JPS6259608A - Copolymerization of ethylene with alpha-olefin - Google Patents
Copolymerization of ethylene with alpha-olefinInfo
- Publication number
- JPS6259608A JPS6259608A JP19778685A JP19778685A JPS6259608A JP S6259608 A JPS6259608 A JP S6259608A JP 19778685 A JP19778685 A JP 19778685A JP 19778685 A JP19778685 A JP 19778685A JP S6259608 A JPS6259608 A JP S6259608A
- Authority
- JP
- Japan
- Prior art keywords
- component
- olefin
- catalyst
- compound
- ethylene
- 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.)
- Pending
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000005977 Ethylene Substances 0.000 title claims abstract description 16
- 239000004711 α-olefin Substances 0.000 title claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- -1 etc. Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 150000003682 vanadium compounds Chemical class 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はエチレンとα−オレフィンの共重合に関し、さ
らに詳細には特定の高活性触媒を用いてゴム状のエチレ
ンとα−オレフィンを重合する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the copolymerization of ethylene and alpha-olefins, and more particularly to a method for polymerizing rubbery ethylene and alpha-olefins using specific highly active catalysts.
エチレンとα−オレフィンを共重合してゴム状ポリマー
を重合する方法としてはバナジウム化合物と有機アルミ
ニウム化合物を触媒として用いる方法が一般的であるが
活性が低（、生産性が悪いため生成ポリマーから触媒残
査を除去する必要があり、そのための設備が必要となり
、また多くのエネルギーを必要とするので製品は高価に
なりそのコストダウンのため高活性触媒の開発が望まれ
ている。A common method for copolymerizing ethylene and α-olefin to produce a rubbery polymer is to use a vanadium compound and an organoaluminum compound as a catalyst, but the activity is low (and the productivity is low, so it is difficult to remove the catalyst from the resulting polymer). It is necessary to remove the residue, which requires equipment and a lot of energy, making the product expensive, and the development of highly active catalysts is desired to reduce costs.
最近、高活性の担体型チタン成分と有機アルミニウム化
合物を触媒とする多数の特許が出願されている。Recently, a large number of patents have been filed using highly active carrier-type titanium components and organoaluminum compounds as catalysts.
エチレンとα−オレフィンの共重合に関しても特開昭５
４−１４８０９３号公報などで出願されているがゴム状
のエチレンとα−オレフィン共重合体を目的としたもの
ではない。Regarding copolymerization of ethylene and α-olefin, JP-A No. 5
No. 4-148093, etc., but it is not intended for rubber-like ethylene and α-olefin copolymers.
特開昭５８−２１０９１２号公報ではゴム状のエチレン
とα−オレフィン共重合体を製造する方法が開示されて
いるが触媒の製造工程が複雑でとくに非常に大量のリン
化合物を使用するのでリン化合物の回収などに多くの費
用を要する。JP-A No. 58-210912 discloses a method for producing a rubber-like ethylene and α-olefin copolymer, but the catalyst production process is complicated and requires a particularly large amount of phosphorus compound. It costs a lot of money to recover the waste.
本発明者らは高活性な触媒を用いてエチレンとα−オレ
フィンを共重合してゴム状の共重合体を製造する方法に
ついて研究した結果
（イ）
（Ａ）マグネシウムハライドと。The present inventors conducted research on a method for producing a rubber-like copolymer by copolymerizing ethylene and α-olefin using a highly active catalyst. (a) (A) Magnesium halide.
（Ｂ）電子供与性基を持たない液状有機化合物を共粉砕
したのち。(B) After co-pulverizing a liquid organic compound that does not have an electron-donating group.
（Ｃ）チタンまたはバナジウム化合物と接触して得られ
た組成物、及び
（ロ）
有機金属化合物
より成る触媒が高活性であり、しかもランダム共重合性
の良好なエチレンとα−オレフィン共重合用としてきわ
めて有効であることを見出し１本発明に到達した。(C) A composition obtained by contacting with a titanium or vanadium compound, and (B) A catalyst made of an organometallic compound is highly active and has good random copolymerizability, and is used for copolymerization of ethylene and α-olefin. We have found that this is extremely effective and have arrived at the present invention.
本発明の方法で（Ａ）成分として用いるマグネシウムハ
ライドとしては塩化マグネシウムが好ましくゝ。The magnesium halide used as component (A) in the method of the present invention is preferably magnesium chloride.
（Ｂ）成分である電子供与性基を持たない液状有機化合
物とは、飽和又は不飽和の炭化水素、ノ・ロゲン化炭化
水素１例えばｎ−ヘキサン、ｎ−ヘプ４タン、ヘキセン
−１，ベンゼン、トルエン、スチレソ、α−メチルスチ
レン、エチレンジクロライド、四塩化炭素、クロルベン
ゼン、ノクロヘキセン、シンクロペンタジェンなどがあ
げられとくにスチレン、α−メチルスチレンなどが好ま
しい。The liquid organic compound having no electron-donating group, which is component (B), refers to saturated or unsaturated hydrocarbons, non-rogenated hydrocarbons, such as n-hexane, n-heptane, hexene-1, benzene. , toluene, styrene, α-methylstyrene, ethylene dichloride, carbon tetrachloride, chlorobenzene, noclohexene, synclopentadiene, etc., and styrene, α-methylstyrene, etc. are particularly preferred.
（Ａ）成分及び（Ｂ）−成分の共粉砕についてはとくに
限定はなく１通常オレフィン重合触媒製造に用いられて
いる公知の方法でよい。その際の粉砕温度は好ましくは
Ｏ０Ｃ〜１００’Ｃ，粉砕時間は１〜１００時間である
。There are no particular limitations on the co-pulverization of component (A) and component (B), and any known method commonly used in the production of olefin polymerization catalysts may be used. The grinding temperature at that time is preferably O0C to 100'C, and the grinding time is preferably 1 to 100 hours.
（Ａ）成分に対して用いる（Ｂ）成分の割合は（Ａ）成
分ｉｏｏ重量部に対して０．１〜７０部、好ましくは１
〜５０部である。The ratio of component (B) to component (A) is 0.1 to 70 parts, preferably 1 to 10 parts by weight of component (A).
~50 copies.
（Ａ）成分と（Ｂ）成分との共粉砕物と接触させる（Ｃ
）成分としてはチタン及び／又はバナジウム化合物が用
いられ、好ましくは四塩化チタン、四塩化バナジウム、
三塩化バナジル、モノ−ｎ−ブトキシチタニウムテトラ
クロライドなどが例示される。この際の接触方法として
は（Ａ）、（Ｂ）の共粉砕物を液状の（Ｃ）成分または
（Ｃ）成分の溶液と接触させれば良く、その際の温度は
室温〜２００℃、好ましくは５０’Ｃ〜１５０℃で行な
う。Contact with co-pulverized product of component (A) and component (B) (C
) As the component, titanium and/or vanadium compounds are used, preferably titanium tetrachloride, vanadium tetrachloride,
Examples include vanadyl trichloride and mono-n-butoxytitanium tetrachloride. In this case, the co-pulverized product of (A) and (B) may be brought into contact with liquid component (C) or a solution of component (C), and the temperature at that time is room temperature to 200°C, preferably is carried out at 50'C to 150C.
上記接触のあとｎ−ヘプタン、ｎ−ヘキサン等の不活性
溶媒で洗浄するか、減圧乾燥して触媒（イ）成分を得る
ことができる。After the above contact, the catalyst (a) component can be obtained by washing with an inert solvent such as n-heptane or n-hexane or by drying under reduced pressure.
触媒（ロ）成分としては有機アルミニウム化合物が好ま
しく、一般式ＡＩＲｍＸ３−ｍ （但し、Ｒは１〜１２
の炭化水素基、Ｘはハロゲン原子、アルコキシ基、水素
原子、を表わし１ｍは１〜３である）で示される化合物
が用いられ１例えばトリメチルアルミニウム、ｌＪエチ
ルアルミニウム、）ＩＪ−ｉｓｏ−ブチルアルミニウム
、ジエチルアルミニウムモノクロライド、ジェムルアル
ミニウムモノエトキシドなどが挙げられる。またこれら
の混合物を用いても良い。The catalyst (b) component is preferably an organoaluminum compound, and has the general formula AIRmX3-m (where R is 1 to 12
A hydrocarbon group, X represents a halogen atom, an alkoxy group, or a hydrogen atom, and 1m is 1 to 3. Examples include diethylaluminium monochloride and gemylaluminum monoethoxide. A mixture of these may also be used.
触媒（Ｂ）成分の使用量は（Ａ）成分中のＴｉ １モ
ルに対して１〜５００倍モル、好ましくは２〜１００倍
モルである。The amount of the catalyst (B) component used is 1 to 500 times, preferably 2 to 100 times, per mole of Ti in component (A).
エチレンと共重合するα−オレフィンとしてはプロピレ
ン、フテンーＩ１１ペンテンー１％ヘキセン−１，４−
メチルペンテン−１，オクテン−１などが挙げられる。α-olefins copolymerized with ethylene include propylene, phthene-I11 pentene-1% hexene-1,4-
Examples include methylpentene-1 and octene-1.
本発明の方法ではエチレンとα−オレフィンの組合わせ
に加えて更にジエンを用いて共重合をすることもでき、
ジエンとしてはジシクロペンタジェン、５−メｆレンー
２−ノルボルネン、５−エチリデン−２−ノルボルネン
、１，４−へキサジエン、シクロオクタジエンなどが使
用でき、これらを共重合させることによって加硫可能な
ゴムとすることができる。In the method of the present invention, in addition to the combination of ethylene and α-olefin, it is also possible to copolymerize using a diene,
As the diene, dicyclopentadiene, 5-meflene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, cyclooctadiene, etc. can be used, and vulcanization is possible by copolymerizing these. It can be made of rubber.
重合温度は０〜１５０°Ｃ１好ましくハ１ｏ〜１ｏＯ℃
、重合圧力は常圧〜１００に９／ｄｉである。The polymerization temperature is 0 to 150°C, preferably 10 to 100°C.
, the polymerization pressure is from normal pressure to 100 to 9/di.
重合は溶液重合及び懸濁重合で行なうことができ、溶液
重合ではヘキサン、ヘプタン、トルエンなどを溶媒とし
て行ない、懸濁重合ではプロピレンなど貧溶媒中で行な
う。Polymerization can be carried out by solution polymerization or suspension polymerization. Solution polymerization is carried out using hexane, heptane, toluene, etc. as a solvent, and suspension polymerization is carried out in a poor solvent such as propylene.
共重合体の分子量は必要により水素など連鎖移動剤を用
いて調節することができる。The molecular weight of the copolymer can be adjusted using a chain transfer agent such as hydrogen, if necessary.
実施例１
（ａ） 直径１２韻の鋼球８０個の入った内容積６０
０−の粉砕用ポットを装備した振動ミルに塩化マグネシ
ウム ２Ｃ１，α−メチルスチレン ３．０ｒｒＬｔを
加えて４０時間粉砕した。Example 1 (a) Internal volume 60 containing 80 steel balls with a diameter of 12 rhymes
Magnesium chloride 2C1, α-methylstyrene 3.0rrLt was added to a vibration mill equipped with a 0- pulverization pot and pulverized for 40 hours.
２００ｒｒＬｔ丸底フラスコに上記粉砕物１（１゜四塩
化チタン ５０−を加えて８０℃で２時間かくはんした
のち、デカンテーシヨンにより上澄液を除き１次にｎ−
ヘフリン １００１ｄを加えて室温で１５分間かくはん
ののちデカンテーシ叢ンで上澄液を除（洗浄操作を７回
繰り返した後、さらにｎ−へブタン１００−を追加して
活性化チタン成分スラリーを得た。The above pulverized product 1 (1° titanium tetrachloride 50-) was added to a 200rrLt round bottom flask and stirred at 80°C for 2 hours. The supernatant was removed by decantation and the first n-
After adding Heflin 1001d and stirring at room temperature for 15 minutes, the supernatant was removed with a decantation tube (after repeating the washing operation 7 times, n-hebutane 100- was further added to obtain an activated titanium component slurry. .
この活性化チタン成分スラリーの一部をサンプリングし
ｎ−へブタンを蒸発させ分析したところ活性化チタン成
分中に １．８０ ｗｔ％のチタンを含有していた。When a part of this activated titanium component slurry was sampled and n-hebutane was evaporated and analyzed, it was found that the activated titanium component contained 1.80 wt% titanium.
（ｂ） 内容積６１の５ＵＥ−３２製オートクレーブ
中にｎ−ヘプタン ３ｏｍｚ、（ａ）で調製した活性化
チタン成分 １０■、トリエチルアルミニウム ０．０
５４をＮ２気流中で装入した。(b) In a 5UE-32 autoclave with an internal volume of 61, n-heptane 3 omz, activated titanium component prepared in (a) 10 μ, triethylaluminum 0.0
54 was charged under a stream of N2.
オートクレーブの気相部をプロピレンで置換したのち液
化プロピレンを１．５ｋｌ？装入し次いで水素を分圧で
１ ｋｇ／ｃｒｄ 、エチレンを分圧で５ｋｇ／ｃ＋＋
ｆに保ち、３０℃で１時間共重合反応を行なった。After replacing the gas phase of the autoclave with propylene, 1.5kl of liquefied propylene was added. After charging, hydrogen was charged at a partial pressure of 1 kg/crd, and ethylene was charged at a partial pressure of 5 kg/c++.
The copolymerization reaction was carried out at 30° C. for 1 hour while maintaining the temperature at 30° C.
重合反応終了後未反応モノマーを除去してエチレンプロ
ピレン共重合体３５０りを得た。After the polymerization reaction was completed, unreacted monomers were removed to obtain 350 ethylene propylene copolymers.
得られた共重合体は粉末状で、極限粘度数１．８３ ｄ
ｌ、Ｑ （１３５℃テトラリン中）、エチレン含有率６
１，２ｗｔ％であった。The obtained copolymer was in powder form and had an intrinsic viscosity of 1.83 d.
l, Q (in tetralin at 135°C), ethylene content 6
It was 1.2 wt%.
得られた共重合体のエチレンとプロピレンのブロック性
の尺度として赤外吸収スペクトルの７３０ｃ！ｒＬ ’
（ポリエチレンの結晶性に基因する吸収）と７２０ ｃ
ｍ ’ （＋ＣＨｚ＋ｎの骨格振動による吸収）との
強度比よりブロック性を次式で求めた。As a measure of the blocking properties of ethylene and propylene in the obtained copolymer, the infrared absorption spectrum was 730c! rL'
(absorption due to crystallinity of polyethylene) and 720 c
The blockiness was determined from the intensity ratio with m' (+CHZ+n absorption due to skeletal vibration) using the following formula.
本実施例で得られたポリマーのブロック性は０．１であ
った。この場合の触媒の活性は３５０００９ ／ ９−
（（）成分、 ｈｒ １９１２ｋｇ／９−Ｔｉ であ
った。The blockiness of the polymer obtained in this example was 0.1. The activity of the catalyst in this case is 350009/9-
(Component (), hr 1912 kg/9-Ti.
実施例２〜５
実施例１の方法に於て塩化マグネシウムと共粉砕するα
−メチルスチレンに代えて種々の化合物を用いる以外は
触媒調製及び重合を実施例１と全く同じ方法で行なった
結果を表ＩＫ示す。Examples 2-5 α co-pulverized with magnesium chloride in the method of Example 1
Table IK shows the results of catalyst preparation and polymerization carried out in exactly the same manner as in Example 1, except that various compounds were used in place of methylstyrene.
比較例１
実施例１の方法に於て本発明の（Ｂ）成分であるα−メ
チルスチレンの添加を行なわずに実験をくり返した結果
を次の表に示す。以上の結果から、本発明の実施結果は
比較例の方法と比べると活性が３〜５倍本発明のほうが
太き（１本発明の（Ｂ）成分の使用が有効であることは
明らかである。Comparative Example 1 The following table shows the results of repeating the experiment in the method of Example 1 without adding α-methylstyrene, component (B) of the present invention. From the above results, the activity of the present invention is 3 to 5 times higher than that of the comparative method (1) It is clear that the use of component (B) of the present invention is effective. .
Claims (1)
供与性基を持たない液状有機化合を共粉砕したのち、 （Ｃ）チタン及び／またはバナジウム化合物と接触して
得られた組成物、及び （ロ）有機金属化合物 の（イ）、（ロ）より成る成分を触媒として用いること
を特徴とするエチレンとα−オレフィンの共重合方法。 ２、（Ｂ）成分が不飽和炭化水素であることを特徴とす
る特許請求の範囲第１項記載の方法。[Claims] 1. (a) After co-pulverizing (A) magnesium halide and (B) a liquid organic compound having no electron-donating group, (C) contacting with titanium and/or vanadium compound; A method for copolymerizing ethylene and α-olefin, characterized in that the obtained composition and (b) components consisting of (a) and (b) of an organometallic compound are used as catalysts. 2. The method according to claim 1, wherein component (B) is an unsaturated hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19778685A JPS6259608A (en) | 1985-09-09 | 1985-09-09 | Copolymerization of ethylene with alpha-olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19778685A JPS6259608A (en) | 1985-09-09 | 1985-09-09 | Copolymerization of ethylene with alpha-olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6259608A true JPS6259608A (en) | 1987-03-16 |
Family
ID=16380326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19778685A Pending JPS6259608A (en) | 1985-09-09 | 1985-09-09 | Copolymerization of ethylene with alpha-olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6259608A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995011928A1 (en) * | 1993-10-27 | 1995-05-04 | Nippon Oil Company, Limited | Component of olefin polymerization catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5248915A (en) * | 1975-10-17 | 1977-04-19 | Oki Electric Ind Co Ltd | Special effect generation system |
| JPS5434428A (en) * | 1977-08-16 | 1979-03-13 | Truetzschler & Co | Fleece compressing apparatus |
| JPS554323A (en) * | 1978-06-26 | 1980-01-12 | Masayuki Ishikawa | 2-phenyl-substituted-1-phthalazone derivative |
| JPS57137303A (en) * | 1981-02-19 | 1982-08-24 | Mitsui Toatsu Chem Inc | Production of catalyst |
| JPS60133010A (en) * | 1983-12-22 | 1985-07-16 | Mitsui Toatsu Chem Inc | Preparation of titanium or vanadium component of carrier type for ethylene or alpha-olefin polymerization |
-
1985
- 1985-09-09 JP JP19778685A patent/JPS6259608A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5248915A (en) * | 1975-10-17 | 1977-04-19 | Oki Electric Ind Co Ltd | Special effect generation system |
| JPS5434428A (en) * | 1977-08-16 | 1979-03-13 | Truetzschler & Co | Fleece compressing apparatus |
| JPS554323A (en) * | 1978-06-26 | 1980-01-12 | Masayuki Ishikawa | 2-phenyl-substituted-1-phthalazone derivative |
| JPS57137303A (en) * | 1981-02-19 | 1982-08-24 | Mitsui Toatsu Chem Inc | Production of catalyst |
| JPS60133010A (en) * | 1983-12-22 | 1985-07-16 | Mitsui Toatsu Chem Inc | Preparation of titanium or vanadium component of carrier type for ethylene or alpha-olefin polymerization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995011928A1 (en) * | 1993-10-27 | 1995-05-04 | Nippon Oil Company, Limited | Component of olefin polymerization catalyst |
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