JPS6312881B2 - - Google Patents
Info
- Publication number
- JPS6312881B2 JPS6312881B2 JP1495178A JP1495178A JPS6312881B2 JP S6312881 B2 JPS6312881 B2 JP S6312881B2 JP 1495178 A JP1495178 A JP 1495178A JP 1495178 A JP1495178 A JP 1495178A JP S6312881 B2 JPS6312881 B2 JP S6312881B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ethylene
- catalyst component
- polymer
- solid
- 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
- 150000001875 compounds Chemical class 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- -1 alkoxy compounds Chemical class 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000011949 solid catalyst Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012442 inert solvent Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing 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
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WYTRYIUQUDTGSX-UHFFFAOYSA-N 1-phenylpropan-2-ol Chemical compound CC(O)CC1=CC=CC=C1 WYTRYIUQUDTGSX-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-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
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 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
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- XBKBZMOLSULOEA-UHFFFAOYSA-L methylaluminum(2+);dibromide Chemical compound C[Al](Br)Br XBKBZMOLSULOEA-UHFFFAOYSA-L 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- XAZHEJSMNNAMRS-UHFFFAOYSA-L pentylaluminum(2+);dichloride Chemical compound [Cl-].[Cl-].CCCCC[Al+2] XAZHEJSMNNAMRS-UHFFFAOYSA-L 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- VALAJCQQJWINGW-UHFFFAOYSA-N tri(propan-2-yl)alumane Chemical compound CC(C)[Al](C(C)C)C(C)C VALAJCQQJWINGW-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
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[]Object of the present invention The present invention relates to a method for producing an ethylene polymer having a wide molecular weight distribution. More specifically, a method for producing an ethylene polymer having a wide molecular weight distribution, which comprises polymerizing ethylene with a catalyst system obtained from a hydrocarbon-insoluble solid catalyst component produced by a specific reaction and an organoaluminum compound. Regarding. [] Background of the present invention High-density to medium-density ethylene polymers are widely produced industrially by polymerizing ethylene with a so-called Ziegler catalyst, and are generally used as resin materials for various molded products. . but,
These molded products are increasingly required to have good surface properties. For example, hollow molded products (blow molded products) are required to have no surface roughness (so-called shark skin). However, in ethylene polymers produced using catalyst systems obtained from common transition metal compounds (eg, titanium tetrachloride) and organoaluminum compounds (eg, trialkylaluminium), this surface roughness is generally significant. This phenomenon of surface roughness is related to the molecular weight distribution of the ethylene polymer that is the raw material. That is,
It is believed that the broader the molecular weight distribution of the polymer, the less rough the surface of the molded product will be. The ratio of weight average molecular weight ( ) to number average molecular weight ( ) is used as a measure of the breadth of molecular weight distribution. It is considered that the larger the ratio (that is, /), the broader the molecular weight distribution. Ethylene polymers having this ratio (/) of 10 or more are promising for producing molded products with good surface properties. Ethylene-based polymers with these characteristics have good fluidity, even in the case of polymers with low melt index, and do not cause melt fractures on the surface of molded products, making it possible to produce high-quality blow and film products. It becomes possible to obtain. [] Structure of the present invention Based on the above, the present inventors have searched various ways to produce ethylene polymers having a wide molecular weight distribution, and have found (A) (1) titanium tetrachloride and (2) ( a) Alcohol compounds whose general formula is R-OH, (b) alkoxytitanium compounds whose general formula is Ti(OR) 4 , and (c)
"Alkoxyaluminum compounds represented by Al(OR) 3 " (hereinafter referred to as "alkoxy compounds")
A catalyst system obtained from a hydrocarbon-insoluble solid catalyst component obtained by aging a reaction product with at least one compound selected from the group consisting of (B) an organoaluminum compound, in which ethylene alone Alternatively, the inventors have discovered that an ethylene polymer with a wide molecular weight distribution, which is the object of the present invention, can be obtained by polymerizing ethylene and a small amount of α-olefin, thereby achieving the present invention. [] Effects of the present invention (1) Since the catalyst raw material is inexpensive, the catalyst cost is low. (2) Since the activity is high, there is little catalyst residue in the produced polymer, and therefore the catalyst removal step can be simplified or omitted. (3) Because the polymer has a wide molecular weight distribution, it is possible to make products without roughening the surface of the molded product. [] Specific description of the present invention The solid catalyst component used in the present invention is a hydrocarbon-insoluble component obtained by aging a reaction product of titanium tetrachloride and an alcohol compound and/or an alkoxy compound. be. (a) Alcohol Compound The general formula of a typical alcohol compound used to produce a solid catalyst component is shown by the following formula [formula ()]. In the R-OH () () formula, R is
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Mwãããã³ïŒã第ïŒè¡šã«ç€ºãã[Formula] (where R 1 is a hydrogen atom or a saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having at most 10 carbon atoms, R 2 and R 3 is the above-mentioned hydrocarbon group.) Typical examples of these alcohol compounds include isopropyl alcohol, tertiary-butyl alcohol, secondary-butyl alcohol, 1-
Buten-3-ol, tertiary-amyl alcohol, secondary-amyl alcohol, diethyl carbinol, 3-methyl-1-buten-3-ol, 2-heptanol, 3-heptanol, 4
-heptanol, tertiary-heptanol, 2-
Octanol, diisobutylcarbinol, phenylethanol, 1-phenyl-1-propanol, 1-phenyl-2-propanol, 2
-phenyl-2-propanol and the like. In carrying out the present invention, it is desirable that R in the above formula () has 20 or less carbon atoms. (b) Alkoxy compounds Among the alkoxy compounds used to produce solid catalyst components, the general formula of typical alkoxy titanium compounds is shown by the following formula [formula ()]. . In the formula Ti(OR) 4 () (), R is represented by R above. Representative examples of the alkoxy titanium compounds include alkyl titanates corresponding to the alcohol compounds mentioned above. Furthermore, the general formula of typical alkoxyaluminum compounds is shown by the following formula [formula ()]. In the formula Al(OR) 3 () (), R is represented by R above. Representative examples of the alkoxyaluminum compounds include alkyl alkonates corresponding to the alcohol compounds mentioned above. (c) Aging ratio The ratio of titanium tetrachloride to the alcohol compound and/or alkoxy compound is generally 0.1.
~1.0, particularly preferably 0.5 to 1.0. If this ratio is less than 0.1, titanium tetrachloride is wasted, which is not economical. On the other hand, if it is 1.0 or more, it is not practical because the polymerization activity of the resulting catalyst system decreases. (d) Aging conditions When titanium tetrachloride is reacted with an alcohol compound or the alkoxy titanium compound, the general formula is TiCl o (OR) 4-o (where n is 1).
Compounds shown in ~3) are said to be produced. Such compounds are soluble in ordinary organic solvents, but only if R in the formulas (), (), and () is secondary or tertiary.
When aged as described below, a solid is produced that is insoluble in hydrocarbons. Although the structure of this solid is not clear, the compound whose general formula is TiCl o (OR) 4-o and this solid are related to solubility in the organic solvent, amount of gas generated during reaction, elemental analysis results, etc. From this, it can be confirmed that the two are different. Even if the compound represented by TiCl o (OR) 4-o is used as a catalyst component,
As is clear from Comparative Example 1, it is not possible to obtain an ethylene polymer with a wide molecular weight distribution. On the other hand, when the hydrocarbon-insoluble solid of the present invention is used, an ethylene polymer with a wide molecular weight distribution can be obtained. The aging temperature and time vary depending on the type of alcohol compound and alkoxy compound and their proportions, but are generally room temperature to 150°C and 10 minutes to 3 hours, particularly 40 to 100°C and 30 minutes to 3 hours. 2 hours is recommended.
If the aging temperature and time are lower than the above, a catalyst system that exhibits sufficient effects cannot be obtained. on the other hand,
Above these, there is no particular merit and it is uneconomical. A solvent is not necessarily required for this ripening. This means that if titanium tetrachloride is added to the extent that it can be stirred and transferred (titanium tetrachloride also serves as a solvent), a solid catalyst component can be produced without adding another solvent (the titanium tetrachloride described above can also be used as a solvent). The ratio of R groups to 1 atomic equivalent is set to about 0.1 to 0.3). but,
Instead of excess titanium tetrachloride, aliphatic hydrocarbons such as n-hexane, n-heptane, octane, nonane, n-paraffin and halogenated hydrocarbons such as trichlene, trichloroethane, tetrachloroethane are preferably used. . The solid catalyst component obtained as described above may be used as a polymerization catalyst component as it is after being subjected to a washing treatment as described below. Furthermore, further effects can be exhibited by reducing using an organoaluminum compound. (e) Reduction reaction Among the organic compounds used in this reduction reaction, the general formula of typical ones is shown below [()
The following formula can be mentioned. AlR 4 o X 3-o () In the formula, R 4 represents an alkyl group having at most 6 carbon atoms, X represents a halogen atom, and n is 1, 1.5, 2 or 3. AlR 3 includes trimethylaluminum,
Mention may be made of triethylaluminum, tri-n-propylaluminium, tri-isopropylaluminium, tri-n-butylaluminum, tri-isobutylaluminum and trihexylaluminum. AlR 2 Examples include diethylaluminum monobromide. Examples of AlR 1.5 AlRX 2 includes methylaluminum dichloride, methylaluminum dibromide,
Mention may be made of ethylaluminum dichloride, ethylaluminum dibromide, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride and n-pentylaluminum dichloride. In addition to the organoaluminum compounds mentioned above, the organoaluminum compounds used in this reduction reaction include tetraalkyldialmoxane obtained by treating 1 mol of the general formula AlR 3 (trialkylaluminum) with 0.5 mol of water; Various organoaluminum compounds containing chlorine and/or hydrogen derivatives and inorganic acid groups such as amide or nitrile or sulfuric or phosphoric acid groups can also be used. In this reduction reaction, the ratio of aluminum atoms in the organoaluminum compound to one atomic equivalent of titanium atoms in the solid catalyst component is generally at most 50 atomic equivalents, particularly 1 to 10 atomic equivalents.
Atomic equivalents are preferred. Although the reaction temperature in this reduction reaction varies depending on the type of organoaluminum compound, it is generally -40 to 150°C, and preferably -20 to +60°C from the viewpoint of the function of the resulting catalyst system and the reaction rate. Although the reaction time varies depending on the reaction temperature, the reaction ratio of the organoaluminum compound to the solid catalyst component, and the concentration of the organoaluminum compound to the solvent when an inert solvent is used, 15 minutes to 5 hours is generally sufficient. . The reaction of titanium tetrachloride with an alcohol compound and/or an alkoxy compound, its aging, and the reduction reaction of its solid catalyst component with an organoaluminum compound are carried out under an inert atmosphere (e.g., under nitrogen) with air and moisture excluded. ) will be carried out. (f) Post-treatment The solid catalyst component obtained as described above and its reduced product are solids that are insoluble in hydrocarbons. These may be decanted or filtered, thoroughly washed with a hydrocarbon (e.g., n-hexane, n-heptane, n-paraffin), and fed directly to the polymerization system as a slurry, or after drying, they may be powdered. You may also use it.
Furthermore, it may be used in the form of fine powder by pulverization. The solid catalyst component and the reduced product thus obtained have an ocher to brown color. (g) Polymerization The solid catalyst component purified as described above or its reduced product (generally 5 to 100 mg per 1 part inert solvent) is mixed with an organoaluminum compound (1 part inert solvent) in a conventional manner. Homopolymerization of ethylene or ethylene and α- The present invention can be achieved by copolymerizing with olefin. Representative examples of organoaluminum compounds used in polymerization include those shown in the reduction reaction described above. Further, the third component is an electron donating compound,
Those known in the polymerization of ethylene can be used. Inert solvents include unsaturated aliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. When copolymerizing with ethylene, the α-olefin used must have at most 12 carbon atoms.
-Olefins are common. Particularly desirable are those having 8 or less carbon atoms (for example, propylene, butene-1, 4-methylpentene-1). The ratio of the α-olefin to ethylene is usually 50 mol% or less, and especially when the content of α-olefin in the obtained copolymer is 20 mol%.
It is preferable to copolymerize so that the amount is as follows (in particular, 10 mol% or less). When copolymerizing, random copolymerization or block copolymerization may be performed. In carrying out the method of the present invention, the polymerization temperature and pressure are not particularly limited, and commonly used conditions can be applied, but in general, room temperature to
A temperature range of 300° C. and a polymerization pressure of 1 to 200 atmospheres are employed. If necessary, a molecular weight regulator such as hydrogen, halogenated hydrocarbon or diethylzinc may be present in the polymerization reaction system to control the molecular weight. (h) Post-treatment and use The ethylene polymer obtained as described above has a fairly high polymerization activity, so it can be used after completely removing the inert solvent used in the polymerization. Depending on the purpose, catalyst residue remaining in the polymer may be removed by a known method. The ethylene polymer obtained in the present invention is
As mentioned above, it has a fairly wide molecular weight distribution, so it is promising for use in films and blow molding. [] Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples. In addition, in the Examples and Comparative Examples, the melt index (MI) was measured according to JIS K-6740. Further, as a measure of molecular weight distribution, / was determined by measurement using gel permeation chromatography (GPC) manufactured by Waters. Example 1 (A) Production of catalyst component (A) A 200 c.c. three-necked flask equipped with a thermometer and a stirrer was sufficiently purged with nitrogen, and 10 ml of trichlene and 5.7 g of titanium tetrachloride were added to the flask. (30 mmol) was added. 1.8 g of isopropyl alcohol [hereinafter referred to as "compound (1)"] (30 mmol) was added to 10 mmol of isopropyl alcohol at room temperature while stirring thoroughly.
It was dripped over a period of minutes. Furthermore, after maintaining the temperature at 40°C for 30 minutes, the reaction system was further heated to 85°C. After 50 minutes had passed since the temperature was raised, solids gradually began to precipitate, and after being maintained at this temperature for 2 hours, it was cooled. After thoroughly washing the insoluble solid with n-hexane, it was dried at a temperature of 40°C under reduced pressure for about 1 hour to obtain 2.5 g.
ocher solid [hereinafter referred to as "catalyst component (A)"]
was gotten. (B) Homopolymerization of ethylene Place the catalyst component (A) obtained in (A) above in a 1.2 autoclave purged with nitrogen (the amount used is shown in Table 2). 1.0 mmol of triisobutylaluminum and 350 g of n-hexane were charged, and the temperature of the polymerization system was raised to 95°C. Furthermore, the partial pressure is 15Kg/
After hydrogen was introduced until the pressure reached cm 2 (gauge pressure, the same applies hereinafter), ethylene was introduced until the partial pressure reached 7 Kg/cm 2 . Polymerization was carried out for 60 minutes while feeding ethylene to maintain the pressure. After purging ethylene, the product was dried at a temperature of 50° C. under reduced pressure for 1 hour to remove n-hexane.
As a result, a white polymer (polyethylene) was obtained. The bulk density of this polymer was 0.36 g/cc. Table 2 shows the amount of catalyst component (A) used, the yield of the obtained polymer, the (weight average molecular weight) and (number average molecular weight) measured by the GPC method, and/or MI (melt index). Shown below. Example 2 The amounts of trichlene and titanium tetrachloride used in (A) of Example 1 were 25 ml and 12.2 g (65
mmol) and further in place of compound (1),
5.6g of isopropyl titanate [hereinafter referred to as âcompound
The heat treatment, washing and drying were carried out in the same manner as in Example 1 (A), except that 20 mmol of the product was used. As a result, 7.2 g of solid was obtained.
4.2 g of this solid, 20 ml n-hexane and 2.4 g
of ethylaluminum sesquichloride (10 mmol) was placed in a 200 ml flask and treated at a temperature of 50° C. for 1 hour. Next, the obtained solid was thoroughly washed with n-hexane and further dried at a temperature of 40°C under reduced pressure for a period of time to obtain 4.0 g of solid (hereinafter referred to as "catalyst component (B)"). It was done. Examples 3 to 8 Titanium tetrachloride was used in the amount shown in Table 1, and the alcohol compound or alkoxy titanate compound was compound (2) and tertiary-butyl titanate [hereinafter referred to as "compound (3)"]. , tertiary-butyl alcohol [hereinafter referred to as "compound (4)"], 2-methyl-3-buten-2-ol [hereinafter referred to as "compound (4)"]
(5)], 2-octyl alcohol (hereinafter referred to as "compound (6)"), or 2-phenyl-2-
Propanol [hereinafter referred to as "compound (7)"] is the first
A catalyst component was prepared in the same manner as in Example 1 (A), except that the amounts shown in the table were used, and then washed and dried. Same as Example 1 (B) except that catalyst component (B) or catalyst component (H) obtained as above was used in the amount shown in Table 2 instead of catalyst component (A). Homopolymerization of ethylene was carried out under these conditions. After the polymerization was completed, purification was carried out in the same manner as in Example 1 (B). The yield of the obtained polymer is shown in Table 2. MI of Example 1 and the polymer obtained above,
Mw and/or are shown in Table 2.
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ã®ã§ãã€ãã[Table] Example 9 Ethylene and butene-1 were combined under the same conditions as in Example 2, except that the amount of catalyst component (B) used was changed to 40 mg, and 10 g of butene-1 was added as α-olefin. Polymerization was carried out. After the copolymerization was completed, purification was carried out in the same manner as in Example 2. As a result, 143g
A copolymer was obtained. The MI of this copolymer is
0.41g/10min, is 17.1Ã 104 ,
n was 1.35Ã10 4 (i.e. w/n
is 18.9). Also, the density of this copolymer is 0.951g/
It was cc. Comparative Example 1 The amounts of trichlene and titanium tetrachloride used in (A) of Example 1 were reduced to 23 ml and 4.4 ml, respectively.
g (23 mmol), and instead of compound (1),
Heat treatment was carried out in the same manner as in Example 1 (A) except that 1.07 g of ethyl alcohol (23 mmol) was used, but no insoluble solid could be obtained, but at a temperature of 50 °C The solvent was distilled off under reduced pressure,
A pale yellow solid was obtained. Example 1 except that 63 mg of this solid was used instead of the catalyst component (A) used in (B) of Example 1, and the ethylene pressure and hydrogen pressure were changed to 10 Kg/cm 2 and 2 Kg/cm 2 , respectively. Ethylene polymerization was carried out in the same manner as in (B). As a result, 191g
A polymer was obtained. The MI of this polymer is 0.14
g/10 minutes. Also, w was 14.3Ã10 4 and n was 1.33Ã10 4 (i.e.,
w/n is 10.8). Comparative Example 2 Example 4 except that 6.5 g of n-butyl titanate (19 mmol) was used instead of compound (3) used in producing catalyst component (D) of Example 4.
Heat treatment was carried out in the same manner as above. However, it was not possible to obtain an insoluble solid. Example 10 In a 200 ml flask, 50 g of titanium tetrachloride (264 mmol) was kept under reflux in a solution of 9.0 g of aluminum triisopropoxide (44.1 mmol) in 50 ml of n-hexane for 1 hour. After cooling, it was thoroughly washed with n-hexane and dried. As a result, 11.1 g of solid was obtained. In place of the catalyst component (A) used in Example 1 (B), 25.7 mg of the solid obtained above was used, and the partial pressures of hydrogen and ethylene were 7 Kg/cm 2 and 10 Kg/cm 2 , respectively. Ethylene polymerization was carried out in the same manner as in Example 1 (B) except that the As a result, 102
g of polymer was obtained. The MI of this polymer is 0.02
g/10 minutes. Further, w was 25.5Ã10 4 and n was 1.05Ã10 4 . That is,
w/Mn is 24.2). Example 11 1.02 g of the catalyst component (B) obtained in Example 2, 60 mmol of triisobutylaluminum, and 60 mmol of n-hexane were charged into a 100 mm autoclave purged with nitrogen. After raising the temperature of the polymerization system to 95°C, hydrogen was introduced until the partial pressure reached 18 kg/cm 2 . Next, ethylene was introduced until the partial pressure reached 10 kg/cm 2 (supplied to maintain that pressure during ethylene polymerization), and polymerization was continued for 2 hours while supplying butene-1 of 3 in 3 parts. I did it. As a result, 12 kg of polymer (MI 0.2 g/10 minutes) was obtained. 0.2 parts by weight of calcium stearate and 0.1 parts by weight of 2,6-di-tertiary-butyl-P-cresol were added to 100 parts by weight of this polymer, and pellets were formed using an extruder. The obtained pellets were subjected to film molding and blow molding. The surface texture of the obtained molded products was all satisfactory.
第ïŒå³ã¯æ¬çºæã®ããŒã°ã©ãŒè§Šåªã®ãããŒãã€
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ã¯ç¬¬äžçŽã®çåæ°ŽçŽ åºã§ããã
FIG. 1 is a flowchart of the Ziegler catalyst of the present invention. In this figure, R is a secondary or tertiary hydrocarbon group.
Claims (1)
ç³»ååç©ã(b)äžè¬åŒãTiïŒORïŒ4ã§ç€ºããã
ã¢ã«ã³ãã·ãã¿ã³ç³»ååç©ããã³(c)äžè¬åŒã
AlïŒORïŒ3ã§ç€ºãããã¢ã«ã³ãã·ã¢ã«ãããŠ
ã ç³»ååç©ïŒãã ããã¯ç¬¬äºçŽãŸãã¯ç¬¬äž
çŽã®çåæ°ŽçŽ åºïŒãããªã矀ããããã°ãã
å°ãªããšãäžçš®ã®ååç©ãšã®åå¿ç©ãçæã
ãããšã«ãã€ãŠåŸãããçåæ°ŽçŽ äžæº¶æ§ã®åº
äœè§Šåªæåãš (B) ææ©ã¢ã«ãããŠã ååç© ãšããåŸããã觊åªç³»ã§ãšãã¬ã³åç¬ãŸãã¯ãšã
ã¬ã³ãšå€ããšã50ã¢ã«ïŒ ã®Î±âãªã¬ãã€ã³ãéå
ããããšãç¹åŸŽãšããæ¹è¯ããããšãã¬ã³ç³»éå
äœã®è£œé æ¹æ³ã[Claims] 1 (A) (1) Titanium tetrachloride; (2) (a) an alcoholic compound whose general formula is R-OH; (b) whose general formula is Ti(OR) 4 The alkoxytitanium compound and (c) general formula are
By aging a reaction product with at least one compound selected from the group consisting of alkoxyaluminum compounds represented by Al(OR) 3 (where R is a secondary or tertiary hydrocarbon group). (B) an organoaluminum compound; and (B) an organoaluminum compound. Method for producing a polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1495178A JPS54107990A (en) | 1978-02-14 | 1978-02-14 | Method of making improved ethylene polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1495178A JPS54107990A (en) | 1978-02-14 | 1978-02-14 | Method of making improved ethylene polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS54107990A JPS54107990A (en) | 1979-08-24 |
JPS6312881B2 true JPS6312881B2 (en) | 1988-03-23 |
Family
ID=11875273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1495178A Granted JPS54107990A (en) | 1978-02-14 | 1978-02-14 | Method of making improved ethylene polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS54107990A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1199833B (en) * | 1986-11-10 | 1989-01-05 | Himont Inc | CATALYSTS FOR THE PREPARATION OF ALPHA-OLEPHINE POLYMERS IN CLOSE DISTRIBUTION OF MOLECULAR WEIGHTS |
-
1978
- 1978-02-14 JP JP1495178A patent/JPS54107990A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS54107990A (en) | 1979-08-24 |
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