JPH02300212A - Production of syndiotactic polypropylene - Google Patents
Production of syndiotactic polypropyleneInfo
- Publication number
- JPH02300212A JPH02300212A JP1118692A JP11869289A JPH02300212A JP H02300212 A JPH02300212 A JP H02300212A JP 1118692 A JP1118692 A JP 1118692A JP 11869289 A JP11869289 A JP 11869289A JP H02300212 A JPH02300212 A JP H02300212A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- transition metal
- catalyst
- aromatic hydrocarbon
- metal 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 16
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 14
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 8
- PGOXJIBERNIRFR-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PGOXJIBERNIRFR-UHFFFAOYSA-L 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 11
- 238000012662 bulk polymerization Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001440806 Tyta Species 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 150000002790 naphthalenes Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 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〕
本発明はシンジオタ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
チックなポリプロピレンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing syndiotactic polypropylene. In particular, the present invention relates to a method for producing syndiotactic polypropylene with high yield per catalyst.
（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イシテイ−が悪く、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、Ａ、ｔ！畦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ベンタフト
分率が０．８を越えるようなタフティシティ−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’ｔｙた
（Ｊ、Ａｍ、Ｃｈｅ＋ｍ、Ｓｏｃ、、１９８Ｂ、１１０
．６２５５−６２５６） 。(Prior art) The existence of syndiotactic polypropylene has been known for a long time, but the conventional low-temperature polymerization method using a catalyst consisting of a vanadium compound, ether, and organoaluminum has poor syndiotactic properties, resulting in syndiotactic polypropylene. It was difficult to say that it represented the characteristics of polypropylene.On the other hand, J, A, t! It was discovered for the first time by N. Uze et al. that polypropylene with good toughness, with a syndiotactic bent tuft fraction exceeding 0.8, could be obtained using a catalyst consisting of a transition metal catalyst with an asymmetrical ligand and aluminoxane. Sa'tyta (J, Am, Che+m, Soc, 198B, 110
．． 6255-6256).
、ヒ記Ｊ、Ａ、開ＥＮらによる方法は遷移金属当たりの
活性が良好であり、しかも得られるポリマーのタフティ
シティ−が高りイ身れた方法であるが、触媒が不安定で
あり、触媒の活性の再現性が悪いと言う問題がありＬ業
的規模で製造するには問題があった。The method by J, A, Kaien et al. has good activity per transition metal and the resulting polymer has high toughness, but the catalyst is unstable and However, there was a problem in that the reproducibility of the catalyst activity was poor, making it difficult to manufacture on a commercial scale.
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
テイシテイ−の高いボリプ１１ピ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。The present inventors have completed the present invention by intensively studying a method for solving the above-mentioned problems and producing borip-11 pyrene with high activity and high syndiotacticity.
＋ａ＋ら、本発明は非対称な配位子含有する遷移金属触
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、予め少星の芳香族炭化水素化合
物中でプロピレンの存在下に遷移金属触媒とアルミノキ
サンを接触しプロピレンを重合した後、該スラリーを用
いて液状プロピレンの存在下にプロピレンを！Ｉ合する
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
！！！遣方法である。+a+ et al., the present invention is a method for polymerizing propylene using a transition metal catalyst containing an asymmetrical ligand and a catalyst consisting of aluminoxane. After polymerizing propylene by contacting aluminoxane with aluminoxane, the slurry is used to produce propylene in the presence of liquid propylene! Of syndiotactic polypropylene, which is characterized by a combination of I! ! ! It is a method of sending.
本発明においてシンジオタクチックポリプロピレンを１
２造するに用いる触媒としては、ト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
配位子を有する遷移金属化合物とアルミノキサンを用い
る限り触媒が上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。In the present invention, syndiotactic polypropylene is
Examples of catalysts used to produce 2 are the compounds described in the above literature, but even if they have a different structure, as long as a transition metal compound and aluminoxane having an asymmetrical ligand are used, the catalyst is different from the above literature. It is also possible to utilize the method of the present invention.
非対称な配位子を存する遷移金属触媒としては上記文献
に記載されたイソプロピル（シクロペンタジェニル−１
−フルオレニル）ハフニウムジクロリド、あるいはイソ
プロピル（シクロペンタジェニル−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、（式中貸は炭素数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口が５以上好ましくは１
０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１０〜１Ｏｏｏｏｏ
ｏモル倍、通常５０〜５０００モル倍である。As a transition metal catalyst containing an asymmetric ligand, isopropyl (cyclopentadienyl-1
-fluorenyl) hafnium dichloride, or isopropyl (cyclopentagenyl-1-fluorenyl)
Zirconium dichloride is exemplified, and examples of aluminoxane include compounds represented by (where R is a hydrocarbon residue having 1 to 3 carbon atoms). In particular, methylaluminoxane in which R is a methyl group, 5 or more preferably 1
0 or more are used. The ratio of aluminoxane to the above transition metal catalyst is 10 to 1 Oooooo
o mole times, usually 50 to 5000 times.
本発明において重要なのは、液状のプロピレンの存在下
に塊状重合を行うに先立ち、芳香族炭化水素化合物中で
プロピレンの存在下に遷移金属触媒とアルミノキサン接
触しプロピレンを重合することにある。ここでアルミノ
キサンとｉ！！４％金属触媒の比は塊状重合を行う際の
条件と同じであっても良いが、その一部を用いて行って
も良い、芳香族炭化水素中での重合は、ｉ１移金金属媒
１ｇ当たり０、１ｇ以上１００００ｇ以下のプロピレン
が重合するまで行うのが好ましく、Ｏ，１ｇ以下では活
性向、Ｌの効果が小さく、１００００ｇ以上では前処理
に用いる装置が大きくなり好ましくなく、またより効果
的な訳でもない。What is important in the present invention is that prior to carrying out bulk polymerization in the presence of liquid propylene, propylene is polymerized by contacting a transition metal catalyst with aluminoxane in the presence of propylene in an aromatic hydrocarbon compound. Here, aluminoxane and i! ! The ratio of 4% metal catalyst may be the same as the conditions for carrying out bulk polymerization, but it may also be carried out using a part of it. It is preferable to carry out polymerization until at least 0.1 g and up to 10,000 g of propylene is polymerized. If it is less than 1 g, the effect of activity and L will be small, and if it is more than 10,000 g, the equipment used for pretreatment will be large, which is not preferable, and it will not be more effective. There's no reason.
芳香族炭化水素化合物は遷移金属触媒１ｇ当たりｔｏ
〜１ｏｏｏｏｏｏ ｄ用いるのが好ましく、ｌＯｄ以下
では活性向上の効果が小さく、１００００００ ｔｒｉ
以りでは塊状重合での活性が充分ではない、より好まし
くは１０００〜ＪＯＯＯＯＯＪｄである。また芳香族炭
化水素化合物１Ｉ１１当たりｌ〇−以上の液状プロピレ
ンを用いるのが塊状重合での活性の点で好ましい。The aromatic hydrocarbon compound is to
It is preferable to use ~1ooooood; below 10d, the effect of improving activity is small;
If it is more than that, the activity in bulk polymerization is not sufficient, and more preferably it is from 1000 to JOOOOOOJd. In addition, it is preferable to use liquid propylene in an amount of 10 - or more per 111 of the aromatic hydrocarbon compound from the viewpoint of activity in bulk polymerization.
重合温度としては芳香族炭化水素溶媒中での重合、ある
いは塊状重合においても−１００〜２００ ’Ｃで行う
のが一般的であり、通常芳香族炭化水素溶媒中での重合
は塊状重合の際より低温でｉテうのが一般的である０重
合圧力としては、芳香族炭化水素溶媒中での重合は常圧
〜ｌｏｋｇ／ｃｄ程度で行うのが−Ｃ的であり、塊状重
合はプロピレンが？＆壮となる圧力条件下に行われる。The polymerization temperature is generally -100 to 200'C even in aromatic hydrocarbon solvents or bulk polymerization. As for the polymerization pressure, which is generally carried out at low temperature, polymerization in an aromatic hydrocarbon solvent is carried out at normal pressure to about 1000 kg/cd, and bulk polymerization is carried out with propylene. & is carried out under intense pressure conditions.
。
本発明においてプロピレンの重合とはプロピレン１１′
Ｎ独川合のみならず２０ｗＬχ程度までのエチレン、ブ
テン−ＪＸどの油のα−オレフィンとの共重合体を！！
！造することをも含有する。. In the present invention, propylene polymerization means propylene 11'
Copolymers with α-olefins such as ethylene, butene-JX and other oils up to about 20wLχ as well as N-Kawaai! !
! It also includes creating.
芳香族炭化水素溶剤中での重合から塊状重合への移行の
方法については特に制限はないが、通常芳香機炭化水素
溶剤スラリーを液状のプロピレンに導入するか、あ′る
いは芳香族炭化水素溶剤スラリーに液状のプロピレンを
追加することで行われる。There are no particular restrictions on the method of transition from polymerization in an aromatic hydrocarbon solvent to bulk polymerization, but usually an aromatic hydrocarbon solvent slurry is introduced into liquid propylene, or an aromatic hydrocarbon solvent is introduced into the liquid propylene. This is done by adding liquid propylene to the slurry.
本発明において芳香族炭化水素溶剤としては、反応条件
下に液状の炭素数６〜２０の芳香族炭化水素化合物が利
用され、具体的にはベンゼン、トルエン、キシレン、エ
チルベンゼン、テトラリンなどヘンビンの水素の一部ま
たは全部が炭素数１〜１２のアルキル残基で１１０した
ものか、あるいは反応アルキル置換ナフタレンなどが例
示される。In the present invention, as the aromatic hydrocarbon solvent, an aromatic hydrocarbon compound having 6 to 20 carbon atoms which is liquid under the reaction conditions is used. Examples include naphthalene partially or entirely substituted with an alkyl residue having 1 to 12 carbon atoms, or naphthalene substituted with a reactive alkyl.
以下に実施例を示しさらに本発明を説明する。 The present invention will be further explained with reference to Examples below.
実ｈｉ例１
内容４Ｎ ２００ｄのオートクレーブにトルエン＋００
−装入し、常法に従って合成したイソゾロビルシクロペ
ンタジェニル−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ブ１コビル（シ
クロペンタジェニル、ｌ−フルオレニル）ジルコニウム
ジクロリド５鵬ｇを入れ、プロピレンを装入して２ ｋ
ｇ／ｃｊ−Ｇとした、次いで東洋アクゾ社製の重合度約
１５のメチルアルミノキサン０．６７ｇをトルエンｌＯ
ｄに溶解したものを加え１０分間重合した。一部を採取
し分析したところ・イソプロピル（シクロペンタジェニ
ル−１−フルオレニル）ジルコニウムジクロリド１ｇあ
たり６００ｇのプロピレンが重合していた０次いで未反
応のブＥｌピレンを除去しスラリーを５１のオートクレ
ーブに移液し、ついでプロピレン１．５ｋｇを挿入して
２５°Ｃで２時間重合した。ｉｒ［今後未反応のプロピ
レンを除去しで取りだしたパウダーを２１／回のヘキサ
ンで３回洗浄してヘキサンに不溶な部分としてシンジオ
タクチックポリプロピレンを２３０ｇ得た。得られたパ
ウダーの１３５°（：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ｌ、４８、シンジオタク
チックベンタフト分率は０．９１８であった。Practical example 1 Contents 4N 200d autoclave with toluene +00
- isobutylcobyl(cyclopentadienyl, l-fluorenyl)zirconium dichloride obtained by lithiation of isozolobylcyclopentagenyl-1-fluorene synthesized according to a conventional method and reacting with zirconium tetrachloride. Put 5g, charge propylene and make 2k.
g/cj-G, then 0.67 g of methylaluminoxane manufactured by Toyo Akzo Co., Ltd. with a degree of polymerization of about 15 was added to toluene lO
The solution dissolved in d was added and polymerized for 10 minutes. When a portion was collected and analyzed, 600 g of propylene was polymerized per 1 g of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride.Next, unreacted butelpyrene was removed and the slurry was transferred to an autoclave of 51. Then, 1.5 kg of propylene was added and polymerized at 25°C for 2 hours. After removing unreacted propylene, the powder was washed three times with 21/time hexane to obtain 230 g of syndiotactic polypropylene as the hexane-insoluble portion. The intrinsic viscosity (hereinafter abbreviated as η) of the obtained powder measured with a tetralin solution at 135° (:) was 1,48, and the syndiotactic bentuft fraction was 0.918.
比較例１
予め、トルエン中で重合することなく５１のオートクレ
ーブにメチルアルミノキサンを０．６７ｇ入れ、プロピ
レン１．５ｋｇ装入したのち、攪拌下にイソプし１ピル
（シクロペンタジェニル−１−フルオレニル）ジルコニ
ウムジク【１リド５−ｇをトルエンｌＯｄに溶解したも
のを同様に４回で分割導入した（イ」！シ圧入は窒素の
圧力で１ｒつだ、）他は実施例１と同様にした。ヘキサ
ンに不溶なパウダーを６３ｇ得た。得られたパウダーの
ηは１．４１、シンジオタクチックベンタフト分率は０
．９０８であった。Comparative Example 1 In advance, 0.67 g of methylaluminoxane was placed in a No. 51 autoclave without polymerization in toluene, and 1.5 kg of propylene was charged therein, and then 1 pyru (cyclopentadienyl-1-fluorenyl) was prepared by isopropylene while stirring. The same procedure as in Example 1 was carried out except that 5 g of zirconium dichloride dissolved in lOd of toluene was introduced in 4 portions in the same manner. 63g of powder insoluble in hexane was obtained. The obtained powder has a η of 1.41 and a syndiotactic bentufut fraction of 0.
．． It was 908.
比較例２
始めのプロピレンの重合での溶剤を、トルエンにかえヘ
キサンを用いて行った他は実施例１と同様にしたところ
ヘキサンに不溶なパウダーを１４２ｇ得た。得られたパ
ウダーのηは１．４６、シンジオタクチックベンタフト
分率は０．９１８であった。なお、ヘキサン中での重合
の際イソプロピル（シクロペンタジェニル−１−フルオ
レニル）ジルコニウムジクロリドＩｇあたり２８０ｇの
プロピレンが重合していた。Comparative Example 2 The same procedure as in Example 1 was conducted except that the solvent used in the initial polymerization of propylene was changed to toluene and hexane was used. 142 g of a powder insoluble in hexane was obtained. The obtained powder had an η of 1.46 and a syndiotactic bentuft fraction of 0.918. During the polymerization in hexane, 280 g of propylene was polymerized per Ig of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride.
実施例２
トルエンにかえエチルベンゼンを用い、メチルアルミノ
キサンを０．２ｇ用いて予め虫合し、さらに塊状重合の
際に、上記スラリー、プロピ【エンを装入した後、０．
４３ｇのメチルアルミノキサンを圧入して重合を行った
。ヘキサンに不溶なパウダーを２０１１ｇ！！）た、得
られたパウダーのηは１．３８、シンジオタクチックベ
ンタフト分率は０．９２０であった。Example 2 Ethylbenzene was used instead of toluene, and 0.2 g of methylaluminoxane was used for incubation. Further, during bulk polymerization, the above slurry and propylene were charged, and then 0.2 g of methylaluminoxane was used.
Polymerization was carried out by pressurizing 43 g of methylaluminoxane. 2011g of powder insoluble in hexane! ! ), the obtained powder had an η of 1.38 and a syndiotactic bentuft fraction of 0.920.
なお、エチルベンゼン中での重合の際イソプロピル（シ
クロペンタジェニル−１−フルオレニル）ジルコニウム
ジクロリドＩｇあたり３１０ｇのプロピレンが重合して
いた。During the polymerization in ethylbenzene, 310 g of propylene was polymerized per Ig of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride.
〔発明の効果］
本発明の方法をｙｌ施するこき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ｊするごとがで
き工業的に掻めて価埴がある。[Effects of the Invention] By applying the method of the present invention, it is possible to produce syndiotactic polypropylene with high activity per catalyst, which is of great value industrially.
第１図は本発明の方法を理解するのを助ける為のフロー
図である。FIG. 1 is a flow diagram to aid in understanding the method of the present invention.
Claims (1)
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、予め少量の芳香族炭化水素化合物中でプロピレ
ンの存在下に遷移金属触媒とアルミノキサンを接触しプ
ロピレンを重合した後、該スラリーを用いて液状プロピ
レンの存在下にプロピレンを重合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。 ２、芳香族炭化水素中での重合を遷移金属触媒１ｇ当た
り０．１ｇ以上１００００ｇ以下のプロピレンが重合す
るまで行う請求項１記載の方法。 ３、芳香族炭化水素化合物を遷移金属触媒１ｇ当たり１
０〜１００００００ｍｌ用い、且つ芳香族炭化水素化合
物１ｍｌ当たり１０ｍｌ以上の液状プロピレンを用いる
請求項１記載の方法。[Claims] 1. In a method of polymerizing propylene using a transition metal catalyst having an asymmetric ligand and a catalyst consisting of aluminoxane, a transition metal is preliminarily prepared in the presence of propylene in a small amount of an aromatic hydrocarbon compound. A method for producing syndiotactic polypropylene, which comprises polymerizing propylene by contacting a catalyst and aluminoxane, and then polymerizing propylene using the slurry in the presence of liquid propylene. 2. The method according to claim 1, wherein the polymerization in the aromatic hydrocarbon is carried out until 0.1 g or more and 10,000 g or less of propylene is polymerized per 1 g of the transition metal catalyst. 3. Add aromatic hydrocarbon compound to 1 g per 1 g of transition metal catalyst.
2. The method according to claim 1, wherein 0 to 1,000,000 ml of liquid propylene is used, and 10 ml or more of liquid propylene is used per 1 ml of aromatic hydrocarbon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118692A JP2764074B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing syndiotactic polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118692A JP2764074B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing syndiotactic polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02300212A true JPH02300212A (en) | 1990-12-12 |
| JP2764074B2 JP2764074B2 (en) | 1998-06-11 |
Family
ID=14742808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1118692A Expired - Fee Related JP2764074B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing syndiotactic polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764074B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009027447A1 (en) | 2009-07-03 | 2011-01-05 | Evonik Degussa Gmbh | Modified polyolefins with a particular property profile, process for their preparation and their use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01152449A (en) * | 1987-12-09 | 1989-06-14 | Matsushita Electric Ind Co Ltd | Color filter |
-
1989
- 1989-05-15 JP JP1118692A patent/JP2764074B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01152449A (en) * | 1987-12-09 | 1989-06-14 | Matsushita Electric Ind Co Ltd | Color filter |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009027447A1 (en) | 2009-07-03 | 2011-01-05 | Evonik Degussa Gmbh | Modified polyolefins with a particular property profile, process for their preparation and their use |
| EP2272933A2 (en) | 2009-07-03 | 2011-01-12 | Evonik Degussa GmbH | Modified polyolefins with particular characteristic profile, method for producing same and use of same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2764074B2 (en) | 1998-06-11 |
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