TW593521B - Impact-resistant polyolefin compositions - Google Patents
Impact-resistant polyolefin compositions Download PDFInfo
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- TW593521B TW593521B TW089118583A TW89118583A TW593521B TW 593521 B TW593521 B TW 593521B TW 089118583 A TW089118583 A TW 089118583A TW 89118583 A TW89118583 A TW 89118583A TW 593521 B TW593521 B TW 593521B
- Authority
- TW
- Taiwan
- Prior art keywords
- propylene
- polymerization
- patent application
- polyolefin composition
- minutes
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 12
- -1 polypropylene Polymers 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- 239000004743 Polypropylene Substances 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 12
- 229920001384 propylene homopolymer Polymers 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000000707 stereoselective effect Effects 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 241000208125 Nicotiana Species 0.000 claims 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims 1
- 239000002685 polymerization catalyst Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012937 correction Methods 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
- 238000001746 injection moulding Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- DFXFBQFUSURGOJ-CRWXNKLISA-N (3R,4S,5S,6S)-7-methyl-1-phenyloct-1-ene-2,3,4,5,6,7-hexol Chemical compound CC([C@H]([C@H]([C@@H]([C@H](C(O)=CC1=CC=CC=C1)O)O)O)O)(O)C DFXFBQFUSURGOJ-CRWXNKLISA-N 0.000 description 1
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XMYDKOZNENQEHO-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclopentane Chemical compound COCC(COC)(C(C)C)C1CCCC1 XMYDKOZNENQEHO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
-
- C—CHEMISTRY; METALLURGY
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593521 五、發明說明(1) 本發明之聚烯烴組成物包含具不同熔體流動速率値之兩 種聚合物成分,選自丙烯均聚物及丙烯-乙烯及/或其化^ -烯烴無規共聚物以及乙烯和C4 - C i 〇 α -烯烴共聚物。 本發明組成物的加工性、機械性及光學性呈現極佳的 平衡。此外,它們呈限很低的泛白性(b 1 u s h )、減低的吐 霜性(blooming)以及低的有機溶劑可萃取份含量。 組成物可用射出成形來容易加工,可應用於許多用途, 如家庭用品及玩具,尤其是接觸食物之用途。 文獻上已知有包含聚丙烯及由乙烯和α -烯烴所形成的 彈性體共聚物之橡膠相的組成物,尤其是記載於歐洲專利 1 70,255及373,660號者。該組成物呈現耐衝擊性,而且 歐洲專利3 73, 660號之製品呈透明性,有許多用途,但是 諸性質之整體平衡性就市場的高標準需求而言,仍是未完 全令人滿意。因此目前強烈需求具有改良性質之此類組成 物。 該目的現已經可藉由本發明之聚烯烴組成物來達成’其 包括以重量百分率計的: (Α)60%〜95%,較佳爲70〜90%,更佳70〜88%的結晶性 聚丙烯成分,其熔體流動速率(MFRA)値(在230 °C以 2.16公斤之荷重測量)爲2.5〜50,較佳爲5〜50, 更佳爲10〜30克/10分鐘,其含有〜80%,較佳 4 0%〜6 0%之部份(A1),其熔體流動速率(MFR1)値(在 2 3 0 °C以2 . 1 6公斤之荷重測量)爲0 _ 5〜8,較佳爲 593521 五、發明說明(2 ) 0.5〜5,更佳爲1〜3克/10分鐘,以及20%〜80%, 較佳爲40%〜60%的部份(A11), (B)5%〜40%,較佳10%至30%,更佳12%〜30%之乙烯和一 或多種C4-C1Q α-烯烴之共聚物,其含有1〇〜40%, 較佳15〜30%,更佳15至25%的C4-C1Q α -烯烴 , 該部份(A1)和(A11)係各獨立地選自於丙烯均聚物和一含 有最高15%,較佳最高40%乙烯及/或C4-C1() α-烯烴的丙 烯無規共聚物;MFRVMFR1之比値爲2〜25,較佳4〜20; (A)和(B)之百分率係對(A)及(B)之重量和而言,(A1)和 (A11)之百分率係對(A1)及(A11)之重量和而言。 由前面的定義顯示”共聚物” 一詞乃含一種以上共聚單體 之聚合物。 如前所述,本發明之組成物利用特別是射出成形技術可 容易地加工成各種成品或半成品,因爲其具相當高的MFR, 以及諸性質(特別是撓曲模數、耐衝擊性、延性/脆性轉移 溫度、霧度及光澤度)之高度平衡。整個組成物之MFR値 (230°C,2.16公斤)等於或高於4克/10分鐘,特別是等 於或高於5克/ 1 0分鐘者爲較佳之本發明組成物。 基於前述之MFR1及MFRA之範圍,利用聚烯烴組成物之 MFR及各別成分之MFR的已知關係,可容易地決定部分 A11之MFR値(MFR11);在本案中,其關係式如下: In MFR =(WAI/WAI+WA11) X In MFR^CW/WW^+Wa11 ) X In MFR11 式中W/及WAU分別代表部分(a1)及(A11)之重量。 593521 五、發明說明(3) 本發明組成物之其它較佳的特徵爲: -在部份(A1)及(A11)中,當它們至少一個爲丙烯共聚物時 ,共聚單體的含量爲:0.5〜15%,更佳0.5-10%,尤其 〇·5〜8%(若只有乙烯存在時,則爲0· 5〜5%,而若只 有C4-C1G α-烯烴存在時,則爲1〜10%,尤其1〜 8%); -在部份(Α1)及(Α11)中,就丙烯共聚物而言,不溶於室溫 (23 °C)二甲苯之聚合物含量(實質上等於等規指數)係不 小於8 0 %,更佳爲不小於8 5 %,尤其不小於9 0 %,而就 丙烯均聚物而言係不小於90%,更佳不小於95%,尤其 不小於97%,該百分率係指單一部分之重量百分率; -(A )之多分散性指數(p I ):等於或大於4,尤其4〜1 2 ; -全組成物在室溫可溶於二甲苯部分之固有粘度[7? ] : 〇 . 8 〜2 · 5分升/克,若要求高透明性,則爲〇 · 8〜2,最佳 0.8〜1.9,尤其0.8〜1.5分升/克。 本發明組成物以DSC(微差掃描量熱法)分析,在高於 140〜145 °C的溫度出現至少有一個熔融峰。該組成物之成 分(B)以DSC測出知在120°C至135t的溫度範圍內通常有 熔融峰。此等熔融蜂乃歸因於聚乙烯型結晶,特別是成分 (A )是由丙烯均聚物所製時,其在整個組成物中通常是可 用DSC偵測得到的。 此外,本發明之組成物較佳爲具有: -當部份(A1)及(A11)中至少之一爲丙烯共聚物時,則撓 五、發明說明(4) 曲模數爲至少700X106 MPa,尤其700〜1300X1 O6 MPa; 當部份(A )爲丙烯均聚物時(亦即(A1)及(A11)均爲丙烯均 聚物),則撓曲模數爲至少1 2 00 X 1 〇6 MPa ,更佳至少 140〇Xl〇6MPa,尤其 1 400 或 1 500 〜2000 xi06MPa; -在23C之乂佐德(Izod)値爲至少50焦耳/米,更佳至少 60焦耳/米,尤其50或60〜500焦耳/米; -降伏點抗拉強度:15〜3 8 X 1 06 Mpa ; -斷裂伸長率:大於40% ; -當彎曲1毫米厚度之試板時,實質上不會白化(泛白); -在己烷中之可萃取部份(FDA 1 77,1 520 ):少於10%, 更佳少於9%,尤其少於5. 5%重量; -在室溫的二甲苯中之溶解量:少於20%,較佳少於15% 〇 延性/脆性轉移溫度及光學性質(霧度及光澤度)主要端 賴於全部組成物在室溫之二甲苯中之可溶部分的固有粘度 (I · V ·)。I · V ·愈大,則延性/脆性轉移溫度愈小,通常是 等於或低於-2 °C,較佳爲等於或低於-5 °C,更佳爲等於或 低於-10°C,而下限爲約-60°(^I.V.愈小,則霧度愈小, 當組成物中的成分(A)由丙烯均聚物所製成時,則霧度較 佳爲小於30%,更佳爲等於或小於25%;當組成物中的部 份(A1)及(A11)中至少之一爲選自於丙烯共聚物,則霧度 等於或小於20%,更佳爲等於或小於15%。該霧度値乃對 由有核組成物(具有二亞苄基山梨糖醇)所製備的1毫米 593521 五、發明說明(5) 厚之試板測定而得。 若I.V.愈小,則光澤度愈大,較佳爲30〜150%,尤佳 爲40〜1 30%,其測定條件同霧度。 因此,可知除前述在室溫可溶部分之I · V .的較佳範圍 外,若欲得極佳的光學性質,則有另一較佳的I . V .範圍 存在著,亦即大於1 . 5〜2 . 5分升/克,如此,低的延性 /脆性轉移溫度,以及在低溫之較佳衝擊強度亦可得。 在此範圍的I .V.之場合下,霧度通常爲45至75%。 本發明組成物之另一特徵在於減少的吐霜程度,此由 老化後(例如在80°C老化9天)通常光澤度値不會降低30% 以上之事實可證實。 可存在於本發明組成物之成分及部分中當作共聚單體的 C4-C1G α -烯烴可用CH2 = CHR表示,式中R係C2-C8直鏈 或分枝烷基,或芳基(尤指苯基)。 該C4-C1G α-烯烴例如是1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯及1-辛烯。特佳爲丨-丁烯。 本發明組成物可依至少三個聚合步驟之連續聚合反應製 得。此種聚合反應是在立體特異性威格勒-納它(Z i e g 1 e r _ Natta)觸媒的存在下進行。該觸媒之主要成分係固體觸 媒成分’其包含具有至少一個鈦-鹵鍵之鈦化物,及電子 供體化合物,此兩者皆被支撐在活性形式之鹵化鎂上。另 一主要成分(輔觸媒)爲有機鋁化物,如烷基鋁化物。可任 意加入外部供體。
五、發明說明(6) 本發明方法中所通用的觸媒係能製得等規指數大於90%, 較佳爲大於9 5 %之聚丙條。 此外,該觸媒必須對於分子量調節劑(特別是氫氣)有足 夠高的敏感性,以便製造具有MFR値爲小於1克/1 0分鐘 至100克/10分鐘或以上之聚丙烯。 具有前述特徵之觸媒爲專利文獻中所熟知,特別有利的 是美國專利4,399, 054號及歐洲專利45977號中所述之觸 媒。其它的例子可參閱美國專利4,472,524號。 用於該觸媒之固體觸媒成分包含當作電子供體(內部供 體)之化合物,選自於醚、酮、內酯,及含氮、磷及/或硫 原子之化合物,以及單·和雙-羧酸之酯。 特別適合之電子供體化合物有酞酸酯,如酞酸二異丁酯 、二辛酯,二苯酯及苄丁酯。 特別適合的供電子劑爲下式之丨,3 -二醚:
Rl1 CH2—0R1V 式中R1與R11相同或不同,係Ci_Ci8烷基、Κι8環烷基 或C7_C18芳基;Rm與RIV相同或不同,係烷基; 或是1,3-一酸’其中第2位置之碳原子屬於由5、6或 7個碳原子所構成並含兩或三個不飽和鍵的環形或多環結 593521 五、發明說明(7) 構。此型醚類記載於已公告的歐洲專利申請案361,493及 728,769 號。 該二醚之代表例有2-甲基-2-異丙基-1,3 -二甲氧基丙犬完 、2,2 -二異丁基-1,3 -二甲氧基丙烷、2 -異丙基-2-環戊基 -1,3 -二甲氧基丙烷、2 -異丙基-2-異戊基-1,3 -二甲氧基 丙烷、9,9 -雙(甲氧基甲基)莽。 前述之觸媒成分可依各種方法製備得。 例如使MgCl2.nROH加成物(尤其是呈球形顆粒形式者)( 式中η通常爲1〜3,而ROH爲乙醇、丁醇或異丁醇)和含 有電子供體化合物之過量TiCl4反應。反應溫度通常爲80 至120°C。然後分離固體,在或不在電子供體化合物的存 在下再一次和TiCl4反應,然後分離,以整份的烴洗,直 到所有的氯離子消失爲止。 在固體觸媒成分中,鈦化物以T i表示時通常佔0 . 5至 10%重量。維持固定於固體觸媒成分上之電子供體化合物 量通常是佔二鹵化鎂莫耳數的5-20%。 可用來製備固態觸媒成分之鈦化物爲鈦之鹵化物及鹵醇 化物。四氯化鈦爲較佳之化合物。 前述反應可形成活性形式鹵化鎂。文獻上已知能產生活 性形式鹵化鎂之其它反應乃利用非鹵化物之鎂化物如羧酸 鏡爲原料製得之。 在固體觸媒成分中之活性形式鹵化鎂可用觸媒成分之X 射線譜確認,即在非活化之鹵化鎂(表面積小於3平方米 593521 五、發明說明(8) /克)的光譜中所出現的最大反射譜線已不存在,而在該處 有一鹵原子之最大強度位置對非活化二鹵化鎂之最大反射 譜線位置已有位移,或是最大的反射譜線在半峰處的寬度 比非活化鹵化鎂之光譜中之一最大反射譜線者至少大30% 。最活性的形式乃前述固態觸媒成分之X射線譜中出現之 鹵素型。 在鹵化鎂中,較佳爲氯化鎂。在氯化鎂之最活性形式場 合下,固體觸媒成分之X射線譜中有鹵素取代非活化氯 化物之反射譜線,而出現在2 . 5 6 A。 用作輔觸媒之烷基鋁化合物包括三烷基鋁,如三乙基鋁 、三異丁基鋁、三正丁基鋁及含有以氧或氮原子、或S04 或S03基連接之兩個或以上鋁原子之線型或環形烷基鋁化 合物。烷基鋁化合物通常之用量係使Al/Ti比爲1至 1 000 ° 可用作爲外部供體之電子供體化合物包含芳族酸酯,如 苯甲酸烷酯,尤其是含至少一個Si-OR鍵之矽化物(或中 R係烴基)。 矽化物例如是(第三丁基)2 Si(OCH3)2,(環己基)(甲基 )Si(OCH3)2,(苯基)2Si(0CH3)2 及(環戊基)2 Si(0CH3)2 ° 亦 可有利地採用前列式子所示之1,3 -二醚。若內部供體爲此 等二醚之一種,則可省略外部供體。 如前述,聚合方法可利用至少三個連續步驟進行,其中 成分(A )及(B )係在其後另外的步驟製備之,除第一步驟外, -10- 593521 五、發明說明(9) 諸步驟係在所形成的聚合物及前一步驟中所用之觸媒的存 在下進行之。雖然觸媒只加在第一步驟中,但在其後之諸 步驟中仍具有活性。 成分(A)較佳爲在成分(B)之目[j製備。 在至少兩個(較佳爲相連的)聚合步驟中,相關的單體係 被聚合成部份(A1)及(A11),而在其它步驟中,乙烯和C4-C10 α -烯烴則被聚合成爲成分(B)。較佳爲部份(Αι)是在 部份(A11)之前就製妥。 分子量的調整是利用已知的調節劑,尤其是氫氣。 在相關的步驟中加入適量的分子量調節劑,則可得前述 之MFR及[]値。 整個聚合步驟可依連續式或分批式,採用下列已知技術, 並在液相中,在或不在惰性稀釋劑中,或在氣相中,或 採用液-氣混合技術進行之。但可用液態丙烯爲稀釋劑進 行丙烯之(共)聚合步驟,而其它的聚合步驟則在氣相中進 行。通常除非需要排放未反應之單體氣體,否則不需有中 間步驟。 此兩個步驟之反應時間、壓力及溫度並無嚴格規定,但 溫度最佳爲20至100°C。壓力可爲大氣壓或更大。觸媒可 預先和少量烯烴接觸(預聚合)。 本發明組成物的製法亦可爲利用和前述相同的觸媒及實 質上在相同的聚合條件下分別製備成分(A )及(B)。或甚至 是部份(A1)、(A11)及成分(B)(亦即不進行整套的依序聚合 -11- 593521
五、發明說明(1 〇 ) 方法,而是在分別的聚合步驟製備諸成分或部分),然後 在熔融或軟化狀態下機械地混合此等成分。可採用普通的 混合裝置、像螺桿擠壓機,尤其是雙螺桿擠壓機。 本發明組成物亦可包含常用於技藝之添加劑,如抗氧化 劑、光安定劑、熱安定劑、成核劑著色劑及塡充料。 具體而言,添加核化劑可明顯地改善重要的物理機械性 質,如撓曲模數,熱變形溫度(HDT ),降伏點抗張強度的 透明性。 成核劑之用量較佳爲佔本發明整個組成物重量的〇.〇5 至2%,尤佳爲〇 . 1至。 添加無機塡充料,如滑石、碳酸鈣及礦物纖維亦能改善 某些重要的機械性質,如撓曲模數及HDT。滑石亦有成核 效果。 茲以非限制本發明範圍之實施例做細節的說明。 實施例1 - 4 在下列實施例中,本發明之聚烯烴組成物乃由連續聚合 而得。 用於聚合反應之固體觸媒成分乃支撐於氯化鎂上之高度 立體特異性威格勒-納它觸媒成分,其含有約2 . 5%重量的 鈦及以酞酸二異丁酯爲內部供體,而其製法記載於已公告 之歐洲專利申請申請案674,991號中。 觸媒系統及預聚合處理 在引入聚合反應器之前,使前述之固體觸媒成分在-5°C -12- 593521 五、發明說明(11 ) 和三乙基鋁(TEAL)及二環戊基二甲氧矽烷(DCPMS)接觸五 分鐘,其中TEAL/DCPMS之重量比爲約4,並使TEAL/Ti 之莫耳比爲6 5。 然後在引入第一聚合反應器之前,使觸媒系統懸浮在 20°C液態丙烯中做預聚合反應約20分鐘。 聚合反應 聚合反應是在三個串聯的氣相反應器中連續地進行,此 等反應器均設有將產物送至緊接之下一反應器之裝置。 在氣相中連續地分析氫氣及單體,並送入反應器中,以 維持所欲之恒定濃度。 在第一氣相反應器中,連續及穩定地流入預聚合過之觸 媒系統、氫氣(做爲分子量調節劑)、氣態之丙烯及乙烯單 體,以便在實施例1 - 3中製造丙烯均聚物或在實施例4中 製造丙烯/乙烯共聚物,如此得到部分(Αι)。 將第一反應器所得聚合物送至第二反應器,於後者送入 適當莫耳比例的單體,而在實施例1 _ 3中製得丙烯均聚物, 或在實施例4中製得丙烯/乙烯共聚物,如此得到部份 (A11)。 將第二反應器所得產物依連續流之方式,並以未反應之 單體沖洗,配合穩定的氫氣,氣態的乙烯及丨_ 丁烯單體 而送至第三氣相反應器中,如此得到成分(B )。 依弟二反應益排出之聚合物顆粒做水蒸氣處理,以移除 反應性單體及揮發性物質,然後乾燥。 -13- 593521 五、發明說明(12) 表1列出聚合條件,反應物之莫耳比及所得聚合物之組 成。 然後在轉筒中加入聚合物顆粒,摻入0.01%重量的亞磷 酸三(2,4-雙第三丁苯)酯(1”&£〇8@168),0.05%重量的 丙酸季戊四醇-四[3-(3, 5 -二第三丁基-4 -羥苯基)]酯 (Irganox®1010)及0.16%重量的3,4·二甲基亞苄基山梨 糖醇(Mi 1 1 ad ⑨ 3988 )。 最後將此聚合物顆粒加入雙螺桿擠壓機(B e r s t 〇 r f f ZE25,螺桿長徑比33),在氮罩下於下列條件擠壓: 轉速 250轉/分鐘 擠壓機出量 6-20公斤/小時 熔融溫度 200-250°G 對於擠出之聚合物做測試,表2列出最後聚合物組成物 相關的數據。 表中數據之測法如下: -谁料氣之莫耳[:卜.· 以氣相層析測定。 -聚合物中乙烯及1 - 丁烯含畺 以紅外線光譜測定。 -熔體流動速率(MFR) 按照美國標準物料試法ASTM D 1 238,條件L測定之。 -一>甲本可浴分率及不溶分率 測法如下: -14- 593521 五、發明說明(13 ) 在裝有冷卻器及磁力攪拌器之玻璃燒瓶中加入2.5克 聚合物及250 cm3二甲苯。在30分鐘內使溫度上升至溶 劑的沸點。使如此所得澄淸溶液保持回流及攪拌另30分 鐘。然後在冰水溶中浸入封閉之燒瓶30分鐘,接著在 25°C之恒溫水浴30分鐘。以速濾紙過濾所形成之固體。 將1 00 cm3之濾液倒入預先秤重之鋁容器中,在加熱板上 加熱並以氮氣吹,以蒸發移除溶劑。然後保持容器於80 °C真空爐中,直到重量不變。然後計算溶於室溫之二甲 苯的聚合物重量百分率。不溶於室溫二甲苯之聚合物重 量百分率即爲聚合物之等規指數。此値實質上等於以沸 騰的正庚烷萃取而測得之等規指數,亦即聚丙烯之等規 指數。 -多分散指數(PI ) PI乃聚合物分子量分佈之一種指標。爲測定PI値, 利用美國流變公司之RMS-800平行板流變儀,振動頻率 由〇 · 01弧度/秒升至100弧度/秒,在200°C以較低的模 量(例如500巴)測定模量之分離。由模量分離値,利用下 列方程式可算出 ΡΙ = 54·6Χ(模量分離 0·1·76) 式中模量分離(MS)之定義如下: MS =在G’=500巴之頻率/在Gn = 5 00巴之頻率 其中V乃”儲能模量n(st〇rageniodiilus),而G"係低 模量 -15- 593521 五、發明說明(14 ) -π烷萃取分率 按照美國食品葯物協會FDA 177,1 520之試法,使欲分 析之組成物的1 0 0微米厚薄膜懸浮在過剩的己焼中,放 入50°C壓熱釜2小時。移開薄膜後,蒸發己烷,稱取乾 燥之殘餘物重量。 -固有粘度(I . V .) 在1 3 5 °C四氫化萘中測定。 -溶融溫度(ΤΙΏ )及糸吉晶溫度(T C ) 以DSC(微差掃描量熱儀)測定。 -捧曲模數 按照國際標準組織I SO 1 78試法測定。 -降伏點··抗張強度 按照ISO R527測定之。 -降伏點伸長率 按照ISO R527測定之。 -斷裂伸長率 按照ISO R527測定之。 -凹口艾佐德衝轚強彦 按照ISO 180/1A測定之。 -延性/脆件轉移溫度(D/B) 有要求時,按照內法MA 1 7324測定之。 按照此法,以自動、電腦化之打擊鎚打擊而測定雙軸 衝擊強度。 -1 6 - 593521 五、發明說明(15) 利用圓形手動沖頭(38毫米直徑)衝切圓形試片。在23 °(:及50%相對溼度下調理至少48小時,然後放入訂在試 驗溫度之恒溫溶中1小時。 將圓形試片放在環形支撐體上,以打擊鎚(5 . 3仟克, 半球形沖頭,直徑1 / 2吋)衝擊時,畫出力量-時間曲 線。所用的裝置爲2型之CEAST ®6758/000儀。 D/B轉移溫度乃指在本衝擊試驗中,50%試片脆裂之溫 度。 -試板之製備 D/B測定用之試板尺寸爲1 27 X 1 27 X 1.5毫米,按照內 法MA 1 7283製備之;霧度測定用之試板1毫米厚,按 照內法MA 1 7 3 3 5,利用射出成形法,依射出時間1秒, 溫度230°C,模溫40°C成形之;光澤度測定用試板,1 毫米厚,按照內法MA 1 7335,利用射出成形法,依射出 時間3秒,溫度200°C,模溫40°C成形之,所有的測定 方法在文獻中均有。 -MA 1 7283 試法 採用注入壓塑機:Negri Bo ssi公司(NB 90型),合模 力90噸。 矩形模穴:127X127X1.5毫米 主要的加工參數如下: 背壓(巴) :20 注入時間(秒) :3 -17- 593521 五、發明說明(16) 最大注入壓力(106巴) :14 注入液壓(106巴) :6-3 第一保持液壓(1〇6巴) :4±2 弟一保持時間(秒) :3 第二保持液壓(106巴) :3±2 弟一保持時間(秒) :7 冷卻時間(秒) :20 模溫(t:) :60 熔融溫度 :220-280〇C -MA 1 7335 試法 採用注入壓塑機:Battenfeld公司BA 500CD型,合 模力50噸,嵌件模可模塑兩個試板(各55 X 60 X 1毫米) -薄膜試樣之製備 利用單螺桿擠壓機(Co 1 1 i η公司,螺桿長/徑比:25 ), 以薄膜抽拉速率7米/分鐘,及熔融溫度2 1 0- 250°C,擠 壓各種試驗組成物,而得厚度50微米之薄膜。使每一 所得薄膜貼附在1 , 000微米厚的丙烯均聚物(等規指數 9 7, MFR-L 2克/10分鐘)。利用壓塑機(Carver公司)在 200°C及9000公斤的荷重下,維持5分鐘,以便將貼 附膜粘合在一起。 使所得層合膜在150°C利用薄膜延伸機(TM Long)沿縱 向及橫向(亦即雙軸)延伸,如此得20微米厚薄膜(18微 米均聚物+2微米試驗組成物)。 -18- 593521 五、發明說明(17 ) -誌I之霧縻 有要求時,以內法MA 1 7270測定之。 使試板在50 ±5%相對溼度及23 ±1°C之條件下調整24 小時。 所用儀器爲比色計(Hunter D25P-9)。按照美國標準物 料試法ASTM-D1 003之試法及計算原理進行測定。 不用試板而以霧度標準試板校正儀器。以五片試板做 霧度測定,求其平均値。 -試板之光澤度 有要求時,以內法MA 1 702 1測定之。 所用的光度計爲Zehntner ZGM 1020或1022型,入射 角爲60° 。測定原則是根據ASTM D2457。利用已知光澤 度値之試樣做儀器校正。對於三片試板之每板均測兩個不 同的位置之光澤度,求其平均値即爲試板之光澤度値。 -薄膜之霧度 按照前述的方法由試驗組成物製備50微米厚薄膜。由 薄膜的中心區切取5 0 X 5 0厘米之試片測量之。所用的儀 器爲Gardner公司之光度計(裝有G.E.1 290燈泡及濾光 片C之霧度儀UX-10)。儀器之校正是利用不放試片時爲 0%霧度,而將光束遮住時爲1 00%混濁度。 -薄膜之光澤度 採用測定霧度所用的試片。 所用的儀益爲入射測星用之1020 Zehntner光度計。 -19- 593521 五、發明說明(18 )校正操作是利用標準光澤度爲96. 2%之黑玻璃做60°入 射角光澤度之校正,而用標準光澤度爲55. 4%之黑玻璃 做45°入射角光澤度之校正。 表1 實施例 1 2 3 4 第一反應器 溫度,°c 70 80 80 80 壓力,MPa 1.8 1.8 1.8 1.8 H2/C3_,莫耳 0.01 0.001 0.001 0.002 CV/CV+C3·,莫耳 - - - 0.019 所得聚合物 產量比率,% 39 41 41 39 C2-,% - - - 2.6 MFRL,克/10分鐘 2.3 1.2 1.2 1.2 第二反應器 溫度,°C 70 80 80 80 壓力,MPa 1.8 1.8 1.8 1.8 H2/C3_,莫耳 0.28 0.439 0.63 0.419 c2_/c2_+c3·,莫耳 - - - 0.019 所得聚合物 產量比率,% 40 41 40 39 (V,% - - - 2.6 MFRL(全部),克/10分鐘 15 17 21 11.7 X.I.(全部),% 98.7 98.7 98.3 96.5 PI 5.5 7.2 8.9 6.01 -20- 593521 五、發明說明(19) 表1 (續) 實施例 1 2 3 4 第三反應器 溫度,。C 70 75 75 70 壓力,MPa 1.8 1.8 1.8 1.6 h2/cv,莫耳 0.48 0.38 0.17 0.466 CV/C2_+C4·,莫耳 0.35 0.35 0.35 0.35 全部組成物 產量比率,% 21 18 20 22 C2-,% 16.8 14.2 16.4 18.4 c4-,% 4.3 3.4 3.8 5.2 MFRL,克/10分鐘 11.2 13.4 9.8 9.4 X.S. ,% 10.4 9.0 9.2 13.6 H.E. - 5.3 3.3 7.7 C2_X.I.中,% 10.6 10 12.4 13.3 (VX.I .中,% <2 <2 <2 <2 I.V.X.S.之 dl/g(升/10 克) 1.24 1.26 2.38 1.29 -21 - 593521 五、發明說明(2〇)
實施例 ----- 1 2 3 4 Tm/Tc,°C 162.6/112.3 163.2/111.7 162.4/111.6 147.6/103.1 撓曲模數106巴 1630 1729 1770 1015 抗張強度,106巴 (降伏點) 32.5 36.1 32.4 25.2 斷裂伸長率,% 100 60 40 650 Izod(23t:),焦耳/米 135 70 80 190 Izod(0°C),焦耳 / 米 35 36 51 75 Izod(-20°C),焦耳 / 米 23 26 43 38 D/B,°C -13 -15 -46 -22 試板霧度,%。 22.4 20.9 62.2 13.3 試板光澤度,%。 103.6 105.1 50.7 115.3 薄膜霧度,%。 5.2 6.1 64.1 6.4 薄膜光澤度,%。 72.6 70 11.4 71.5 註:cv =乙烯;(:3·=丙烯;cv =卜丁烯;c2·(全部)=由特 定反應器排出之聚合物中乙燒含量;產量比率=在 特定反應器中所製之聚合物量佔全量之比率;X · I ·= 二甲苯不溶率;X.I.(全部)=由特定反應器排出之 聚合物的Χ·Ι·; X.S.=二甲苯可溶率;Η·Ε·=己烷 可萃取率;除伸長率及光澤度/霧度外,所有百分率 均以重量計算之。 -22-
Claims (1)
- 593521 修正i ____ *.,》*· _ _ _ _____——六、申請專利範圍 第89 1 1 8583號「耐衝擊性聚烯烴組成物」專利案 (92年8月修正) 六申請專利範圍 1. 一種聚烯烴組成物,包括以重量百分率計的: (Α) 60%〜95%之結晶性聚丙烯成分,其熔體流動速率 (MFRA)値(在230°C以2.16公斤之荷重測量)爲2.5 〜50克/10分鐘且含有20%至80%的熔融流動速率 (MFR1)値(在230°C以2.16公斤之荷重測量)爲0.5 〜8克/10分鐘的部份(A1)以及20%至80%的部份 (A11); (B)5%〜40%之乙烯和一或多種CrG。α-烯烴之共聚 物,其含有1〇至40%的CVh。α -烯烴〆 該部份(Α1)及(Α11)各獨立地選自於丙烯均聚物和一含 有0.5〜15%乙烯及/或C4-C1G α-烯烴的丙烯無規共 聚物;MFRVMFR1之比値爲2〜25;該(Α)和(Β)之百 分率係相對於(Α)及(Β)之和而言,該(Α1)和(Α11)之百 分率係相對於(Α1)及(Α11)之和而言; 其中可溶於室溫二甲苯部分之固有粘度爲〇.8〜2. 5 分升/克’且就丙烯共聚物而言,部份(Α1)和(Α11)中 不溶於室溫二甲苯之聚合物含量係不少於80%,或就 丙烯均聚物而言係不少於90%(百分率係對單一部分之 重量而言)。 2·如申請專利範圍第1項之聚烯烴組成物,其熔體流動 -23- 593521 六、申請專利範圍 速率値(23 0°C,2.16公斤)爲4〜25克/10分鐘。 3. 如申請專利範圍第1項之聚烯烴組成物,其中當部 份(A1)和(Au )中至少一爲選自於丙烯共聚物,則部份 (A1)和(A11)各自之共聚單體含量爲〇·5〜10%重量。 4. 如申請專利範圍第1項之聚烯烴組成物,其延性/脆 性轉移溫度等於或低於-2°C。 5. —種製造如申請專利範圍第1項之聚烯烴組成物之 方法,包括至少三個連續步驟,其中在至少兩個聚合 步驟中,相關單體係聚合以形成部份(A1)和(A11 ),而 在其它步驟中,乙燒和C 4 - C 3。-燒煙混合物係聚合 以形成成分(Β),除第一步驟外,各步驟係在所形成 的聚合物及前一步驟中所用的觸媒之存在下操作, 其中聚合觸媒係立體特異性戚格勒-納它觸媒,包 含當作觸媒形成成分之含鈦化合物的固體成分及有機 鋁化物,該含鈦化物具有至少一個鈦-鹵鍵及電子供 體化合物,兩者皆被支撐在活性形式的鹵化鎂上。 6. 如申請專利範圍第 5項之方法,其中所有的聚合步 驟皆在氣相中進行。 7. 如申請專利範圍第 5項之方法,其中丙烯(共)聚合 步驟係利用液態丙烯當作稀釋劑,而其它聚合步驟係 在氣相中進行。 -24-
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ID (1) | ID28962A (zh) |
MY (1) | MY120633A (zh) |
NO (1) | NO20012326L (zh) |
PL (1) | PL198071B1 (zh) |
RU (1) | RU2232783C2 (zh) |
TR (1) | TR200101320T1 (zh) |
TW (1) | TW593521B (zh) |
WO (1) | WO2001019915A1 (zh) |
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CN107805349B (zh) * | 2016-09-09 | 2020-10-23 | 中国石油化工股份有限公司 | 一种聚烯烃组合物及其制备方法和聚烯烃材料 |
CN107805340B (zh) * | 2016-09-09 | 2021-07-02 | 中国石油化工股份有限公司 | 一种聚烯烃组合物和聚烯烃材料 |
CN112469745B (zh) * | 2018-08-22 | 2023-11-24 | 巴塞尔聚烯烃意大利有限公司 | 无规丙烯-乙烯共聚物 |
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CA2349297A1 (en) | 2001-03-22 |
RU2232783C2 (ru) | 2004-07-20 |
NO20012326D0 (no) | 2001-05-11 |
JP2003509562A (ja) | 2003-03-11 |
EP1135440B1 (en) | 2004-08-11 |
WO2001019915A1 (en) | 2001-03-22 |
ES2225220T3 (es) | 2005-03-16 |
AR025636A1 (es) | 2002-12-04 |
CA2349297C (en) | 2008-11-18 |
BR0007075A (pt) | 2001-07-10 |
DE60012879D1 (de) | 2004-09-16 |
BR0007075B1 (pt) | 2009-05-05 |
AU776743B2 (en) | 2004-09-23 |
CN1132865C (zh) | 2003-12-31 |
KR100635888B1 (ko) | 2006-10-18 |
PL347656A1 (en) | 2002-04-22 |
TR200101320T1 (tr) | 2001-12-21 |
DE60012879T2 (de) | 2005-08-11 |
MY120633A (en) | 2005-11-30 |
NO20012326L (no) | 2001-05-11 |
ID28962A (id) | 2001-07-19 |
PL198071B1 (pl) | 2008-05-30 |
KR20010086444A (ko) | 2001-09-12 |
HUP0104592A3 (en) | 2003-08-28 |
HUP0104592A2 (hu) | 2002-03-28 |
CZ20012131A3 (cs) | 2002-03-13 |
EP1135440A1 (en) | 2001-09-26 |
CZ292977B6 (cs) | 2004-01-14 |
ATE273347T1 (de) | 2004-08-15 |
AU7517000A (en) | 2001-04-17 |
JP4732649B2 (ja) | 2011-07-27 |
CN1321178A (zh) | 2001-11-07 |
US6441094B1 (en) | 2002-08-27 |
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