JPS63108007A - Polymerization of olefin - Google Patents
Polymerization of olefinInfo
- Publication number
- JPS63108007A JPS63108007A JP25356186A JP25356186A JPS63108007A JP S63108007 A JPS63108007 A JP S63108007A JP 25356186 A JP25356186 A JP 25356186A JP 25356186 A JP25356186 A JP 25356186A JP S63108007 A JPS63108007 A JP S63108007A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- transition metal
- olefin
- polymerization
- hydrocarbon residue
- 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
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000006116 polymerization reaction Methods 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- -1 titanium halide Chemical class 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100264179 Oryza sativa subsp. japonica RIXI gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- KLWZLMKMCYTORE-UHFFFAOYSA-N cyclohexane;hydrobromide Chemical compound Br.C1CCCCC1 KLWZLMKMCYTORE-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はオレフィンの重合方法に関する。詳しくは特定
の方法で得たハロゲン化マグネシウムを担体とする触媒
を用いるオレフィンの重合方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for polymerizing olefins. Specifically, the present invention relates to a method for polymerizing olefins using a catalyst having a magnesium halide obtained by a specific method as a carrier.
オレフィンの重合用にハロゲン化マグネシウムなどの担
体にハロゲン化チタンを担持してなる遷移金属触媒と有
機金属化合物からなる触媒を用いることは特公昭３９−
１２１０５号で開示されて以来、種々の改良方法が提案
されており、かなり優れた性能のものが得られている。The use of a transition metal catalyst consisting of a titanium halide supported on a carrier such as magnesium halide and a catalyst consisting of an organometallic compound for the polymerization of olefins was disclosed in Japanese Patent Publication No. 39-1989.
Since the disclosure in No. 12105, various improved methods have been proposed, and some with considerably superior performance have been obtained.
オレフィンを重合して得たポリオレフィン中に残存する
触媒残渣の量は少なければ少ない方が良く、又かさ比重
も大きければ大きい方が良い。したがって、さらに高性
能の触媒の開発が望まれている。The smaller the amount of catalyst residue remaining in the polyolefin obtained by polymerizing olefin, the better, and the larger the bulk specific gravity, the better. Therefore, it is desired to develop a catalyst with even higher performance.
本発明者らは、上記問題を解決する方法について鋭意検
討し、特定の方法で製造できるハロゲン化マグネシウム
が担体として好適であることを見出し、本発明を完成し
た。The present inventors have conducted extensive studies on methods for solving the above problems, and have found that magnesium halide, which can be produced by a specific method, is suitable as a carrier, and have completed the present invention.
即ち、本発明は一般式１？１ＭｇＸ１（式中、Ｒ１は炭
化水素残基、χ１は臭素又は沃素原子である。）で表わ
されるグリニヤール試薬と一般式Ｒ”、、ＳｉＸ２４−
ｎ（式中、Ｒ２は炭化水素残基、Ｘｌは塩素原子、ｎは
０〜３の整数である。）で表される塩素化ケイ素化合物
との反応で得られる）’ＩｇＸ’Ｘ２にハロゲン化チタ
ンを担持して得た遷移金属触媒と周期律表第１族ないし
第３族の有機金属化合物からなる触媒を用いることを特
徴とするオレフィンの重合方法である。That is, the present invention provides a Grignard reagent represented by the general formula 1?1MgX1 (wherein R1 is a hydrocarbon residue and χ1 is a bromine or iodine atom) and a Grignard reagent represented by the general formula R'', SiX24-
halogenated 'IgX'X2 (obtained by reaction with a chlorinated silicon compound represented by This is an olefin polymerization method characterized by using a transition metal catalyst obtained by supporting titanium and a catalyst consisting of an organometallic compound of Groups 1 to 3 of the periodic table.
本発明は、担体として用いるＭｇＸ’Ｘ２（式中、Ｘｌ
は臭素又は沃素、×２は塩素である。）の製法に特徴が
あり、得られた担体にハロゲン化チタンを担持する方法
については特に制限はなく、種々の方法を採用すること
ができる。例えば担体を予めカルボン酸エステル、エー
テル、オルソエステル、アルコキシケイ素、リン酸エス
テル、アルコール、ケトンなどの含酸素化合物と接触或
いは共粉砕し、次いでハロゲン化チタンと接触処理する
か或いは共粉砕する方法が挙げられる。The present invention provides MgX'X2 (wherein Xl
is bromine or iodine, and x2 is chlorine. ) is characterized by its manufacturing method, and there is no particular restriction on the method of supporting titanium halide on the obtained carrier, and various methods can be adopted. For example, there is a method in which the carrier is contacted or co-milled in advance with an oxygen-containing compound such as a carboxylic acid ester, ether, orthoester, alkoxy silicon, phosphoric acid ester, alcohol, or ketone, and then contacted with or co-milled with a titanium halide. Can be mentioned.
ここでハロゲン化チタンとしては好ましくは塩化チタン
が例示でき、四塩化チタン、三塩化チタンが具体例とし
て挙げられる。Here, the titanium halide is preferably titanium chloride, and specific examples include titanium tetrachloride and titanium trichloride.
本発明において重要なＭｇＸ’Ｘ２で示されるハロゲン
化マグネシウムを製造するに際して用いられるＲ１Ｍｇ
Ｘ１（式中、Ｒ１は炭化水素残基、Ｘｌは臭素又は沃素
原子である）は公知の方法で製造することができ、一般
にはＲＩＸＩで示されるハロゲン化炭化水素と金属マグ
ネシウムを反応せしめることで製造できる。ここで炭化
水素残基としては脂肪族、脂環族、芳香族、などの炭化
水素残基が使用でき特に制限はないが、炭素数１〜２０
程度のものが用いられる。また、Ｘｌとしてはヨウ素、
臭素原子である。R1Mg used in producing magnesium halide represented by MgX'X2, which is important in the present invention
X1 (wherein R1 is a hydrocarbon residue and Xl is a bromine or iodine atom) can be produced by a known method, generally by reacting a halogenated hydrocarbon represented by RIXI with magnesium metal. Can be manufactured. Here, as the hydrocarbon residue, aliphatic, alicyclic, aromatic, etc. hydrocarbon residues can be used, and there is no particular restriction, but the number of carbon atoms is 1 to 20.
A certain degree is used. In addition, as Xl, iodine,
It is a bromine atom.
ＭｇＸ１Ｘ２を製造するに際し用いる一方の成分である
一般式１７”、 ＳｉＸ”ｎ−７（式中、Ｒ２は炭化水
素残基、Ｘｌは塩素原子ｎは０〜３の整数である。）で
表される塩素化ケイ素化合物としては、炭化水素残基Ｒ
２として水素の他に炭素数１〜２０の飽和又は不飽和の
炭化水素残基を有し、具体例として、例えばテトラクロ
ロシラン、トリクロロシラン、メチルトリクロルシラン
、ジメチルジクロルシラン、トリメチルクロルシラン、
エチルトリクロルシラン、ジエチルジクロルシラン、ト
リエチルクロルシランなどの飽和炭化水素残基を有する
化合物、又はビニルトリクロルシラン、ビニルメチルジ
クロルシラン、フェニルトリクロルシラン、ジフェニル
トリクロルシラン、フェニルメチルジクロルシランなど
の不飽和炭化水素残基を存する化合物が例示される。One component used in producing MgX1X2 is represented by the general formula 17'', SiX''n-7 (wherein, R2 is a hydrocarbon residue, Xl is a chlorine atom, and n is an integer from 0 to 3). As the chlorinated silicon compound, hydrocarbon residue R
2 has a saturated or unsaturated hydrocarbon residue having 1 to 20 carbon atoms in addition to hydrogen, and specific examples include tetrachlorosilane, trichlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane,
Compounds with saturated hydrocarbon residues such as ethyltrichlorosilane, diethyldichlorosilane, and triethylchlorosilane, or compounds with saturated hydrocarbon residues such as vinyltrichlorosilane, vinylmethyldichlorosilane, phenyltrichlorosilane, diphenyltrichlorosilane, and phenylmethyldichlorosilane. Compounds containing saturated hydrocarbon residues are exemplified.
上記グリニヤール試薬と塩素化ケイ素化合物の反応は極
めて早く、室温ないし使用した触媒の沸点付近で、収率
良＜ ＭｇＸ１Ｘ２が得られる。The reaction between the Grignard reagent and the chlorinated silicon compound is extremely fast, and MgX1X2 can be obtained in good yield at room temperature or around the boiling point of the catalyst used.
本発明において用いる周期律表第１族ないし第３族金属
の有機金属化合物としては、有機リチウム、有機ナトリ
ウム、有機マグネシウム、有機ベリラム、有機アルミニ
ウムなどが例示され、なかでも有機アルミニウムが好ま
しく用いられる。Examples of the organometallic compounds of metals from Groups 1 to 3 of the periodic table used in the present invention include organolithium, organosodium, organomagnesium, organoberyllum, and organoaluminium, among which organoaluminum is preferably used.
本発明において用いられるオレフィンとしてはエチレン
、プロピレン、ブテン−１、ペンテン−１、ヘキセン−
１、オクテン−１、スチレン、ビニルナフタレンなどが
例示され、それらの単独重合或いは相互の共重合さらに
はジエンとの共重合などに用いられる。The olefins used in the present invention include ethylene, propylene, butene-1, pentene-1, and hexene-1.
Examples include 1, octene-1, styrene, and vinylnaphthalene, which are used for homopolymerization, copolymerization with each other, and copolymerization with diene.
本発明において、オレフィンの重合は、上記した方法で
製造したハロゲン化マグネシウム担体を用いる他は従来
のオレフィンの重合方法が適用でき、溶媒を用いる溶液
重合、オレフィン自身を媒体とする塊状重合或いは溶媒
の実質的に含まない気相重合などがとりうる。In the present invention, conventional olefin polymerization methods can be applied to the olefin polymerization except for using the magnesium halide carrier produced by the method described above, such as solution polymerization using a solvent, bulk polymerization using the olefin itself as a medium, or solvent polymerization. Gas-phase polymerization, which does not contain substantially any of the above substances, can be used.
以下、実施例を挙げ本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１
３００ｍｌの丸底フラスコにマグネシウム７．４ｇ、ジ
エチルエーテル２０ｍ Ｉ入れ、エーテルの還流下に臭
化シクロヘキサン５（Ｉｇとジエチルエーテル１００ｍ
１の混合物を２時間かけて滴下した。その後さらに１時
間還流下撹拌処理し、Ｃ６ＨＩ ＋ＭｇＢｒのエチルエ
ーテル溶液を調製した。Example 1 7.4 g of magnesium and 20 m of diethyl ether were placed in a 300 ml round bottom flask, and under reflux of ether, cyclohexane bromide (5 g and 100 m of diethyl ether) was added.
1 was added dropwise over 2 hours. Thereafter, the mixture was further stirred under reflux for 1 hour to prepare an ethyl ether solution of C6HI + MgBr.
次いでエチルエーテルの還流下に四塩化ケイ素１３ｇを
５０１Ｗ１のｎ−ヘキサンに溶解したものを３時間かけ
て滴下し、さらに還流下に４時間攪拌した。Next, a solution of 13 g of silicon tetrachloride dissolved in 501W1 n-hexane was added dropwise to the ethyl ether under reflux over 3 hours, and the mixture was further stirred for 4 hours under reflux.
次いで室温でろ過し、固形分をエチルエーテルで洗浄し
、窒素気流で乾燥して、固形分４０ｇを得た。得られた
固形分はＭｇ：ＣＩｔ ：Ｂｒがほぼ１：１：１であり
、ＭｄｒＣｌｌであった。Then, it was filtered at room temperature, and the solid content was washed with ethyl ether and dried with a nitrogen stream to obtain 40 g of solid content. The solid content obtained had a ratio of Mg:CIt:Br of approximately 1:1:1, and was MdrClI.
上記固形分１０ｇを２００ｍ１丸底フラスコに入れ、四
塩化チタン５０ｍ１、トルエン５０＋ｎｌを入れ、９０
°Ｃで１時間攪拌処理し、次いで静置して上澄を除去し
た。さらに四塩化チタン５０ｍ１． ）ルエン５０ｍ１
を入れ、９０℃で１時間攪拌処理し、次いで静置して上
澄を除去し、得られた固形分をトルエンで７回洗浄して
遷移金属触媒とした。分析の結果はチタンを１．３ｔｓ
ｔ％含有していた。Put 10g of the above solid content into a 200ml round bottom flask, add 50ml of titanium tetrachloride, 50+nl of toluene,
The mixture was stirred at °C for 1 hour, then allowed to stand and the supernatant was removed. Additionally, 50ml of titanium tetrachloride. ) Ruen 50m1
The mixture was stirred at 90° C. for 1 hour, then left to stand, the supernatant was removed, and the resulting solid content was washed seven times with toluene to obtain a transition metal catalyst. The result of the analysis was 1.3ts of titanium.
It contained t%.
上記操作で得た遷移金属触媒を用いてエチレンを重合し
た。内容積２βのオートクレーブにｎ−へブタンｌｌ入
れ、上記遷移金属触媒２０ｍｇ、トリエチルアルミニウ
ム０．５ｍｌを加え、水素を２Ｋｇ／ｃＪゲージまで入
れ、さらにエチレンを６Ｋｇ／ｃ４ゲージまで加えた後
７５℃に昇温し、１０Ｋｇ／ｃＪゲージになるようにエ
チレンを追加しなから７５°Ｃで２時間重合した。その
後冷却し、未反応のエチレンをパージした後ろ過して、
ポリエチレンパウダーを得た。Ethylene was polymerized using the transition metal catalyst obtained in the above operation. Pour 1 liter of n-hebutane into an autoclave with an internal volume of 2β, add 20 mg of the above transition metal catalyst and 0.5 ml of triethylaluminum, add hydrogen up to 2 Kg/cJ gauge, and then add ethylene up to 6 Kg/c4 gauge, then heat to 75°C. The temperature was raised and polymerization was carried out at 75°C for 2 hours without adding ethylene to give a gauge of 10 kg/cJ. After that, it is cooled, unreacted ethylene is purged, and then filtered.
Polyethylene powder was obtained.
乾燥秤量したところ１９５ｇであった。このパウダーの
極限粘度数は３．０１（１３５℃テトラリン溶液で測定
した。）かさ比重は０．４３、粒度は２００メソシユ以
下の微粉０．３％、１０メツシュ以上の粗粒０．０％で
あった。Ｔｉ当たりの収率は、７５０ｈ／ｇ−Ｔｉであ
り、かさ比重も良好であり、粒度分布も比較的シャープ
であった。The dry weight was 195 g. The intrinsic viscosity of this powder is 3.01 (measured with a tetralin solution at 135°C), the bulk specific gravity is 0.43, and the particle size is 0.3% of fine particles of 200 mesh or less and 0.0% of coarse particles of 10 mesh or more. there were. The yield per Ti was 750 h/g-Ti, the bulk specific gravity was also good, and the particle size distribution was also relatively sharp.
実施例２
実施例１で得た遷移金属触媒を用いてプロピレンを重合
した。２１のオートクレーブにｎ−へブタンｌｌ入れ、
遷移金属触媒３０ｍｇ 、ジエチルアルミニウムクロラ
イド０ 、３２ｍ ｌ、トルイル酸メチル０．１２ｍ１
、トリエチルアルミニウム０．２０ｍ１を加え、水素０
．１Ｋｇ／ｃａｔゲージ、プロピ１フ２Ｋｇ／ｃｎ！ゲ
ージ入れ、次いで内温を７０℃とし、全圧６Ｋｇ／ａｎ
ｔゲージで２時間重合した。重合終了後未反応のプロピ
レンをパージし、スラリーをろ過してポリプロピレンパ
ウダー１４９ｇを得、ろ液よりアククチツクポリプロピ
レンを３．９ｇ得た。Example 2 The transition metal catalyst obtained in Example 1 was used to polymerize propylene. Put 1 liter of n-hebutane into a No. 21 autoclave,
Transition metal catalyst 30mg, diethylaluminum chloride 0, 32ml, methyl toluate 0.12ml
, add 0.20ml of triethylaluminum, and add 0.20ml of triethylaluminum.
．． 1Kg/cat gauge, propi 1f 2Kg/cn! Insert the gauge, then set the internal temperature to 70°C and increase the total pressure to 6Kg/an.
Polymerization was carried out on a t-gauge for 2 hours. After the polymerization was completed, unreacted propylene was purged, the slurry was filtered to obtain 149 g of polypropylene powder, and 3.9 g of acid polypropylene was obtained from the filtrate.
ポリプロピレンパウダーの沸騰ｎ−へブタン抽出残率の
割合は９７．４％（ソツクレスレー抽出器を用い沸騰ｎ
−へブタンで６時間抽出）であり、極限粘度数は２．０
８、かさ比重は０．４２であった。The residual ratio of polypropylene powder extracted with boiling n-hebutane is 97.4% (boiling
-extracted with hebutane for 6 hours) and has an intrinsic viscosity of 2.0.
8. The bulk specific gravity was 0.42.
実施例３
四塩化ケイ素１３ｇにかえてトリクロロビニルシラン１
６．５ｇにかえた他は実施例１と同様にしたところチタ
ン１．２ｉ＋ｔ％の遷移金属触媒を得、同様に重合した
ところポリエチレンパウダー２２５ｇを得た。Example 3 Trichlorovinylsilane 1 instead of 13 g silicon tetrachloride
The same procedure as in Example 1 was carried out except that the amount was changed to 6.5 g to obtain a transition metal catalyst containing 1.2i+t% of titanium, and 225 g of polyethylene powder was obtained by polymerizing in the same manner.
このパウダーの極限粘度数は２．９５、かさ比重は０゜
３９であった。This powder had an intrinsic viscosity of 2.95 and a bulk specific gravity of 0°39.
本発明の方法を実施することにより収率よくポリオレフ
ィンを製造することが可能となり工業的に価値がある。By carrying out the method of the present invention, it is possible to produce polyolefins in good yield, which is industrially valuable.
第１図はオレフィン重合触媒に関するフローチャート図
である。FIG. 1 is a flowchart regarding an olefin polymerization catalyst.
Claims (1)
、Ｘ＾１は臭素又は沃素原子である。）で表わされるグ
リニャール試薬と一般式Ｒ＾２＿ｎＳｉＸ＾２＿４＿−
＿ｎ（式中、Ｒ＾２は炭化水素残基、Ｘ＾２は塩素原子
、ｎは０〜３の整数である。）で表される塩素化ケイ素
化合物との反応で得られるＭｇＸ＾１Ｘ＾２にハロゲン
化チタンを担持して得た遷移金属触媒と周期律表第１族
ないし第３族の有機金属化合物からなる触媒を用いるこ
とを特徴とするオレフィンの重合方法。A Grignard reagent represented by the general formula R^1MgX^1 (wherein R^1 is a hydrocarbon residue, and X^1 is a bromine or iodine atom) and the general formula R^2_nSiX^2_4_-
MgX^1X^ obtained by reaction with a chlorinated silicon compound represented by _n (wherein R^2 is a hydrocarbon residue, X^2 is a chlorine atom, and n is an integer from 0 to 3). A method for polymerizing olefins, which comprises using a transition metal catalyst obtained by supporting titanium halide on 2 and a catalyst comprising an organometallic compound of Groups 1 to 3 of the periodic table.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253561A JPH0794493B2 (en) | 1986-10-27 | 1986-10-27 | Olefin Polymerization Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253561A JPH0794493B2 (en) | 1986-10-27 | 1986-10-27 | Olefin Polymerization Method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63108007A true JPS63108007A (en) | 1988-05-12 |
| JPH0794493B2 JPH0794493B2 (en) | 1995-10-11 |
Family
ID=17253078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61253561A Expired - Lifetime JPH0794493B2 (en) | 1986-10-27 | 1986-10-27 | Olefin Polymerization Method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794493B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5274686A (en) * | 1975-12-18 | 1977-06-22 | Sumitomo Chem Co Ltd | Process for polymerizing olefins |
| JPS54112983A (en) * | 1978-02-23 | 1979-09-04 | Sumitomo Chem Co Ltd | Preparation of highly crystalline olefin polymer |
| JPS5630407A (en) * | 1979-08-22 | 1981-03-27 | Sumitomo Chem Co Ltd | Preparation of highly stereoregular alpha-olefin polymer |
| JPS5759903A (en) * | 1980-09-26 | 1982-04-10 | Sumitomo Chem Co Ltd | Preparation of polyolefin |
| JPS57115407A (en) * | 1981-11-19 | 1982-07-17 | Sumitomo Chem Co Ltd | Preparation of solid catalytic system for olefin polymerization |
-
1986
- 1986-10-27 JP JP61253561A patent/JPH0794493B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5274686A (en) * | 1975-12-18 | 1977-06-22 | Sumitomo Chem Co Ltd | Process for polymerizing olefins |
| JPS54112983A (en) * | 1978-02-23 | 1979-09-04 | Sumitomo Chem Co Ltd | Preparation of highly crystalline olefin polymer |
| JPS5630407A (en) * | 1979-08-22 | 1981-03-27 | Sumitomo Chem Co Ltd | Preparation of highly stereoregular alpha-olefin polymer |
| JPS5759903A (en) * | 1980-09-26 | 1982-04-10 | Sumitomo Chem Co Ltd | Preparation of polyolefin |
| JPS57115407A (en) * | 1981-11-19 | 1982-07-17 | Sumitomo Chem Co Ltd | Preparation of solid catalytic system for olefin polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0794493B2 (en) | 1995-10-11 |
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