mole of transition metal atom,
A catalyst for polyolefin production comprising a combination of
And supported on this catalyst.
Intrinsic viscosity measured in 0.01-100 g of 135 ° C. tetralin per gram of transition metal compound component [η_D For the purpose of (co) polymerization of less than 10 dl / g, and
Inherent viscosity measured in 0.01 to 5,000 g of 135 ° C. tetralin per gram of transition metal compound catalyst component [η_A ] Polyethylene (a) in which is from 15 to 100 dl / g, and
Inherent viscosity measured in 0.01 to 5,000 g of 135 ° C. tetralin per gram of transition metal compound catalyst component [η_B ] Is the intrinsic viscosity [η] of (a)_A ] And a polyethylene (b) of 10 to 50 dl / g.
[0070]
In the pre-activated catalyst, the polyethylene (a) has an intrinsic viscosity [η measured in tetralin at 135 ° C._A ] Of ethylene homopolymer or ethylene polymerized unit in the range of 15 to 100 dl / g, preferably 17 to 50 dl / g, and ethylene having 50 wt% or more, preferably 70 wt% or more, more preferably 90 wt% or less It is a copolymer with a C3-C12 olefin.
[0071]
In the preactivated catalyst, polyethylene (b) has an intrinsic viscosity [η measured in tetralin at 135 ° C._B ] Is the intrinsic viscosity [η] of (a)_A The ethylene homopolymer or ethylene polymer unit in the range of 10 to 50 dl / g, preferably 10 to 25 dl / g, is 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or less. Is a copolymer of ethylene and an olefin having 3 to 12 carbon atoms.
[0072]
The supported amount per 1 g of the transition metal compound catalyst component of polyethylene (a) and (b) is 0.01 to 5,000 g, preferably 0.05 to 2,000 g, more preferably 0.1 to 1,000 g. . When the supported amount per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension of the polypropylene composition obtained after the (co) polymerization is insufficient, and the effect of improving the moldability is insufficient. It is. On the other hand, when the amount exceeds 5,000 g, not only the improvement of the effects is not remarkable, but also the homogeneity of the polypropylene composition may be deteriorated.
[0073]
On the other hand, polypropylene has an intrinsic viscosity [η measured in tetralin at 135 ° C._B ] Is smaller than 10 dl / g, and has the same composition as that of the component (c) component polypropylene for the purpose of (co) polymerization, and is incorporated as a part of the component (c) component polypropylene of the polypropylene composition.
[0074]
On the other hand, the supported amount of polypropylene per 1 g of the transition metal compound catalyst component is preferably 0.01 to 100 g, in other words, 0.001 to 1% by weight based on the polypropylene composition.
[0075]
The pre-activated catalyst is used for the purpose of the present (co) polymerization in the presence of a polyolefin production catalyst comprising a combination of a transition metal compound catalyst component, an organometallic compound (AL1) and an optional electron donor (E1). Propylene or propylene and other olefins are pre-copolymerized to produce polypropylene, and then ethylene or ethylene and other olefins are pre-activated (co-) polymerized to produce polyethylene (a) and further ethylene or Produced by a preactivation process in which ethylene and other olefins are preactivated (co) polymerized to produce polyethylene (b) and the transition metal compound catalyst component carries polypropylene, polyethylene (a) and polyethylene (b). To do.
[0076]
In this preactivation treatment, the transition metal compound catalyst component, 0.01 to 1,000 moles, preferably 0.05 to 500 moles of the organometallic compound (AL1), and catalyst with respect to 1 mole of the transition metal in the catalyst component 0 to 500 mol, preferably 0 to 100 mol, of an electron donor (E1) is combined with 1 mol of a transition metal in the component and used as a catalyst for polyolefin production.
[0077]
This polyolefin production catalyst is 0.001 to 5,000 millimoles, preferably 0.01 to 5 in terms of transition metal atoms in the catalyst component per liter of (co) polymerization volume of ethylene or ethylene and other olefins. In the absence of solvent or in the absence of solvent or in a solvent of up to 100 liters per gram of transition metal compound catalyst component, this (co) polymerization propylene or a mixture of propylene and other olefins 0.01- 500 g is supplied and preliminarily (co) polymerized to produce 0.01 to 100 g of polypropylene with respect to 1 g of the transition metal compound catalyst component, and then ethylene or a mixture of ethylene, ethylene and other olefins 0.01 g to 10, 1 g of transition metal compound catalyst component by pre-activation (co) polymerization 0.01 to 5,000 g of polyethylene (a) is produced and then preactivated (co) polymerized by supplying 0.01 g to 10,000 g of ethylene or a mixture of ethylene, ethylene and other olefins. By producing 0.01 to 5,000 g of polyethylene (b) per 1 g of the transition metal compound catalyst component, polypropylene, polyethylene (a) and polyethylene (b) are coated and supported on the transition metal compound catalyst component.
[0078]
In this specification, the term “polymerization volume” means the volume of the liquid phase portion in the polymerization vessel in the case of liquid layer polymerization, and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. To do.
[0079]
The amount of the transition metal compound catalyst component used is preferably within the above range in order to maintain an efficient and controlled (co) polymerization reaction rate of propylene. In addition, if the amount of the organometallic compound (AL1) used is too small, the (co) polymerization reaction rate becomes too slow, and even if it is increased, the (co) polymerization reaction rate cannot be expected to increase correspondingly. This is not preferable because the residue of the organometallic compound (AL1) increases in the product. Furthermore, when the usage-amount of an electron donor (E1) is too large, the (co) polymerization reaction rate will fall. When the amount of the solvent used is too large, not only a large reaction vessel is required, but also it is difficult to efficiently control and maintain the (co) polymerization reaction rate.
[0080]
Pre-activation treatment includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane, and dodecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, toluene, xylene, and ethylbenzene. In addition, it can be carried out in a liquid phase using an inert solvent such as gasoline fraction or hydrogenated diesel oil fraction, olefin itself as a solvent, and in the gas phase without using a solvent. It is also possible to do this.
[0081]
The preactivation treatment may be performed in the presence of hydrogen, but the intrinsic viscosity [η_A ] 15-100 dl / g of high molecular weight polyethylene (a) and intrinsic viscosity [η_B In order to produce a high molecular weight polyethylene (b) having a molecular weight of 10 to 50 dl / g, it is preferable not to use hydrogen.
[0082]
In the pre-activation treatment, the pre- (co) polymerization condition of propylene for the purpose of (co) polymerization or a mixture of propylene and other olefins is such that polypropylene is produced in an amount of 0.01 to 100 g per 1 g of the transition metal compound catalyst component. Usually, it is carried out at a temperature of −40 ° C. to 100 ° C. under a pressure of 0.1 MPa to 5 MPa for 1 minute to 24 hours. The preactivation (co) polymerization conditions for ethylene or a mixture of ethylene and other olefins are 0.01 to 5,000 g, preferably 0.000, per gram of transition metal compound catalyst component of polyethylene (a) and (b). If it is the conditions which produce | generate in the quantity of 05-2,000g, More preferably, 0.1-1,000g, there will be no restriction | limiting in particular, Usually, -40 degreeC-40 degreeC, Preferably it is -40 degreeC-30 degreeC, More preferably, under a relatively low temperature of about −40 ° C. to 20 ° C., 0.1 MPa to 5 MPa, preferably 0.2 MPa to 5 MPa, particularly preferably 0.3 MPa to 5 MPa, and 1 minute to 24 hours. The time is preferably 5 minutes to 18 hours, particularly preferably 10 minutes to 12 hours.
[0083]
In addition, after the preactivation treatment, addition polymerization with propylene for the purpose of main (co) polymerization or a mixture of propylene and other olefins for the purpose of suppressing a decrease in the main (co) polymerization activity due to the preactivation treatment. May be carried out with a reaction amount of 0.01 to 100 g of polypropylene per 1 g of the transition metal compound catalyst component. In this case, the use amount of the organometallic compound (AL1), the electron donor (E1), the solvent, and propylene or a mixture of propylene and other olefins is preactivated polymerization with ethylene or a mixture of ethylene and other olefins. It can be carried out in the same range, but it is preferably carried out in the presence of 0.005 to 10 mol, preferably 0.01 to 5 mol of an electron donor per mol of transition metal atom. Moreover, about reaction conditions, it implements under the pressure of 0.1-5 MPa under the temperature of -40-100 degreeC for 1 minute to 24 hours.
[0084]
As for the kind of organometallic compound (AL1), electron donor (E1), and solvent used in the addition polymerization, those similar to the preactivation polymerization using ethylene or a mixture of ethylene and other olefins can be used. Or about the mixture of a propylene and another olefin, the thing of the composition similar to this (co) polymerization purpose is used.
[0085]
The preactivation catalyst is used as it is or as an olefin main (co) polymerization catalyst further containing an additional organometallic compound (AL2) and an electron donor (E2). It can be used for the main (co) polymerization of olefins.
[0086]
The olefin main (co) polymerization catalyst is composed of an organometallic compound (AL2) and an organometallic compound (AL1) in the activation catalyst with respect to 1 mol of the transition metal atom in the preactivation catalyst and the preactivation catalyst. In total (AL1 + AL2) 0.05 to 3,000 mol, preferably 0.1 to 1,000 mol and 1 mol of transition metal atom in the activation catalyst, the electron donor (E2) in the preactivation catalyst The total (E1 + E2) with the electron donor (E1) is 0 to 5,000 mol, preferably 0 to 3,000 mol.
[0087]
If the content of the organometallic compound (AL1 + AL2) is too small, the (co) polymerization reaction rate in the main (co) polymerization of propylene or propylene and other olefins is too slow. Not only is the rate not expected to increase as expected, it is not efficient, but also the organometallic compound residue remaining in the final polypropylene composition increases, which is not preferable. Furthermore, when the content of the electron donor (E1 + E2) is excessive, the (co) polymerization reaction rate is significantly reduced.
[0088]
The types of the organometallic compound (AL2) and the electron donor (E2) that are additionally used as necessary for the olefin main (co) polymerization catalyst are as described above for the organometallic compound (AL1) and the electron donor (E1). The same as can be used. One kind of single use may be used, or two or more kinds may be used in combination. Moreover, it may be the same as or different from that used in the preliminary activation treatment.
[0089]
The olefin main (co) polymerization catalyst is removed by filtering or decanting the solvent, unreacted olefin, organometallic compound (AL1), electron donor (E1), etc. present in the pre-activated catalyst. Or a suspension obtained by adding a solvent to this powder, and an additional organometallic compound (AL2) and optionally an electron donor (E2) And a suspension obtained by adding a solvent to a granular material obtained by evaporating and removing the solvent to be reacted and unreacted olefin by distillation under reduced pressure or an inert gas flow, and an organometallic compound (AL2) if desired And an electron donor (E2).
[0090]
In the method for producing a polypropylene composition, the amount of the pre-activated catalyst or the olefin main (co) polymerization catalyst used is 0.001 in terms of transition metal atoms in the pre-activated catalyst per liter of polymerization volume. ˜1,000 mmol, preferably 0.005 to 500 mmol is used. By making the usage-amount of a transition metal compound catalyst component into the said range, the efficient and controlled (co) polymerization reaction rate of the mixture of propylene or a propylene, and a composition olefin can be maintained.
[0091]
For the main (co) polymerization of propylene or a mixture of propylene and other olefins in a polypropylene composition, a known olefin (co) polymerization process can be used as the polymerization process. Specifically, propane, butane, pentane can be used. , Hexane, heptane, octane, isooctane, decane, dodecane and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane and other alicyclic hydrocarbons, toluene, xylene, ethylbenzene and other aromatic hydrocarbons, and gasoline Slurry polymerization method to carry out (co) polymerization of olefins in an inert solvent such as water fraction or hydrogenated diesel oil fraction, bulk polymerization method using olefin itself as solvent, (co) polymerization of olefins in gas phase Gas phase polymerization method to be carried out, and polyolefin produced by (co) polymerization There can be used the polymerization process combining liquid phase polymerization is liquid, or two or more of these processes.
[0092]
When using any of the above polymerization processes, the polymerization temperature is 20 to 120 ° C., preferably 30 to 100 ° C., particularly preferably 40 to 100 ° C., and the polymerization pressure is 0.1 to 5 MPa. The polymerization time is preferably in the range of about 5 minutes to 24 hours continuously, semi-continuously, or batchwise in the range of 0.3 to 5 MPa. By adopting the above polymerization conditions, the component (c) polypropylene can be produced at a highly efficient and controlled reaction rate.
[0093]
In a preferred embodiment according to the method for producing a polypropylene composition, the intrinsic viscosity of the component (c) polypropylene composition produced in the present (co) polymerization [η_T] In the range of 0.2 to 10 dl / g, preferably 0.7 to 5 dl / g, and in the resulting polypropylene composition, the polyethylene (a) derived from the preactivated catalyst used is 0.01 to The polymerization conditions are selected so that the range is 5% by weight and the polyethylene (b) is in the range of 0.01 to 5% by weight.
[0094]
After the completion of the main (co) polymerization, a polypropylene composition is obtained through post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step as necessary.
[0095]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Definitions of terms and measurement methods used in Examples and Comparative Examples are as follows.
Intrinsic viscosity [η]: A value (unit: dl / g) measured with an Ostwald viscometer (manufactured by Mitsui Toatsu Chemical Co., Ltd.) as an intrinsic viscosity measured in tetralin at 135 ° C.
Number of fish eyes: The composition was extruded at a melting temperature of 250 ° C. using a 65 mm caliber (diameter) extruder and a T die, and rapidly cooled with a cooling roll having an air chamber and a surface temperature of 30 ° C. to form a 30 μm thick film. Of 500cm² The number of fish eyes of 50 μm or more was visually quantified and evaluated as follows to obtain the number of fish eyes (unit: ke / 500 cm).² ).
[0096]
[Example 1]
(1) Preparation of transition metal compound catalyst component
In a stainless steel reactor equipped with a stirrer, 37.5 liters of decane, 7.14 kg of anhydrous magnesium chloride, 28.3 kg of orthotitanate-n-butyl, and 35.1 liters of 2-ethyl-1-hexanol were mixed. While stirring, a heating reaction was performed at 140 ° C. for 4 hours to obtain a uniform solution. 1.67 kg of phthalic anhydride was added to the homogeneous solution, and further stirred and mixed at 130 ° C. for 1 hour to dissolve the phthalic anhydride in the homogeneous solution.
[0097]
The obtained homogeneous solution was cooled to room temperature (23 ° C.), and then the entire amount of this homogeneous solution was dropped into 200 liters of titanium tetrachloride maintained at −20 ° C. over 3 hours. After dropping, the temperature was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 liters of di-i-butyl phthalate was added, and the reaction was carried out by stirring and holding at 110 ° C. for 2 hours. After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended with 275 liters of titanium tetrachloride, and then the reaction was continued again at 110 ° C. for 2 hours.
[0098]
After completion of the reaction, the solid part was again collected by hot filtration and sufficiently washed with n-hexane until no free titanium was detected in the washing solution. Subsequently, the solvent was separated by filtration, and the solid part was dried under reduced pressure to obtain a titanium-containing supported catalyst component (transition metal compound catalyst component) containing 2.4% by weight of titanium.
[0099]
(2) Preparation of preactivated catalyst
After replacing the stainless steel reactor with inclined blades with an inner volume of 30 liters with nitrogen gas, 18 g of n-hexane, 60 mmol of triethylaluminum (organometallic compound (AL1)) and 150 g of the titanium-containing supported catalyst component prepared in the previous section ( After adding 75.16 mmol in terms of titanium atom), 500 g of propylene was supplied, and prepolymerization was performed at −2 ° C. for 40 minutes.
[0100]
Separately, as a result of analyzing the polymer produced after the prepolymerization performed under the same conditions, 3.2 g of polypropylene (D) was produced per 1 g of the titanium-containing supported catalyst component, and the 135 ° C. tetralin of this polypropylene (D) was produced. Intrinsic viscosity measured in [η_D ] Was 2.8 dl / g.
[0101]
After completion of the reaction time, unreacted propylene was discharged out of the reactor, the gas phase of the reactor was purged with nitrogen once, and then the temperature in the reactor was maintained at -1 ° C. Ethylene was continuously supplied to the reactor for 5 hours so as to maintain the pressure at 0.59 MPa, and the first stage pre-activation polymerization was performed.
[0102]
Separately, as a result of analyzing the polymer produced after the preactivation polymerization performed under the same conditions, it was found that 65.3 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic property of the polymer measured in tetralin at 135 ° C. Viscosity [η_T1] Was 30.4 dl / g.
[0103]
Amount of polyethylene (A) per gram of titanium-containing supported catalyst component produced by preactivation polymerization with ethylene (W_A ) Is the amount of polymer produced per gram of titanium-containing supported catalyst component after the preactivation treatment (W_T1) And the amount of polypropylene (D) produced per gram of titanium-containing supported catalyst component after prepolymerization (W_D ) And the following equation.
W_A = W_T1-W_D
[0104]
In addition, the intrinsic viscosity [η of polyethylene (A) produced by preactivation polymerization with ethylene [η_A ] Is the intrinsic viscosity [η of the polypropylene (D) produced by prepolymerization_D ] And the intrinsic viscosity of the polymer produced by the preactivation treatment [η_T1] From the following equation.
[Η_A ] = ([Η_T1] X W_T1− [Η_D ] X W_D ) / (W_T1-W_D )
According to the above formula, the amount of polyethylene (A) produced in the first stage pre-activation polymerization with ethylene was 62.1 g per 1 g of titanium-containing supported catalyst component, and the intrinsic viscosity [η_A ] Was 31.8 dl / g.
[0105]
After completion of the reaction time, unreacted ethylene is discharged out of the reactor, the gas phase of the reactor is purged with nitrogen once, and the pressure in the reactor is maintained while maintaining the temperature in the reactor at 10 ° C. Then, ethylene was continuously supplied to the reactor for 3 hours so as to maintain the pressure at 0.49 MPa, and second-stage preactivation polymerization was performed.
[0106]
Separately, as a result of analyzing the polymer produced after the preactivation polymerization performed under the same conditions, 97.5 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic property of the polymer measured in tetralin at 135 ° C. Viscosity [η_T2] Is 27.0 dl / g, and the amount of polyethylene (B) produced by the pre-activation polymerization of the second stage calculated in the same manner as above was 32.2 g per 1 g of titanium-containing supported catalyst component. Viscosity [η_B ] Was 20.1 dl / g.
[0107]
After completion of the reaction time, unreacted ethylene was discharged out of the reactor, and the gas phase portion of the reactor was purged with nitrogen once to obtain a preactivated catalyst slurry for this (co) polymerization.
[0108]
(3) Manufacture of polypropylene composition (book (co) polymerization of propylene)
25 kg of polypropylene powder was introduced into a continuous horizontal gas phase polymerization vessel (length / diameter = 3.7) equipped with a stirrer with an internal volume of 110 liters purged with nitrogen, and the preactivated catalyst slurry contained titanium. 0.61 g / h as a supported catalyst component, a 15 wt% n-hexane solution of triethylaluminum (organometallic compound (AL2)) and diisopropyldimethoxysilane (electron donor (E2)) in the titanium-containing supported catalyst component The titanium atoms were continuously fed so that the molar ratios were 90 and 15, respectively.
[0109]
Further, under a polymerization temperature of 60 ° C., ethylene was added so that the hydrogen concentration ratio to propylene concentration in the polymerization vessel was 0.08 and the ethylene concentration ratio to propylene concentration was 0.02, and the pressure in the polymerization vessel was 2 Propylene was supplied into the polymerization vessel so as to maintain .15 MPa, and propylene / ethylene copolymerization was continuously performed for 150 hours.
[0110]
During the polymerization period, the polymer was extracted from the polymerization vessel at a rate of 11.4 kg / h so that the retained level of the polymer in the polymerization vessel was maintained at 60% by volume.
[0111]
The extracted polymer was contact-treated with nitrogen gas containing 5% by volume of water vapor at 100 ° C. for 30 minutes, and the intrinsic viscosity [η_T ] Obtained the polypropylene composition which is 1.75 dl / g.
[0112]
The obtained polymer has a polyethylene content of 0.33% by weight in the first stage corresponding to the component (a) and a preactivation treatment in the second stage corresponding to the component (b). The polyethylene content produced by the above is 0.17% by weight, and the intrinsic viscosity of the polypropylene corresponding to component (c) [η_C ] Was 1.62 dl / g.
[0113]
0.1 parts by weight of 2,6-di-t-butyl-p-cresol and 0.1 parts by weight of calcium stearate are mixed with 100 parts by weight of the obtained polypropylene composition, and the mixture is extruded with a screw diameter of 40 mm. Granulation was performed at 230 ° C. using a granulator to obtain pellets. When various physical properties of the pellet were evaluated and measured, the MFR was 7.3 g / 10 min and the melt tension (MS) was 1.4 cN. The number of fish eyes is 12 / 500cm² Met. Detailed physical properties are summarized in the table.
[0114]
[Examples 2 to 4]
Example 1 is different from Example 1 except that the preactivation polymerization conditions with the first and second stages of ethylene are changed to change the amount of polyethylene (a) and (b) produced or the intrinsic viscosity. A polypropylene composition was produced under the same conditions, and the evaluation samples of Examples 2 to 4 were prepared.
Various conditions of the obtained polypropylene composition are shown in the table.
[0115]
[Comparative Example 1]
(1) Preparation of transition metal compound catalyst component
In a stainless steel reactor equipped with a stirrer, 0.3 l of decane, 48 g of anhydrous magnesium chloride, 170 g of orthotitanate-n-butyl and 195 g of 2-ethyl-1-hexanol were mixed and stirred at 130 ° C. for 1 hour. A heating reaction was performed to obtain a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was heated and held for 2.5 hours. The solid was separated from the solution and a solid product washed with hexane was obtained.
[0116]
The total amount of the solid product is mixed with 1.5 liters of titanium tetrachloride dissolved in 1.5 liters of 1,2-dichloroethane, and then 36 g of di-i-butyl phthalate is added and reacted at 100 ° C. with stirring for 2 hours. After removing the liquid phase part by decantation at the same temperature, 1.5 liters of 1,2-dichloroethane and 1.5 liters of titanium tetrachloride were added again, and the mixture was stirred and held at 100 ° C. for 2 hours and washed with hexane. Then, a titanium-containing supported catalyst component (transition metal compound catalyst component) containing 2.8% by weight of titanium was obtained.
[0117]
(2) Preparation of preactivated catalyst
A titanium-containing supported catalyst component prepared by replacing 2.8 liters of n-hexane, 4 millimoles of triethylaluminum (organometallic compound (AL1)) and the above-mentioned item after replacing a stainless steel reactor with inclined blades having an inner volume of 5 liters with nitrogen gas After adding 9.0 g (5.26 mmol in terms of titanium atom), 20 g of propylene was supplied, and prepolymerization was performed at −2 ° C. for 10 minutes.
[0118]
Separately, as a result of analyzing the polymer produced after the prepolymerization performed under the same conditions, 1.8 g of polypropylene (D) was produced per 1 g of the titanium-containing supported catalyst component, and 135 ° C. tetralin of this polypropylene (D) was produced. Intrinsic viscosity measured in [η_D ] Was 2.7 dl / g.
[0119]
After completion of the reaction time, unreacted propylene was discharged out of the reactor, the gas phase of the reactor was purged with nitrogen once, and then the temperature in the reactor was maintained at -1 ° C. Ethylene was continuously supplied to the reactor for 2 hours so as to maintain the pressure at 0.59 MPa, and the first stage pre-activation polymerization was performed.
[0120]
Separately, as a result of analyzing the polymer produced after the preactivation polymerization performed under the same conditions, 24.0 g of the polymer existed per 1 g of the titanium-containing supported catalyst component, and the inherent property measured in the tetralin at 135 ° C. of the polymer Viscosity [η_T1] Was 31.4 dl / g.
[0121]
From these results, the amount of polyethylene (A) produced in the first stage pre-activation polymerization with ethylene was 22.2 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η_A ] Was 33.7 dl / g.
[0122]
After completion of the reaction time, unreacted ethylene was discharged out of the reactor, and the gas phase portion of the reactor was purged with nitrogen once. Then, diisopropyldimethoxysilane (electron donor (E1)) 1.6 was introduced into the reactor. After adding the millimole, 20 g of propylene was supplied and maintained at 1 ° C. for 10 minutes to carry out the second stage pre-activation polymerization.
[0123]
Separately, as a result of analyzing the polymer produced after the second stage pre-activation polymerization performed under the same conditions, 25.9 g of polymer was present per 1 g of the titanium-containing supported catalyst component, and the polymer contained in 135 ° C. tetralin. Intrinsic viscosity measured in [η_T2] Was 29.3 dl / g, and the amount of polypropylene produced by the second-stage pre-activation polymerization calculated in the same manner as above was 1.9 g per 1 g of titanium-containing supported catalyst component, and the intrinsic viscosity [η_B ] Was 2.8 dl / g.
[0124]
After completion of the reaction time, unreacted propylene was discharged out of the reactor, and the gas phase part of the reactor was purged with nitrogen once to obtain a preactivated catalyst slurry for the present (co) polymerization.
[0125]
(3) Manufacture of polypropylene composition (book (co) polymerization of propylene)
A stainless steel polymerization vessel equipped with a stirrer with an internal volume of 500 liters was purged with nitrogen, and at 20 ° C., 240 liters of n-hexane, 780 mmol of triethylaluminum (organometallic compound (AL2)), diisopropyldimethoxysilane (electron donor (E2) )) 78 mmol and 1/2 of the preactivated catalyst slurry obtained above were charged into the polymerization reactor. Subsequently, the hydrogen concentration ratio and the ethylene concentration ratio with respect to the propylene concentration were supplied so as to be 0.02 and 0.05, and after the temperature was raised to 60 ° C., the pressure in the gas phase portion of the polymerization vessel was maintained at 0.79 MPa. While propylene, hydrogen and ethylene were continuously fed into the polymerization vessel for 2 hours, propylene / ethylene copolymerization was carried out.
[0126]
After the polymerization time has elapsed, the unreacted gas is continuously discharged, 1 liter of methanol is introduced into the polymerization vessel, a catalyst deactivation reaction is carried out at 60 ° C. for 15 minutes, solvent separation and polymer drying are performed, and the intrinsic viscosity [ η_T ] Of 4.5.6 dl / g of polymer was obtained.
[0127]
The obtained polymer had a polyethylene content of 0.22% by weight produced by preactivation in the first stage corresponding to the component (a), and an intrinsic viscosity [η of polypropylene corresponding to the component (c)_C ] Was 1.63 dl / g.
[0128]
Subsequently, granulation was performed using an extrusion granulator under the same conditions as in Example 1 to obtain polymer pellets. The results of measuring various physical properties of this pellet are shown in the table.
[0129]
[Comparative Example 2]
A polypropylene composition was obtained under the same conditions as in Example 1 except that the second stage pre-activation polymerization was omitted. The results of measuring various physical properties of this pellet are shown in the table.
[0130]
[Table 1]

[0131]
【The invention's effect】
As explained above, according to the present invention, a catalyst for pre-activation is used in which a small amount of polypropylene for main (co) polymerization and polyethylene having two or more specific intrinsic viscosities are supported on a polyolefin production catalyst. Thus, a composition obtained by subjecting propylene to main (co) polymerization can provide an olefin (co) polymer composition having a high melt tension, excellent moldability, and little fish eye generated during film formation.

Claims (16)

It is an olefin (co) polymer composition containing the following components (a) to (c), and 0.01 to 5.0 parts by weight of component (a) with respect to 100 parts by weight of component (c), (B) Olefin (co) polymer composition characterized by including 0.01-5.0 weight part of component.
( _A ) _A high molecular weight polyethylene having an intrinsic viscosity [η _A ] measured with tetralin at 135 ° C. of 15 to 100 dl / g.
(B) _A high molecular weight polyethylene having an intrinsic viscosity [η _B ] measured with tetralin at 135 ° C. in the range of 10 to 50 dl / g and smaller than the intrinsic viscosity [η _A ] of the component (a).
(C) Olefin (co) polymers other than the high molecular weight polyethylene (a) and (b). The olefin (co) polymer composition according to claim 1, wherein the olefin (co) polymer composition has an intrinsic viscosity [η _T ] measured with tetralin at 135 ° C of 0.2 to 10 dl / g. 2. The olefin (co) polymer of component (c) is at least one polymer selected from a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units. The olefin (co) polymer composition described in 1. The olefin (co) polymer composition has a melt tension (MS) at 230 ° C. and an intrinsic viscosity [η _T ] measured in tetralin at 135 ° C.
log (MS)> 4.24 × log [η _T ] − 0.75
The olefin (co) polymer composition according to claim 1, having a relationship represented by: The olefin (co) polymer composition has a melt tension (MS) at 230 ° C. and an intrinsic viscosity [η _T ] measured in tetralin at 135 ° C.
log (MS)> 4.24 × log [η _T ] − 0.72
The olefin (co) polymer composition according to claim 1, having a relationship represented by: The olefin (co) polymer composition has a melt tension (MS) at 230 ° C. and an intrinsic viscosity [η _T ] measured in tetralin at 135 ° C.
log (MS)> 4.24 × log [η _T ] − 0.70
The olefin (co) polymer composition according to claim 1, having a relationship represented by: It is a manufacturing method of the olefin (co) polymer composition including the process of following (a)-(c), Comprising: With respect to 100 weight part of olefin (co) polymer obtained at (c) process, (a) Olefins characterized by polymerizing the high molecular weight polyethylene obtained in the step in an amount of 0.01 to 5.0 parts by weight and the high molecular weight polyethylene obtained in the step (b) in a range of 0.01 to 5.0 parts by weight. Co) polymer composition production method.
( _A ) _A prepolymerization step for polymerizing a high molecular weight polyethylene having an intrinsic viscosity [η _A ] measured with tetralin at 135 ° C. in the range of 15 to 100 dl / g.
(B) Prepolymerization for polymerizing high molecular weight polyethylene having an intrinsic viscosity [η _B ] measured with tetralin at 135 ° C. in the range of 10 to 50 dl / g and smaller than the intrinsic viscosity [η _A ] of component (a). Process.
(C) This (co) polymerization step of polymerizing an olefin (co) polymer other than the high molecular weight polyethylene (a) and (b). The method for producing an olefin (co) polymer composition according to claim 7, wherein the step (b) is performed after the step (a). In any of the steps selected from the prepolymerization step (a) and the prepolymerization step (b), transition metal compound catalyst component, the transition metal atom per mol 0.01 to 1,000 mole of the periodic table (1991 version ) An organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 and an electron donor of 0 to 500 moles per mole of transition metal atom The method for producing an olefin (co) polymer composition according to claim 7 or 8, wherein the polymer is polymerized using a preactivated catalyst comprising a combination of (E1). The propylene homopolymer or propylene polymerized unit is contained in an amount of 50% by weight or more in the presence of a preactivated catalyst in which two or more kinds of polyethylene having different intrinsic viscosities are supported using the preactivated catalyst according to claim 9. The method for producing an olefin (co) polymer composition according to claim 9, wherein at least one polymer selected from propylene-olefin copolymers to be subjected to main (co) polymerization. In any step selected from the prepolymerization step (a) and the prepolymerization step (b) , the transition metal compound catalyst component, a periodic table of 0.01 to 1,000 moles per mole of transition metal atoms (1991 edition) An organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 and 0 to 500 moles of electron donor per mole of transition metal atoms ( The method for producing an olefin (co) polymer composition according to claim 7 or 8, wherein the polymer is polymerized using a pre-activated catalyst comprising a combination of E1). A propylene homopolymer or a propylene polymerized unit is contained in an amount of 50% by weight or more in the presence of a preactivated catalyst in which two or more kinds of polyethylenes having different intrinsic viscosities are supported using the preactivated catalyst according to claim 11. The method for producing an olefin (co) polymer composition according to claim 11, wherein at least one polymer selected from propylene-olefin copolymers is subjected to main (co) polymerization. An olefin (co) polymer composition comprising a pre-activated catalyst and an organic metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13 of the Periodic Table (1991 edition) The total amount of the metal compound (AL2) and the organometallic compound (AL1) contained in the preactivation catalyst is 0.05 to 5,000 mol per mol of transition metal atom, and the electron donor (E2) is preactivated In the presence of the olefin main (co) polymerization catalyst further containing 0 to 3,000 moles per mole of transition metal atoms in the preactivated catalyst in total with the electron donor (E1) contained in the catalyst. 9 or 8 obtained by subjecting at least one polymer selected from propylene homopolymers or propylene-olefin copolymers containing 50% by weight or more of propylene polymerized units to main (co) polymerization. Method for producing a mounting of the olefin (co) polymer composition. The pre-activated catalyst has an intrinsic viscosity [η _A ] of 15 to 100 dl / g and an intrinsic viscosity [η _B ] measured in tetralin at 135 ° C. per gram of transition metal compound catalyst component, and the intrinsic viscosity [η _A ]. The method for producing an olefin (co) polymer composition according to any one of claims 9 to 13, wherein each of polyethylenes in the range of 10 to 50 dl / g carries 0.01 to 5,000 g. The pre-activated catalyst was measured in 0.01 to 100 g of polypropylene having an intrinsic viscosity [η _D ] measured in 135 ° C. tetralin of less than 10 dl / g and in 135 ° C. tetralin per gram of transition metal compound catalyst component. The intrinsic viscosity [η _A ] is 15 to 100 dl / g, the intrinsic viscosity [η _B ] is smaller than the intrinsic viscosity [η _A ], and the polyethylene in the range of 10 to 50 dl / g is 0.01 to 5,000 g, respectively. The method for producing an olefin (co) polymer composition according to any one of claims 9 to 13, wherein the olefin (co) polymer composition is supported. Claims wherein the olefin (co) polymer is produced in a catalytic amount of 0.01 to 1,000 mmol in terms of transition metal atoms in the catalyst per liter of (co) polymerization volume of propylene or propylene and other olefins Item 16. A method for producing an olefin (co) polymer composition according to any one of Items 7 to 15.