JPH06128331A - Production of ethylene copolymer - Google Patents
Production of ethylene copolymerInfo
- Publication number
- JPH06128331A JPH06128331A JP27735592A JP27735592A JPH06128331A JP H06128331 A JPH06128331 A JP H06128331A JP 27735592 A JP27735592 A JP 27735592A JP 27735592 A JP27735592 A JP 27735592A JP H06128331 A JPH06128331 A JP H06128331A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polymerization
- tetrahydrofuran
- polymer
- solid catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001038 ethylene copolymer Polymers 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 42
- 239000011949 solid catalyst Substances 0.000 abstract description 30
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 10
- 150000008282 halocarbons Chemical class 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 7
- 239000002841 Lewis acid Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 150000007517 lewis acids Chemical class 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 28
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 23
- 229910052723 transition metal Inorganic materials 0.000 description 14
- 150000003624 transition metals Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-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
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hexane and heptane Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 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
【０００１】[0001]
【産業上の利用分野】本発明は、エチレンとα−オレフ
ィンとの共重合体に係り、特に新規なチ−グラ−型触媒
系を用いて１２５℃以上の高い温度、２００ｋｇ／ｃｍ
2 以上の高い圧力下でエチレン共重合体を製造する方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer of ethylene and .alpha.-olefin, and in particular, using a novel Ziegler type catalyst system, a high temperature of 125.degree.
The present invention relates to a method for producing an ethylene copolymer under a high pressure of 2 or more.
【０００２】[0002]
【従来の技術】１２５℃以上の温度、２００ｋｇ／ｃｍ
2 以上の圧力でエチレンをチーグラー型触媒の存在下に
重合させる方法は高圧イオン重合と呼ばれ公知である。
上記触媒としては、チタン成分、例えば三塩化チタン、
マグネシウム化合物に担持されたチタン化合物と有機ア
ルミニウム化合物との組み合わせが提案されている
（例、特開昭６１−２０４２０４号公報、同６１−２７
６０８号公報、特開平４−４６９０７等）。得られた重
合体をフィルムやラミネート等の用途で使用する際、優
れた低温ヒートシール性、ホットタック性、透明性が不
可欠である。それらの性質を向上するためにはランダム
性が良く、ＤＳＣ測定により９０〜１１０℃および１１
０〜１３０℃にそれぞれ少なくとも１個の融点を示すこ
とが望ましいが、いずれの系もこの点で不十分である。2. Description of the Related Art Temperature above 125 ° C., 200 kg / cm
A method of polymerizing ethylene at a pressure of 2 or more in the presence of a Ziegler type catalyst is known as high pressure ionic polymerization.
Examples of the catalyst include titanium components such as titanium trichloride,
A combination of a titanium compound supported on a magnesium compound and an organoaluminum compound has been proposed (eg, JP-A-61-204204 and 61-27).
No. 608, JP-A-4-46907). When the obtained polymer is used in applications such as films and laminates, excellent low temperature heat sealability, hot tackiness and transparency are essential. Randomness is good for improving those properties, and it is 90 to 110 ° C. and 11 by DSC measurement.
It is desirable to exhibit at least one melting point at each of 0 to 130 ° C., but any system is insufficient in this respect.
【０００３】[0003]
【発明が解決しようとする課題】かかる現状において本
発明の解決すべき課題は、高温、高圧領域において触媒
残渣の除去が不必要なほど触媒活性が十分に高く、生成
ポリマーのランダム性が良好な触媒系によるエチレンと
α−オレフィンとの共重合体の製造方法を提供すること
にある。Under such circumstances, the problems to be solved by the present invention are that the catalyst activity is sufficiently high so that the removal of the catalyst residue is unnecessary in the high temperature and high pressure region, and the randomness of the produced polymer is good. It is an object of the present invention to provide a method for producing a copolymer of ethylene and α-olefin using a catalyst system.
【０００４】[0004]
【課題を解決するための手段】本発明の課題は、チーグ
ラー型触媒の存在下にエチレンと炭素数３以上のα−オ
レフィンを１２５℃以上の温度、２００ｋｇ／ｃｍ2 以
上の圧力下で高圧イオン重合させる際に、 成分（Ａ） 塩化チタン化合物とテトラヒドロフランか
らなる固体錯体化合物と 成分（Ｂ） 塩化マグネシウムとテトラヒドロフランか
らなる固体錯体化合物の混合物に、 成分（Ｃ） ハロゲン化炭化水素 を加え、成分（Ａ）のみを選択的に溶解した懸濁液を、 成分（Ｄ） ＡｌＲ(3-a) Ｘa （Ｒは炭素原子数１４以
下のアルキル基、Ｘはハロゲン原子であり、ａは１、２
または３である）で表わされるルイス酸性化合物で処理
することによって得られる固体触媒成分と有機アルミニ
ウム化合物からなる触媒系を用いることを特徴とする密
度が０．８９〜０．９３の重合体の示差走査熱分析（Ｄ
ＳＣ）で示される融点が８０〜１１０℃および１１０〜
１３０℃の温度領域にそれぞれ少なくとも１個有するエ
チレン共重合体の製造方法によって解決することができ
る。The object of the present invention is to provide ethylene and an α-olefin having 3 or more carbon atoms in the presence of a Ziegler type catalyst at a temperature of 125 ° C. or more and a pressure of 200 kg / cm 2 or more to obtain high pressure ions. When polymerizing, a component (C) halogenated hydrocarbon is added to a mixture of component (A) a solid complex compound composed of a titanium chloride compound and tetrahydrofuran and component (B) a solid complex compound composed of magnesium chloride and tetrahydrofuran, and a component (C) is added. Component (D) AlR (3-a) X a (R is an alkyl group having 14 or less carbon atoms, X is a halogen atom, and a is 1 or 2)
Or 3), a polymer having a density of 0.89 to 0.93 characterized by using a catalyst system consisting of a solid catalyst component obtained by treatment with a Lewis acidic compound represented by Scanning thermal analysis (D
SC) has a melting point of 80 to 110 ° C. and 110 to 110 ° C.
It can be solved by a method for producing an ethylene copolymer having at least one each in a temperature range of 130 ° C.
【０００５】以下、本発明について具体的に説明する。
成分（Ａ）は塩化チタン化合物とテトラヒドロフランか
らなる固体錯体化合物である。三塩化チタンあるいは四
塩化チタンをテトラヒドロフランに溶解させた後、６０
〜１００℃で加熱処理する。加熱後、過剰のテトラヒド
ロフランを除去し、例えばＴｉＣｌ3 （ＴＨＦ）3 ある
いはＴｉＣｌ4 （ＴＨＦ）2 のような錯体化合物を析出
させることにより得られる。成分（Ｂ）は塩化マグネシ
ウムとテトラヒドロフランからなる固体錯体化合物であ
る。塩化マグネシウムをテトラヒドロフランに溶解させ
た後、６０〜１００℃で加熱処理する。加熱後、過剰の
テトラヒドロフランを除去し、例えばＭｇＣｌ2 （ＴＨ
Ｆ）2 のような錯体化合物を析出させることにより得ら
れる。The present invention will be specifically described below.
The component (A) is a solid complex compound composed of a titanium chloride compound and tetrahydrofuran. After dissolving titanium trichloride or titanium tetrachloride in tetrahydrofuran, 60
Heat treatment at -100 ° C. After heating, excess tetrahydrofuran is removed, and a complex compound such as TiCl 3 (THF) 3 or TiCl 4 (THF) 2 is deposited, for example. The component (B) is a solid complex compound composed of magnesium chloride and tetrahydrofuran. After dissolving magnesium chloride in tetrahydrofuran, it is heat-treated at 60 to 100 ° C. After heating, excess tetrahydrofuran is removed, for example MgCl 2 (TH
It is obtained by depositing a complex compound such as F) 2 .
【０００６】成分（Ｃ）はハロゲン化炭化水素である。
本発明では、ハロゲン化炭化水素が成分（Ａ）を溶解さ
せるが、成分（Ｂ）をほとんど溶解させない性質を利用
するものである。このうち、好ましくはハロゲン原子１
〜４個、炭素数２〜６個からなるハロゲン化炭化水素で
ある。具体例としては１−クロロプロパン、２−クロロ
プロパン、１ークロロブタン、１−クロロペンタン、１
−クロロ−２−メチルプロパン、２−クロロ−２−メチ
ルプロパン、１，２−ジクロロエタン、１，１−ジクロ
ロエタン、１，１，１−トリクロロエタン、１，１，２
−トリクロロエタン、１，１，２，２−テトラクロロエ
タン、１，２，３−トリクロロプロパン、１−クロロ−
２−ブロモエタン、１−クロロ−ヘキサン、１，２−ジ
クロロプロパン等が挙げられる。好ましくは１，２−ジ
クロロエタンが用いられる。Component (C) is a halogenated hydrocarbon.
The present invention utilizes the property that the halogenated hydrocarbon dissolves the component (A) but hardly dissolves the component (B). Of these, preferably a halogen atom 1
It is a halogenated hydrocarbon having 4 to 4 carbon atoms and 2 to 6 carbon atoms. Specific examples include 1-chloropropane, 2-chloropropane, 1-chlorobutane, 1-chloropentane, 1
-Chloro-2-methylpropane, 2-chloro-2-methylpropane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,1-trichloroethane, 1,1,2
-Trichloroethane, 1,1,2,2-tetrachloroethane, 1,2,3-trichloropropane, 1-chloro-
2-Bromoethane, 1-chloro-hexane, 1,2-dichloropropane and the like can be mentioned. Preferably 1,2-dichloroethane is used.
【０００７】成分（Ｄ）はＡｌＲ(3-a) Ｘa （Ｒは炭素
原子数１４以下のアルキル基、Ｘはハロゲン原子であ
り、ａは１、２または３である）で表わされるルイス酸
性を示す有機アルミニウム化合物である。具体例とし
て、ジメチルアルミニウムクロライド、ジエチルアルミ
ニウムクロライド、ジエチルアルミニウムセスキクロラ
イド、エチルアルミニウムジクロライド、ジエチルアル
ミニウムブロマイド、ジイソブチルアルミニムクロライ
ド、ジヘキシルアルミニウムクロライド、三塩化アルミ
ニム等が挙げられる。Component (D) is a Lewis acid represented by AlR (3-a) X a (R is an alkyl group having 14 or less carbon atoms, X is a halogen atom, and a is 1, 2 or 3). Is an organoaluminum compound. Specific examples include dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, diisobutyl aluminum chloride, dihexyl aluminum chloride, aluminum trichloride and the like.
【０００８】成分（Ａ）と成分（Ｂ）を成分（Ｃ）中で
４０〜１００℃で反応させ、成分（Ａ）は溶解するが成
分（Ｂ）は溶解しない懸濁液を得る。得られた懸濁液に
ルイス酸性化合物である成分（Ｄ）を４０〜１００℃で
０．５〜１０時間反応させる。成分（Ｄ）の使用量は懸
濁液中のチタンおよびマグネシウムの総モル数の１〜１
０倍モル、好ましくは３〜５倍モルである。得られる固
体触媒成分を不活性炭化水素溶媒で洗浄する。不活性炭
化水素溶媒の具体例としてはヘキサン、ヘプタン等の脂
肪族炭化水素またはトルエン等の芳香族炭化水素が挙げ
られる。固体触媒成分中のＴｉ含有量が０．１〜１０、
好ましくは１〜３重量％、ＴＨＦ含有量が０〜２０、好
ましくは１０重量％以下に制御することで良好な共重合
性を発現することができる。得られた固体触媒成分は、
各種の有機アルミニウム、ヘキセン−１、有機溶媒を用
いて、予め予重合して使用することもできる。Component (A) and component (B) are reacted in component (C) at 40 to 100 ° C. to obtain a suspension in which component (A) is dissolved but component (B) is not dissolved. Component (D), which is a Lewis acidic compound, is reacted with the obtained suspension at 40 to 100 ° C. for 0.5 to 10 hours. The amount of component (D) used is 1 to 1 of the total number of moles of titanium and magnesium in the suspension.
The molar ratio is 0 times, preferably 3 to 5 times. The solid catalyst component obtained is washed with an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as toluene. Ti content in the solid catalyst component is 0.1 to 10,
A good copolymerizability can be exhibited by controlling the content to be preferably 1 to 3% by weight and the THF content to be 0 to 20 and preferably 10% by weight or less. The solid catalyst component obtained is
It can also be used by preliminarily prepolymerizing with various kinds of organic aluminum, hexene-1, and an organic solvent.
【０００９】本発明における重合条件は、重合温度が１
２５℃以上、好ましくは１５０〜２５０℃である。重合
圧力は２００ｋｇ／ｃｍ2 以上、好ましくは５００〜３
０００ｋｇ／ｃｍ2 である。重合系内でのモノマーの平
均滞留時間は２〜１８０秒、好ましくは１０〜１００秒
である。装置としては撹拌式槽型反応器が使用される。
重合形式としてはバッチ式、連続式いずれも可能である
が連続式で行う方が好ましい。重合は単一領域でも行わ
れるが、１つの反応器を複数の反応領域に区切って行う
かあるいは複数個の反応器を直列または並列に連結して
行うこともできる。複数反応領域あるいは複数反応器で
重合させる方法では、各反応帯域ごとに温度、圧力、ガ
ス組成を変えることにより特性の違った共重合体を生産
することも可能である。重合時に助触媒として用いる有
機アルミニウム化合物の具体例としては、トリメチルア
ルミニウム、トリエチルアルミニウム、トリイソブチル
アルミニウム、トリオクチルアルミニウム、ジエチルア
ルミニウムクロライド、ジエチルアルミニウムセスキク
ロライド、メチルアルミノキサン、エチルアルミノキサ
ン等が挙げられるが、トリイソブチルアルミニウムが特
に好ましい。The polymerization condition in the present invention is that the polymerization temperature is 1
The temperature is 25 ° C or higher, preferably 150 to 250 ° C. Polymerization pressure is 200 kg / cm 2 or more, preferably 500 to 3
It is 000 kg / cm 2 . The average residence time of the monomer in the polymerization system is 2 to 180 seconds, preferably 10 to 100 seconds. A stirred tank reactor is used as the device.
The polymerization system may be either batch system or continuous system, but continuous system is preferred. The polymerization is carried out in a single zone, but it is also possible to divide one reactor into a plurality of reaction zones or to connect a plurality of reactors in series or in parallel. In the method of polymerizing in a plurality of reaction zones or a plurality of reactors, it is also possible to produce copolymers having different characteristics by changing the temperature, pressure and gas composition for each reaction zone. Specific examples of the organoaluminum compound used as a cocatalyst at the time of polymerization include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, methylaluminoxane, ethylaluminoxane, and the like. Isobutylaluminum is particularly preferred.
【００１０】本発明に係るエチレンとα−オレフィンか
らなる共重合体はメルトフロ−レ−ト（ＭＦＲ）が０．
０１〜１００ｇ／10分、好ましくは０．０５〜５０ｇ／
10分である。密度は０．８９〜０．９３ｇ／ｃｍ3 であ
る。本発明に係るエチレンとα−オレフィンからなる共
重合体を１０℃／分で２００℃まで昇温し融解した後、
１０℃／分の降温速度で２５℃まで冷却し結晶化させ、
再度１０℃／分で１８０℃まで昇温した際に得られるＤ
ＳＣパターンは８０〜１１０℃および１１０〜１３０℃
の温度領域にそれぞれ少なくとも１個の融点ピークを示
す。このようにＤＳＣパターンが複数個の融点ピークを
示す共重合体はランダム性が良く、フィルムやラミネー
ト等の用途に関して低温ヒートシール性、ホットタック
性、透明性に優れる。The copolymer of ethylene and α-olefin according to the present invention has a melt flow rate (MFR) of 0.
01 to 100 g / 10 minutes, preferably 0.05 to 50 g /
10 minutes. The density is 0.89 to 0.93 g / cm 3 . After the copolymer of ethylene and α-olefin according to the present invention is heated to 200 ° C. at 10 ° C./min and melted,
At a temperature decreasing rate of 10 ° C / min, it is cooled to 25 ° C for crystallization,
D obtained when the temperature was raised again to 180 ° C at 10 ° C / minute
SC pattern is 80-110 ° C and 110-130 ° C
At least one melting point peak is shown in each of the temperature regions of. Thus, the copolymer showing a plurality of melting point peaks in the DSC pattern has good randomness and is excellent in low-temperature heat-sealing property, hot-tack property and transparency in applications such as films and laminates.
【００１１】[0011]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれら実施例に限定されるものではない。
尚、実施例における重合体の性質は、下記の方法により
測定した。 （１）メルトフローレート（ＭＦＲ）はASTM D 1238 に
従い測定した。 （２）密度はJIS K 6760に規定された方法により測定し
た。 （３）示差走査熱分析（ＤＳＣ）はPERKIN-ELMER社製Ｄ
ＳＣ−７を用いた。 完全融解後、徐冷した後に昇温サーモグラムを測定し
た。熱プレスにより作成した厚さ０．５ｍｍのシートか
ら切りだした約２ｍｇのサンプルを用い、１０℃／分で
２００℃まで昇温し、５分間保持した後、１０℃／分の
降温速度にて２５℃まで冷却する。５分間保持した後、
１０℃／分で１８０℃まで昇温しサーモグラムを得る。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The properties of the polymers in the examples were measured by the following methods. (1) Melt flow rate (MFR) was measured according to ASTM D1238. (2) Density was measured by the method specified in JIS K 6760. (3) Differential scanning calorimetry (DSC) is PEKIN-ELMER D
SC-7 was used. After complete melting and slow cooling, the temperature rising thermogram was measured. Using a sample of about 2 mg cut out from a 0.5 mm-thick sheet prepared by hot pressing, the temperature was raised to 200 ° C. at 10 ° C./min, held for 5 minutes, and then at a temperature lowering rate of 10 ° C./min. Cool to 25 ° C. After holding for 5 minutes,
The temperature is raised to 180 ° C at 10 ° C / minute to obtain a thermogram.
【００１２】（実施例１） （１）固体触媒成分の調製 窒素雰囲気下、無水塩化マグネシウム４３ｇおよび三塩
化チタンと塩化アルミニウムの共晶体（ＴｉＣｌ3 ・１
／３ＡｌＣｌ3 ）１０ｇをテトラヒドロフラン６６０ｍ
ｌに溶解し、８０℃で２時間加熱還流を行った。還流
後、過剰のテトラヒドロフランを除去することで塩化マ
グネシウムと三塩化チタンのテトラヒドロフラン錯体を
得た。固体錯体成分を１，２−ジクロロエタン８００ｍ
ｌ中、７０℃で３０分間加熱撹拌し、三塩化チタンのテ
トラヒドロフラン錯体のみを溶解し、次いでエチルアル
ミニウムジクロライドの１モル／ｌヘキサン溶液１５０
０ｍｌを加え、９０℃で２時間加熱還流を行い、固体触
媒成分を析出させた。得られた固体触媒成分を濾別し、
ｎ−ヘキサンで洗浄した。 （２）重合 内容積４l の撹拌式槽型反応器に、エチレンを２０ｋｇ
／hrの割合で連続的に供給し、エチレンとともにヘキセ
ン−１を８０重量％の割合で供給する。９００ｋｇ／ｃ
ｍ2 まで昇圧し、２００℃に加熱後、固体触媒のトルエ
ンスラリーを１l ／hrの割合で連続的に供給し、同時に
１０重量％のトリエチルアルミニウムをＡｌ／Ｔｉ比が
約５０になるように供給することでエチレンとヘキセン
−１の共重合を行った。滞留時間は約１００秒で行っ
た。重合の結果、遷移金属１ｇ当たり３２５，０００ｇ
の重合体が得られ、活性は十分に高い。得られた重合体
のＭＦＲは１．２（ｇ／１０分）、密度は０．９１７
（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラムより１０
８．７、１１９．４、１２１．９℃に融点ピークを示し
た。[0012] (Example 1) (1) Under Preparation nitrogen atmosphere the solid catalyst component, anhydrous magnesium chloride 43g and titanium trichloride and aluminum chloride eutectic (TiCl 3 · 1
/ 3AlCl 3 ) 10 g of tetrahydrofuran 660 m
It was dissolved in 1 and heated to reflux at 80 ° C. for 2 hours. After refluxing, excess tetrahydrofuran was removed to obtain a tetrahydrofuran complex of magnesium chloride and titanium trichloride. 1,2-dichloroethane 800m solid complex component
In 1 l, it is heated and stirred at 70 ° C. for 30 minutes to dissolve only the tetrahydrofuran complex of titanium trichloride, and then a 1 mol / l hexane solution of ethylaluminum dichloride 150
0 ml was added and the mixture was heated under reflux at 90 ° C. for 2 hours to precipitate a solid catalyst component. The resulting solid catalyst component is filtered off,
It was washed with n-hexane. (2) Polymerization 20 kg of ethylene was added to a stirred tank reactor with an internal volume of 4 liters.
It is continuously supplied at a rate of / hr, and hexene-1 is supplied together with ethylene at a rate of 80% by weight. 900 kg / c
After pressurizing to m 2 and heating to 200 ° C., toluene slurry of solid catalyst is continuously supplied at a rate of 1 l / hr, and at the same time 10% by weight of triethylaluminum is supplied so that the Al / Ti ratio becomes about 50. By doing so, copolymerization of ethylene and hexene-1 was performed. The residence time was about 100 seconds. As a result of polymerization, 325,000 g per 1 g of transition metal
The polymer is obtained and the activity is sufficiently high. The polymer obtained had an MFR of 1.2 (g / 10 minutes) and a density of 0.917.
(G / cm 3 ). 10 from DSC thermogram
Melting point peaks were shown at 8.7, 119.4 and 121.9 ° C.
【００１３】（実施例２） （１）固体触媒成分の調製 実施例１において、ハロゲン化炭化水素に１−クロロブ
タンを用いた以外は実施例１と同様に調製を行った。 （２）重合 重合は実施例１と同様に行った。重合の結果、遷移金属
１ｇ当たり３１０，０００ｇの重合体が得られた。得ら
れた重合体のＭＦＲは１．３（ｇ／１０分）、密度は
０．９１８（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラ
ムより１０６．３、１１９．４、１２１．９℃に融点ピ
ークを示した。(Example 2) (1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 except that 1-chlorobutane was used as the halogenated hydrocarbon. (2) Polymerization Polymerization was performed in the same manner as in Example 1. As a result of the polymerization, 310,000 g of a polymer was obtained per 1 g of the transition metal. The polymer obtained had an MFR of 1.3 (g / 10 min) and a density of 0.918 (g / cm 3 ). From the DSC thermogram, melting point peaks were shown at 106.3, 119.4, and 121.9 ° C.
【００１４】（実施例３） （１）固体触媒成分の調製 実施例１において、ルイス酸に三塩化アルミニウムの１
３５ｇを用いた以外は実施例１と同様に調製を行った。 （２）重合 重合は実施例１と同様に行った。重合の結果、遷移金属
１ｇ当たり２６０，０００ｇの重合体が得られた。得ら
れた重合体のＭＦＲは２．０（ｇ／１０分）、密度は
０．９１８（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラ
ムより１０７．８、１１９．７、１２２．０℃に融点ピ
ークを示した。(Example 3) (1) Preparation of solid catalyst component In Example 1, Lewis acid was mixed with aluminum trichloride of 1: 1.
Preparation was performed in the same manner as in Example 1 except that 35 g was used. (2) Polymerization Polymerization was performed in the same manner as in Example 1. As a result of the polymerization, 260,000 g of a polymer was obtained per 1 g of the transition metal. The polymer obtained had an MFR of 2.0 (g / 10 minutes) and a density of 0.918 (g / cm 3 ). From the DSC thermogram, melting point peaks were shown at 107.8, 119.7 and 122.0 ° C.
【００１５】（実施例４） （１）固体触媒成分の調製 実施例１において、ルイス酸にエチルアルミニウムセス
キクロライドの１モル／ｌヘキサン溶液１５００ｍｌを
用いた以外は実施例１と同様に調製した。 （２）重合 重合は実施例１と同様に行った。重合の結果、遷移金属
１ｇ当たり２８０，０００ｇの重合体が得られた。得ら
れた重合体のＭＦＲは２．２（ｇ／１０分）、密度は
０．９１６（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラ
ムより１０６．８、１１８．８、１２０．９℃に融点ピ
ークを示した。(Example 4) (1) Preparation of solid catalyst component A catalyst was prepared in the same manner as in Example 1 except that 1500 ml of a 1 mol / l hexane solution of ethylaluminum sesquichloride was used as the Lewis acid. (2) Polymerization Polymerization was performed in the same manner as in Example 1. As a result of the polymerization, 280,000 g of a polymer was obtained per 1 g of the transition metal. The polymer obtained had an MFR of 2.2 (g / 10 min) and a density of 0.916 (g / cm 3 ). From the DSC thermogram, melting point peaks were shown at 106.8, 118.8 and 120.9 ° C.
【００１６】（実施例５） （１）固体触媒成分の調製 実施例１において、ルイス酸にジエチルアルミニウムク
ロライドの１モル／ｌヘキサン溶液１５００ｍｌを用い
た以外は実施例１と同様に調製した。 （２）重合 重合は実施例１と同様に行った。重合の結果、遷移金属
１ｇ当たり２５０，０００ｇの重合体が得られた。得ら
れた重合体のＭＦＲは２．７（ｇ／１０分）、密度は
０．９１６（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラ
ムより１０７．２、１１９．０、１２１．１℃に融点ピ
ークを示した。(Example 5) (1) Preparation of solid catalyst component It was prepared in the same manner as in Example 1 except that 1500 ml of a 1 mol / l hexane solution of diethylaluminum chloride was used as the Lewis acid. (2) Polymerization Polymerization was performed in the same manner as in Example 1. As a result of the polymerization, 250,000 g of a polymer was obtained per 1 g of the transition metal. The MFR of the obtained polymer was 2.7 (g / 10 minutes) and the density was 0.916 (g / cm 3 ). From the DSC thermogram, melting point peaks were shown at 107.2, 119.0, and 121.1 ° C.
【００１７】（実施例６）実施例１において、重合温度
を１６０℃とした以外は実施例１と同様に重合を行っ
た。重合の結果、遷移金属１ｇ当たり３５５，０００ｇ
の重合体が得られた。得られた重合体のＭＦＲは４．８
（ｇ／１０分）、密度は０．９１８（ｇ／ｃｍ3 ）であ
った。ＤＳＣサーモグラムより１０８．４、１２０．
２、１２２．０℃に融点ピークを示した。(Example 6) Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 160 ° C. As a result of polymerization, 355,000 g per 1 g of transition metal
Was obtained. The MFR of the obtained polymer was 4.8.
(G / 10 minutes) and the density was 0.918 (g / cm 3 ). From the DSC thermogram, 108.4, 120.
A melting point peak was found at 2,122.0 ° C.
【００１８】（実施例７）実施例１において、重合温度
を２４０℃とした以外は実施例１と同様に重合を行っ
た。重合の結果、遷移金属１ｇ当たり３０７，０００ｇ
の重合体が得られた。得られた重合体のＭＦＲは１．７
（ｇ／１０分）、密度は０．９１８（ｇ／ｃｍ3 ）であ
った。ＤＳＣサーモグラムより１０５．１、１１９．
０、１２１．８℃に融点ピークを示した。Example 7 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 240 ° C. As a result of polymerization, 307,000 g per 1 g of transition metal
Was obtained. The MFR of the obtained polymer was 1.7.
(G / 10 minutes) and the density was 0.918 (g / cm 3 ). From DSC thermogram 105.1, 119.
It showed a melting point peak at 0, 121.8 ° C.
【００１９】（実施例８）実施例１において、コモノマ
ーにブテン−１を用いた以外は実施例１と同様に重合を
行った。重合の結果、遷移金属１ｇ当たり３４４，００
０ｇの重合体が得られた。得られた重合体のＭＦＲは
２．４（ｇ／１０分）、密度は０．９２０（ｇ／ｃｍ
3 ）であった。ＤＳＣサーモグラムより１０８．４、１
２０．２、１２２．６℃に融点ピークを示した。(Example 8) Polymerization was carried out in the same manner as in Example 1 except that butene-1 was used as the comonomer. As a result of the polymerization, 344,00 per 1 g of transition metal
0 g of polymer was obtained. The polymer obtained had an MFR of 2.4 (g / 10 minutes) and a density of 0.920 (g / cm).
3 ) was. 108.4, 1 from DSC thermogram
Melting point peaks were shown at 20.2 and 122.6 ° C.
【００２０】（比較例１） （１）固体触媒成分の調製 窒素雰囲気下、無水塩化マグネシウム４３ｇおよび三塩
化チタンと塩化アルミニウムの共晶体（ＴｉＣｌ3 ・１
／３ＡｌＣｌ3 ）１０ｇを１，２−ジクロロエタン８０
０ｍｌ中、７０℃で３０分間加熱撹拌し、エチルアルミ
ニウムジクロライドの１モル／ｌヘキサン溶液１５００
ｍｌを加え、９０℃で２時間加熱還流を行った。得られ
た固体触媒成分を濾別し、ｎ−ヘキサンで洗浄した。 （２）重合 上記（１）で得られた固体触媒成分を用いた以外は実施
例１と同様に重合を行った。結果を表１に示す。重合の
結果、遷移金属１ｇ当たり７７，０００ｇの重合体が得
られた。得られた重合体のＭＦＲは０．９（ｇ／１０
分）、密度は０．９２３（ｇ／ｃｍ3 ）であった。ＤＳ
Ｃサーモグラムより１２３．３℃に融点ピークを示し
た。表１より、塩化マグネシウムおよび三塩化チタンの
ＴＨＦ錯体を経由しない系では触媒活性が低く、ＤＳＣ
の融点ピークは１個のみである。[0020] (Comparative Example 1) (1) Under Preparation nitrogen atmosphere the solid catalyst component, anhydrous magnesium chloride 43g and titanium trichloride and aluminum chloride eutectic (TiCl 3 · 1
/ 3AlCl 3 ) 10 g of 1,2-dichloroethane 80
In 0 ml, the mixture was heated and stirred at 70 ° C. for 30 minutes, and a 1 mol / l hexane solution of ethylaluminum dichloride 1500 was added.
ml was added, and the mixture was heated under reflux at 90 ° C. for 2 hours. The solid catalyst component obtained was filtered off and washed with n-hexane. (2) Polymerization Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component obtained in (1) above was used. The results are shown in Table 1. As a result of the polymerization, 77,000 g of a polymer was obtained per 1 g of the transition metal. The MFR of the obtained polymer was 0.9 (g / 10
Min) and the density was 0.923 (g / cm 3 ). DS
From the C thermogram, a melting point peak was found at 123.3 ° C. Table 1 shows that the catalyst activity is low in the system which does not pass through the THF complex of magnesium chloride and titanium trichloride, and DSC
Has only one melting point peak.
【００２１】（比較例２） （１）固体触媒成分の調製 実施例１において１，２−ジクロロエタンの代わりにト
ルエンを用いた以外は実施例１と同様に調製した。 （２）重合 上記（１）で得られた固体触媒成分を用いた以外は実施
例１と同様に重合を行った。重合の結果、遷移金属１ｇ
当たり５７，０００ｇの重合体が得られた。得られた重
合体のＭＦＲは３．６（ｇ／１０分）、密度は０．９２
１（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラムより１
２２．５℃に融点ピークを示した。表１より、反応溶媒
にトルエンを用いた場合、触媒活性が低く、ＤＳＣの融
点ピークは１個のみである。Comparative Example 2 (1) Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as in Example 1 except that toluene was used instead of 1,2-dichloroethane. (2) Polymerization Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component obtained in (1) above was used. As a result of polymerization, 1 g of transition metal
57,000 g of polymer were obtained per hour. The polymer obtained had an MFR of 3.6 (g / 10 minutes) and a density of 0.92.
It was 1 (g / cm 3 ). 1 from DSC thermogram
It showed a melting point peak at 22.5 ° C. From Table 1, when toluene is used as the reaction solvent, the catalytic activity is low, and the melting point peak of DSC is only one.
【００２２】（比較例３） （１）固体触媒成分の調製 実施例１において、１，２−ジクロロエタンの代わりに
ヘキサンを用いた以外は実施例１と同様に調製した。 （２）重合 上記（１）で得られた固体触媒成分を用いた以外は実施
例１と同様に重合を行った。重合の結果、遷移金属１ｇ
当たり４８，０００ｇの重合体が得られた。得られた重
合体のＭＦＲは２．８（ｇ／１０分）、密度は０．９２
２（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラムより１
２２．６℃に融点ピークを示した。表１より、反応溶媒
にヘキサンを用いた場合、触媒活性が低く、ＤＳＣの融
点ピークは１個のみである。Comparative Example 3 (1) Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as in Example 1 except that hexane was used instead of 1,2-dichloroethane. (2) Polymerization Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component obtained in (1) above was used. As a result of polymerization, 1 g of transition metal
48,000 g of polymer were obtained per unit. The polymer obtained had an MFR of 2.8 (g / 10 minutes) and a density of 0.92.
It was 2 (g / cm 3 ). 1 from DSC thermogram
It showed a melting point peak at 22.6 ° C. From Table 1, when hexane is used as the reaction solvent, the catalytic activity is low, and the melting point peak of DSC is only one.
【００２３】（比較例４） （１）固体触媒成分の調製 実施例１において、１，２−ジクロロエタンの代わりに
ヘプタンを用いた以外は実施例１と同様に調製した。 （２）重合 上記（１）で得られた固体触媒成分を用いた以外は実施
例１と同様に重合を行った。重合の結果、遷移金属１ｇ
当たり５２，０００ｇの重合体が得られた。得られた重
合体のＭＦＲは２．０（ｇ／１０分）、密度は０．９２
３（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラムより１
２２．９℃に融点ピークを示した。表１より、反応溶媒
にヘプタンを用いた場合、触媒活性が低く、ＤＳＣの融
点ピークは１個のみである。Comparative Example 4 (1) Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as in Example 1 except that heptane was used in place of 1,2-dichloroethane. (2) Polymerization Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component obtained in (1) above was used. As a result of polymerization, transition metal 1g
52,000 g of polymer were obtained per unit. The polymer obtained had an MFR of 2.0 (g / 10 minutes) and a density of 0.92.
It was 3 (g / cm 3 ). 1 from DSC thermogram
It showed a melting point peak at 22.9 ° C. From Table 1, when heptane is used as the reaction solvent, the catalytic activity is low, and the melting point peak of DSC is only one.
【００２４】（比較例５） （１）固体触媒成分の調製 窒素雰囲気下、無水塩化マグネシウム４３ｇおよび三塩
化チタンと塩化アルミニウムの共晶体（ＴｉＣｌ3 ・１
／３ＡｌＣｌ3 ）１０ｇをテトラヒドロフラン６６０ｍ
ｌに溶解し、８０℃で２時間加熱還流を行った。還流
後、過剰のテトラヒドロフランを除去することで塩化マ
グネシウムと三塩化チタンのテトラヒドロフラン錯体を
得た。固体錯体成分を１，２−ジクロロエタン８００ｍ
ｌ中、９０℃で２時間加熱撹拌した後、減圧乾燥するこ
とで固体触媒成分を得た。得られた固体触媒成分をヘキ
サンで洗浄した。 （２）重合 上記（１）で得られた固体触媒成分を用いた以外は実施
例１と同様に重合を行った。重合の結果、遷移金属１ｇ
当たり２４，０００ｇの重合体が得られた。得られた重
合体のＭＦＲは１．７（ｇ／１０分）、密度は０．９２
５（ｇ／ｃｍ3 ）であった。ＤＳＣサーモグラムより１
２３．４℃に融点ピークを示した。表１より、ルイス酸
処理を行わない場合、触媒活性が低く、ＤＳＣの融点ピ
ークは１個のみである。[0024] (Comparative Example 5) (1) Under Preparation nitrogen atmosphere the solid catalyst component, anhydrous magnesium chloride 43g and titanium trichloride and aluminum chloride eutectic (TiCl 3 · 1
/ 3AlCl 3 ) 10 g of tetrahydrofuran 660 m
It was dissolved in 1 and heated to reflux at 80 ° C. for 2 hours. After refluxing, excess tetrahydrofuran was removed to obtain a tetrahydrofuran complex of magnesium chloride and titanium trichloride. 1,2-dichloroethane 800m solid complex component
After heating and stirring in 90 ° C. for 2 hours at 90 ° C., the solid catalyst component was obtained by drying under reduced pressure. The obtained solid catalyst component was washed with hexane. (2) Polymerization Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component obtained in (1) above was used. As a result of polymerization, 1 g of transition metal
24,000 g of polymer were obtained per hour. The polymer obtained had an MFR of 1.7 (g / 10 minutes) and a density of 0.92.
It was 5 (g / cm 3 ). 1 from DSC thermogram
It showed a melting point peak at 23.4 ° C. From Table 1, when the Lewis acid treatment is not carried out, the catalyst activity is low and the melting point peak of DSC is only one.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明によれば、１２５℃以上の温度、
２００ｋｇ／ｃｍ2 以上の圧力下でエチレンの共重合体
を製造する方法において、遷移金属当たりの触媒活性が
高いことにより、生成する共重合体中の触媒残渣が少な
く、触媒除去工程を必要としない。さらに、生成共重合
体のランダム性が良好なため、フィルムやラミネート等
の用途で使用する際、低温ヒートシール性、ホットタッ
ク性および透明性に優れている。According to the present invention, a temperature of 125 ° C. or higher,
In the method for producing an ethylene copolymer under a pressure of 200 kg / cm 2 or more, since the catalyst activity per transition metal is high, the catalyst residue in the produced copolymer is small and the catalyst removal step is not required. . Furthermore, since the produced copolymer has good randomness, it is excellent in low-temperature heat-sealing property, hot-tack property and transparency when used in applications such as films and laminates.
【図１】本発明の理解を助けるためのフローチャート図
である。FIG. 1 is a flow chart diagram to assist in understanding the present invention.
Claims (1)
炭素数３以上のα−オレフィンを１２５℃以上の温度、
２００ｋｇ／ｃｍ2 以上の圧力下で高圧イオン重合させ
る際に、 成分（Ａ） 塩化チタン化合物とテトラヒドロフランか
らなる固体錯体化合物と 成分（Ｂ） 塩化マグネシウムとテトラヒドロフランか
らなる固体錯体化合物の混合物に、 成分（Ｃ） ハロゲン化炭化水素 を加え、成分（Ａ）のみを選択的に溶解した懸濁液を、 成分（Ｄ） ＡｌＲ(3-a) Ｘa （Ｒは炭素原子数１４以
下のアルキル基、Ｘはハロゲン原子であり、ａは１、２
または３である）で表わされるルイス酸性化合物で処理
することによって得られる固体触媒成分と有機アルミニ
ウム化合物からなる触媒系を用いることを特徴とする密
度が０．８９〜０．９３の重合体の示差走査熱分析（Ｄ
ＳＣ）で示される融点が８０〜１１０℃および１１０〜
１３０℃の温度領域にそれぞれ少なくとも１個有するエ
チレン共重合体の製造方法。1. Ethylene and an α-olefin having 3 or more carbon atoms at a temperature of 125 ° C. or more in the presence of a Ziegler type catalyst,
When high-pressure ionic polymerization is performed under a pressure of 200 kg / cm 2 or more, a mixture of a component (A) a solid complex compound composed of a titanium chloride compound and tetrahydrofuran and a component (B) a solid complex compound composed of magnesium chloride and tetrahydrofuran is added to the component ( C) A suspension in which a halogenated hydrocarbon is added and only component (A) is selectively dissolved is prepared as component (D) AlR (3-a) X a (R is an alkyl group having 14 or less carbon atoms, X Is a halogen atom and a is 1, 2
Or 3), a polymer having a density of 0.89 to 0.93 characterized by using a catalyst system consisting of a solid catalyst component obtained by treatment with a Lewis acidic compound represented by Scanning thermal analysis (D
SC) has a melting point of 80 to 110 ° C. and 110 to 110 ° C.
A method for producing an ethylene copolymer having at least one each in a temperature range of 130 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27735592A JPH06128331A (en) | 1992-10-15 | 1992-10-15 | Production of ethylene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27735592A JPH06128331A (en) | 1992-10-15 | 1992-10-15 | Production of ethylene copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06128331A true JPH06128331A (en) | 1994-05-10 |
Family
ID=17582374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27735592A Pending JPH06128331A (en) | 1992-10-15 | 1992-10-15 | Production of ethylene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06128331A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075203A1 (en) * | 1999-06-07 | 2000-12-14 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
| WO2000075202A1 (en) * | 1999-06-07 | 2000-12-14 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
-
1992
- 1992-10-15 JP JP27735592A patent/JPH06128331A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075203A1 (en) * | 1999-06-07 | 2000-12-14 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
| WO2000075202A1 (en) * | 1999-06-07 | 2000-12-14 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
| JP2003501526A (en) * | 1999-06-07 | 2003-01-14 | イーストマン ケミカル カンパニー | Method for producing ethylene / olefin copolymer |
| JP2011017030A (en) * | 1999-06-07 | 2011-01-27 | Westlake Longview Corp | Method for producing ethylene/olefin interpolymer |
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