JPH02292311A - Production of syndiotactic polypropylene - Google Patents
Production of syndiotactic polypropyleneInfo
- Publication number
- JPH02292311A JPH02292311A JP1111987A JP11198789A JPH02292311A JP H02292311 A JPH02292311 A JP H02292311A JP 1111987 A JP1111987 A JP 1111987A JP 11198789 A JP11198789 A JP 11198789A JP H02292311 A JPH02292311 A JP H02292311A
- Authority
- JP
- Japan
- Prior art keywords
- aluminoxane
- transition metal
- metal catalyst
- propylene
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 2
- PDBMBIIQRMIHJS-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PDBMBIIQRMIHJS-UHFFFAOYSA-L 0.000 abstract 1
- 229910052735 hafnium Inorganic materials 0.000 abstract 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- LSRGDVARLLIAFM-UHFFFAOYSA-N sulfuric acid;hexahydrate Chemical compound O.O.O.O.O.O.OS(O)(=O)=O LSRGDVARLLIAFM-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FNBLFENJPIGHHL-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=2CC3=CC=CC=C3C=2C=C1)[Zr+2] Chemical compound [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=2CC3=CC=CC=C3C=2C=C1)[Zr+2] FNBLFENJPIGHHL-UHFFFAOYSA-L 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical class C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical class CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical class C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Chemical class C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はシンジオククチックポリプロピレンの製造方法
に関する．詳しくは、触媒当たり高収率でシンジオタク
チシクなポリプロピレンを製造する方法に関する．
〔従来技術〕
シンジオタクチックポリプロピレンについては古くより
その存在は知られていたが、従来のバナジウム化合物と
エーテルおよび有機アルミニウムからなる触媒で低温重
合する方法はシンジオタクティシティーが悪《、シンジ
オタクチックなポリプロピレンの特徴を表しているとは
言い難かった．これに対して、Ｊ．＾．［ＷＩ！Ｎらに
より非対称な配位子を有する遷移金属触媒とアルミノキ
サンからなる触媒によってシンジオタクチックペンタッ
ド分率が０．８を越えるようなタクティシティーの良好
なポリプロピレンを得られることが初めて発見された（
Ｊ．＾一．Ｃｈｅ＋＊．Ｓｏｃ．．１９Ｂ８，１１０．
６２５５−６２５６） ．〔発明が解決しようとする課
題〕
上記Ｊ．Ａ．ＥＷＥＮらによる方法は遷移金属当たりの
活性が良好であり、しかも得られるボリマーのタクティ
シティーが高く優れた方法であるが、触媒が不安定であ
り触媒の活性が再現性が悪いと言う問題があり工業的規
模で製造するには問題があった．
〔課題を解決するための手段〕
本発明者らは上記問題を解決して高活性にシンジオタク
ティシティーの高いボリプロビレンを製造する方法につ
いて鋭意検討し本発明を完成した．即ち、本発明は非対
称な配位子を有する遷移金属触媒とアルミノキサンから
なる触媒を用いてプロピレンを重合する方法において、
非対称な配位子を有する遷移金属触媒を予めプロピレン
で処理した後、重合条件下でアルミノキサンと接触する
ことを特徴とするシンジオククチックポリプロピレンの
製造方法である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing syndiocctic polypropylene. More specifically, it relates to a method for producing syndiotactic polypropylene with high yield per catalyst. [Prior Art] The existence of syndiotactic polypropylene has been known for a long time, but the conventional low-temperature polymerization method using a vanadium compound, an ether, and an organic aluminum catalyst has poor syndiotacticity. It was difficult to say that it represented the characteristics of polypropylene. On the other hand, J. ^． [WI! It was discovered for the first time by N et al. that polypropylene with good tacticity, with a syndiotactic pentad fraction exceeding 0.8, could be obtained using a catalyst consisting of a transition metal catalyst with an asymmetrical ligand and aluminoxane (
J. ^1. Che+*. Soc. ．． 19B8,110.
6255-6256). [Problem to be solved by the invention] J. above. A. The method by EWEN et al. is an excellent method with good activity per transition metal and high tacticity of the polymer obtained, but there are problems in that the catalyst is unstable and the reproducibility of the catalyst activity is poor. There were problems with manufacturing it on an industrial scale. [Means for Solving the Problems] The present inventors have completed the present invention by intensively studying a method for producing polypropylene with high activity and high syndiotacticity by solving the above problems. That is, the present invention provides a method for polymerizing propylene using a transition metal catalyst having an asymmetrical ligand and a catalyst comprising aluminoxane.
This is a method for producing syndiocctic polypropylene, which is characterized in that a transition metal catalyst having an asymmetrical ligand is previously treated with propylene and then brought into contact with aluminoxane under polymerization conditions.
本発明においてシンジオタクチ・ンクポリプロピレンを
製造するに用いる触媒としては、上記文献に記載された
化合物が例示できるが、異なる構造であっても非対称な
配位子を有ずる遷移金属化合物とアルミノキサンを用い
る限り触媒が−ヒ記文献と異なっても本発明の方法を利
用することが可能である．
非対称な配位子を有する遷移金属触媒としては上記文献
に記載されたイソブロビル（シク［Ｉペンタジエニル−
１−フルオレニル）ハフニウムジクロリド、あるいはイ
ソプロビル（シクロペンタジエニル−１−フルオレニル
）ジルコニウムジクロリドなどが例示され、またアルミ
ノキサンとしては、一般式、Ｒ− （Ａ ｆｆ Ｏ）．
＾ｆ−Ｒ．あるいは一石冒只Ｒ
Ｒ（式中Ｒは炭素数１〜３の炭
化水素残基。）で表される化合物が例示でき特にＲがメ
チル基であるメチルアルミノキサンでｎが５以上好まし
くは１０以上のものが利用される。上記遷移金属触媒に
対するアルミノキサンの使用割合としては１０−１００
００００モル倍、通常５０〜５０００モル倍である．ま
た重合条件については特に制限はなく不活性媒体を用い
る溶媒重合法、或いは実質的に不活性媒体の存在しない
塊状重合法、気相重合法も利用できる．重合温度として
は−１００〜２００℃、重合圧力としては常圧〜１００
ｋｇ／ｃ＋ａ−Ｇで行うのが一般的Ｃある．好ましく
は−１００ 〜１００ ’Ｃ、常圧〜５ ０ ｋｇ ／
ｔｅａである．
本発明において、重要なのは遷移金属触媒の重合系への
導入の方法であり、アルミノキサンと接触する前にブロ
ビレンと予め接触しておくこと、さらにはアルミノキサ
ンと重合条件下に接触することにある．
回分的に重合する際には、プロピレン雰囲気下にｉ！！
移金属触媒を重合反応槽に導入し、攬１＋−シながらア
ルミノキサンを連続的、あるいは断続的に添加すること
で上記条件は達成される．またプロピレン雰囲気下にア
ルミノキサンを重合反応槽に導入し、撹拌しながらブロ
ビレン雰囲気に保たれた遷移金屈触媒溶液を連続的、あ
るいは断続的に添加することでも上記条件は達成される
．連続的に重合するには、重合反応槽にアルミノキサン
及びプロピレン雰囲気に保たれた遷移金属触媒溶液を連
続的に導入し、重合したスラリーを連続的あるいは断続
的に重合反応槽から抜き出すことで達成できる．
遷移金属触媒を溶解するに用いる溶剤としては、重合に
際して用いる不活性溶剤を用いることができ、プロパン
、ペンタン、ヘキサン、ヘブクン、オクタン、ノナン、
デカン、シクロペンタン、シクロヘキサンなどの飽和炭
化水素化合物の他にベンゼン、トルエン、キシレンなど
の芳香族炭化水素化合物も利用できる．またプロピレン
自身を溶剤として用いることでプロピレン雰囲気とする
ことも可能である．プロピレン雰囲気における遷移金属
触媒に対するプロピレンの足比としてはｊ２移金属触媒
１モルに対し１モル以上とするのが好ましい．
〔実施例〕
以下に実施例を示しさらに本発明を説明する。Examples of the catalyst used in the production of syndiotactic polypropylene in the present invention include the compounds described in the above-mentioned documents, but as long as a transition metal compound and aluminoxane having an asymmetrical ligand are used even if they have different structures. It is possible to use the method of the present invention even if the catalyst is different from that in the literature. As a transition metal catalyst having an asymmetrical ligand, isobrovir (cyc[I pentadienyl-
Examples include 1-fluorenyl) hafnium dichloride and isoprobyl(cyclopentadienyl-1-fluorenyl) zirconium dichloride. Examples of the aluminoxane include the general formula R-(A ff O).
^f-R. Or one stone adventure R
Examples include compounds represented by R (in the formula, R is a hydrocarbon residue having 1 to 3 carbon atoms), and in particular, methylaluminoxane in which R is a methyl group and n is 5 or more, preferably 10 or more is used. . The ratio of aluminoxane to the above transition metal catalyst is 10-100.
0,000 mol times, usually 50 to 5,000 mol times. Furthermore, there are no particular restrictions on the polymerization conditions, and solvent polymerization methods using an inert medium, bulk polymerization methods and gas phase polymerization methods in which substantially no inert medium is present can also be used. The polymerization temperature is -100 to 200℃, and the polymerization pressure is normal pressure to 100℃.
C is generally done using kg/c+a-G. Preferably -100 to 100'C, normal pressure to 50 kg/
It is tea. In the present invention, what is important is the method of introducing the transition metal catalyst into the polymerization system, including contacting it with brobylene in advance before contacting it with aluminoxane, and furthermore, contacting it with aluminoxane under polymerization conditions. When polymerizing batchwise, use i! in a propylene atmosphere. !
The above conditions can be achieved by introducing a transfer metal catalyst into a polymerization reaction tank and adding aluminoxane continuously or intermittently while pumping. The above conditions can also be achieved by introducing aluminoxane into a polymerization reaction tank under a propylene atmosphere and continuously or intermittently adding a transition metal catalyst solution maintained in a brobylene atmosphere while stirring. Continuous polymerization can be achieved by continuously introducing aluminoxane and a transition metal catalyst solution maintained in a propylene atmosphere into a polymerization reactor, and then extracting the polymerized slurry from the polymerization reactor continuously or intermittently. ．． As the solvent used to dissolve the transition metal catalyst, inert solvents used during polymerization can be used, such as propane, pentane, hexane, hebukun, octane, nonane,
In addition to saturated hydrocarbon compounds such as decane, cyclopentane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, and xylene can also be used. It is also possible to create a propylene atmosphere by using propylene itself as a solvent. The ratio of propylene to transition metal catalyst in a propylene atmosphere is preferably 1 mole or more per mole of j2 transition metal catalyst. [Example] The present invention will be further explained by showing examples below.
実施例１
内容積２Ｉ！のオ一トクレープにトルエンｌｌ．装入し
、常法に従って合成したイソプロビルシク１′】ペンタ
ジエニル−１−フルオレンをリチウム化し、四塩化ジル
コニウムと反応することで得たイソプロビル（シクロペ
ンタジエニル−１−フルオレニル）ジルコニウムジクロ
リド５ｍｇを入れ、プロピレンを装入して６ｋｇ／ｃｄ
−Ｇとした、次いで六水和硫酸銅とトリメチルアルミニ
ウムをトルエン中で反応することで得られた重合度約１
５のメチルアルミノキサン０．６７ｇをトルエン１０ｆ
ｆｌ２に溶解したものを始めに４威圧人して重舎を開始
し、２５゜Ｃで２ｋｇ／ｄ−Ｇに保ちながら１０分後に
２ｉｄ，３０分後に２ｄ５０分後に２ ｍｌ加えさらに
１時間ｌＯ分重合した．重合反応後スラリーをメタノー
ルで処理しさらに酸性の水で洗浄した後濾過し、パウダ
ーは２ｆｆｉ／回のトルエンで３回洗浄してシンジオタ
クチックポリプロピレンを１０５ｇ得た．得られたパウ
ダーのｌ３５゜Ｃのテトラリン溶液で測定した極限粘度
（以下、ηと略記する）は１．２８、シンジオタクチッ
クペンタッド分率は０．９３４であった．
比較例１
オートクレープにメチルアルミノキサンを０．６７ｇ入
れ、撹拌下にイソプロビル（シクロペンタジエニル−ｌ
−フルオレニル）ジルコニウムジクロリド５鵬ｇをトル
エンｌＯＩＩ１に溶解したものを同様に４回で分割導入
した（但し圧入は窒素の圧力で行った．）他は実施例ｌ
と同様にした．パウダーを６１ｇ得た．得られたパウダ
ーのηはｌ．２１、シンジオタクチックペンタッド分率
は０．９１８であった．実施例２
イソプロビル（シクロペンタジエニル−１−フルオレニ
ル）ジルコニウムジクロリドヲ２ｌＩ８用い、メチルア
ルミノキサン０．３４ｇをトルエン５ ｍｌに溶解した
ものを一度に圧人し重合を１時間行った他は実施例ｌと
同様にした．シンジオタクチックポリプロピレンを４９
ｇ得た．得られたパウダーのηは１．３１、シンジオタ
クチンクペンタッド分率は０．９２８であった．
比較例２
オートクレープにメチルアルミノキサンを入れ、イソプ
ロビル（シクロペンタジエニル−１−フルオレニル）ジ
ルコニウムジクロリドを窒素で圧入した他は実施例２と
同様にした．シンジオタクチンクポリプロピレンを３２
ｇ得た．得られたパウダーのηは１．３０、シンジオタ
クチックペンタツド分率は０．９０５であった．
〔発明の効果〕
本発明の方法を実施することにより触媒当たり高活性で
シンジオタクチックポリプロピレンを得ることができ工
業的に極めて価値がある．特許出願人 三井東圧化学株
式会社Example 1 Internal volume 2I! of toluene to the oat crepe. 5 mg of isoprobyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained by lithiation of isoprobyl cyclopentadienyl-1-fluorene synthesized according to a conventional method and reacting with zirconium tetrachloride. 6kg/cd by charging propylene.
-G, and then the degree of polymerization was about 1 obtained by reacting hexahydrated copper sulfate and trimethylaluminum in toluene.
Add 0.67 g of methylaluminoxane from Step 5 to 10 f of toluene.
First, add 4 ml of the solution dissolved in fl2, then start the overgrowth, maintain it at 25°C and 2 kg/d-G, add 2 ml after 10 minutes, 2 ml after 30 minutes, 2 ml after 50 minutes, and add 1 ml for another 1 hour. Polymerized. After the polymerization reaction, the slurry was treated with methanol, further washed with acidic water, and then filtered, and the powder was washed three times with toluene at 2ffi/time to obtain 105 g of syndiotactic polypropylene. The intrinsic viscosity (hereinafter abbreviated as η) of the resulting powder measured in a tetralin solution at 135°C was 1.28, and the syndiotactic pentad fraction was 0.934. Comparative Example 1 0.67 g of methylaluminoxane was placed in an autoclave, and while stirring, isoprovil (cyclopentadienyl-l)
-Fluorenyl) zirconium dichloride (5g) dissolved in 1OII of toluene was introduced in 4 portions in the same manner (however, the injection was carried out under nitrogen pressure).The rest were Example 1.
I did the same thing. 61g of powder was obtained. η of the obtained powder is l. 21, the syndiotactic pentad fraction was 0.918. Example 2 Same as Example except that isoprobyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride was used and 0.34 g of methylaluminoxane dissolved in 5 ml of toluene was pressed at once and polymerization was carried out for 1 hour. I did the same as l. Syndiotactic polypropylene 49
I got g. The obtained powder had an η of 1.31 and a syndiotactic pentad fraction of 0.928. Comparative Example 2 The same procedure as Example 2 was carried out except that methylaluminoxane was placed in an autoclave and isoprobyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride was pressurized with nitrogen. 32 syndiotactic polypropylene
I got g. The obtained powder had an η of 1.30 and a syndiotactic pentad fraction of 0.905. [Effects of the Invention] By carrying out the method of the present invention, syndiotactic polypropylene can be obtained with high activity per catalyst, which is extremely valuable industrially. Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
からなる触媒を用いてプロピレンを重合する方法におい
て、非対称な配位子を有する遷移金属触媒を予めプロピ
レンで処理した後、重合条件下でアルミノキサンと接触
することを特徴とするシンジオタクチックポリプロピレ
ンの製造方法。In a method of polymerizing propylene using a catalyst consisting of a transition metal catalyst having an asymmetrical ligand and aluminoxane, the transition metal catalyst having an asymmetrical ligand is previously treated with propylene and then brought into contact with aluminoxane under polymerization conditions. A method for producing syndiotactic polypropylene, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1111987A JP2764052B2 (en) | 1989-05-02 | 1989-05-02 | Method for producing syndiotactic polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1111987A JP2764052B2 (en) | 1989-05-02 | 1989-05-02 | Method for producing syndiotactic polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02292311A true JPH02292311A (en) | 1990-12-03 |
| JP2764052B2 JP2764052B2 (en) | 1998-06-11 |
Family
ID=14575107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1111987A Expired - Fee Related JP2764052B2 (en) | 1989-05-02 | 1989-05-02 | Method for producing syndiotactic polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764052B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200439A (en) * | 1990-04-13 | 1993-04-06 | Mitsui Toatsu Chemicals, Inc. | Method for increasing intrinsic viscosity of syndiotactic polypropylene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
-
1989
- 1989-05-02 JP JP1111987A patent/JP2764052B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200439A (en) * | 1990-04-13 | 1993-04-06 | Mitsui Toatsu Chemicals, Inc. | Method for increasing intrinsic viscosity of syndiotactic polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2764052B2 (en) | 1998-06-11 |
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