JPS6251285B2 - - Google Patents
Info
- Publication number
- JPS6251285B2 JPS6251285B2 JP55085151A JP8515180A JPS6251285B2 JP S6251285 B2 JPS6251285 B2 JP S6251285B2 JP 55085151 A JP55085151 A JP 55085151A JP 8515180 A JP8515180 A JP 8515180A JP S6251285 B2 JPS6251285 B2 JP S6251285B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- mmol
- titanium
- polyethylene
- magnesium
- 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.)
- Expired
Links
- -1 polyethylene Polymers 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 41
- 239000004698 Polyethylene Substances 0.000 claims description 33
- 229920000573 polyethylene Polymers 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000012265 solid product Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
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ã¬ã³ãå¹çãã補é ããæ¹æ³ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyethylene, and more particularly to a method for efficiently producing polyethylene with a wide molecular weight distribution using a specific catalyst.
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ã®åºããã®ãæãŸããŠããã Generally, polyethylene is widely used as an excellent synthetic resin in various fields, but polyethylene with a wide molecular weight distribution is desired from the viewpoint of moldability and physical properties of molded products.
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ãã By the way, as a catalyst for producing polyethylene,
It is known that a magnesium compound supported by reacting a titanium halide has higher activity than a simple Ziegler catalyst. However, in conventional production methods, when attempting to widen the molecular weight distribution of polyethylene, the catalyst activity decreases, resulting in lower production efficiency and the need for a large amount of catalyst, so a step is required to remove the catalyst from the resulting polyethylene. There were drawbacks such as having to do it.
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ãã The present inventors have conducted extensive research to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method for producing polyethylene with a wide molecular weight distribution using a highly active catalyst. As a result, the inventors discovered that the object could be achieved by using a solid product obtained by a specific treatment as a component of the catalyst, leading to the completion of the present invention.
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æ³ãæäŸãããã®ã§ããã That is, the present invention provides a solid content produced by reacting a compound containing at least titanium, magnesium, and halogen with tetraalkoxyzirconium and/or zirconium tetrahalide, which has the general formula Ti(OR 1 ) o X 1 4-o ( In the formula, R 1 is an alkyl group, X 1 is a halogen atom, and n is 0
âŠn<4. The present invention provides a method for producing polyethylene, which is characterized by using a solid product obtained by reacting a halogen-containing titanium compound represented by B) and a catalyst containing an organoaluminum compound B as an active ingredient.
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CH3OSiCl3ïŒïŒCH3OïŒ2SiCl2ïŒïŒCH3OïŒ3SiClïŒSi
ïŒOCH3ïŒ4ïŒC2H5OSiCl3ïŒïŒC2H5OïŒ2SiCl2ïŒ
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ããããšãå¯èœã§ããã The catalyst used in the method of the present invention is prepared from the above-mentioned components A and B, and among these, the compound containing at least titanium, magnesium, and halogen, which is the base of the solid product that is component A, is particularly You can think of various things without being limited. Specifically, the following can be cited as suitable examples. That is,
Solid substances obtained by reacting titanium halides with magnesium inorganic compounds such as magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, and magnesium halides, or by reacting various magnesium compounds with silicon halides,
Examples include solid substances obtained by reacting alcohol and titanium halide in sequence, and solid substances obtained by reacting dialkoxymagnesium such as magnesium diethoxide with magnesium sulfate and titanium halide. In addition, silicon halides or organosilicon compounds (e.g. SiCl 4 ,
CH3OSiCl3 , ( CH3O ) 2SiCl2 , ( CH3O ) 3SiCl ,Si
(OCH 3 ) 4 , C 2 H 5 OSiCl 3 , (C 2 H 5 O) 2 SiCl 2 ,
(C 2 H 5 O) 3 SiCl, Si(OC 2 H 5 ) 4 , etc.) and a solid material obtained by reacting titanium halides can also be used, and in addition, dialkoxymagnesium and MgCl 2.6C 2 H Reacting alcohol adducts of magnesium halides such as 5 OH,
It is also possible to use a solid material obtained by reacting a titanium halide with a product obtained by subsequent alcohol treatment.
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ãã A solid product, which is component A in the catalyst used in the method of the present invention, is prepared by the operation shown below.
First, a solid material obtained by the above-described treatment, that is, a compound containing at least titanium, magnesium, and halogen, is reacted with tetraalkoxyzirconium and/or zirconium tetrahalide. Here, specific examples of the tetraalkoxyzirconium include tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium, among which tetrabutoxyzirconium is particularly preferred. On the other hand, specific examples of zirconium tetrahalide include tetrachlorozirconium and tetrabromzirconium. There is no limit to the blending ratio of the compounds used in this case, and it may be selected appropriately depending on various conditions, but usually 1 mole of titanium atoms in the above-mentioned solid substance, that is, a compound containing at least titanium, magnesium, and halogen. 0.1 to 20% of tetraalkoxyzirconium
mol, preferably in the range of 0.2 to 10 mol, and zirconium tetrahalide is appropriately determined in the range of 0 to 20 mol. Other conditions for the above reaction include a temperature of 0 to 200°C, preferably 20 to 150°C, a reaction time of 5 minutes to 5 hours, preferably 30 minutes to 3 hours, and pentane, hexane, heptane, octane, etc. It is preferable to use an inert hydrocarbon such as , cyclohexane, benzene or toluene as the solvent.
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ã溶åªãšããŠäœ¿çšããããšãã§ããã After thoroughly washing the solid content generated in the above reaction,
Further, this solid content is reacted with a halogen-containing titanium compound represented by the general formula Ti(OR 1 ) o X 1 4-o . As this halogen-containing titanium compound, various compounds can be considered as long as R 1 , X 1 , and n in the above formula are appropriately determined within the definition, but for example, TiCl 4 ,
TiBr4 , Ti( OCH3 ) Cl3 ,Ti( OC2H5 ) 2Cl2 , Ti
Preferred examples include (OC 2 H 5 ) 3 Cl and mixtures thereof. The amount of the halogen-containing titanium compound to be blended is usually 1 to 200 mol, preferably 10 to 100 mol, per 1 mol of titanium atoms in the solid content. In addition, this reaction, that is, the reaction between the solid content and the halogen-containing titanium compound, is carried out at 20 to 200°C, preferably at 50°C.
~150â for 5 minutes to 10 hours, preferably 30 minutes to 5 hours
It only needs to be carried out under certain time conditions, and in addition, pentane,
Inert hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene can be used as solvents.
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åãšããŠçšããã In the method of the present invention, the solid product obtained by the above reaction is washed as necessary and used as component A of the catalyst.
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ããšãã§ããã Next, various types of organoaluminum compounds can be considered as component B of the catalyst used in the method of the present invention, but they usually have the general formula AlR 2 n X 2 3-n (in the formula,
R 2 is an alkyl group, X 2 is a halogen atom, and m satisfies 0<MâŠ3. ),
Alternatively, the general formula AlR 3 k (OR 4 ) 3-k (where R 3 , R 4
represents an alkyl group, and k is 0<kâŠ3. ) is used. Specific examples of the above organoaluminum compounds include trimethylaluminum, triethylaluminum,
Triisopropylaluminium, triisobutylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride,
Diisobutylaluminum monochloride, dioctylaluminum monochloride, ethylaluminum dichloride, diethylaluminum monoethoxide, isopropylaluminum dichloride,
Examples include ethylaluminum sesquichloride.
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0.001ã10ããªã¢ã«ïŒã奜ãŸããã¯0.005ã0.5ã
ãªã¢ã«ïŒãšãã¹ãã§ããã The method of the present invention is to produce polyethylene using a catalyst containing the above-mentioned components A and B as active ingredients. The mixing ratio of component A and component B in this catalyst is not particularly limited, but usually 5 to 1000 aluminum atoms in component B to 1 titanium atom in component A (molar ratio), preferably 20 to 500.
(molar ratio). There is no particular restriction on the amount of the catalyst consisting of both components A and B used in the production of polyethylene, and it can be determined according to various conditions, but it is usually calculated in terms of titanium atoms.
It should be between 0.001 and 10 mmol/, preferably between 0.005 and 0.5 mmol/.
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ç¥ã®æ段ãäŸãã°æ°ŽçŽ çã«ããè¡ãªãã°ããã When producing polyethylene by polymerizing ethylene by the method of the present invention, a catalyst prepared from the above components A and B is added to the reaction system, and then ethylene is introduced. The polymerization method and conditions are not particularly limited, and any of solution polymerization, suspension polymerization, gas phase polymerization, etc. is possible, and both continuous polymerization and discontinuous polymerization are possible. As the catalyst for the reaction system, inert solvents such as butane, heptane, hexane, cyclohexane, heptane, benzene, and toluene are preferred. Furthermore, the ethylene pressure in the reaction system is 2
-100Kg/ cm2 , preferably 5-50Kg/ cm2 , and the reaction temperature is 20-200â, preferably 50-150â,
The desired polyethylene can be obtained by reacting for 5 minutes to 10 hours, preferably 30 minutes to 5 hours. The molecular weight during polymerization may be controlled by known means such as hydrogen.
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ãŒãªã©ããããããã The types of polyethylene that can be polymerized by the method of the present invention include not only ethylene homopolymers but also copolymers of ethylene and a small amount of α-olefin.
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ãŠæå¹ãªæ¹æ³ã§ããã Since the method of the present invention uses the catalyst as described above,
It has a high catalytic activity, and a sufficient effect can be obtained with a small amount of use, and as a result, the deashing step (catalyst removal step) can be omitted. Moreover, the polyethylene obtained has a large bulk specific gravity, a good particle size, a small amount of fine powder, and a wide molecular weight distribution.
Therefore, this polyethylene has very good moldability and excellent physical properties. In addition, the method of the present invention is an extremely effective method because the molecular weight distribution of the resulting polyethylene can be controlled within a desired range by appropriately selecting the catalyst compounding ratio, polymerization conditions, etc.
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ãªã€ãããŸãååéååžã®è©äŸ¡ã¯ã190âã2.16
Kgè·éã®ã¡ã«ãã€ã³ããã¯ã¹ïŒMI2.16ïŒã«å¯Ÿãã
21.6Kgã®è·éã®ã¡ã«ãã€ã³ããã¯ã¹ïŒMI21.6ïŒã®
æ¯ã§ãã溶èæµãã®æ¯ïŒF.RïŒã§è¡ãªã€ãã Next, examples of the present invention will be shown. In addition, in the following examples, all operations were performed under an argon stream. In addition, the evaluation of molecular weight distribution was performed at 190â, 2.16
Kg load for melt index ( MI 2.16 )
The melt flow ratio (FR) was the ratio of the melt index (MI 21.6 ) at a load of 21.6 Kg.
å®æœäŸ ïŒ
(1) å°ãªããšããã¿ã³ããã°ãã·ãŠã ããã³ãã
ã²ã³ãå«æããååç©ã®è£œé ãExample 1 (1) Production of a compound containing at least titanium, magnesium and halogen.
500ml容ã®åã€å£ãã©ã¹ã³ã«ã也ç¥ããïœâã
ããµã³150mlããã°ãã·ãŠã ãžãšããã·ã10.0ïœ
ïŒ88ããªã¢ã«ïŒãåå¡©åã±ã€çŽ 3.7ïœïŒ22ããªã¢
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ã€ãã In a 500ml four-necked flask, add 150ml of dry n-hexane and 10.0g of magnesium diethoxide.
(88 mmol) and 3.7 g (22 mmol) of silicon tetrachloride were added, and while stirring at 20°C, 2.0 g (33 mmol) of isopropyl alcohol was added dropwise over 30 minutes.Then, the temperature was raised and refluxed for 3 hours. Made it react. Next, 42 g (220 mmol) of titanium tetrachloride was added dropwise, and the reaction was carried out under reflux for 3 hours. After cooling and standing, the supernatant liquid was removed, and the generated solid substance was
- The target compound containing titanium, magnesium and halogen was obtained by washing with hexane. The titanium content in this compound was 6.2% by weight.
(2) 觊åªã®ïŒ¡æåã®è£œé ã(2) Production of component A of the catalyst.
200ml容ã®ãã©ã¹ã³ã«ã也ç¥ããïœâãããµã³
50mlããã³äžèš(1)ã§åŸãããååç©ãããã°ãã·
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ãåºäœçæç©ãåŸãã In a 200ml flask, add dry n-hexane.
To 50 ml of the compound obtained in (1) above, 8.8 mmol of magnesium (1.3 mmol of titanium) and 3 mmol of tetrabutoxyzirconium were added, and the mixture was reacted at 70° C. for 2 hours with stirring. The system was then cooled to room temperature, left to stand, the supernatant was removed, and the precipitate was washed once with 50 ml of n-hexane, followed by the addition of 8.8 mmol of titanium tetrachloride and 70
The reaction was carried out at â for 3 hours. After cooling, the precipitate was
- Washed 5 times with 50 ml of hexane to obtain a solid product which is component A of the catalyst.
(3) ããªãšãã¬ã³ã®è£œé ã(3) Manufacture of polyethylene.
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çæç©ããã¿ã³ãšããŠ0.005ããªã¢ã«å ãã80â
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ãçœè²ã®ããªãšãã¬ã³139ïœãåŸããããåŸãã
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0.52ïŒF.R.ã¯46ã§ãã€ãã In a 1-volume stainless steel autoclave, 400 ml of dry n-hexane, 2.0 mmol of triisobutylaluminum, which is the B component of the catalyst, and 0.005 mmol of titanium, the solid product which is the A component of the catalyst obtained in (2) above. In addition, 80â
The temperature rose to . Hydrogen 2 is then added to this system as a partial pressure.
Kg/cm 2 and 6 kg/cm 2 of ethylene were introduced under pressure, and polymerization was carried out at 80° C. for 1 hour while continuously supplying ethylene to maintain this pressure. After the reaction was completed, unreacted gas was removed and the polymer was separated and dried to obtain 139 g of white polyethylene. The bulk density of the obtained polyethylene was 0.29 g/cm 2 , and the MI 2.16 was
0.52, FR was 46.
å®æœäŸ ïŒ (1) 觊åªã®ïŒ¡æåã®è£œé ãExample 2 (1) Production of component A of the catalyst.
200ml容ã®ãã©ã¹ã³ã«ãåèšå®æœäŸïŒ(1)ã§åŸã
ããååç©ããã°ãã·ãŠã ãšããŠ8.8ããªã¢ã«
ïŒãã¿ã³ãšããŠ1.3ããªã¢ã«ïŒãããã©ãããã·ãž
ã«ã³ããŠã 1.0ããªã¢ã«ããã³ä¹Ÿç¥ããïœâãã
ãµã³50mlããå ããŠæ¹æããªãã70âã§ïŒæéå
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æåã§ããåºäœçæç©ãåŸãã 8.8 mmol of the compound obtained in Example 1 (1) as magnesium (1.3 mmol as titanium), 1.0 mmol of tetrabutoxyzirconium, and 50 ml of dry n-hexane were added to a 200 ml flask, and the mixture was stirred for 70 ml. The reaction was carried out at â for 2 hours. Next, 22 mmol of titanium tetrachloride was added to this system, and the mixture was reacted at 70°C for 3 hours. After cooling, the precipitate was washed 5 times with 50 ml of n-hexane to remove the catalyst A.
A solid product was obtained.
(2) ããªãšãã¬ã³ã®è£œé ã(2) Manufacture of polyethylene.
觊åªã®ïŒ¡æåãšããŠäžèš(1)ã§åŸãããåºäœçæ
ç©ãçšããããšä»¥å€ã¯å®æœäŸïŒãšåãæ¡ä»¶ã§ãšã
ã¬ã³ã®éåãè¡ãªã€ãããã®çµæãããªãšãã¬ã³
84ïœãåŸããããã®ããªãšãã¬ã³ã®åµ©å¯åºŠã¯0.27
ïœïŒcm2ïŒMI2.16ã¯0.41ïŒF.R.ã¯46ã§ãã€ãã Ethylene polymerization was carried out under the same conditions as in Example 1 except that the solid product obtained in (1) above was used as component A of the catalyst. As a result, polyethylene
84g was obtained, and the bulk density of this polyethylene was 0.27
g/cm 2 , MI 2.16 was 0.41, and FR was 46.
å®æœäŸ ïŒ (1) 觊åªã®ïŒ¡æåã®è£œé ãExample 3 (1) Production of component A of the catalyst.
200ml容ã®ãã©ã¹ã³ã«ãåèšå®æœäŸïŒ(1)ã§åŸã
ããååç©ããã°ãã·ãŠã ãšããŠ8.8ããªã¢ã«
ïŒãã¿ã³ãšããŠ1.3ããªã¢ã«ïŒãããã©ãããã·ãž
ã«ã³ããŠã 2.0ããªã¢ã«ãåå¡©åãžã«ã³ããŠã 2.0
ããªã¢ã«ããã³ä¹Ÿç¥ããïœâãããµã³50mlãå ã
ãŠæ¹æããªãã70âã§ïŒæéåå¿ãããã次ãã§
ãã®ç³»ã«åå¡©åãã¿ã³22ããªã¢ã«ãå ã70âã§ïŒ
æéåå¿ããããå·åŽåŸé眮ããŠäžæŸæ¶²ãé€ãã
æ²æŸ±ç©ãïœâãããµã³50mlã§ïŒåæŽæµããŠè§Šåªã®
æåã§ããåºäœçæç©ãåŸãã In a 200 ml flask, add 8.8 mmol of the compound obtained in Example 1 (1) as magnesium (1.3 mmol as titanium), 2.0 mmol of tetrabutoxyzirconium, and 2.0 mmol of zirconium tetrachloride.
mmol and 50 ml of dry n-hexane were added, and the mixture was reacted at 70° C. for 3 hours with stirring. Next, 22 mmol of titanium tetrachloride was added to this system and the mixture was heated at 70°C.
Allowed time to react. After cooling, let it stand and remove the supernatant liquid.
The precipitate was washed five times with 50 ml of n-hexane to obtain a solid product, which is component A of the catalyst.
(2) ããªãšãã¬ã³ã®è£œé ã(2) Manufacture of polyethylene.
ã¹ãã³ã¬ã¹è£œã®ïŒå®¹ãªãŒãã¯ã¬ãŒãã«ã也ç¥
ããïœâãããµã³400mlã觊åªã®ïŒ¢æåã§ããã
ãªã€ãœããã«ã¢ã«ãããŠã 2.0ããªã¢ã«ãããã³
äžèš(1)ã§åŸããã觊åªã®ïŒ¡æåã§ããåºäœçæç©
ããã¿ã³ãšããŠ0.01ããªã¢ã«å ããŠ80âã«ææž©ã
ãã次ãã§ãã®ç³»ã«åå§ãšããŠæ°ŽçŽ ïŒKgïŒcm2ããš
ãã¬ã³ïŒKgïŒcm2ãå§å
¥ãã以éãã®å§åãç¶æã
ãããã«ãšãã¬ã³ãé£ç¶çã«äŸçµŠããªãã80âã§
ïŒæééåããããåå¿çµäºåŸãæªåå¿ã¬ã¹ãé€
å»ããããªããŒãåé¢ä¹Ÿç¥ãããšãããçœè²ã®ã
ãªãšãã¬ã³ã105ïœåŸããããåŸãããããªãšã
ã¬ã³ã®åµ©å¯åºŠã¯0.25ïœïŒcm2ïŒMI2.16ã¯0.38ïŒF.R.
ã¯54ã§ãã€ãã In a 1-volume stainless steel autoclave, 400 ml of dry n-hexane, 2.0 mmol of triisobutylaluminum, which is the B component of the catalyst, and 0.01 mmol of titanium, the solid product which is the A component of the catalyst obtained in (1) above. In addition, the temperature was raised to 80°C. Next, 3 kg/cm 2 of hydrogen and 5 kg/cm 2 of ethylene were pressurized into the system as partial pressures, and polymerization was carried out at 80° C. for 1 hour while continuously supplying ethylene to maintain this pressure. After the reaction was completed, unreacted gas was removed and the polymer was separated and dried to obtain 105 g of white polyethylene. The bulk density of the obtained polyethylene was 0.25 g/cm 2 , MI 2.16 was 0.38, FR
was 54.
å®æœäŸ ïŒ (1) 觊åªã®ïŒ¡æåã®è£œé ãExample 4 (1) Production of component A of the catalyst.
200ml容ã®ãã©ã¹ã³ã«ãåèšå®æœäŸïŒ(1)ã§åŸã
ããååç©ããã°ãã·ãŠã ãšããŠ8.8ããªã¢ã«
ïŒãã¿ã³ãšããŠ1.3ããªã¢ã«ïŒããšãã«ã¢ã«ãããŠ
ã ãžã¯ãã©ã€ã44ããªã¢ã«ããã³ä¹Ÿç¥ããïœâã
ããµã³50mlãå ããŠæ¹æããªãã70âã§ïŒæéå
å¿ããããå·åŽåŸé眮ããŠäžæŸæ¶²ãé€ã也ç¥ïœâ
ãããµã³ã§æŽæµããã次ãã§åŸãããåºäœã®ã¹ã©
ãªãŒã«ä¹Ÿç¥ïœâãããµã³50mlãå ããããã©ãã
ãã·ãžã«ã³ããŠã 4.0ããªã¢ã«ãæ·»å ãã70âã§
ïŒæéåå¿ãããããã«åå¡©åãã¿ã³22ããªã¢ã«
ãå ããŠ70âã§ïŒæéåå¿ããããå·åŽåŸé眮ã
ãŠäžæŸæ¶²ãé€ãã也ç¥ïœâãããµã³ã§æŽæµããŠè§Š
åªã®ïŒ¡æåã§ããåºäœçæç©ãåŸãã Into a 200 ml flask were added 8.8 mmol of the compound obtained in Example 1 (1) as magnesium (1.3 mmol as titanium), 44 mmol of ethylaluminum dichloride, and 50 ml of dry n-hexane, and the mixture was heated at 70°C with stirring. The reaction was carried out for 1 hour. After cooling, let it stand, remove the supernatant liquid, and dry it.
Washed with hexane. Next, 50 ml of dry n-hexane was added to the resulting solid slurry, 4.0 mmol of tetrabutoxyzirconium was added, and the mixture was reacted at 70°C for 3 hours. Further, 22 mmol of titanium tetrachloride was added and the mixture was reacted at 70°C for 3 hours. . After cooling, the mixture was allowed to stand, the supernatant liquid was removed, and the mixture was washed with dry n-hexane to obtain a solid product, which is component A of the catalyst.
(2) ããªãšãã¬ã³ã®è£œé ã(2) Manufacture of polyethylene.
ã¹ãã³ã¬ã¹è£œã®ïŒå®¹ãªãŒãã¯ã¬ãŒãã«ã也ç¥
ããïœâãããµã³400mlããã³è§Šåªã®ïŒ¢æåã§ã
ãããªã€ãœããã«ã¢ã«ãããŠã 2.0ããªã¢ã«ããª
ãã³ã«äžèš(1)ã§åŸããã觊åªã®ïŒ¡æåã§ããåºäœ
çæç©ããã¿ã³ãšããŠ0.02ããªã¢ã«å ãã80âã«
ææž©ããã次ãã§å®æœäŸïŒãšåãæ¡ä»¶ã§ãšãã¬ã³
ãéåããããªãšãã¬ã³98ïœãåŸããåŸãããã
ãªãšãã¬ã³ã®åµ©å¯åºŠã¯0.26ïœïŒcm3ïŒMI2.16ã¯
0.13ïŒF.R.ã¯63ã§ãã€ãã In a 1-volume stainless steel autoclave, 400 ml of dry n-hexane, 2.0 mmol of triisobutylaluminum, which is the B component of the catalyst, and 0.02 mmol of the solid product, which is the A component of the catalyst obtained in (1) above, as titanium. In addition, the temperature was raised to 80°C. Next, ethylene was polymerized under the same conditions as in Example 3 to obtain 98 g of polyethylene. The bulk density of the obtained polyethylene was 0.26 g/cm 3 , and MI 2.16 was
0.13, FR was 63.
æ¯èŒäŸ (1) 觊åªæåã®è£œé ãComparative example (1) Production of catalyst components.
200ml容ã®ãã©ã¹ã³ã«ã也ç¥ããïœâãããµã³
50mlãå®æœäŸïŒ(1)ã§åŸãããååç©ããã°ãã·ãŠ
ã ãšããŠ8.8ããªã¢ã«ïŒãã¿ã³ãšããŠ1.3ããªã¢
ã«ïŒããã³åå¡©åãã¿ã³8.8ããªã¢ã«ãå ããŠæ¹
æããªãã70âã§ïŒæéåå¿ãè¡ãªã€ããåå¿çµ
äºåŸå·åŽããŠé眮ããäžæŸæ¶²ãé€ããããã«ä¹Ÿç¥
ïœâãããµã³ã§æŽæµããŠè§ŠåªæåãšããŠã®åºäœç
æç©ãåŸãã In a 200ml flask, add dry n-hexane.
50 ml of the compound obtained in Example 1 (1) was added with 8.8 mmol of magnesium (1.3 mmol of titanium) and 8.8 mmol of titanium tetrachloride, and the reaction was carried out at 70° C. for 3 hours with stirring. After the reaction was completed, the mixture was cooled and allowed to stand, the supernatant liquid was removed, and the mixture was further washed with dry n-hexane to obtain a solid product as a catalyst component.
(2) ããªãšãã¬ã³ã®è£œé ã(2) Manufacture of polyethylene.
ã¹ãã³ã¬ã¹è£œã®ïŒå®¹ãªãŒãã¯ã¬ãŒãã«ã也ç¥
ããïœâãããµã³400mlã觊åªã®ïŒ¢æåã§ããã
ãªã€ãœããã«ã¢ã«ãããŠã 2.0ããªã¢ã«ããã³äž
èš(1)ã§åŸãããåºäœçæç©ããã¿ã³ãšããŠ0.005
ããªã¢ã«å ããŠ80âã«ææž©ããã次ãã§ãã®ç³»ã«
åå§ãšããŠæ°ŽçŽ ïŒKgïŒcm2ããšãã¬ã³ïŒKgïŒcm2ãå§
å
¥ãã以éãã®å§åãç¶æããããã«ãšãã¬ã³ã
é£ç¶çã«äŸçµŠããªãã80âã§ïŒæééåãããã
åå¿çµäºåŸãæªåå¿ã¬ã¹ãé€å»ããããªããŒãå
é¢ä¹Ÿç¥ãããšãããçœè²ã®ããªãšãã¬ã³ã225ïœ
åŸããããåŸãããããªãšãã¬ã³ã®åµ©å¯åºŠã¯0.29
ïœïŒcm3ïŒMI2.16ã¯0.50ïŒF.R.ã¯31ã§ãã€ãã In a 1-volume stainless steel autoclave, 400 ml of dry n-hexane, 2.0 mmol of triisobutylaluminum, which is component B of the catalyst, and 0.005 titanium of the solid product obtained in (1) above were placed in a 1-volume stainless steel autoclave.
mmol was added and the temperature was raised to 80°C. Next, 2 kg/cm 2 of hydrogen and 6 kg/cm 2 of ethylene were pressurized into the system as partial pressures, and polymerization was carried out at 80° C. for 1 hour while continuously supplying ethylene to maintain this pressure.
After the reaction was completed, the unreacted gas was removed and the polymer was separated and dried, resulting in 225g of white polyethylene.
Obtained. The bulk density of the obtained polyethylene is 0.29
g/cm 3 , MI 2.16 was 0.50, and FR was 31.
第ïŒå³ã¯æ¬é¡çºæã®æ¹æ³ã§çšãã觊åªã®èª¿è£œå·¥
çšãè¡šãããå³é¢ã§ããã
FIG. 1 is a diagram showing the preparation process of a catalyst used in the method of the present invention.
Claims (1)
ãã²ã³ãå«æããååç©ãšããã©ã¢ã«ã³ãã·ãžã«
ã³ããŠã ããã³ïŒãŸãã¯ãžã«ã³ããŠã ããã©ãã©
ã€ããåå¿ãããŠçæããåºåœ¢åã«ãäžè¬åŒTi
ïŒOR1ïŒoX1 4-oïŒåŒäžãR1ã¯ã¢ã«ãã«åºãX1ã¯ãã
ã²ã³ååã瀺ãããŸãïœã¯ïŒâŠïœïŒïŒã§ãããïŒ
ã§è¡šããããããã²ã³å«æãã¿ã³ååç©ãåå¿ã
ããŠåŸãããåºäœçæç©ããã³ïŒ¢ææ©ã¢ã«ãããŠ
ã ååç©ãæå¹æåãšãã觊åªãçšããããšãç¹
城ãšããããªãšãã¬ã³ã®è£œé æ³ã ïŒ ææ©ã¢ã«ãããŠã ååç©ããäžè¬åŒ
AlR2 nX2 3-nïŒåŒäžãR2ã¯ã¢ã«ãã«åºãX2ã¯ãã
ã²ã³ååã瀺ãããŸãïœã¯ïŒïŒïœâŠïŒã§ãããïŒ
ãããã¯äžè¬åŒAlR3 kïŒOR4ïŒ3-kïŒåŒäžãR3ïŒR4
ã¯ã¢ã«ãã«åºã瀺ãããŸãïœã¯ïŒïŒïœâŠïŒã§ã
ããïŒã§è¡šãããããã®ã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬
ïŒé èšèŒã®è£œé æ³ã[Scope of Claims] 1 A: A solid content produced by reacting a compound containing at least titanium, magnesium and a halogen with tetraalkoxyzirconium and/or zirconium tetrahalide, which has the general formula Ti
(OR 1 ) o X 1 4-o (In the formula, R 1 is an alkyl group, X 1 is a halogen atom, and n is 0âŠn<4.)
A method for producing polyethylene, which comprises using a solid product obtained by reacting a halogen-containing titanium compound represented by the formula B, and a catalyst containing an organoaluminum compound B as an active ingredient. 2 The organoaluminum compound has the general formula
AlR 2 n X 2 3-n (In the formula, R 2 is an alkyl group, X 2 is a halogen atom, and m is 0<mâŠ3.)
Alternatively, the general formula AlR 3 k (OR 4 ) 3-k (where R 3 , R 4
represents an alkyl group, and k is 0<kâŠ3. ) The manufacturing method according to claim 1, which is represented by:
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8515180A JPS5712006A (en) | 1980-06-25 | 1980-06-25 | Production of polyethylene |
EP19810104669 EP0043473B1 (en) | 1980-06-25 | 1981-06-17 | Process for the production of polyethylene |
DE8181104669T DE3171693D1 (en) | 1980-06-25 | 1981-06-17 | Process for the production of polyethylene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8515180A JPS5712006A (en) | 1980-06-25 | 1980-06-25 | Production of polyethylene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5712006A JPS5712006A (en) | 1982-01-21 |
JPS6251285B2 true JPS6251285B2 (en) | 1987-10-29 |
Family
ID=13850657
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8515180A Granted JPS5712006A (en) | 1980-06-25 | 1980-06-25 | Production of polyethylene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5712006A (en) |
-
1980
- 1980-06-25 JP JP8515180A patent/JPS5712006A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5712006A (en) | 1982-01-21 |
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