JPS63105007A - Solid catalytic component for olefin polymerization - Google Patents
Solid catalytic component for olefin polymerizationInfo
- Publication number
- JPS63105007A JPS63105007A JP24954486A JP24954486A JPS63105007A JP S63105007 A JPS63105007 A JP S63105007A JP 24954486 A JP24954486 A JP 24954486A JP 24954486 A JP24954486 A JP 24954486A JP S63105007 A JPS63105007 A JP S63105007A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- catalyst component
- solid catalyst
- reaction
- ticl4
- 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
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 40
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract 3
- 239000007787 solid Substances 0.000 title description 4
- 239000000126 substance Substances 0.000 claims abstract description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 16
- -1 aromatic halogenated hydrocarbon Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000011949 solid catalyst Substances 0.000 claims description 28
- 238000010298 pulverizing process Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052740 iodine Inorganic materials 0.000 abstract description 5
- 239000011630 iodine Substances 0.000 abstract description 5
- 150000005690 diesters Chemical class 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 abstract description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 23
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229960002380 dibutyl phthalate Drugs 0.000 description 4
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- POXXQVSKWJPZNO-UHFFFAOYSA-N 1-o-ethyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC(C)C POXXQVSKWJPZNO-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- JEABIFHLYSDNRJ-UHFFFAOYSA-N 2-o-butyl 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC JEABIFHLYSDNRJ-UHFFFAOYSA-N 0.000 description 1
- GWSSHOOLMLNSKS-UHFFFAOYSA-N 2-pentan-3-yloxycarbonylbenzoic acid Chemical compound CCC(CC)OC(=O)C1=CC=CC=C1C(O)=O GWSSHOOLMLNSKS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YDFHVOKEEMMIBE-RDJQXTLESA-N M-factor Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CSC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(=O)OC)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](NC(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](NC(=O)[C@@H](N)CC=1C=CC(O)=CC=1)[C@@H](C)O)C(C)C)C1=CC=C(O)C=C1 YDFHVOKEEMMIBE-RDJQXTLESA-N 0.000 description 1
- 101710204204 M-factor Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JANBFCARANRIKJ-UHFFFAOYSA-N bis(3-methylbutyl) benzene-1,2-dicarboxylate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1C(=O)OCCC(C)C JANBFCARANRIKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 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、オレフィン類の重合に供した際に、高活性に
作用し、しかも立体規則性重合体を高収率で得ることの
できる高性能固体触媒成分に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a high-density polymer that exhibits high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. It relates to performance solid catalyst components.
近時、プロピレンをはじめとするオレフィン類重合用触
媒として従来周知の三塩化チタン触媒成分に代り、新し
い型の触媒として活性成分であるチタンを塩化マグネシ
ウムに電子供与体と共に担持したものが数多く開発され
提案されている。Recently, instead of the conventionally well-known titanium trichloride catalyst component as a catalyst for the polymerization of olefins such as propylene, many new types of catalysts have been developed in which the active component titanium is supported on magnesium chloride together with an electron donor. Proposed.
これらの中で最も初期に開発されたものとしては電子供
与体としての有機モノカルボン酸エステルと四塩化チタ
ンとの錯体を塩化マグネシウムと共粉砕したものがあり
、あるいは電子供与体としての有機モノカルボン酸エス
テルと塩化マグネシウムとの共粉砕生成物を四塩化チタ
ンで処理したものがある。Among these, the earliest developed was a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride co-pulverized with magnesium chloride, or a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride, or There is a co-pulverized product of acid ester and magnesium chloride treated with titanium tetrachloride.
しかし、これらは工業的規模で用いるためには満足すべ
き特性を有するものとは言えず種々の特性を改善するも
のとして例えば塩化マグネシウムの代りにジェトキシマ
グネシウムを用いるもの、電子供与体として特殊な化合
物を用いるものあるいはまた前記各物質の組合せ方法や
接触手段等に改変を行ったものも種々提案されている。However, these cannot be said to have satisfactory properties for use on an industrial scale, and there are methods to improve various properties, such as those using jetoxymagnesium instead of magnesium chloride, and special ones as electron donors. Various methods have been proposed in which compounds are used, or methods of combining the substances, contact means, etc. are modified.
例えば特開昭５４−９４５９０号公報では、マグネシウ
ムジノ・ロゲン化物を出発原料として触媒成分を調製し
、有機アルミニウム化合物、有機カルボン酸エステルお
よびＭ−０−Ｒ基を有する化合物などを組合せてオレフ
ィン類の重合に用いる方法が開示されており、また特開
昭５７−６３３１０号公報においては電子供与体として
の各種エステル類と活性形の塩化マグネシウムとチタン
化合物とを組合せて触媒成分を調製し、さらにＳｌ−〇
結合または５ｉ−Ｎ結合を有する化合物と有機アルミニ
ウム化合物を用いてプロピレンの重合を行なう方法が開
示されている。For example, in JP-A No. 54-94590, a catalyst component is prepared using magnesium dino-loganide as a starting material, and an olefin is prepared by combining an organoaluminum compound, an organic carboxylic acid ester, a compound having an M-0-R group, etc. In addition, in JP-A-57-63310, a catalyst component is prepared by combining various esters as electron donors with active magnesium chloride and a titanium compound, and A method for polymerizing propylene using a compound having an Sl-〇 bond or a 5i-N bond and an organoaluminum compound is disclosed.
従来技術において、担体物質としてその主流？占めてい
る塩化マグネシウムに含有される塩素は、チタンハロゲ
ン化物中のノ・ロゲン元素と同様に、生成重合体に対し
、悪影響を及ぼすという欠点を有しているため、それに
対し、塩素の影響を実質上、無視し得る程度の高活性が
要求され、あるいはまた塩化マグネシウムそのものの濃
度を低くおさえる々どの対策がとられている。In conventional technology, is it the mainstream as a carrier material? The chlorine contained in magnesium chloride has the disadvantage of having an adverse effect on the produced polymer, similar to the chlorine elements in titanium halides. Practically speaking, negligible high activity is required, and measures are being taken to keep the concentration of magnesium chloride itself low.
また、前記塩化マグネジ９ムを担体とする触媒成分を有
機アルミニ１ム化合物と組合せて用いてオレフィン類の
重合、特にプロピレン、１−ブテン等の立体規則性重合
を工業的に行なう場合、重合反応を行なう際に電子供与
体として有機モノカルボン酸エステルを用いることが必
須とされている。しかしこの場合有機モノカルボン酸エ
ステルを極めて多量に用いることが必要であり、その結
果、生成重合体に、特有のエステル臭を付与するという
問題点が存在した。In addition, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially using a catalyst component having magnesium chloride as a carrier in combination with an organic aluminum compound, the polymerization reaction When performing this, it is essential to use an organic monocarboxylic acid ester as an electron donor. However, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, and as a result, there is a problem in that the resulting polymer has a characteristic ester odor.
さらに、前記塩化マグネシウムを担体とする触媒成分を
用いた触媒など、いわゆる高活性担持型触媒においては
、重合初期の活性は高いものの経時的失活が大きくプロ
セス操作上問題となると共に、ブロック共重合等の重合
時間をより長くする場合、実質上それを使用することは
不可能であった。Furthermore, in so-called highly active supported catalysts, such as catalysts using catalyst components with magnesium chloride as a carrier, although the activity is high at the initial stage of polymerization, deactivation over time causes problems in process operation, and block copolymerization For longer polymerization times, it was virtually impossible to use it.
この点を改良するものとして前記特開昭５４−９４５９
０号のものが提案されているが、同公報の記載からも明
らかなようにこの場合、触媒調製時ならびに重合時にも
有機カルボン酸エステルを用いることが必要とされてい
る。一般に、触媒中に含まれる有機カルボン酸エステル
は、チタンハロゲン化物による処理あるいは有機溶媒に
よる洗浄などにより、生成重合体の臭いの問題を無視し
得る程度の量となっている。To improve this point, the above-mentioned Japanese Patent Application Laid-Open No. 54-9459
No. 0 has been proposed, but as is clear from the description in the same publication, in this case it is necessary to use an organic carboxylic acid ester during catalyst preparation and during polymerization. Generally, the amount of organic carboxylic acid ester contained in the catalyst is reduced to such an extent that the odor problem of the produced polymer can be ignored by treatment with a titanium halide or washing with an organic solvent.
しかし、重合時に用いる有機カルボン酸エステルは前述
のように触媒中に含まれる量に比して極めて多量であり
、なおかつ液体あるいは気体のモノマー中で重合を行な
った場合、その殆んど全てが生成重合体中に含まれてし
まうのが現状であり、従って、生成重合体の臭いの問題
は重合時に有機カルボン酸エステルを用いる限り解決し
得ないものといえる。また同公報に開示されている方法
は、その実施例からも判るように、非常に煩雑な操作を
必要とすると共に得られた触媒は性能的にも活性の持続
性におりても実用上充分なものとはいえな込のが実状で
ある。However, as mentioned above, the amount of organic carboxylic acid ester used during polymerization is extremely large compared to the amount contained in the catalyst, and when polymerization is carried out in liquid or gaseous monomers, almost all of it is produced. At present, it is contained in the polymer, and therefore, it can be said that the problem of odor in the produced polymer cannot be solved as long as an organic carboxylic acid ester is used during polymerization. Furthermore, as can be seen from the examples, the method disclosed in the same publication requires very complicated operations, and the resulting catalyst is insufficient for practical use in terms of performance and sustainability of activity. The reality is that the situation is poor.
本発明者らは、かかる従来技術における種々の問題点を
解決するため、鋭意研究を行い、鼓に新規なオレフィン
類重合用固体触媒成分を提供することに成功した。The present inventors conducted extensive research in order to solve the various problems in the prior art, and succeeded in providing a novel solid catalyst component for polymerizing olefins.
本発明は、
金属マグネシウム粉末と２倍モル以上のアルキルモノハ
ロゲン化物とを溶媒の不存在下、ヨウ素の存在下で反応
させて得られる物質（ａ）を、７タル酸のジエステル（
ｂ）および四塩化チタン（Ｑ）と共に共粉砕して得られ
る生成物を、さらに、常温で液体の芳香族炭化水素又は
芳香族ハロゲン化炭化水素の存在下で、四塩化チタンと
接触させることを特徴とするオレフィン類重合用固体触
媒成分
を提供するものである。In the present invention, a substance (a) obtained by reacting a metallic magnesium powder and an alkyl monohalide in an amount of 2 times the mole or more in the absence of a solvent and in the presence of iodine is converted into a diester of heptalacid (
The product obtained by co-pulverizing with b) and titanium tetrachloride (Q) is further contacted with titanium tetrachloride in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon that is liquid at room temperature. The present invention provides a characteristic solid catalyst component for polymerizing olefins.
本発明における前記（ａ）の金属マグネシウム粉末トア
ルキルモノハロゲン化物との反応によって得られる物質
（以下単に０物質という）を得るには、市販の金属マグ
ネシウム粉末と、アルキルモノハロゲン化物とを有機溶
媒の不存在下、ヨウ素の存在下で反応させるが、この際
、アル＃ ｋ −Ｔ−７ハロゲン化物は金属マグネシウ
ム粉末１モルに対して２モル以上用いることが必要であ
る。また、反応温度及び反応時間は、上記の反応が充分
に進む限り任意であり、特に限定されるものではないが
、通常２０℃以上で１０分間以上、好ましくは４０℃以
上で３０分間以上行なわれる。この反応は、グリニア型
の反応であり、反応によって得られた（ａ）物質の工Ｒ
スペクトルを測定するとアルキル基の吸収が見られる。In order to obtain the substance (hereinafter simply referred to as 0 substance) obtained by the reaction of (a) metal magnesium powder with the alkyl monohalide in the present invention, commercially available metal magnesium powder and the alkyl monohalide are mixed in an organic solvent. The reaction is carried out in the absence of iodine and in the presence of iodine. At this time, it is necessary to use 2 moles or more of Al#k-T-7 halide per 1 mole of metal magnesium powder. Further, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited, but the reaction is usually carried out at 20°C or higher for 10 minutes or more, preferably at 40°C or higher for 30 minutes or more. . This reaction is a Grignard-type reaction, and the process R of the (a) substance obtained by the reaction is
When the spectrum is measured, absorption of alkyl groups can be seen.
上記（ａ）物質の製造に用いられるアルキルモノハロゲ
ン化物としては、常温で液体の脂肪族炭化水素の塩化物
が好ましく、その例としては、例えばｎ−プロピルクロ
ライド、イソプロピルクロライド、ｎ−ブチルクロライ
ド、インブチルクロライド、ペンチルクロライド、ヘキ
シルクロライドおよびオクチルクロライド等があげられ
る。The alkyl monohalides used in the production of the substance (a) above are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-propyl chloride, isopropyl chloride, n-butyl chloride, Examples include inbutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.
本発明における前記（ｂ）のフタル酸のジエステル（以
下、単に（ｂ）物質とい５）としてはジメチルフタレー
ト、ジエチルフタレート、ジインプロピルフタレート、
ジプロピルフタレート、ジブチルフタレート、ジイソブ
チルフタレート、シアミルフタレート、ジイソアミルフ
タレート、エチルブチルフタレート、エチルイソブチル
フタレートおよびエチルプロピルフタレート等を例とし
てあげることができる。In the present invention, the diesters of phthalic acid (hereinafter simply referred to as (b) substances 5) of (b) include dimethyl phthalate, diethyl phthalate, diimpropyl phthalate,
Examples include dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethylpropyl phthalate.
本発明における前記（ｄ）の常温で液体の芳香族炭化水
素又は芳香族ハロゲン化炭化水素（以下、単に（ｄ）物
質という）としては、例えば、トルエン、キシレン、な
どの芳香族炭化水素、クロロベンゼン、０−ジクロロベ
ンゼン、ブロモベンゼンなどの芳香族ハロゲン化炭化水
素などがめげられる。In the present invention, (d) aromatic hydrocarbons or aromatic halogenated hydrocarbons that are liquid at room temperature (hereinafter simply referred to as (d) substance) include, for example, aromatic hydrocarbons such as toluene, xylene, and chlorobenzene. Examples include aromatic halogenated hydrocarbons such as , 0-dichlorobenzene, and bromobenzene.
本発明における固体触媒成分を得る際、該固体触媒成分
を構成する各原料物質の使用割合は、生成する固体触媒
成分の性能に悪影響を及ぼすことのない限り任意であり
特に限定されるものではないが、通常、前記（ａ）物質
１？に対し、前記（ｂ）物質は１０１〜１ｔの範囲であ
り、前記四塩化チタンについては、前記（ａ）物質およ
び（ｂ）物質と共粉砕する際にはα０１〜１ｆの範囲で
ろり、その共粉砕により得られた生成物と接触させる際
には、α１１以上好ましくは１を以上の範囲である。こ
の接触の際に共存させる（Ａ’）物質の量は、四塩化チ
タン１−に対してα０１〜１０〇−好ましくは１１〜１
０ｗｔの範囲である。When obtaining the solid catalyst component in the present invention, the proportion of each raw material constituting the solid catalyst component is arbitrary and not particularly limited as long as it does not adversely affect the performance of the solid catalyst component to be produced. However, usually the above (a) substance 1? On the other hand, the material (b) is in the range of 101 to 1t, and the titanium tetrachloride is milled in the range of α01 to 1f when co-pulverized with the material (a) and (b). When brought into contact with the product obtained by co-pulverization, α is in the range of 11 or more, preferably 1 or more. The amount of the substance (A') coexisting during this contact is α01 to 100, preferably 11 to 1, relative to 1 of titanium tetrachloride.
It is in the range of 0wt.
前記の（ａ）物質、（ｂ）物質および四塩化チタン（ｃ
）の共粉砕は、通常１０分間以上、好ましくは、３０分
間以上にわたって行なわれる。The above (a) substance, (b) substance and titanium tetrachloride (c
) The co-pulverization is usually carried out for at least 10 minutes, preferably for at least 30 minutes.
前記の共粉砕によって得られた生成物ｔ （ｄ）物質の
存在下で四塩化チタンと接触させる場合には、通常−１
０℃から四塩化チタンの沸点までの温度範囲で、１０分
間〜１００時間程度の時間で処理を行うのが好ましい。The product obtained by said co-milling, t (d), when brought into contact with titanium tetrachloride in the presence of the substance, usually -1
It is preferable to carry out the treatment at a temperature ranging from 0° C. to the boiling point of titanium tetrachloride for a period of about 10 minutes to 100 hours.
この接触の後、得られた生成物に対して、さらに四塩化
チタンを繰り返し接触させることができる。その際の接
触においては、（ｄ）物質を共存させても、また、させ
なくても、いずれでもよい。こうして得られた生成物は
所望により、ｎ−へブタン等の有機溶媒を用いて洗浄し
てもよい。After this contact, the resulting product can be repeatedly contacted with further titanium tetrachloride. In the contact at that time, the substance (d) may or may not coexist. The product thus obtained may be washed with an organic solvent such as n-hebutane, if desired.
これらの態様は、いずれも本発明の実施における一態様
に包含される。All of these aspects are included in one aspect of implementing the present invention.
本発明における固体触媒成分の調製に関する一連の操作
は酸素および水分等の不存在下に行なわれる仁とが好ま
しい。The series of operations for preparing the solid catalyst component in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.
以上の如くして調製された固体触媒成分は、有機アルミ
ニウム化合物と組合され、オレフィン類重合用触媒を構
成するが、この際ピペリジン誘導体あるいは５１−０結
合を有する有機ケイ素化合物など芳香族カルボン酸エス
テル以外の電子供与性化合物を共存させることが好まし
い。The solid catalyst component prepared as described above is combined with an organoaluminum compound to constitute a catalyst for polymerizing olefins. It is preferable to coexist with an electron donating compound other than the above.
本発明において使用される有機アルミニウム化合物とし
てはトリアルキルアルミニウムが好ましく、固体触媒成
分中のチタン２原子当り１〜１０００モルで用いられ、
また該電子供与性化合物は有機アルミニウム化合物に対
するモル比において１以下、好ましくはＱ、００５〜ｔ
。As the organoaluminum compound used in the present invention, trialkylaluminum is preferred, and is used in an amount of 1 to 1000 mol per 2 titanium atoms in the solid catalyst component,
In addition, the electron donating compound has a molar ratio of 1 or less to the organoaluminum compound, preferably Q, 005 to t.
.
の範囲で用いられる。Used within the range of
本発明に係るオレフィン類重合用固体触媒成分を用いて
の重合反応は有機溶媒の存在下でもあるいは不存在下で
も行なうことができ、また、使用するオレフィン単量体
は気体および液体のいずれの状態でも用いることができ
る。重合温度は２００℃以下好ましくは１００℃以下で
あり、重合圧力は１００ ｋｇ７ｃｍ”・Ｇ以下好まし
くは５ｏｋｉ９／傭２・Ｇ以下である。The polymerization reaction using the solid catalyst component for olefin polymerization according to the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer used can be in either a gas or liquid state. It can also be used. The polymerization temperature is 200° C. or less, preferably 100° C. or less, and the polymerization pressure is 100 kg 7 cm”·G or less, preferably 5 ki9/m2·G or less.
本発明に係るオレフィン類重合用固体触媒成分を用いて
単独重合または共重合されるオレフィン類はエチレン、
フロピレン、１−ブテン等である。The olefins to be homopolymerized or copolymerized using the solid catalyst component for olefin polymerization according to the present invention are ethylene,
These include phlopylene and 1-butene.
本発明に係るオレフィン類重合用固体触媒成分は、これ
を用いて、オレフィン類の重合を行なった場合、従来予
期し得ない程の高い活性を示すため生成重合体中に存在
する触媒残渣に？。When the solid catalyst component for olefin polymerization according to the present invention is used to polymerize olefins, it exhibits an unexpectedly high activity. .
極めて低くおさえることができ、しかも残留塩素が極め
て微量であるために生成物については脱灰工程を全く必
要としない程度にまで塩素の影響を低減することができ
る。Furthermore, since the amount of residual chlorine is extremely small, the influence of chlorine can be reduced to such an extent that no deashing process is required for the product.
生成重合体中に残存する塩素は造粒、成形などの工程に
用いる機器の腐食の原因となると共に生成重合体そのも
のの劣化、黄変等の原因ともなるものであるので、この
課題を解決し得ることは当該技術分野に対し大きな利益
をもたらすものである。Chlorine remaining in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, as well as deterioration and yellowing of the produced polymer itself. The results obtained will be of great benefit to the field of technology.
また、本発明の触媒によれば重合時に有機カルボン酸エ
ステルを添加しないことにより生成重合体に対するエス
テル臭の付着という大きな問題をも解決することができ
る。In addition, according to the catalyst of the present invention, by not adding an organic carboxylic acid ester during polymerization, it is possible to solve the major problem of adhesion of ester odor to the produced polymer.
さらに、従来、触媒の単位時間当りの活性が、重合の経
過に伴なって大幅に低下するという、いわゆる高活性担
持型触媒における共通の欠点が存在したが、本発明に係
る固体触媒成分を用いて得られた触媒においては、重合
時間の経過に伴なう活性の低下が、従来公知の触媒に比
較し、極めて小さい九め、共重合等重合時間をより長く
する場合にも有用であり、かつ、より高い重合圧力を採
用した場合における活性の増加が大きいため、最近注目
さねているバルク重合および気相重合にも幅広く用いる
ことができる。Furthermore, conventionally, there has been a common drawback in so-called highly active supported catalysts that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but the solid catalyst component according to the present invention In the catalyst obtained by this method, the decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, and it is also useful when the polymerization time is longer, such as in copolymerization. In addition, since the activity increases greatly when a higher polymerization pressure is employed, it can be widely used in bulk polymerization and gas phase polymerization, which have been attracting attention recently.
しかも、本発明に係る触媒によれば、高度の立体規則性
を有する重合体が得られる。Moreover, according to the catalyst according to the present invention, a polymer having a high degree of stereoregularity can be obtained.
さらに付言すると、工業的なオレフィン重合体の製造に
おいては重合時に水素を共存させることがＭ工制御など
の点から一般的とされているが、従来の塩化マグネシウ
ムを担体とし、有機カルボン酸エステルを用いた触媒は
水素共存下では活性および立体規則性が大幅に低下する
という欠点を有していた。しかし、本発明に係る固体触
媒成分を用いて得られた触媒では水素共存下にオレフイ
／の重合を行なった場合、生成重合体のＭ工が極めて高
い場合においても、活性および立体規則性は低下しない
。かかる効果は、当業者にとって強く望まれていたもの
であった。また、工業的なポリオレフィンの製造におい
ては重合装置の能力、後処理工程の能力などの点で生成
重合体の嵩比重が非常に大きな問題となるが、本発明に
係る触媒は、この点においても、極めて優れた特性を有
している。Furthermore, in the production of industrial olefin polymers, it is common to coexist hydrogen during polymerization from the viewpoint of controlling the M process, but using conventional magnesium chloride as a carrier and organic carboxylic acid ester. The catalyst used had the disadvantage that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, in the catalyst obtained using the solid catalyst component according to the present invention, when olefin/olefin polymerization is performed in the coexistence of hydrogen, the activity and stereoregularity decrease even when the M-factor of the resulting polymer is extremely high. do not. Such an effect was strongly desired by those skilled in the art. In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem in terms of the capacity of polymerization equipment, the capacity of post-treatment processes, etc., but the catalyst according to the present invention also has this problem. , has extremely excellent properties.
以下に、本発明を実施例および比較例によりさらに具体
的に説明する。The present invention will be explained in more detail below using Examples and Comparative Examples.
実施例１
（１） （ａ）物質の調製
攪拌機を具備し九容＠Ｚ、Ｏ１の丸底フラスコを用い、
これを窒素ガスで充分に置換した後、金属マグネシウム
粉末３０２、ヨウ素ｔｏ？およびｎ−ブチルクロライド
ｔ２ｔ’ｒ、装入し、ｎ−プチルクロライドの沸点下で
５時間反応させた。反応終了後、上澄液を除去し、生成
物を５００−のｎ−ブチルクロライドで３回洗浄した後
、減圧乾燥して粉末状の物質を得た。Example 1 (1) (a) Preparation of substances Using a 9 volume @Z, O1 round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, metal magnesium powder 302, iodine to? and n-butyl chloride t2t'r were charged and reacted for 5 hours at the boiling point of n-butyl chloride. After the reaction was completed, the supernatant liquid was removed, and the product was washed three times with 500-n-butyl chloride, and then dried under reduced pressure to obtain a powdery substance.
（２） 固体触媒成分の調製
上記（１）で得られた粉末状物質３０Ｆ、ジブチルフタ
ンート１α０−およびＴｉＯ４４＆ Ｑ−を窒素ガス雰
囲気下で、２５瓢φのステンレスボールを全容積の％充
填した容ｉｌｌ １． ＯＬの振動ミルポットに装入し
、振動数１４３０ Ｖ、ｐ、ｌＱ、振幅３．５Ｗｍで２
０時間の共粉砕処理を行なった。(2) Preparation of solid catalyst component A 25-diameter stainless steel ball was filled with the powdered substance 30F obtained in (1) above, dibutyl phthanate 1α0-, and TiO44&Q- in a nitrogen gas atmosphere in % of the total volume. 1. It was charged into a vibrating mill pot of OL, and was heated at a frequency of 1430 V, p, lQ, and an amplitude of 3.5 Wm.
Co-pulverization treatment was carried out for 0 hours.
攪拌機を具備した容１ｓｏｏ−の丸底フラスコを用い、
窒素ガスで充分に置換した後、それに前記共粉砕処理に
よって得られた固体組成物５２をとり、それに、ＴｉＣ
４，３０−およびトルエン７０ＷＬｔを加え、１１５℃
に昇温しで２時間反応させた。反応終了後上澄液を除去
し、生成物に、新たにＴｉＯ４７０Ｍｔおよびトルエン
７〇−を加えて１１５℃で２時間反応させた。反応終了
後、４０℃まで冷却し、生成物をｎ−へブタン１００−
で１０回洗浄し、固体触媒成分を得た。Using a 1 soo-volume round bottom flask equipped with a stirrer,
After sufficient substitution with nitrogen gas, take the solid composition 52 obtained by the co-pulverization treatment, and add TiC to it.
Add 4,30- and toluene 70WLt and heat to 115°C.
The temperature was raised to 1, and the reaction was carried out for 2 hours. After the reaction was completed, the supernatant liquid was removed, and 70 Mt of TiO and 70 - of toluene were newly added to the product, and the mixture was reacted at 115°C for 2 hours. After the reaction was completed, the product was cooled to 40°C and converted into n-hebutane 100-
was washed 10 times to obtain a solid catalyst component.
々お、この際、該固体触媒成分中のチタン含有率を測定
したところ１．９８重量係であった。At this time, the titanium content in the solid catalyst component was measured and found to be 1.98% by weight.
（３） プロピレンの重合
内容積２．０ｔの攪拌装置付オートクレーブを用い、こ
れを窒素ガスで完全に置換した後、トリエチルアルミニ
ウム１９３η、２，２，６．６−テメチルビペリジン２
４ｘｇおよび前記固体触媒成分中〇ηを装入した。その
後、水素ガス１．８ｔ。(3) Polymerization of propylene Using an autoclave with a stirring device and an internal volume of 2.0 t, after completely replacing the autoclave with nitrogen gas, triethylaluminum 193η, 2,2,6.6-temethylbiperidine 2
4xg and 〇η of the solid catalyst components were charged. After that, 1.8 tons of hydrogen gas.
液化プロピレン１．４ｔを装入し、７０℃で１時間重合
反応を行なった。重合反応終了後、生成した重合体ｔ−
８０℃で減圧乾燥し、得られたものの１ｔ−（４）とす
る。またこのものを沸騰ｎ−へブタンで６時間抽出して
ｎ−へブタンに不溶解の重合体を得、このものの役をＣ
Ｂ）とする。1.4 tons of liquefied propylene was charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer t-
The obtained product was dried under reduced pressure at 80° C. and designated as 1t-(4). In addition, this product was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and the role of this product was
B).
使用した固体触媒成分中夛の重合活性（０）を以下の式
で表わす。The polymerization activity (0) of the solid catalyst component used is expressed by the following formula.
また全結晶性重合体の収率（Ｄ）を下記の式で表わす。Further, the yield (D) of the total crystalline polymer is expressed by the following formula.
さらに生成重合体中の残留塩素ｍ ｔ−（ｍ）、生成重
合体のＭｌを（Ｆ）、嵩比重を（Ｇ）で表わし、得られ
た結果を第１表に示す。Further, the residual chlorine m t-(m) in the produced polymer, the Ml of the produced polymer are expressed as (F), and the bulk specific gravity is expressed as (G), and the obtained results are shown in Table 1.
実施列２
重合時間を３０分間としに以外は実施例１と同様にして
実験を行なった。得られた結果は、第１表に示す通りで
ある。Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 30 minutes. The results obtained are shown in Table 1.
実施例３
重合反応を以下の方法で行なった以外は実施列１と同様
にして実験を行なった。Example 3 An experiment was carried out in the same manner as in Example 1, except that the polymerization reaction was carried out in the following manner.
窒素ガスで完全に置換された内容積２．０ｔの攪拌装置
付オートクレーブに、ｎ−へブタン７００ｄｆ装入し、
窒素ガス雰囲気を保ちつつトリエチルアルミニウム３０
１ ｍｇ、２，２．４６−テトラメチルピペリジン３７
岬、次いで実施例１の方法で調製した固体触媒成分ｔ−
１Ｑ、ＯＨ１装入した。その後水素ガス１５０ｄを装入
し７０℃に昇温しでプロピレンガスを導入しつつ、６ゆ
／σ１．０の圧力を維持して１時間、重合反応を行なっ
た。重合反応終了後、得られた固体重合体’ｋＦ別し、
８０℃に加温して減圧乾燥した。700 df of n-hebutane was charged into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which was completely purged with nitrogen gas.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1 mg, 2,2.46-tetramethylpiperidine 37
Misaki, then the solid catalyst component t- prepared by the method of Example 1
1Q, 1 OH was charged. Thereafter, 150 d of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, a polymerization reaction was carried out for 1 hour while maintaining a pressure of 6 Yu/σ1.0. After the completion of the polymerization reaction, the obtained solid polymer was separated by 'kF',
It was heated to 80°C and dried under reduced pressure.
一方、ろ液を凝縮して重合溶媒に溶存する重合体の１ｔ
（６）とし、固体重合体のＲｅ（１）とする。On the other hand, 1 t of polymer dissolved in the polymerization solvent by condensing the filtrate
(6) and the solid polymer Re(1).
また、得られた固体重合体を沸ＪＩＧ ｎ−へブタンで
６時間抽出し、ｎ−へブタンに不溶解の重合体を得、こ
の量を（Ｊ）とする。Further, the obtained solid polymer was extracted with boiling JIG n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (J).
固体触媒成分当りの重合活性（イ）を下記式で表わす。The polymerization activity (a) per solid catalyst component is expressed by the following formula.
また結晶性重合体の収率部）ヲ、下記の式で表わし、 全結晶性重合体の収率〜）を、下記の式で求める。In addition, the yield part of the crystalline polymer) is expressed by the following formula, The yield of total crystalline polymer ~) is determined by the following formula.
さらに生成重合体中の残留塩素を（ト））、生成重合体
のＭｌを（０）、嵩比重を使）で表わす。得られた結果
は第２表に示す通りである。Further, residual chlorine in the produced polymer is expressed as (g)), Ml of the produced polymer is expressed as (0), and bulk specific gravity is used). The results obtained are shown in Table 2.
実施例４
重合時間を２時間にした以外は、実施例３と同様にして
実験を行なった。得られた結果は第２表に示す通りであ
る。Example 4 An experiment was conducted in the same manner as in Example 3, except that the polymerization time was 2 hours. The results obtained are shown in Table 2.
実施例５
ジブチルフタレートの代りに同量のジプロピルフタレー
トを用いた以外は実施列１と同様にして実験を行なった
。なお、この際の固体触媒成分中のチタン含有率は２．
０１重ｉ％であった。Example 5 An experiment was carried out in the same manner as in Example 1 except that the same amount of dipropylphthalate was used instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 2.
It was 01 weight i%.
重合に際しては実施例１と同様にして実験を行なった。During polymerization, an experiment was conducted in the same manner as in Example 1.
得られた結果は第１表に示す通りである。The results obtained are shown in Table 1.
実施例６
ジブチルフタレート１（１０−およびＴ ｉ ０１４＆
ローの代りにジプロピル７タレートＺ５−およびＴｉ０
ｔ、五〇ｄ用いた以外は実施列１と同様にして固体触媒
成分の調製全行なった。なお、この際の固体触媒成分中
のチタン含有率はｔ７７重量係であった。重合に際して
は実′Ｍｆ４例１と同様にして実験を行なった。得られ
た結果は第１表に示す通りである。Example 6 Dibutyl phthalate 1 (10- and T i 014&
Dipropyl 7 tallate Z5- and Ti0 instead of rho
The solid catalyst component was prepared in the same manner as in Example 1 except that t and 50 d were used. Incidentally, the titanium content in the solid catalyst component at this time was t77 weight ratio. The polymerization was conducted in the same manner as in Example 1 of Mf4. The results obtained are shown in Table 1.
第 １ 表
第 ２ 表
なお、従来技術による比較例１および比較列２を以下に
掲げる。Table 1 Table 2 Comparative example 1 and comparison column 2 according to the prior art are listed below.
比較例１
市販のＭｇＯ１２２０ｆ 、ジブチルフタレート５、０
ｇ／を実施８ｉ′ｌＪ１と同様の条件で粉砕する。そ
の後、該粉砕組成物５りを窒素ガス雰囲気下で内容積５
００−のガラス製容器に装入し、Ｔｉ０６４２００−を
加えて１２０ｔ：で２時間攪拌反応を行なった。反応終
了後上澄液を除去し、新たにＴｉ０ｔ４２００−を加え
て１２０℃で２時間反応させた。Comparative Example 1 Commercially available MgO1220f, dibutyl phthalate 5,0
g/ is ground under the same conditions as in Run 8i'lJ1. Thereafter, 5 liters of the pulverized composition was heated to an inner volume of 5 ml under a nitrogen gas atmosphere.
The mixture was placed in a 00-glass container, Ti064200- was added thereto, and a stirring reaction was carried out at 120 t for 2 hours. After the reaction was completed, the supernatant liquid was removed, and Ti0t4200- was newly added and reacted at 120°C for 2 hours.
反応終了後４０℃まで冷却しｎ−へブタン２００−で１
０回洗浄して固体触媒成分とした。After the reaction was completed, it was cooled to 40°C and diluted with 200°C of n-hebutane.
It was washed 0 times to obtain a solid catalyst component.
なお、この際該固体触媒成分中のチタン含有率を測定し
たところ１．６４重′Ｍｋ係であった。At this time, when the titanium content in the solid catalyst component was measured, it was found to be 1.64 weight'Mk.
重合に際しては上記固体触媒成分’に６．Ｏ！使用した
以外は実施例１と同様にして実験を行なった。得られた
結果は第３表に示す通りである。During polymerization, add 6. to the above solid catalyst component'. O! The experiment was conducted in the same manner as in Example 1 except that the following materials were used. The results obtained are shown in Table 3.
比較例２
重合時間を３０分間とした以外は比較例１と同様にして
実験を行なった。得られた結果は第３表に示す通りであ
る。Comparative Example 2 An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization time was 30 minutes. The results obtained are shown in Table 3.
第３表Table 3
第１図は本発明の理解を助けるための模式的図面である
。FIG. 1 is a schematic drawing to help understand the present invention.
Claims (1)
ノハロゲン化物とを溶媒の不存在下、ヨウ素の存在下で
反応させて得られる物質（ａ）、フタル酸のジエステル
（ｂ）および四塩化チタン（ｃ）を共粉砕して得られる
生成物を、常温で液体の芳香族炭化水素又は芳香族ハロ
ゲン化炭化水素の存在下で、さらに、四塩化チタンと接
触させることを特徴とするオレフィン類重合用固体触媒
成分。1. Substance (a) obtained by reacting metallic magnesium powder with at least twice the mole of alkyl monohalide in the absence of a solvent and in the presence of iodine, diester of phthalic acid (b) and titanium tetrachloride ( For polymerization of olefins, the product obtained by co-pulverizing c) is further brought into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon that is liquid at room temperature. Solid catalyst component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24954486A JPH0830092B2 (en) | 1986-10-22 | 1986-10-22 | Solid catalyst component for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24954486A JPH0830092B2 (en) | 1986-10-22 | 1986-10-22 | Solid catalyst component for olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63105007A true JPS63105007A (en) | 1988-05-10 |
| JPH0830092B2 JPH0830092B2 (en) | 1996-03-27 |
Family
ID=17194569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24954486A Expired - Fee Related JPH0830092B2 (en) | 1986-10-22 | 1986-10-22 | Solid catalyst component for olefin polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830092B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0685497A1 (en) | 1994-05-31 | 1995-12-06 | Borealis Holding A/S | Stereospecific catalyst system for polymerisation of olefins |
| US5869418A (en) * | 1994-05-31 | 1999-02-09 | Borealis Holding A/S | Stereospecific catalyst system for polymerization of olefins |
-
1986
- 1986-10-22 JP JP24954486A patent/JPH0830092B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0685497A1 (en) | 1994-05-31 | 1995-12-06 | Borealis Holding A/S | Stereospecific catalyst system for polymerisation of olefins |
| US5869418A (en) * | 1994-05-31 | 1999-02-09 | Borealis Holding A/S | Stereospecific catalyst system for polymerization of olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0830092B2 (en) | 1996-03-27 |
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