JPH037704A - Polypropylene having ultra-high-molecular weight and production thereof - Google Patents
Polypropylene having ultra-high-molecular weight and production thereofInfo
- Publication number
- JPH037704A JPH037704A JP20377789A JP20377789A JPH037704A JP H037704 A JPH037704 A JP H037704A JP 20377789 A JP20377789 A JP 20377789A JP 20377789 A JP20377789 A JP 20377789A JP H037704 A JPH037704 A JP H037704A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- propylene
- molecular weight
- organic
- ultra
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 60
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 47
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004711 α-olefin Substances 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 150000003609 titanium compounds Chemical class 0.000 claims description 14
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000007787 solid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 4
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001399 aluminium compounds Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100284769 Drosophila melanogaster hemo gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- PVQVJLCMPNEFPM-UHFFFAOYSA-N bis(2-methylpropyl) hydrogen phosphate Chemical compound CC(C)COP(O)(=O)OCC(C)C PVQVJLCMPNEFPM-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 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
- 238000013507 mapping Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-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
- 235000012149 noodles Nutrition 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
〔産業上の利用分野〕
本発明は、高い結晶性を有し、成形性及び成形品の機械
的特性に優ねた超高分子量ポリプロピレンに1141−
1’ル。
〔従来技術及び発明が解決しようとする課題〕超高分子
量ポリエチレンは、従来のポリエチレンに比べて耐衝撃
性、#摩耗性、耐薬品性および引張強度等に優ねており
、エンジニアリングプラスチックとしての用途が広かつ
ている。ポリプロピレンについても分子量を大きくする
ことによってポリエチレンと同様に機械的特性が向上す
ると予想される。そして、例えは、特開昭62−228
08号公報では、粘度平均分子量が200〜500力、
或いはそれ以上の超高分子量ポリプロピレンが得られて
イル。
しかしながら、上記の超高分子量ポリプロピレンは、分
子量が十分に大きいが、結晶性が低いという欠点があっ
た。本発明者らがs詔したところによると、ポリプロピ
レンの分子量を大きくすると結晶性が低下するという傾
向が認められた。このために(3)
超高分子量で且つ高結晶性という二つの要件を同時に満
たすポリプロピレンは伶られていない。
〔課題を解決するための手段〕
本発明者らは、超高分子量で且つ高結晶性のポリフロピ
レンを得ることを目的として鋭意、研究を1ねた結果、
上記の二つの要件を同時に満した優れた物性を示すポリ
フロピレンの製造に成功し、本発明を完成させる←至っ
た。
即ち、本発明は、
囚 フロピレンに基づく単鎗体車位が95モル%を越え
て100モル%以下、プロピレン以外のα−オレフィン
に基づく単組体単位が0モル%以上5モル%未満であり
、
(片 1量平均分子組が100万以上であり、且つ
(C4P−キシレン可溶分が1.01f1%以下である
ことを特徴とする超高分子量ポリ(4)
フロピレンである
本発明の超高分子にポリプロピレンは、プロピレンの単
独重合体又は、エチレン、1−プデン、1−ヘキセン、
1−オクテン、4−メチル−1ペンテン等のプロピレン
以外のα−オレフィン5モル%未満と95モル%を越え
るフロピレンとのランダム共1合体である。
本発明の超高分子量ポリプロピレンは、電量平均分子量
が100万以上である。l量平均分子量が100万未満
の場合には、超高分子量ポリプロピレンに特有の優れた
機械的特性が発揮されないために好ましくない。本発明
の超高分子量ポリプロピレンのit平均分子h1は10
0万以上であれは良いか、優れた機械的特性を得るため
には150カ〜700力、さらには150カ〜300力
の範囲であることが好ましい
本発明の超高分子量ポリプロピレンは、高結晶性である
。即ち、P−キシレン可溶(5)
分は1011%以下である。P−キシレン可溶分が10
重量%を超えた場合には、分子量を大きくしたことによ
る機械的特性の向上というメリットが十分に発揮されな
いために好ましくない。P−キシレン可溶分はtoi1
%以下であれば良いが、0.81i%以下、さらにはo
、6mM%以下という極めて高結晶性のポリプロピレン
と−f’ルこともできる。
尚、上記のP−キシレン可溶分は後述する方法により測
定された値である。
本発明の超高分子量ポリプロピレンの上記した結晶性に
は、立体規則性が大きく影智する。本発明の超高分子量
ポリプロピレンの立体規則性は、+3C−核磁気共鳴ス
ペクトル(以下、13C−NMRと略記する)により測
定されたペンタッド分率で表示すると0.96以上とな
り、097以上、さらには0.98以上とすることもで
きる。
また、本発明の超高分子量ポリプロビレ(6)
ンは、低分子量成分の鼠が著しく少ないために、さらに
良好な機械的特性を示す。即ち、ゲルパーミェーション
・クロマトグラフィー(GPC)で測定した溶出曲線に
おいて、分子量1カ以下の成分が全体の10重it%以
下、さらには0.5 li @%以下である超高分子量
ポリプロピレンが得られる。
本発明の超高分子量ポリプロピレンは、重合により粉体
として得られる。この粉体の見掛は比重は、通常0.3
0〜0.4 s 11/cdの範囲であり、取扱いの点
からは0.35〜0.4Of?/−の範囲であることが
好ましい。
本発明の超高分子量ポリプロピレンは、次のような挙動
を示す。即ち、重合により得られた超高分子量ポリプロ
ピレンの粉体は、130℃のP−キシレンに1m!t%
の濃度で溶解させた場合、通常は金粉体のうち80!膳
%以上、さらには後述する実施例では100*敞Sが溶
解する。しかし、−旦溶解させた後にP−キシレンを蒸
発又は冷却することによって回収した粉体は、130℃
のP−キシレンにlX堵%の濃度で溶解させようとして
も、金粉体の高々40重量%しか溶解しない。
また、1合により得られた上記の粉体は、射出成形、押
出成形、プレス成形等の通常の成形方法により容易に成
形可能であるが、−度成形されたものは、再び通常の成
形方法では成形できなくなる。しかも、−度成形された
ものは、上記した130℃のP−キシレンに一旦溶解さ
せたものと同様に、130℃のP−キシレンには溶解し
麺くなる。
本発明の超高分子量ポリプロピレンが上記したような挙
動を示す原因は、未だ解明されていないが、本発明者ら
は次のように推測している。超高分子量ポリプロピレン
が、−良熱的または浴剤により溶融または溶解さね、そ
れが再び結晶化する際に高分子鎖が絡まりあい、あたか
も架橋したかのような挙動を示す。このために再度の熱
的な溶融や溶剤による溶解が困難になるものと考えてい
る。
本発明の超高分子量ポリプロピレンは、どのような方法
によって得ても良いが、特に次の方法が好ましく採用さ
れる。
下記成分A、B及びC
A、チタン化合物
B、有機アルミニワム化合物
C0一般式CI)
Rn S i (OR’ ) 4−m
で示される有機ケイ素化合物
の存在下にプロピレンの予備立合多段で、且つ各予備重
合段階で異なる有機ケイ素化合物を用いて行なった後、
D。予備重合で得られたチタン含有ポリプロピレン
E、上記Bと同様の有機アルミニ9ム化合物
F、上記Cと同様の有機クイ素化合物
(9)
の存在下にプロピレンの単独重合又はプロピレンとプロ
ピレン以外のα−オレフィンとの共1合を行なう方法で
ある。予m重合で用いられるチタン化合物(A) は
、オレフィンの重合に使用されることが公知の化合物が
佃ら制限なく採用される。特に、チタン、マグネシウム
及びハpゲンを成分とする触媒活性の高いチタン化合物
か好適である。このような触媒活性の高いチタン化合物
は、ハロゲン化チタン、特に画境化チタンを種々のマグ
ネシウム化合物に担持させたものとなっている。
この触媒の製法は、公知の方法か側ら制限なく採用され
る。例えば、特開昭56−155206号公報、同56
−136806号公報。
同57−34103号公報、同58−8706号公報、
同58−83006号公報、同5B−138708号公
報、同58−183709号公報、同59−20640
8号公報。
同59−219311号公報、同60−81208号公
報、同60−81209号公報。
(10)
特開昭60−186508号公報、同6〇−19270
8号公報、同61−211309号公報、同61−27
1304号公報、同62−15209号公報、同62−
11706号公報、同62−72702号公報、同62
−104810号公報等に示されている方法が採用され
る。具体的には、例えは、四塩化チタンを塩化マグネ・
シ゛ウムのようなマグネシウム化合物と共粉砕する方法
、アルコール。
エーテル、エステル、ケトン又はアルデヒド等の電子供
与体の存在下にハロゲン化チタンとマグネシウム化合物
とを共粉砕する方法、又は、溶媒中でハロゲン化チタン
、マグネシウム化合物及び電子供与体を接触させる方法
等が挙げられる。
次に有機アルミニウム化合物(2) も、オレフィン
の重合に使用されることが公知の化合物が伺ら制限なく
採用される 例えは、トリメチルアルミニウム、トリエ
チルアルミニウム、トリーnプロピ”ルアルミニウム、
トリーnブチルアルミニウム、トリー1ブチルアルミニ
ウム、トリーnへ午ジルアルミニウム。
トリーnオクチルアルミニウム、トリーnデシルアルミ
ニウム等のトリアルキルアルミニワム類;ジエチルアル
ミニウムモノクロライド等のジエチルアルミニウムモノ
ハライド類;メチルアルミニウムセスキクロライド、エ
チルアルミニウムセスキクロライド、エチルアルミニウ
ムジクロライド等のアルキルアルミニウムハライド類な
どが挙げられる。他に七ノエト千シジエチルアルミニウ
ム、ジェトキシモノエチルアルミニウム等のアルコキシ
アルミニウム類を用いることができる。中でもトリエチ
ルアルミニウムが最も好ましい。
各千m’M合波階で使用する有機アルミニウム化合物の
使用縁はチタン化合物中のTi1lX子に対しA[/T
i (モル比)で1〜100、好萱しくは2〜2θであ
る。
さらに、有機ケイ素化合物〔C〕は、前記−般式(I)
で示される化合物が側ら制限なく採用される。一般式(
I)中のR及びR’は、アルキル基、アルケニル基、ア
ル牛ニル基及びアリール基等の炭化水素基である。本発
明において好適に用いられる有機ケイ素化合物を例示す
ると、次のとおりである。例えは、トリメチルメトキシ
シラン、トリメチルエトキシシラン、ジメチルジメトキ
シシラン、ジメチルジメトキシシラン、ジフェニルジメ
ト牛ジシラン、メチルフエニルジメトキシシラン。
ジフェニルジェトキシシラン、エチルトリメトキシシラ
ン、メチルトリメト牛ンシラン。
ヒニルトリメトキシシラン、フェニルトリメト午ジシラ
ン、エチルトリエトキシシラン。
エチルトリエトキシシラン、ビニルトリエト牛ジシラン
、ブチルトリエト千ジシラン5 フェニルトリエトキシ
シラン、6−ドリエト千シシリル2−ノルボルネンなど
である。
各予備重合段階で用いる有機tイ素化合物の使用量はチ
タン化合物中のTii子に対しSi/Ti (%ル比)
で0.1〜100.好ましく13)
くは05〜】0である。
本発明においては、上記したチタン化合物〔A〕、有機
アルミニウム化合物CB〕及び有機ケイ素化合物(C)
に加えて、下記一般式(n)R″−1(1)
で示されるg9素化合物CD)を用いることが、得られ
る超高分子量ポリプロピレンの結晶性がさらに高くなる
ために好ましい。
前記一般式(n)中、R″で示される炭化水素基は、ア
ル牛ル基、アルケニル基、アルキニル基又はアリール基
等である。本発明で好適に使用し得るヨウ素化合物を具
体的に示すと次のとおりである。例えは、ヨウ素、ヨウ
化メチル、ヨウ化エチル、ヨウ化10ヒル、ヨウ化ブチ
ル、ヨードベンゼン、P−ヨウ化トルエン等である。中
でもヨウ化メチル、ヨウ化エチルが好ましい。各チ@重
合段階で用いるヨウ素化合物の使用量はチタン化合物中
の(14)
チタン原子に対し、I/Tt(モル比)で、0. IN
2O3,好ましくはα5〜5oである。
本発明において、予備1合を多設階に行なうとは、上記
(A)、 [:2)、 (C)および必要により用いら
れるCD)の各成分の存在下にプロピレンをf Ii
1[合し、得られたチタン含有ポリプロピレンと上記C
B]、 (C) および必要により用いらねる(D)
の各成分の存在下にさらにプロピレンの予備1合をMt
り返し行なうことをいう。予備重合は2〜5回の範囲で
行なうことが好ましい。各予備重合段階で用いる上記の
各成分は逐次添加されてもよく、−括混合したものを用
いても良い3.各予備重合段階でのプロピレンの1合財
は、チタン化合物II当り、0,1〜100.9’、好
ましくは1〜100どの範囲であり、工業的には2〜5
0.9の範囲が好適である。
各予備重合段階では、夫々異なる種類の有機ケイ素化合
物が用いられる。有機ナイ素化合物としては、nσ記一
般式CI)中のR及びR′の少くとも一方が嵩尚い炭化
水素基、例えばフェニル基、シクロヘキシル基又はノル
ボルニル基等である化合物を用いることが、高結晶性の
超高分子にポリプロピレンが得られるために好ましい。
各予備重合段階で用いられる有機ケイ素化合物の使用順
序は特に制限されない。
各チ(illlf合ではプロピレンを単独で1合させて
も良く、エチレン、1−ブテン、l−ペンテン、1−ヘ
キセン、4−メチルペンテン−1などのプロピレン以外
のα−オレフィンとプロピレンとを共1合させても良い
。しかし、立体規則性の向上を勘案すると、プロピレン
を95モル第以上用いることが好箇しい。
また各予備重合の段階で水素を共存させることも可能で
ある。
各予備重合は通常スラリー重合を適用させるのが好まし
く、溶媒として、ヘキサン、ヘプタン。シクロへ牛サン
、ベンゼン、トルエンなどの飽和脂肪族炭化水素若しく
は芳香族炭化水素を単独で、又はこれらの混合溶媒を用
いることかできる。、各予in合温度は、−20〜10
0℃、特に0〜60℃の温度が好1しく、予備重合の各
段階では真なる温度の条件下で行ってもよい、予備1合
時聞は、テ備1合温度及び予備重合での重合蓋に応し適
宜決定すれば良く、予備重合における圧力は、限定され
るものではないが、スラリー1合の場合は、一般に大気
圧〜5%G&i度である。各予備重合は、回分、半回分
、連続のいずれの方法で行ってもよい。各予備1合終了
後には、ヘキサン、ヘプタン、シクロヘキサン、ベンゼ
ン、トルエン等の飽和脂肪族炭化水素若しくは芳香族炭
化水素を単独で、または混合溶媒で洗浄することが好ま
しく、洗浄回数は通常の場合5〜6回が好ましい。
上記予備重合の後に本1合が行なわれる。
本重合は、上記の予備1合により得られ、たチタン含有
ポリプロピレン、有機アルミニウム化合物、有機ケイ素
化合物の存在下に行なわ(17)
れる。
本重合で用いられる有機アルミニウム化合物は、前述の
予備重合に用いたものが使用でき、最も好ましくはトリ
エチルアルミニウムである。有機アルミニウム化合物の
使用量はチタン含有ポリプロピレン中のチタン原子に対
し、Am!/Tt(モル比)で、10〜1000゜好ま
しくは、50〜500である。
さらに、有機ケイ素化合物は、前記一般式CIEで示さ
れる化合物が伺らl11限なく採用される。本1合で用
いる有機ケイ素化合物の使用量はチタン含有ポリプロピ
レン中のTiff1子に対しSt/Tt (%#比)
で0.1〜1000゜好ましくは0.5〜500である
。
その他の1合条件は、本発明の効果が認められる限り、
特に制限はしないが、一般には次の条件が好ましい。1
合温度は20〜200℃、好ましくは50〜150℃で
あり、分子jltM節剤として水素を共存させることも
できる。また、重合はスラリー重合、無溶媒重合(]8
)
及び気相重合にも適用でき、回分式、牛回分式、連続式
の伺れの方法でもよく、更に1合を条件の異なる2段以
上に分けて行うこともできる。
本重合ではプロピレンを単独で1合させてもi<、エチ
レン、1−プデン、1−ペンテン、1−ヘキセン、4−
メチルペンテン−1などのプロピレン以外のα−オレフ
ィンとプロピレンとを共重合させても良い。共1合を行
なう場合は、得られる超高分子量ポリプロピレンの単量
体単位の組成がプロピレンに基づく単量体単位が95モ
ル%を越え、プロピレン以外のα−オレフィンに基づく
単量体単位が5モル%未満となるように共重合が行なわ
れる。
更に炭X数3以上のオレフィンの立体規則性制御のため
、エーテル、アミン、アミド。
含硫黄化合物、ニトリル、カルボン酸、酸アミド、酸無
水物、酸エステルなどの電子供与体を共存させることが
できる。
本発明の超高分子量ポリプロピレンは、射出成形、押出
成形、プレス成形など各種の成形法により種々の形状を
有する成形品にすることができる。
成形に際し、本発明の超高分子量ポリプロピレンに、従
来のポリオレフィンに用いられている各種の添加剤及び
成形助剤を添加してもよい。
〔効 果〕
本発明の超高分子量ポリプロピレンは、分子量が大きく
且つ結晶性も高い1.従って、超高分子量であることに
よる機械的特性の向上というメリットが十分に発揮され
、優れた物性を有するポリプロピレンとなる。即ち、本
発明の超高分子量ポリプロピレンは、曲げ弾性率、耐熱
性、*撃強度に優れたものである。
このため、本発明の超高分子量ポリプロピレンハ、 歯
車、パツキン、ガスケット等の機械部品;ラジェーター
タンク、ウオッシャ−タンク、インナーパネル等の自動
車部品;スポーツ用品材料;各種ライニング材として市
いることができる。
〔実施例〕
以下、本発明を実施例及び比較例を掲けて説明するが、
本発明はこれらの実施例に限定されるものではない。
以下の実施例において用いた測定方法について説明する
。
(1) 重量平均分子量
GPC(ゲルパーミェーションクルマドグラフィー)法
により測定した。ウォーターズ社製GPC−150Cに
より、0−ジクロルベンゼンを溶媒とし、135℃で行
った。用いたカラムは、東ソー製TSKgep GM
H6−HT、ゲルサイズ10〜15μである。較正曲線
は標準試料としてI11量平均分子社が950.290
0. ]万。
5万、49.8力、270力、675万のポリスチレン
を用いて作成した。
(2メルトインデックス(以下、Mlと略す)(21)
ASTMD−1238に準拠
(3)P−キシレン可溶分
ポリ?−1,9ikP−キシレン1ooccに加え攪拌
しながら130℃に昇温した後、更に30分攪拌を続け
、均一なP−キシレン溶液を調製した。その後室温(2
3℃)まで放冷後、24時間放置した。析出したゲル状
物はろ別し、P−キシレン溶液を完全に濃縮することで
可溶公証を求めた。
P−キシレン可溶分(%)=P−キシレン可溶分IJX
100で表わされる。
(4) 13C−NMRペンタッド分率A、 zaw
belli等によってMacro+noleaulee
6,925 (1973)に発表されている方法、
すなわち、I3C−NMRを用いポリマー分子鎖中の連
続した七ツマー5個のアイソタクチックに結合した分率
である。
測定はJ EOLGSX−270を用いてパルス幅90
0.パルス間隔15秒、積算1oooo回で行った。ピ
ークの帰属はMac(22)
rornoleculea 8,697 (1975)
に従って行った。
(5) 見掛は比憲
JIS K6721 (1977年)に準拠した。
(6)曲げ弾性率
日本製鋼所 J120SA[型 射出成形機により63
.6mX I 17mX0.31tmの試験片を作成し
ASTM:1)−790に準じて行った。
(7) 熱変形温度
日本製鋼所J120SA11型 射出成形機により63
,6寓冨XI 2.7mmX0.31Nの試験片を作成
し、ASTM : D−648に準じて行った。
(8) アイゾツト幽撃敏
日本製鋼所J120SAII型 射出成形機により12
7 X ] Z 7 X 3.17511111 /
ツチ付試験片を作成し、ASTM:D−256[Industrial Application Field] The present invention is directed to ultra-high molecular weight polypropylene having high crystallinity and excellent moldability and mechanical properties of molded products.
1'le. [Prior art and problems to be solved by the invention] Ultra-high molecular weight polyethylene has superior impact resistance, abrasion resistance, chemical resistance, tensile strength, etc. compared to conventional polyethylene, and is suitable for use as engineering plastics. is wide. It is expected that increasing the molecular weight of polypropylene will improve its mechanical properties in the same way as polyethylene. For example, JP-A No. 62-228
In Publication No. 08, the viscosity average molecular weight is 200 to 500,
Or even higher ultra-high molecular weight polypropylene can be obtained. However, although the above-mentioned ultra-high molecular weight polypropylene has a sufficiently large molecular weight, it has a drawback of low crystallinity. According to the edicts of the present inventors, it has been observed that as the molecular weight of polypropylene is increased, the crystallinity tends to decrease. For this reason, polypropylene that simultaneously satisfies the two requirements of (3) ultra-high molecular weight and high crystallinity is no exception. [Means for Solving the Problems] As a result of intensive research aimed at obtaining ultra-high molecular weight and highly crystalline polypropylene, the present inventors have found that
We have succeeded in producing polypropylene that exhibits excellent physical properties that simultaneously satisfy the above two requirements, and have completed the present invention. That is, the present invention is characterized in that the proportion of monomer units based on fluoropylene is more than 95 mol% and less than 100 mol%, and the monoassembly unit based on α-olefin other than propylene is 0 mol% or more and less than 5 mol%, The ultra-high molecular weight poly(4) fluoropylene of the present invention is characterized by having a weight average molecular set of 1,000,000 or more and a (C4P-xylene soluble content of 1.01f1% or less). The molecule of polypropylene is a propylene homopolymer, ethylene, 1-butene, 1-hexene,
It is a random comonomer of less than 5 mol % of α-olefin other than propylene such as 1-octene and 4-methyl-1 pentene and more than 95 mol % of propylene. The ultra-high molecular weight polypropylene of the present invention has a coulometric average molecular weight of 1 million or more. If the weight average molecular weight is less than 1 million, it is not preferable because the excellent mechanical properties characteristic of ultra-high molecular weight polypropylene are not exhibited. The it average molecule h1 of the ultra-high molecular weight polypropylene of the present invention is 10
The ultra-high molecular weight polypropylene of the present invention has a high crystallinity. It is gender. That is, the P-xylene soluble (5) content is 1011% or less. P-xylene soluble content is 10
If it exceeds % by weight, it is not preferable because the advantage of improved mechanical properties due to increased molecular weight will not be fully exhibited. P-xylene soluble content is toi1
% or less, but 0.81i% or less, and even o
, 6mM% or less, extremely highly crystalline polypropylene. The above P-xylene soluble content is a value measured by the method described below. The above-mentioned crystallinity of the ultra-high molecular weight polypropylene of the present invention is greatly influenced by stereoregularity. The stereoregularity of the ultra-high molecular weight polypropylene of the present invention is 0.96 or more when expressed as a pentad fraction measured by +3C-nuclear magnetic resonance spectrum (hereinafter abbreviated as 13C-NMR), 097 or more, and even more. It can also be set to 0.98 or more. Furthermore, the ultra-high molecular weight polypropylene (6) of the present invention exhibits even better mechanical properties because it contains significantly less low molecular weight components. That is, in the elution curve measured by gel permeation chromatography (GPC), ultra-high molecular weight polypropylene in which the component with a molecular weight of 1 or less is less than 10 wt % of the total, and even less than 0.5 li @ %. is obtained. The ultra-high molecular weight polypropylene of the present invention is obtained as a powder by polymerization. The apparent specific gravity of this powder is usually 0.3
It is in the range of 0 to 0.4 s 11/cd, and from the point of view of handling, it is 0.35 to 0.4Of? A range of /- is preferable. The ultra-high molecular weight polypropylene of the present invention exhibits the following behavior. That is, the ultra-high molecular weight polypropylene powder obtained by polymerization was immersed in P-xylene at 130°C for 1 m! t%
When dissolved at a concentration of , typically 80! % or more, and even more so in the examples described later, 100*敞S is dissolved. However, the powder recovered by evaporating or cooling the P-xylene after it has been dissolved is
Even if an attempt is made to dissolve the gold powder in P-xylene at a concentration of 1X%, only 40% by weight of the gold powder will be dissolved at most. In addition, the above-mentioned powder obtained by 1-degree molding can be easily molded by ordinary molding methods such as injection molding, extrusion molding, and press molding. This makes it impossible to mold. Moreover, the molded product dissolves in P-xylene at 130°C to form noodles, similar to the above-mentioned product once dissolved in P-xylene at 130°C. Although the reason why the ultra-high molecular weight polypropylene of the present invention exhibits the above-described behavior has not yet been elucidated, the present inventors speculate as follows. Ultra-high molecular weight polypropylene is melted or undissolved by heat or bath agents, and when it crystallizes again, the polymer chains become entangled and behave as if they were crosslinked. It is believed that this makes it difficult to thermally melt the material again or to dissolve it using a solvent. The ultra-high molecular weight polypropylene of the present invention may be obtained by any method, but the following method is particularly preferably employed. The following components A, B and C A, titanium compound B, organic aluminum compound C0 general formula CI) Rn Si (OR') 4-m Pre-preposition of propylene in multiple stages in the presence of an organosilicon compound represented by After being carried out with different organosilicon compounds in the prepolymerization step, D. Homopolymerization of propylene or propylene and α other than propylene in the presence of titanium-containing polypropylene E obtained by prepolymerization, an organic aluminum compound F similar to B above, and an organic aluminium compound (9) similar to C above. - This is a method for co-merging with olefins. As the titanium compound (A) used in the prepolymerization, any compound known to be used in the polymerization of olefins can be used without any restriction. Particularly suitable are titanium compounds with high catalytic activity that contain titanium, magnesium, and halogen. Such titanium compounds with high catalytic activity are those in which titanium halide, particularly bordered titanium, is supported on various magnesium compounds. The method for producing this catalyst may be any known method without limitation. For example, JP-A-56-155206, JP-A-56-155206;
-136806 publication. Publication No. 57-34103, Publication No. 58-8706,
58-83006, 5B-138708, 58-183709, 59-20640
Publication No. 8. Publications No. 59-219311, No. 60-81208, and No. 60-81209. (10) JP-A-60-186508, JP-A No. 60-19270
Publication No. 8, Publication No. 61-211309, Publication No. 61-27
No. 1304, No. 62-15209, No. 62-
No. 11706, No. 62-72702, No. 62
The method disclosed in Japanese Patent No.-104810 and the like is adopted. Specifically, for example, titanium tetrachloride is replaced by magnetic chloride.
Method of co-grinding with magnesium compounds such as sium, alcohol. A method of co-pulverizing a titanium halide and a magnesium compound in the presence of an electron donor such as an ether, an ester, a ketone, or an aldehyde, or a method of bringing a titanium halide, a magnesium compound, and an electron donor into contact in a solvent, etc. Can be mentioned. Next, as the organoaluminum compound (2), any compound known to be used in the polymerization of olefins can be used without any restriction.For example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
tri-n butyl aluminum, tri-n butyl aluminum, tri-n hemo dial aluminum. Trialkylaluminums such as tri-n octyl aluminum and tri-n-decyl aluminum; diethyl aluminum monohalides such as diethyl aluminum monochloride; alkyl aluminum halides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, and ethyl aluminum dichloride; Can be mentioned. In addition, alkoxyaluminums such as 7-ethylaluminum and jetoxymonoethylaluminum can be used. Among them, triethylaluminum is most preferred. The edge of the organoaluminum compound used in each 1,000m'M multiplexing floor is A [/T
i (molar ratio) is 1 to 100, preferably 2 to 2θ. Furthermore, the organosilicon compound [C] is represented by the general formula (I)
Compounds represented by can be employed without restriction. General formula (
R and R' in I) are hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, and an aryl group. Examples of organosilicon compounds preferably used in the present invention are as follows. Examples are trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. Diphenyljethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane. Hinyltrimethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane. Examples include ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, 5 phenyltriethoxysilane, and 6-dryethoxysilane 2-norbornene. The amount of organic compound used in each prepolymerization step is Si/Ti (% ratio) based on Ti atoms in the titanium compound.
0.1~100. Preferably 13) is 05 to 0. In the present invention, the above titanium compound [A], organoaluminum compound CB] and organosilicon compound (C)
In addition, it is preferable to use the g9 compound CD) represented by the following general formula (n)R''-1(1) because the crystallinity of the obtained ultra-high molecular weight polypropylene is further increased. In (n), the hydrocarbon group represented by R'' is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or the like. Specific examples of iodine compounds that can be suitably used in the present invention are as follows. Examples are iodine, methyl iodide, ethyl iodide, 10hi iodide, butyl iodide, iodobenzene, p-toluene iodide, and the like. Among them, methyl iodide and ethyl iodide are preferred. The amount of the iodine compound used in each Ti@polymerization step is I/Tt (molar ratio), based on the (14) titanium atom in the titanium compound. IN
2O3, preferably α5-5o. In the present invention, carrying out the preparation on multiple floors means that propylene is prepared in the presence of each of the components (A), [:2), (C) and CD used as necessary.
1 [by combining the obtained titanium-containing polypropylene and the above C
B], (C) and (D) if necessary.
An additional 1 cup of propylene is added to Mt in the presence of each component of Mt.
It means doing something over and over again. Prepolymerization is preferably carried out 2 to 5 times. The above-mentioned components used in each prepolymerization step may be added sequentially or may be mixed together.3. One mass of propylene in each prepolymerization step is in the range of 0.1 to 100.9', preferably 1 to 100, and industrially 2 to 5.
A range of 0.9 is preferred. A different type of organosilicon compound is used in each prepolymerization step. As the organic nitrogen compound, it is preferable to use a compound in which at least one of R and R' in the nσ general formula CI) is a bulky hydrocarbon group, such as a phenyl group, a cyclohexyl group, or a norbornyl group. This is preferred because polypropylene can be obtained as a crystalline superpolymer. The order of use of the organosilicon compounds used in each prepolymerization step is not particularly limited. In each case, propylene may be combined alone, or propylene may be combined with α-olefin other than propylene such as ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methylpentene-1. However, considering the improvement of stereoregularity, it is preferable to use 95 moles or more of propylene.It is also possible to coexist hydrogen at each prepolymerization stage.Each prepolymerization It is usually preferable to apply slurry polymerization to the polymerization, and as a solvent, a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, or toluene is used alone, or a mixed solvent thereof is used. , each pre-in combination temperature is -20 to 10
A temperature of 0°C, especially 0 to 60°C is preferred, and each stage of prepolymerization may be carried out under true temperature conditions. The pressure in the prepolymerization is not limited and may be appropriately determined depending on the polymerization lid, but in the case of 1 cup of slurry, it is generally from atmospheric pressure to 5% G&I degree. Each prepolymerization may be carried out in batch, semi-batch or continuous manner. After each preliminary 1 cup is completed, it is preferable to wash with a saturated aliphatic hydrocarbon or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, toluene, etc. alone or with a mixed solvent, and the number of washings is usually 5. ~6 times is preferred. After the above preliminary polymerization, the main polymerization is carried out. The main polymerization is carried out in the presence of the titanium-containing polypropylene, organoaluminum compound, and organosilicon compound obtained in the preliminary 1 reaction described above (17). As the organoaluminum compound used in the main polymerization, those used in the prepolymerization described above can be used, and triethylaluminum is most preferred. The amount of organoaluminum compound used is Am! based on the titanium atoms in the titanium-containing polypropylene. /Tt (mole ratio) is 10 to 1000°, preferably 50 to 500. Further, as the organosilicon compound, a compound represented by the general formula CIE can be used without any limitation. The amount of organosilicon compound used in this first case is St/Tt (%# ratio) per Tiff in the titanium-containing polypropylene.
is 0.1 to 1000°, preferably 0.5 to 500°. The other conditions are as long as the effects of the present invention are recognized.
Although not particularly limited, the following conditions are generally preferred. 1
The combination temperature is 20 to 200°C, preferably 50 to 150°C, and hydrogen can also be present as a molecular jltM moderating agent. In addition, polymerization can be slurry polymerization, solventless polymerization (]8
) It can also be applied to gas phase polymerization, and may be carried out in batch, batch, or continuous methods, and it is also possible to divide one batch into two or more stages under different conditions. In the main polymerization, even if propylene is combined alone, i<, ethylene, 1-puden, 1-pentene, 1-hexene, 4-
Propylene may be copolymerized with α-olefin other than propylene, such as methylpentene-1. When carrying out the co-1 polymerization, the composition of the monomer units of the obtained ultra-high molecular weight polypropylene is such that the proportion of monomer units based on propylene exceeds 95 mol %, and the proportion of monomer units based on α-olefins other than propylene is 5 mol %. Copolymerization is carried out so that the amount is less than mol %. Furthermore, ethers, amines, and amides are used to control the stereoregularity of olefins having 3 or more carbon atoms. Electron donors such as sulfur-containing compounds, nitriles, carboxylic acids, acid amides, acid anhydrides, and acid esters can be present. The ultra-high molecular weight polypropylene of the present invention can be made into molded articles having various shapes by various molding methods such as injection molding, extrusion molding, and press molding. During molding, various additives and molding aids used in conventional polyolefins may be added to the ultra-high molecular weight polypropylene of the present invention. [Effects] The ultra-high molecular weight polypropylene of the present invention has a large molecular weight and high crystallinity.1. Therefore, the advantage of improved mechanical properties due to the ultra-high molecular weight is fully exhibited, resulting in polypropylene having excellent physical properties. That is, the ultra-high molecular weight polypropylene of the present invention has excellent flexural modulus, heat resistance, and impact strength. Therefore, the ultra-high molecular weight polypropylene of the present invention can be commercially used as mechanical parts such as gears, packings, and gaskets; automobile parts such as radiator tanks, washer tanks, and inner panels; sports equipment materials; and various lining materials. [Example] The present invention will be explained below with reference to Examples and Comparative Examples.
The present invention is not limited to these examples. The measurement method used in the following examples will be explained. (1) Weight average molecular weight Measured by GPC (gel permeation columnar mapping) method. The test was carried out at 135° C. using 0-dichlorobenzene as a solvent using GPC-150C manufactured by Waters. The column used was TSKgep GM manufactured by Tosoh.
H6-HT, gel size 10-15μ. The calibration curve is 950.290 by I11 weight average molecular company as a standard sample.
0. ]Ten thousand. It was created using polystyrene with a strength of 50,000, 49.8, 270, and 6,750,000. (2 melt index (hereinafter abbreviated as Ml) (21) Based on ASTM D-1238 (3) P-xylene soluble content Poly?-1,9ik After adding to 100cc of P-xylene and raising the temperature to 130 ° C. with stirring, Stirring was continued for another 30 minutes to prepare a homogeneous P-xylene solution.
After cooling to 3° C.), it was left for 24 hours. The precipitated gel was filtered off, and the P-xylene solution was completely concentrated to obtain a soluble notary. P-xylene soluble content (%) = P-xylene soluble content IJX
It is expressed in 100. (4) 13C-NMR pentad fraction A, zaw
Macro+noleaulee by belli et al.
6,925 (1973),
That is, it is the fraction of isotactic bonding of five consecutive seven-mers in a polymer molecular chain using I3C-NMR. Measurements were made using J EOLGSX-270 with a pulse width of 90
0. The pulse interval was 15 seconds, and the total number of pulses was 1oooo. The peak assignment is Mac (22) ronoleculea 8,697 (1975)
I followed. (5) Appearance conforms to Hiken JIS K6721 (1977). (6) Bending elastic modulus Japan Steel Works J120SA [63 by injection molding machine]
.. A test piece of 6 m x I 17 m x 0.31 tm was prepared and tested in accordance with ASTM:1)-790. (7) Heat distortion temperature 63 by Japan Steel Works J120SA11 type injection molding machine
A test piece of 2.7 mm x 0.31 N was prepared and tested in accordance with ASTM: D-648. (8) Izotsu Yugeki Bin Japan Steel Works J120SAII type injection molding machine 12
7 X ] Z 7 X 3.17511111 /
Create a test piece with an edge, ASTM: D-256
【隼して
23℃で測定を行った。
実施例1
〔チタン化合物の調製〕
チタン成分の調製方法は、特開昭58−83006号公
報の実施例1の方法に準して行った。すなわち無水塩化
マクネシウム095g (10mmol) 、デカン1
O−9及び2−エチルヘキシルアルコール4−7 ”
(30mmol)を125℃で2時間加熱攪拌した後、
この溶液中に無水フタル酸0.55Ji’ (3,75
mmol)を添加し、125℃にてさらに1時間攪拌混
合を行い、均一溶液とした。室温まで冷却した後、12
0℃に保持された四塩化チタン40’LL (0,36
1o1)中に1時間にわたって全量滴下装入した。装入
終了後、この混合液の温度を2時聞かけて110℃に昇
温し、110℃に達したところでジインブチルフタレー
ト0.54117(15を五m01)を添加し、これよ
り2時間同温度にて攪拌下保持した。2時間の反応路T
後熱濾過にて固体部を採取し、この固体部を200鮎の
TtC14にて再懸濁させた後、再び110℃で2時1
均、加熱反応を行なった5反応終了後、再び熱濾過にて
固体部を採取し、デカン汲ひへ牛サンにて、洗液中に遊
離のチタン化合物が検出されなくなるまで充分洗浄した
。以上の製造方法にて調製された固体Ti触媒成分は、
ヘプタンスラリーとして保存した。固体1゛1触媒成分
の組成はチタン2.11量%、壌素571敏%、マグネ
シウム18.0重量婆、及びジイソブチルフタレー)2
1.911ノ%であった。
〔ヂ備1合〕
N2置換をhした1/オートクレーブ中に精製へブタン
201)+1.トリエチルアルミニウム50 mmol
、ジフェニルジメトキシシラン10 mmol 、ヨ
ウ化エチル50 mmol及び固体T1触媒成分をTi
原子換算で5濯mol装入した後、プロピレンを固体T
1触媒成分1gに対し59となるように1時間連続的に
反応器に導入しデ備1合1回目を施した。なお、この間
の温度は15℃に保持した。1時(25)
間抜プロピレンの導入を停止し、反応器内なN2で充分
に置換した。得られたスラリーの固体部分を精製へブタ
ンで6回洗浄した。
更にこの固体成分なN2置換を施したll−オートクレ
ーブ中に装入し、精製へブタン2001Lt、)すxチ
ルアルミニウム50mmo1゜6−ドリエトキシシリル
2−ノルボルネン10 mmol 、ヨウ化エチル10
mmolを加えた後、プロピレンを更に固体T1触媒
成分】9に対し、5.9となるように1時間、連続的に
反応器内に導入し、予備重合2回目を施した。なおこの
間の温度は15℃に保持した。
得られたスラリーの固体部分な精製ヘプタンで6回洗浄
し、チタン含有ポリプロピレンを得た。
〔本1合〕
N2置換を施した内容量400ノのオートクレーブに、
プロピレン2001 ヲ装入し、トリエチルアルミニウ
ム274 mmol、 ジフェニルジメトキシシラン
274 mmolを装入(26)
した後、オートクレーブの内温を65℃に昇温し、チタ
ン含有ポリプロヒレンをチタン原子としてl、 l @
mol 装入し、続いてオートクレーブの内温を75
℃まで昇温し、3時間σププロピレンの1合を行つtこ
。1合圧力は34製であり、この間の温度は75℃に保
持した。
3時間後未反応のプロピレンをパージし、白色顆粒状の
重合体(m合バウター)を得た。
全重合体の収量は26ゆであり、この時の活性は104
00 g −PPl& −C&t 4Hrであった。
ポリマーの重量平均分子il、メルトインデックス、P
−牛シレン可溶分、 13C−NMRベンクツド分率
、GPC曲線1万以下の重量%、見掛比重1曲げ弾性率
、熱変形温度、アイゾツト衝ml ff&について表1
に示した。
実施例2
実施例1の本1合に於いて、プロピレンを2007!装
入し、tジエチルアルミニウム274 mmol 、ジ
フェニルジメト午ジシラン274 @molを装入した
後、エチレン濃度が0.3mo1%になるようにエチレ
ンカスを装入し、オートクレーブの内温を65℃に昇温
し、予備1合で得られたチタン含有ポリプロヒレンをチ
タン原子として1.1mmol 装入し、続いてオート
クレーブの内温を70℃まで昇温し3時間σ)]i合を
行った。重合槽内のエチレン濃度は0.3mo1%に保
つようにガスクロマトク゛ラフで確認しながら断続的に
エチレンガスをフィードした。3時間後、未反応のモノ
マーをパージし、白色顆粒状の1合体を得た。
結果を表1に示した。
実施例3〜5
実施例1の本ム合に於いて、分子量調節剤として水素を
101(実施例3)、20d(実施例4)、30117
(実施例5)装入した以外は実施例1と同様の操作を行
った。結果を表1に示した。
比較例1
特開昭62−22808号公報の実施例1に示された方
法に準して、触媒成分の調製及びプロピレンの重合を行
った。結果を表1に示した。
比較例2.3
実施例1の1合に於いて、分子ixi剤として水素を8
01Ll(比較例2)、120威(比較例3)装入した
以外は実施例1と同様の操作を行った。結果を表1に示
した。
実施例6〜9
実施例10予備重合において、f備1合の2回目で用い
る有機ケイ素化合物を6−ドリエトキシシリルー2−ノ
ルボルネンσノ代わりにフェニルトリエトキシシラン(
実施例6)。
メチルトリエトキシシラン(実施例7)、メチルフエニ
ルジエト千ンシランl施例s)。
ブチルトリニドキシンラン(実施例9)を用いた以外は
実施例1と同様の操作を行゛〕だ。
結果を表2に示した。
(31)
実施例10
〔チタン化合物の調製〕
チタン化合物の調製方法は、特開昭62−104810
号公報の実施例1の方法に準して行った。
すなわち、三塩化アルミニクム(無水)100Iと水酸
化マグネシウム29.9を振動ミルで250℃にて3時
間粉砕させながら反応させた。加熱終了後、窒素気流中
で冷却し、固体生成物(I)を得た。
ガラスフラスコ中において、精製デカン15−1固体生
成物(I) ?−sy、オルトチタン酸n−ブチル8.
512−エチル−1−ヘキサノール9.8gを混合し、
攪拌しながら130℃に1.5時間加熱して溶解させ均
一な溶液とした。その溶液を70℃とし、P−)ルイル
酸エチル1.8.91を加え1時間反応させた後、攪拌
しながら四塩化ケイ素26.9を2時間かけて滴下し固
体を析出させ、更に70℃、1時曲攪拌した。面体を溶
液から分離しく33)
精製へ牛サンにより洗浄し固体生成物(II)を得た4
その固体生成物(II)全量に1.2−ジクロルエタン
301および四塩化チタン301とともに7タル酸ジイ
ンブチル1.59を加え、攪拌しながら100℃に2時
間反応させた後、同温度にてデカンテーションにより液
相部を除き、再び1,2−ジクロルエタン3Qd。
四塩化チタン30−、フタル酸ジイソブチル1、5.9
を加え、攪拌しながら100℃に2時間反応させた後、
熱濾過にて固体部を採取して精製へキサンで洗浄し、2
5℃減圧下で1時間乾燥して固体生成物(■)を得た。
固体生成物(II)は球形であり、平均粒径は15μm
で、七〇粒径分布は極めて狭いものであった。この固体
生成物(m)を固体T1触媒成分とした。
なお、該固体T1触媒成分の組成分析結果は、T 13
.0重i1%(以後%と記す)、CA’56.2襲、M
717.6%、A11.7%、フタ(34)
ル酸ジイソブチル20.1%、ブトキシ基11%、2−
エチルヘキノ千シ基02%、P−トルイル酸エチル0.
1%であった。
その後の5−備重合及び重合は実施例1と同様に行った
。また、得られた1合体の物性を表3に示した。
実施例11
〔チタン化合物の調製〕
チタン化合物の調製方法は、特開昭62−11706号
公報の実施例1の方法に準じて行った。
すなわち、窒素置換した500−内容積のガラス鯛三ツ
ロフラスコ(温度計、al拌機付き)に、50ILlの
精製へブタン、50鹸のチタンテトラブト千シト、7.
OJi’の無水塩化マグネシウムを加える。その後、フ
ラスコを90℃に昇温し、2時間かけて塩化マグネシウ
ムを完全に溶解させた。次にフラスコを40℃まで冷却
し、メチルハイドロジエンポリシロキサンlO−を添加
することにより、塩化マグネシウム、チタンテトシプト
キシド錯体を析出させた。これを精製へブタンで洗浄し
て、灰白色の固体を得た。
窒素置換した300m1内容積のガラス製三ツロフラス
コ(温度側、攪拌機付き)に、上記で得た析出固体10
gを含むヘプタンスラリー501を導入した。次いで、
四環化クイ素5.8ittを含むヘプタン溶液20−を
室温で30分かけて加えて、さらに30℃で45分間反
応させた。さらに90℃で1.5時間反応させ、反応終
了後、精製へブタンで洗浄した。
次いで、フタル酸ジヘプチル1.51L/を含むヘプタ
ン溶液501を加えて50℃で2時間反応させ、この後
、精製へブタンで洗浄し、さらに四塩化チタン25耐を
加えて90℃で2時間反応させた。これを精製へブタン
で洗浄して、固体T1触媒成分を得た。
固体T1触媒成分中のチタン含量は、3.04m1%で
あった。その後の予備重合、及び重合は実施例1と同様
に行った。また、得られた重合体の物性を表3に示した
。
比較例4
実施例1Oで得られた固体T1触媒成分を用い、比較例
1と同様の操作を行った。結果を表3に示した。
比較例5
実施例11で得られた固体T1触媒成分を用い、比較例
1と同様の操作を行った。結果を表3に示した。
実施例12〜14
実施例20本重合において、エチレンのかわりに1−プ
デン(実施例12)、4−メチルペンテン−1(実施例
13)及び1−ヘキセン(実施例14)を用い、夫々の
モノマに基づく単置体単位の組成が表4に示す値となる
ように共重合を行なった。その結果を表4に万(した。
参考例1
実施例1で得られた超高分子蓋ボリプpピレンの1合パ
ウダーを用いて220℃の熱板上で20寵X20+m厚
さ0.3酊のシートを作成した。このシートを130℃
のP−キシレン100−に1重1%の濃度で溶解を試み
たが、均一な溶液は得られず、膨潤したゲル状物が残存
していた。溶解量はシート重量の20″i置%であった
。
参考例2
実施例]で得られた超高分子量ポリプロピレン重合パウ
ダーを押出し機で造粒しペレット状とした。仁のペレッ
ト19を130℃のP−キシレン1QQsc/に溶解を
試みたが均一な溶液は得られず膨油したゲル状物が残存
していた。溶解量は全ペレット重量の18重重量子あっ
た。[Measurements were carried out at 23°C using a Hayabusa. Example 1 [Preparation of titanium compound] The titanium component was prepared according to the method of Example 1 of JP-A-58-83006. That is, 095 g (10 mmol) of anhydrous magnesium chloride, 1 decane
O-9 and 2-ethylhexyl alcohol 4-7”
(30 mmol) was heated and stirred at 125°C for 2 hours,
In this solution, 0.55Ji' of phthalic anhydride (3,75
mmol) was added thereto, and the mixture was further stirred and mixed at 125° C. for 1 hour to obtain a homogeneous solution. After cooling to room temperature, 12
Titanium tetrachloride 40'LL (0,36
The entire amount was added dropwise into a 1.0-1.0 liter vessel over a period of 1 hour. After charging, the temperature of this mixed solution was raised to 110°C over 2 hours, and when it reached 110°C, diimbutyl phthalate 0.54117 (5 m01 of 15) was added, and the mixture was heated for 2 hours. The temperature was maintained under stirring. 2 hour reaction route T
After collecting the solid part by hot filtration, this solid part was resuspended in 200 Ayu TtC14, and then heated again at 110°C for 2 hours and 1 hour.
After the completion of the 5 homogeneous and heated reactions, the solid portion was again collected by hot filtration and thoroughly washed with decane and beef saline until no free titanium compound was detected in the washing liquid. The solid Ti catalyst component prepared by the above manufacturing method is
Saved as a heptane slurry. The composition of the solid 1゛1 catalyst component is 2.11% by weight of titanium, 571% by weight of hydrogen, 18.0% by weight of magnesium, and diisobutyl phthalate)2
It was 1.911%. [Prepared 1 cup] N2-substituted 1/purified hebutane in an autoclave 201) + 1. Triethyl aluminum 50 mmol
, 10 mmol of diphenyldimethoxysilane, 50 mmol of ethyl iodide and the solid T1 catalyst component.
After charging 5 moles in terms of atoms, propylene was converted into solid T.
The catalyst component was continuously introduced into the reactor for 1 hour at a ratio of 59% to 1g of catalyst component, and the first reaction was carried out. Note that the temperature during this time was maintained at 15°C. At 1 o'clock (25), the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N2. The solid portion of the resulting slurry was washed six times with purified hebutane. Furthermore, this solid component was charged into a ll-autoclave subjected to N2 substitution, purified hebutane 2001 Lt, 50 mmol of 6-dryethoxysilyl 2-norbornene, 10 mmol of ethyl iodide,
After adding mmol, propylene was further continuously introduced into the reactor for 1 hour so that the solid T1 catalyst component [9] became 5.9 to perform a second prepolymerization. Note that the temperature during this time was maintained at 15°C. The solid portion of the obtained slurry was washed six times with purified heptane to obtain titanium-containing polypropylene. [1 cup] In an autoclave with an internal capacity of 400 tons that was subjected to N2 substitution,
After charging propylene 2001, 274 mmol of triethylaluminum, and 274 mmol of diphenyldimethoxysilane (26), the internal temperature of the autoclave was raised to 65°C, and the titanium-containing polyprohylene was converted into titanium atoms.
mol, then lower the internal temperature of the autoclave to 75
Raise the temperature to ℃ and add 1 cup of σ propylene for 3 hours. The combined pressure was 34, and the temperature during this time was maintained at 75°C. After 3 hours, unreacted propylene was purged to obtain a white granular polymer (m-butter). The total polymer yield was 26 ml, and the activity at this time was 104 ml.
00 g -PPl&-C&t 4Hr. Weight average molecule il of the polymer, melt index, P
- Table 1 regarding the soluble content of beef siren, 13C-NMR bent fraction, weight % of GPC curve of 10,000 or less, apparent specific gravity 1 flexural modulus, heat distortion temperature, Izot impact ml ff &
It was shown to. Example 2 In the first cup of Example 1, propylene was added to 2007! After charging 274 mmol of diethylaluminum and 274 @mol of diphenyldimethodisilane, ethylene sludge was charged so that the ethylene concentration was 0.3 mol%, and the internal temperature of the autoclave was raised to 65°C. The temperature was raised, and 1.1 mmol of the titanium-containing polypropylene obtained in Preliminary 1 was charged as titanium atoms. Subsequently, the internal temperature of the autoclave was raised to 70°C, and a σ)]i reaction was performed for 3 hours. Ethylene gas was intermittently fed while checking with a gas chromatograph to maintain the ethylene concentration in the polymerization tank at 0.3 mo1%. After 3 hours, unreacted monomers were purged to obtain a white granular agglomerate. The results are shown in Table 1. Examples 3 to 5 In this combination of Example 1, hydrogen was used as a molecular weight regulator at 101 (Example 3), 20d (Example 4), and 30117
(Example 5) The same operation as in Example 1 was performed except for charging. The results are shown in Table 1. Comparative Example 1 Catalyst components were prepared and propylene was polymerized according to the method shown in Example 1 of JP-A-62-22808. The results are shown in Table 1. Comparative Example 2.3 In one cup of Example 1, hydrogen was added as molecular ixi agent to 8
The same operation as in Example 1 was performed except that 01Ll (Comparative Example 2) and 120Ll (Comparative Example 3) were charged. The results are shown in Table 1. Examples 6 to 9 In the prepolymerization of Example 10, phenyltriethoxysilane (
Example 6). Methyltriethoxysilane (Example 7), methylphenyldiethoxysilane (Example s). The same procedure as in Example 1 was carried out except that butyl trinidoxin run (Example 9) was used. The results are shown in Table 2. (31) Example 10 [Preparation of titanium compound] The method for preparing a titanium compound is described in JP-A-62-104810.
This was carried out in accordance with the method of Example 1 of the publication. That is, 100 I of aluminum trichloride (anhydrous) and 29.9 g of magnesium hydroxide were reacted while being ground at 250° C. for 3 hours in a vibration mill. After the heating was completed, the mixture was cooled in a nitrogen stream to obtain a solid product (I). In a glass flask, purified decane 15-1 solid product (I)? -sy, n-butyl orthotitanate8.
Mix 9.8 g of 512-ethyl-1-hexanol,
While stirring, the mixture was heated to 130° C. for 1.5 hours to dissolve and form a uniform solution. The solution was heated to 70°C, 1.8.91% of P-)ethyl ruylate was added and reacted for 1 hour, and then 26.9% of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid. ℃ and stirred for 1 hour. To separate the facepiece from the solution, 33) For purification, it was washed with beef sanitation to obtain a solid product (II). 4 The total amount of the solid product (II) was added with 1,2-dichloroethane 301 and titanium tetrachloride 301, as well as diynbutyl 7-talate. After adding 1.59 and reacting at 100°C for 2 hours with stirring, the liquid phase was removed by decantation at the same temperature, and 1,2-dichloroethane 3Qd was added again. Titanium tetrachloride 30-, diisobutyl phthalate 1,5.9
was added and reacted at 100°C for 2 hours with stirring,
The solid part was collected by hot filtration, washed with purified hexane, and
The mixture was dried at 5° C. under reduced pressure for 1 hour to obtain a solid product (■). The solid product (II) is spherical, with an average particle size of 15 μm
70 The particle size distribution was extremely narrow. This solid product (m) was used as a solid T1 catalyst component. In addition, the composition analysis result of the solid T1 catalyst component is T 13
.. 0 weight i1% (hereinafter referred to as %), CA'56.2 attack, M
717.6%, A11.7%, lid (34) diisobutyl phosphate 20.1%, butoxy group 11%, 2-
Ethylhexyl group 02%, ethyl P-toluate 0.
It was 1%. The subsequent 5-bipolymerization and polymerization were carried out in the same manner as in Example 1. In addition, Table 3 shows the physical properties of the obtained monomer. Example 11 [Preparation of titanium compound] A titanium compound was prepared according to the method of Example 1 of JP-A-62-11706. That is, 50 ILl of purified hebutane, 50 liters of titanium tetrabutane, 7.
Add OJi' anhydrous magnesium chloride. Thereafter, the temperature of the flask was raised to 90° C., and the magnesium chloride was completely dissolved over a period of 2 hours. Next, the flask was cooled to 40°C, and methylhydrodienepolysiloxane lO- was added to precipitate a magnesium chloride and titanium tetocyptoxide complex. This was washed with purified butane to obtain an off-white solid. The precipitated solid 10 obtained above was placed in a glass Mitsuro flask (temperature side, equipped with a stirrer) with an internal volume of 300 ml that was purged with nitrogen.
A heptane slurry 501 containing g was introduced. Then,
A heptane solution containing 5.8 itt of tetracyclized quimine was added over 30 minutes at room temperature, and the mixture was further reacted at 30° C. for 45 minutes. The reaction was further carried out at 90° C. for 1.5 hours, and after the reaction was completed, the reaction mixture was washed with purified hebutane. Next, a heptane solution 501 containing 1.51 L of diheptyl phthalate was added and reacted at 50°C for 2 hours, then washed with purified hebutane, and further titanium tetrachloride 25 resistant was added and reacted at 90°C for 2 hours. I let it happen. This was washed with purified butane to obtain a solid T1 catalyst component. The titanium content in the solid T1 catalyst component was 3.04 ml%. The subsequent preliminary polymerization and polymerization were performed in the same manner as in Example 1. Further, the physical properties of the obtained polymer are shown in Table 3. Comparative Example 4 The same operation as in Comparative Example 1 was performed using the solid T1 catalyst component obtained in Example 1O. The results are shown in Table 3. Comparative Example 5 Using the solid T1 catalyst component obtained in Example 11, the same operation as in Comparative Example 1 was performed. The results are shown in Table 3. Examples 12 to 14 Example 20 In this polymerization, 1-pudene (Example 12), 4-methylpentene-1 (Example 13) and 1-hexene (Example 14) were used instead of ethylene, and the respective Copolymerization was carried out so that the composition of monomer units based on the monomers was as shown in Table 4. The results are shown in Table 4. Reference Example 1 A powder of 1 powder of the ultra-polymer pyrene obtained in Example 1 was heated on a hot plate at 220°C to a thickness of 20 cm x 20 + m and a thickness of 0.3 m. A sheet was prepared.This sheet was heated to 130℃.
An attempt was made to dissolve it in 1% by weight of P-xylene 100-, but a homogeneous solution could not be obtained and a swollen gel-like substance remained. The amount dissolved was 20% of the sheet weight. Reference Example 2 The ultra-high molecular weight polypropylene polymer powder obtained in Example] was granulated using an extruder to form pellets. An attempt was made to dissolve the pellet in P-xylene 1QQsc/, but a homogeneous solution could not be obtained and a swollen gel-like substance remained.The amount dissolved was 18 deuterons of the total pellet weight.
第1図は、実施例1で得られた本発明の超高分子量ポリ
プロピレンの13C−核磁気共鳴(41)
スペク
トルのチャートである。FIG. 1 is a chart of the 13C-nuclear magnetic resonance (41) spectrum of the ultra-high molecular weight polypropylene of the present invention obtained in Example 1.
Claims (2)
%を越えて100モル%以下、プロピレン以外のα−オ
レフィンに基づく単量体単位が0モル%以上5モル%未
満であり、(2)重量平均分子量が100万以上であり
且つ (C)P−キシレン可溶分が1.0重量%以下であるこ
とを特徴とする超高分子量ポリプロピレン。(1) (A) Monomer units based on propylene are more than 95 mol% and less than 100 mol%, monomer units based on α-olefins other than propylene are 0 mol% or more and less than 5 mol%, 2) Ultra-high molecular weight polypropylene having a weight average molecular weight of 1 million or more and a (C) P-xylene soluble content of 1.0% by weight or less.
アルミニウム化合物C、一般式〔 I 〕RnSi(OR
’)_4_−_n〔 I 〕 [但し、R及びR’は、同種又は異種の炭化水素基であ
り、nは1〜3の整数である。]で示される有機ケイ素
化合物の存在下にプロピレンの予備重合を多段で、且つ
各予備重合段階で異なる有機ケイ素化合物を用いて行な
つた後、 D、予備重合で得られたチタン含有ポリプロピレン E、上記Bと同様の有機アルミニウム化合物 F、上記Cと同様の有機ケイ素化合物の存在下に、プロ
ピレンの単独重合又はプロピレンとプロピレン以外のα
−オレフィンとの共重合を行なうことを特徴とする特許
請求の範囲第(1)項記載の超高分子量ポリプロピレン
の製造方法。(2) The following components A, B and CA, titanium compound B, organoaluminum compound C, general formula [I]RnSi(OR
')_4_-_n [I] [However, R and R' are the same or different hydrocarbon groups, and n is an integer of 1 to 3. D, titanium-containing polypropylene obtained by prepolymerization E, In the presence of an organoaluminum compound F similar to the above B and an organosilicon compound similar to the above C, homopolymerization of propylene or propylene and α other than propylene
- A method for producing ultra-high molecular weight polypropylene according to claim (1), which comprises copolymerizing with an olefin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1203777A JP2691023B2 (en) | 1989-03-20 | 1989-08-08 | Ultra high molecular weight polypropylene and method for producing the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1-65938 | 1989-03-20 | ||
JP6593889 | 1989-03-20 | ||
JP1203777A JP2691023B2 (en) | 1989-03-20 | 1989-08-08 | Ultra high molecular weight polypropylene and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH037704A true JPH037704A (en) | 1991-01-14 |
JP2691023B2 JP2691023B2 (en) | 1997-12-17 |
Family
ID=26407107
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JP1203777A Expired - Lifetime JP2691023B2 (en) | 1989-03-20 | 1989-08-08 | Ultra high molecular weight polypropylene and method for producing the same |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008140835A1 (en) * | 2007-01-19 | 2008-11-20 | Tonen Chemical Corporation | Polymeric material and its manufacture and use |
US7872086B2 (en) | 2008-01-17 | 2011-01-18 | Tonen Chemical Corporation | Polymeric material and its manufacture and use |
CN103980396A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Ultrahigh-molecular-weight isotactic polypropylene resin for 3D printing, preparation method and application thereof |
WO2015193291A1 (en) * | 2014-06-20 | 2015-12-23 | Sabic Global Technologies B.V. | Process for the polymerization of propylene |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | Ultra-high molecular weight isotactic polypropylene resin composition and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
-
1989
- 1989-08-08 JP JP1203777A patent/JP2691023B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008140835A1 (en) * | 2007-01-19 | 2008-11-20 | Tonen Chemical Corporation | Polymeric material and its manufacture and use |
JP2010516842A (en) * | 2007-01-19 | 2010-05-20 | 東燃化学株式会社 | Polymer materials and their manufacture and use |
US8008417B2 (en) | 2007-01-19 | 2011-08-30 | Toray Tonen Specialty Separator Godo Kaisha | Polymeric material and its manufacture and use |
US7872086B2 (en) | 2008-01-17 | 2011-01-18 | Tonen Chemical Corporation | Polymeric material and its manufacture and use |
CN103980396A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Ultrahigh-molecular-weight isotactic polypropylene resin for 3D printing, preparation method and application thereof |
CN103980396B (en) * | 2014-04-30 | 2016-06-15 | 中国科学院化学研究所 | A kind of super high molecular weight isotactic polypropylene resin that can be used for 3D printing and its preparation method and application |
WO2015193291A1 (en) * | 2014-06-20 | 2015-12-23 | Sabic Global Technologies B.V. | Process for the polymerization of propylene |
CN106459285A (en) * | 2014-06-20 | 2017-02-22 | Sabic环球技术有限责任公司 | Process for the polymerization of propylene |
US9988474B2 (en) | 2014-06-20 | 2018-06-05 | Sabic Global Technologies B.V. | Process for the polymerization of propylene |
CN106459285B (en) * | 2014-06-20 | 2019-05-21 | Sabic环球技术有限责任公司 | Method for polypropylene |
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JP2691023B2 (en) | 1997-12-17 |
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