CN1128163C - Polypropylene for films and preparation process of films - Google Patents
Polypropylene for films and preparation process of films Download PDFInfo
- Publication number
- CN1128163C CN1128163C CN99107556A CN99107556A CN1128163C CN 1128163 C CN1128163 C CN 1128163C CN 99107556 A CN99107556 A CN 99107556A CN 99107556 A CN99107556 A CN 99107556A CN 1128163 C CN1128163 C CN 1128163C
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- Prior art keywords
- film
- polypropylene
- stripping
- temperature
- weight
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- -1 Polypropylene Polymers 0.000 title claims abstract description 140
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 119
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 19
- 238000010828 elution Methods 0.000 abstract 4
- 238000005194 fractionation Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 228
- 239000002994 raw material Substances 0.000 description 48
- 238000006116 polymerization reaction Methods 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 23
- 229910052719 titanium Inorganic materials 0.000 description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 20
- 239000010936 titanium Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 229920001519 homopolymer Polymers 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 239000002216 antistatic agent Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
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- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000013461 design Methods 0.000 description 5
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- 238000011156 evaluation Methods 0.000 description 5
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- 239000002002 slurry Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
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- 229920001577 copolymer Polymers 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-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
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002899 organoaluminium compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- ARIWANIATODDMH-UHFFFAOYSA-N rac-1-monolauroylglycerol Chemical compound CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
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- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CPHJEACXPATRSU-UHFFFAOYSA-N 2-[2-hydroxyethyl(tetradecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCN(CCO)CCO CPHJEACXPATRSU-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001941 cyclopentenes Chemical class 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- JRTVEUGOGWTHTR-UHFFFAOYSA-N dodecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCC JRTVEUGOGWTHTR-UHFFFAOYSA-N 0.000 description 2
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- 229940068939 glyceryl monolaurate Drugs 0.000 description 2
- 230000008676 import Effects 0.000 description 2
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
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- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QJARJRBYFJRFGX-UHFFFAOYSA-N 1-aminohexadecan-2-ol Chemical compound CCCCCCCCCCCCCCC(O)CN QJARJRBYFJRFGX-UHFFFAOYSA-N 0.000 description 1
- GHJOEPMHSNXADF-UHFFFAOYSA-N 1-aminoicosan-2-ol Chemical compound CCCCCCCCCCCCCCCCCCC(O)CN GHJOEPMHSNXADF-UHFFFAOYSA-N 0.000 description 1
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- KUWKSBXGRPUGGY-UHFFFAOYSA-N 2-[hexadecyl(2-hydroxyethyl)amino]ethanol;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCN(CCO)CCO KUWKSBXGRPUGGY-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 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 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- WERMRYHPOOABQT-UHFFFAOYSA-N dimethoxy-bis(prop-2-enyl)silane Chemical compound C=CC[Si](OC)(CC=C)OC WERMRYHPOOABQT-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- SRSBRBJUZOPZGQ-UHFFFAOYSA-N dodecanoic acid;2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCCN(CCO)CCO SRSBRBJUZOPZGQ-UHFFFAOYSA-N 0.000 description 1
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HTSRFYSEWIPFNI-UHFFFAOYSA-N ethyl-dimethoxy-methylsilane Chemical group CC[Si](C)(OC)OC HTSRFYSEWIPFNI-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
- 229920006379 extruded polypropylene Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NHJGUALUPXMDGR-UHFFFAOYSA-N hexadecanoic acid;2-[2-hydroxyethyl(tetradecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCN(CCO)CCO NHJGUALUPXMDGR-UHFFFAOYSA-N 0.000 description 1
- MUJKVUYFJGYWRX-UHFFFAOYSA-N hexadecanoic acid;2-[hexadecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCN(CCO)CCO MUJKVUYFJGYWRX-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization 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
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- DCBSHORRWZKAKO-UHFFFAOYSA-N rac-1-monomyristoylglycerol Chemical compound CCCCCCCCCCCCCC(=O)OCC(O)CO DCBSHORRWZKAKO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- CDZULFMEYKOAEF-UHFFFAOYSA-N triethoxy(ethynyl)silane Chemical compound CCO[Si](OCC)(OCC)C#C CDZULFMEYKOAEF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- 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
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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Abstract
The invention obtains a polypropylene for films which allows continuous high- speed orientation over a long term and yields a film having a good thickness precision and a high transparency and appearance, and to provide a preparation process of a polypropylene film using this polypropylene. The polypropylene wherein, in an elution curve obtained through a temperature rising elution fractionation method, the proportion of an eluted component with an elution temperature of lower than 20 DEG C is from 0.5 to 3.5 wt%, the proportion of an eluted component with an elution temperature of from 20 DEG C to 70 DEG C is from 1.5 to 3.5 wt%, the peak temperature is from 114 to 124 DEG C and the crystalline distribution is from 5 to 18 DEG C, the swell ratio is from 1.1 to 1.6 and the total ash amount is adjusted to 300 ppm or less, is used as a film material and subjected to high-speed film-formation to obtain a polypropylene film.
Description
The invention relates to new polypropylene for films and use this polypropylene for films to obtain the polypropylene film manufacture method of oriented film.
Stretched polypropene film, particularly BiOriented Polypropylene Films have favorable mechanical performance and optical property, thereby are widely used in wrapping material etc.Its manufacture method generally is with tenter machine two-way stretch one by one.
In recent years, along with the high speed and the maximization of production equipment, bring into use the film coiling speed to reach 200m/ gradually and divide above high-speed stretch device.Therefore, adopt above-mentioned high speed masking technique, use the occasion of the film of common usefulness, frequently break during stretching, cause productivity low, because thickness and precision reduces, cause the quality of product low in addition with raw material manufacturing polypropylene film.
As the film raw material that the high speed system film that addresses the above problem is used, stress jumpy when stretching in order to absorb, urgent hope appropriateness increases the more soft polypropylene that low melting point becomes component.
Based on this consideration, as making at a high speed the film raw material that film is used, the spy opens the peak temperature and the stripping peak width of the stripping curve that has proposed to adopt intensification precipitation staging mensuration among the flat 7-309912 and adjusts to polypropylene specified range, that contain more low melting point composition.
In above-mentioned polypropylene, making film has certain effect at a high speed for improving though the increase low melting point becomes component, still leaves some room for improvement with the raw material use as making membrane films at a high speed.
That is, about using above-mentioned polypropylene to divide with 200m/ carry out high speed system film that film batches at a high speed the time, only by adjusting low melting point the distribution of crystallizability of controlling polymers that become to assign to, the disrumpent feelings still frequent generation of film in film-forming process.
In addition, when above-mentioned polypropylene being used at a high speed make film, thickness precision of estimating by resulting film homogeneity and the film appearance by the void content evaluation that exists in the gained film also have further room for improvement.
Therefore, the objective of the invention is, provide and the production unit high speed of stretched polypropene film, thickness precision and the film appearance good film raw material that maximizes and adapt, fracture and gained film seldom take place when making film at a high speed.
In order to address the above problem, the inventor studies repeatedly, found that, the increase of the total ash content that the fracture of film is represented owing to the element total amount that contains in the above-mentioned polypropylene, detect with fluorescent X-ray in the high speed film-forming process causes.
Promptly, when using above-mentioned known film raw material to carry out high speed system film, check the position that the film fracture takes place one by one, found that the incipient scorch of film, the incipient scorch of this film is relevant with the usefulness detected amount of element of fluorescent X ray (total ash content) in the film, when at a high speed making film, when the total ash content in the film raw material surpasses a certain higher limit, incipient scorch and fracture with the corresponding film of this ash oontent will take place.
In addition, the inventor also finds, in general, compare with the raw material polypropylene with common film, the above-mentioned polypropylene that contains more low melting point composition contains the more catalyst residue that is produced by polymerizing catalyst, in addition, also contain the stablizer of necessary amount etc., therefore, in the film-forming process of film, divide to form the total ash content that material works and surpass 300ppm usually, sometimes even surpass 500ppm as above-mentioned solid shape.
Based on above-mentioned opinion, the inventor finds after further research, by use have with intensification precipitation staging measure have rerum natura (hereinafter to be referred as the polymkeric substance rerum natura) such as specific distribution of crystallizability and ratio of expansion and total ash content is controlled at the polypropylene of specified range as the film raw material, can thoroughly address the above problem, thereby finish the present invention.
Promptly, the present invention is a polypropylene for films, it is characterized in that, in the stripping curve of obtaining with intensification precipitation staging, the stripping temperature is 0.5-3.5% (weight) at the stripping composition below 20 ℃, and the stripping composition of stripping temperature between 20-70 ℃ is 1.5-3.5% (weight), peak temperature is 114-124 ℃, distribution of crystallizability is 5-18 ℃, and ratio of expansion is 1.1-1.6, and total ash content is below the 300ppm.
As mentioned above, at the film raw material that is used for making at a high speed film, amount by the element-specific that exists in the strictness restriction polypropylene, represent with total ash content, and the combination of polymkeric substance rerum natura such as polyacrylic above-mentioned total ash content and specific low temperature stripping composition, distribution of crystallizability, ratio of expansion, can solve the problems referred to above when making film at a high speed fully, this is found first by the present invention.
Intensification precipitation staging (hereinafter to be referred as TREF) described in the present invention is to utilize crystalline distribution, and promptly the difference of the solvent temperature in solvent is with polyolefine fractionated methods such as polypropylene.Specifically, sample solution is imported with in the post of Chromosorb (Network ロ モ ソ Le Block) as weighting agent, this sample is adsorbed on the above-mentioned weighting agent surface, one side heats up post, one side orthodichlorobenzene wash-out, detect according to relation, can measure the polymer concentration of stripping with column temperature.
The scope of such mensuration temperature is set at the scope of the whole strippings of polymkeric substance.For object polypropylene of the present invention, the scope of this mensuration temperature is 10-140 ℃.
Here said peak temperature (hereinafter to be referred as Tp), be meant expression stripping temperature (℃) with the stripping curve of stripping quantity (weight %) relation in stripping quantity reach peaked peak position (℃).Fig. 1 be the polyacrylic stripping temperature made among the following embodiment 1 of expression (℃) with the stripping curve of stripping quantity (weight %) relation, wherein, the temperature of the peak position of representing with the C point is Tp for 118.4 ℃.
Film of the present invention is 114-124 ℃ with the polyacrylic peak temperature scope of determining with TREF of raw material.When this peak temperature was lower than above-mentioned scope, the film rerum natura reduced, and the dimensional stability when making film at a high speed reduces, and the performance of gained film suffers damage.Otherwise, when peak temperature is higher than above-mentioned scope, resin sclerosis itself, the stretchiness of film and the reduction of system film, film ruptures again and again when making film at a high speed, and productivity reduces.Film of the present invention is 118-122 ℃ with the preferred peak temperature scope of raw material.
In addition, the temperature that described in the present invention distribution of crystallizability (σ) is the temperature of accumulation stripping quantity when reaching 20% (weight) when reaching 90% (weight) poor can be obtained with following formula.In σ=T (90)-T (20) formula, the temperature when T (90) expression accumulation stripping quantity is 90% (weight) (℃), T (20) be the temperature of accumulation stripping quantity when being 20% (weight) (℃).
Fig. 2 be the polyacrylic stripping temperature made among the following embodiment 1 of expression (℃) with the stripping curve of the relation of accumulation stripping quantity (weight %).Among the figure, the E point is T (90), and numerical value is 121.1 ℃, and the D point is T (20), and numerical value is 110.1 ℃.Therefore, distribution of crystallizability in this case (σ) is (121.1-110.1) promptly 11.0 ℃.
Film of the present invention with raw material polyacrylic distribution of crystallizability must be in 5-18 ℃ scope.This is polyacrylic distribution of crystallizability during less than above-mentioned scope, and the stretchiness when making film at a high speed is low, and film breaks, and the productivity of film is low.Otherwise distribution of crystallizability when being higher than above-mentioned scope, the mechanical property of film reduces, and dimensional stability is low, thereby causes the quality of film to worsen.Above-mentioned polyacrylic distribution of crystallizability preferable range is 8-14 ℃.
Polypropylene for films of the present invention, the stripping quantity (weight %) that adopts TREF to determine must be the scope of 0.5-3.5% (weight) below 20 ℃ in the stripping temperature.The composition of stripping temperature below 20 ℃ described here is with the expression of the accumulation stripping quantity (weight %) till the A point that reaches 20 ℃ shown in the transverse axis in TREF stripping curve shown in Figure 2.
In the present invention, film, just can fully reach and improve the effect of making film at a high speed as long as in 0.5-3.5% (weight) scope with the polyacrylic above-mentioned stripping quantity below 20 ℃ of raw material.Above-mentioned stripping quantity below 20 ℃ is lower than the polypropylene of this scope, and stretchiness is bad, and film breaks again and again when making film at a high speed.Otherwise the stripping quantity below 20 ℃ is higher than the polypropylene of above-mentioned scope, and the adhesion phenomenon of film is very serious.Preferred stripping quantity scope below 20 ℃ is 1-3% (weight).
In addition, among the present invention, the stripping quantity (weight %) of the described 20-70 ℃ of scope of determining with TREF of stripping temperature is the stripping quantity (weight %) of temperature between 20-70 ℃ of transverse axis in the stripping curve of TREF of presentation graphs 2.That is, the stripping quantity of ordering with 70 ℃ B (weight %) deducts the numerical value of the stripping quantity (weight %) that 20 ℃ A orders.
Film of the present invention is 1.5-3.5% (weight) with the stripping quantity between the polyacrylic 20-70 of raw material ℃.When the stripping quantity between this polyacrylic 20-70 ℃ is lower than above-mentioned scope, the difficulty that stretches, film frequently breaks when making film at a high speed.Otherwise when the stripping quantity between this polyacrylic 20-70 ℃ was higher than above-mentioned scope, the adhesion phenomenon of film was very serious.Stripping quantity between preferred 20-70 ℃ is 2-3%.
In the present invention, described ratio of expansion be meant when the resin that will melt fully under 230 ℃ temperature melt extrudes from the nib of diameter 2.095mm with the load of 2.16kg die throat diameter with extrude after the ratio of external diameter (mm) of resin, can be with following formulate.
External diameter (the mm)/die throat diameter (mm) of the resin of ratio of expansion=after extruding
Film of the present invention is 1.1-1.6 with the polyacrylic ratio of expansion scope of raw material.When polyacrylic ratio of expansion is lower than this scope, is easy to generate during stretching and stretches inhomogeneously, membrane quality such as thickness precision worsens when particularly making film at a high speed, and film usually breaks, and productivity is low.
In addition, when ratio of expansion was higher than above-mentioned scope, the percent thermal shrinkage of film increased, and membrane quality is low.Ratio of expansion is 1.2-1.5 preferably, preferably 1.3-1.45.
In the present invention, described total ash content is to represent with the detected element total amount of x-ray fluorescence analysis.That is, in the fluorescent X-ray analysis, detect aluminium, magnesium, titanium, chlorine, sulphur, phosphorus, silicon, iron etc. as element, total ash content just is meant the element total amount that these are detected.
Therefore, total ash content recited above, its detected object are the above-mentioned detection elements that contained originally in the polypropylene, contained in the additive such as necessary catalyzer or stablizer during for example propylene polymerization and owing to polluting the whole of the above-mentioned detection elements of sneaking into.
No matter total ash content in the polypropylene for films of the present invention is the occasion that constitutes film with individual layer, as the occasion that constitutes film at least as central core of following multilayer film, generally must be below the 300ppm, preferably below the 250ppm still.
Above-mentioned total ash content is defined as below the 300ppm combines, just can fully realize effect of the present invention with above-mentioned these two conditions of polyacrylic above-mentioned polymkeric substance rerum natura that relate to.When this total ash content surpassed above-mentioned scope, even satisfy other condition, the reason film owing to ash content when making film at a high speed also usually can break.
The polypropylene that uses among the present invention as long as satisfy above-mentioned condition of the present invention, can be the homopolymer of propylene or the multipolymer of other alpha-olefin beyond propylene and the propylene.Other alpha-olefin as above-mentioned copolymer composition for example can be enumerated: cyclic olefins such as the alpha-olefin of 2-20 carbon atoms such as ethene, butene-1, amylene-1,3-methyl-1-butene, hexene-1,3-Methyl-1-pentene, 4-methyl-1-pentene, heptene-1, octene-1, nonylene-1, decylene-1, dodecylene-1, tetradecene-1, cetene-1, vaccenic acid-1, eicosylene-1 and cyclobutene, cyclopentenes, tetrahydrobenzene, cyclooctene.
These other alpha-olefin can contain a kind ofly separately as copolymer composition, also can contain several combining.Its content ratio is different according to the kind of other alpha-olefin, and in general, ratio shared in multipolymer can be selected below 5% (mole).For example, when other alpha-olefin was ethene, in order to use the definite peak temperature place of TREF within the scope of the invention, the ratio of ethene in multipolymer was preferably below 1% (mole).
Polyacrylic manufacture method of the present invention has no particular limits, and generally can adopt method described below, for example, with some kinds of polyacrylic catalyst component mixing of giving different legislates by polymerization, makes polypropylene.
The preferred method that adopts is, with solid titanium catalyst component, organo-aluminium compound composition and provide the electron donor of the different acrylic resin of legislate to mix the method for polypropylene more than 2 kinds.
Above-mentioned solid titanium catalyst component has no particular limits so long as be used for the known compound of propylene polymerization and get final product.Preferentially select for use with titanium, magnesium and halogen as the high solid titanium catalyst of the catalytic activity of composition.This catalyst component preferably is carried on halogenated titanium, particularly titanium tetrachloride various magnesium compounds particularly on the magnesium chloride and the catalyzer that obtains.
Organo-aluminium compound can use the known compound that uses in the propylene polymerization, has no particular limits.For example can enumerate: trialkylaluminium classes such as trimethyl aluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, three positive decyl aluminium; Alkyllithium dihalide classes such as diethyl aluminum monohalide class, methylaluminum dichloride, ethylaluminum dichloride such as diethyl monochlor(in)ate aluminium.In addition, can also use aluminum alkoxide classes such as an oxyethyl group diethyl aluminum, diethoxy one aluminium triethyl.Wherein, triethyl aluminum most preferably.The consumption of organo-aluminium compound, with respect to the titanium atom in the solid titanium catalyst component, aluminium/titanium (mol ratio) is advisable in the scope of 10-1000, preferably 50-500.
In above-mentioned polymerization process, described electron donor can use known electron donor in the propylene polymerization, has no particular limits.Preferably simultaneously and with the silicoorganic compound shown in following general formula (I) and the general formula (II), be in polypropylene in the specified range of the present invention with the distribution of crystallizability stripping temperature of TREF mensuration at the stripping composition of the stripping composition below 20 ℃ and 20-70 ℃ because can obtain like this.
In the formula, R
1And R
2Be identical or different alkyl, n is 0 or 1.
R
3-Si-(OC
2H
5)
3 (II)
In the formula, R
3It is alkyl.
In the silicoorganic compound shown in above-mentioned general formula (I) and the general formula (II), R
1, R
2And R
3Shown alkyl can be enumerated straight chain shape, a chain, cyclic aliphatic alkyl, perhaps aromatic hydrocarbyl.Its carbonatoms has no particular limits.Preferred alkyl for example has the alkyl of 1-6 carbon atoms such as methyl, ethyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl; The alkynyl of 2-6 carbon atoms such as vinyl, propenyl, allyl group; The cycloalkyl of 5-7 carbon atoms such as cyclopentyl, cyclohexyl, suberyl; The aryl of 6-12 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, wherein, preferred R
3Be straight chain shape alkyl, alkenyl, aryl person.In addition, n is 0 or 1.
The silicoorganic compound of preferentially selecting for use among the present invention can be exemplified below.By the silicoorganic compound of general formula (I) expression, for example can enumerate: dimethyldimethoxysil,ne, diethyl dimethoxy silane, dipropyl dimethoxy silane, divinyl dimethoxy silane, diallyl dimethoxy silane, two-1-propenyl dimethoxy silane, diacetylene dimethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, tertiary butyl ethyl dimethoxy silane, ethyl-methyl dimethoxy silane, the propyl group methyl dimethoxysilane, cyclohexyl trimethoxy silane, diisopropyl dimethoxy silane, dicyclopentyl dimethoxyl silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, allyltrimethoxysilanis etc.
Silicoorganic compound by general formula (II) expression for example can be enumerated: Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, butyl triethoxyl silane, amyl triethoxysilane, sec.-propyl triethoxyl silane, 1-propenyl triethoxyl silane, pseudoallyl triethoxyl silane, ethynyl triethoxyl silane, octyltri-ethoxysilane, dodecyl triethoxyl silane, phenyl triethoxysilane, allyltriethoxysilane etc.
By the consumption of the silicoorganic compound of general formula (I) and general formula (II) expression, with respect to the Ti atom of solid titanium catalyst component, Si/Ti (mol ratio) is respectively 0.1-500, preferably 1-100.In addition, the usage ratio of these two kinds of silicoorganic compound is calculated (I) with mol ratio: (II)=1: 10-1: 20.Silicoorganic compound (I) and usage ratio (II) are higher than at 1: 20 o'clock, 114 ℃ of polyacrylic stripping peak temperature (Tp) less thaies of determining with TREF of gained, the stripping temperature surpasses 3.5% (weight) at the stripping quantity below 20 ℃, and the thermotolerance of the biaxially oriented film of making is low.In addition, silicoorganic compound (I) are lower than at 1: 10 o'clock with (II) usage ratio, gained polyacrylic with TREF determine distribution of crystallizability less than 5 ℃, the stretchiness during the system film is low, mechanical load increases, and breaks during film stretching.
The interpolation of above-mentioned each composition has no particular limits in proper order, can be with general formula (I) and the mixing feed simultaneously of the silicoorganic compound (II), and also can be with they feed respectively.In addition, they are contacted, then feed with organo-aluminium compound.
Other polymerizing condition only otherwise infringement effect of the present invention get final product, has no particular limits, and in general wishes to press following condition polymerization.Polymerization temperature 20-200 ℃, preferably 50-150 ℃, also can coexist with hydrogen as molecular weight regulator.Polymerization can be adopted methods such as slurry polymerization, solvent-free polymeric and vapour phase polymerization, can adopt any mode in intermittent type, semibatch, the continous way, and in addition, polymerization also can be divided into the stage of 2 different conditions and carry out.Before the polymerization of propylene, also can carry out propylene or other monomeric prepolymerization.In addition, above-mentionedly be divided into several steps and carry out the polymeric method,, thereby preferentially selected for use because ratio of expansion widens.
In addition, the polypropylene that satisfies specific distribution of crystallizability and total ash content of the present invention, in the polyacrylic polymerization of using the metalloscene catalyst constitute by Metallocenic compound and ァ Le モ キ サ Application, also can the while and obtain the polyacrylic catalyst component more than 2 kinds of different legislates with polymerization.
The melt flow rate (MFR) of polypropylene for films of the present invention has no particular limits, preferably the 0.1-10g/10 branch.
In aforesaid method, the polymkeric substance rerum natura is adjusted in the polypropylene that obtains in the scope of the invention, total ash content former by catalyst component and pollution etc. thereby that cause often surpasses 300ppm, if also comprise the increase of the total percent of ash amount that causes owing to the interpolation stablizer, then total ash content will be above 500ppm.
In the present invention, the means that total ash content is adjusted to below the 300ppm have no particular limits, and preferable methods can be exemplified below.
That is, make polypropylene in forcing machine by the less screen cloth of eyelet, to reduce the method for contained ash amount, perhaps wash the method etc. of above-mentioned polypropylene powder with appropriate solvent.
Method with the above-mentioned polypropylene powder of solvent wash can be enumerated, after above-mentioned polymerization, in polymerization reactor, add lower alcohols such as water or methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol as polymerization retarder, make catalyst deactivation, wash resulting polypropylene with appropriate solvent then, dry then, to reduce the ash amount in the polypropylene.
Above-mentioned cleaning solvent generally can use Skellysolve A, normal hexane, normal heptane, octane, octane-iso, toluene, xylol, p-Xylol etc., and wash temperature generally is a normal temperature to 100 ℃.Pressure when dry can be from the pressurized conditions that reduces pressure.
In addition; the polypropylene that polymerization is obtained passes through the less screen cloth of eyelet in forcing machine; can enumerate following method with the method that reduces contained ash amount; eyelet size promptly is installed is 60-70 μ m, the screen cloth of 20-40 μ m preferably near the import of the screw tip of forcing machine (tablets press) or squeeze film, make above-mentioned polypropylene pass through this screen cloth.Make above-mentioned polypropylene in forcing machine by the less screen cloth of eyelet to reduce the method for contained ash amount, can tube just remove and deash, thereby preferentially selected for use, implement this method in the time of for example can melt extruding with the polypropylene fusion granulation time or in the thin film fabrication process.
Use the film of the invention described above to make oriented film with the raw material polypropylene, can with high velocity-stabilization obtain polypropylene film.Promptly, the invention provides the manufacture method of polypropylene film, it is characterized in that, the polypropylene for films of the invention described above is melt extruded slabbing, this flap is carried out longitudinal stretching at least with 3-10 stretching ratio doubly, and when carrying out above-mentioned stretching, the coiling speed V of film is in following ranges.
V≥2000/T
V: the coiling speed of film (m/ branch)
T: resulting film thickness (μ m)
Film raw material in the inventive method can use polypropylene of the present invention separately, in addition, in satisfying the scope of above-mentioned condition of the present invention, also can use by other polypropylene of blend.Certainly, also can be with polypropylene of the present invention blend use each other.
Use polypropylene for films of the present invention, when the thickness T that requires film is 20 μ m, can make film, when the thickness T that requires film is 40 μ m, can make film with the film coiling speed V that V 〉=50m/ divides with the film coiling speed V that V 〉=100m/ divides.The thickness of film and speed is by heating, the cooling power decision of the plasticating capacity of film-making machine and film-making machine, when the extrusion capacity of raw material approaches the higher limit of forcing machine, and the general and proportional reduction of film thickness of film speed.At this moment, depending on the thickness of film, is different for the thermal conduction of the sheet stock before stretching, and film thickness is big more, and heat passage speed to the thin film center position is low more, in order to address this problem, must to underspeed or improves design temperature.But if improve the fusing point that design temperature substantially exceeds raw material, film surface will melt and form albefaction, cause the film appearance quality bad, not be the terms of settlement that suits.Thereby, the general method that reduces the film coiling speed that adopts.In addition, because design temperature has higher limit, reach when further improving coiling speed after the higher limit, the increase of film thickness, simultaneously, the thicker sheet stock owing to stretch, tensile stress raises, because the concentration of local of tensile stress is compared with the situation of above-mentioned 20 μ m, even coiling speed is reduced to the 50m/ branch, film also breaks easily.That is, if film thickness increases, film speed must reduce, and for example, for the film of 40 μ m, batches film with the speed of V 〉=50m/ branch and has just made film at a high speed at last.
When using polypropylene for films of the present invention, also can be with following high film coiling speed V system film.
V 〉=4000/T, spy be in addition 10000/T 〉=V 〉=4000/T still, the upper limit of coiling speed V can not surpass the performance limitations of apparatus for manufacturing thin film, generally is below 400m/ divides, and preferably carries out below 300m/ divides.
In the manufacture method of above-mentioned polypropylene film of the present invention, the longitudinal stretching multiplying power is during less than 3 times, and it is inhomogeneous to take place significantly to stretch, and the possibility that thickness precision and productivity are low increases.Otherwise the longitudinal stretching multiplying power is broken during greater than 10 times, and productivity significantly reduces.Most preferred longitudinal stretching multiplying power scope is 4-7 times.
In addition, the film that obtains with the inventive method, the thickness of the layer that is formed by above-mentioned film raw material is advisable at 5-100 μ m, preferably 10-60 μ m.
The drawing process of polypropylene film of the present invention preferably adopts two-way stretch.The tensile mode can adopt any mode in stretching one by one and stretching simultaneously, can use arbitrary known method such as tentering method or tubulose plastic uptake method, is not limited in this respect.
With bidirectional extending method one by one is example, with T pattern head should polypropylene moldedly be sheet stock or film, supply with longitudinal tensile fixture then, stretch by this stretching ratio scope with 120-170 ℃ heating roller temperature, in the tenter machine baking oven, carry out cross directional stretch as required then with 3-15 stretching ratio doubly, subsequently, in order to keep dimensional stability, under 80-180 ℃, carry out 0-25% heat and relax.
Certainly, after these stretch, can also stretch once more, in addition, in the longitudinal stretching process, can be used in combination drawing process such as multistage stretching, calendering.
In addition, the polypropylene film that uses polypropylene for films of the present invention to obtain can be individual layer also can be multiwalled.
When using polypropylene for films of the present invention to constitute the multiwalled polypropylene film, preferably adopt at least to constitute central core with polypropylene for films of the present invention, three layers melt extrude the method that forms flap simultaneously.
Concrete embodiment can be enumerated: all each layers all are the film of the present invention polyacrylic modes of raw material; Central core is this film raw material, the outer mode that is made of the polyolefin-based resins that contains anti; Central core is this film raw material, the mode that at least one side skin is made of the low melting point polyolefin resin etc.
In the mode that above-mentioned skin is made of the polyolefin-based resins that contains anti, anti can use known product, has no particular limits.Its representative example can be enumerated: dissolving during film stretchings such as spherical crosslinked melamine resin, spherical and amorphous silicon oxide, spherical cross-linked silicone, spherical crosslinked methyl methacrylate resin, cubic lime carbonate, porous matter calcium phosphate and polyethylene, make the polymer substance of surface coarsening.These antis may be used alone, can also be used in combination, in addition, also can carry out physics or chemical surface treatment to the surface of these antis after, perhaps infiltrate for using behind the high material of polyolefine intermiscibility and affinity.These antis preferably use the particulate state of median size 0.5-5 μ m.
In addition, constituting outer field said polyolefins is resin, can use with the known polypropylene-based resin of film raw material of the present invention as representative, has no particular limits.
Preferably in the outer field polyolefin-based resins of above-mentioned formation, allocate the anti of 0.01-0.5% (weight) into.Anti forms projection on the top layer of film, can improve film adhesive and oilness to each other.
When the addition of anti is less than above-mentioned scope, can not get sufficient preventing adhesiving effect, during more than above-mentioned scope, the transparency of film reduces, and film appearance is bad, and quality is low.The amount of the anti that uses in the above-mentioned skin is 0.03-0.2% (weight) preferably.
In the above-mentioned embodiment, in order to keep making film at a high speed, the total ash content of central core must be controlled at specific value.Therefore, anti in fact only adds in the skin.
In addition, in following thin film fabrication technology, carry out as required, for adjusting the gained thin-film width its end is cut off the film offal that obtains, can add above-mentioned film to and use with reclaiming in the raw material.This occasion tends to increase as the ash amount in the polypropylene of film raw material, therefore, must control reclaim the amount of using, so that this total ash content does not exceed above-mentioned scope.
In addition, be in the embodiment that constitutes of resin by low melting point polyolefin at above-mentioned at least one side skin, in order to give heat sealer, this resin uses the resin of 60-150 ℃ of fusing point to be advisable.When fusing point was lower than this scope, gonorrhoea appearred in film, and the transparency reduces, and percent thermal shrinkage increases, and causes dimensional stability low.Otherwise when using fusing point to be higher than the resin of this scope, heat sealer is low.More preferably fusing point 80-135 ℃ resin.
As constituting above-mentioned outer field low melting point polyolefin is resin, can use the known polyolefin resin that in the past used in order to give the polypropylene film heat sealer, has no particular limits.For example, can use homopolymer, above-mentioned alpha-olefin multipolymer each other or the mixture of terpolymer and these resins of alpha-olefins such as ethene, propylene, 1-butylene.
Using in the laminate film of raw material as central core with above-mentioned film of the present invention, the thickness of central core generally will be adjusted to and account for more than at least 70% of overall film thickness, can give full play to effect of the present invention like this.
In the present invention, can be as required at film raw material with constitute in outer field each resin, allocate additives such as oxidation inhibitor, chlorine trapping agent, thermo-stabilizer, antistatic agent, anti-clouding agent, UV light absorber, lubricant, nucleator, surface-modifying agent, pigment, other resin in allowed limits into.
Above-mentioned antistatic agent has no particular limits, and can use known antistatic agent.For example can use the lipid acid of 6-22 carbon atom and the monoester compound of glycerol, the alkyl diethanolamine of 10-22 carbon atom, alkyl monoethanolamine or their high-grade aliphatic ester, the fatty diglycollic amide of 11-17 carbon atom.Can use wherein a kind of separately, also can use together more than two kinds.
The lipid acid of preferred 6-22 carbon atom and the monoester compound of propionic acid alcohol for example have among the present invention: glyceryl monolaurate, Tetradecanoic acid, monoester with 1,2,3-propanetriol, Zerol, glyceryl monooleate etc.Preferred alkyl diethanolamine for example has: dodecyl diethanolamine, tetradecyl diethanolamine, hexadecyl diethanolamine, octadecyldiethanol amine etc.Preferred alkyl monoethanolamine for example has: dodecyl monoethanolamine, tetradecyl monoethanolamine, hexadecyl monoethanolamine, octadecyl monoethanolamine etc.In addition, the high-grade aliphatic ester of preferred alkyl diethanolamine or alkyl monoethanolamine for example has: dodecyl diethanolamine mono-laurate, dodecyl diethanolamine monostearate, tetradecyl diethanolamine list myristinate, tetradecyl diethanolamine monopalmitate, hexadecyl diethanolamine monopalmitate, hexadecyl diethanolamine monostearate, octadecyldiethanol amine monoleate etc.
The addition of these antistatic agents is advisable in 0.01-2.0% (weight) scope.When being lower than 0.01% (weight), anti-static effect is insufficient, and when surpassing 2.0% (weight), superfluous antistatic agent is exuded on the film surface, causes bad orders such as albefaction, and adhesive significantly reduces, and membrane quality is low.Preferred addition is 0.05-1.0% (weight).
In the present invention, preferably antistatic agent is used for the central core of multilayer, promptly not with cooling contact with warming mill the layer.If add in the layer that contacts with above-mentioned roller, after oozing out, antistatic agent may pollute above-mentioned roller, and cause film surface to produce fault, productivity significantly worsens.
Nucleator has no particular limits, and can use known nucleator.For example can use Sorbitol Powder is polymer nucleators such as inorganic nucleators such as organic nucleating agents such as nucleator, aluminum benzoate, talcum, polyvinyl eyclohexane, poly--3-methyl butene-1, poly-cyclopentenes.
In the present invention, in order to give full play to the effect of nucleator, preferably it is added in the central core of multilayer film.
Lubricant adds for the sliding effect of giving full play to film, can use organic silicone oils such as aliphatic amide, silicon rubber such as erucicamide or silicone elastomer etc.In addition, in the occasion of multilayer film, can in known scope, add in arbitrary layer by without stint.
More than the additive of polypropylene for films of the present invention is illustrated, but no matter use any additive, all must suitably select the kind of additive or limit its consumption, so that constitute film integral or reach below the 300ppm with the total ash content in the raw material at the film of the present invention that the multiwalled occasion constitutes central core in the occasion of individual layer.
Compare with known polypropylene in the past, when using polypropylene for films of the present invention to make oriented film, can carry out high-speed stretch for a long time, continuously, the thickness and precision of gained film is good, and the transparency and exterior quality are also fine.By being stretching in the multi-layer sheet that the polyolefin-based resins layer that contains anti is set on the top layer, can not reduce high-speed stretch, obtain having the film of good adhesion inhibiting properties, in addition, by being stretching in the multi-layer sheet that the low melting point polyolefin resin is set on the top layer, can not reduce high-speed stretch, obtain having the film of good heat sealer.
Embodiment
In order to be described more specifically the present invention, to narrate embodiments of the invention and comparative example below, but the invention is not restricted to these embodiment.
In embodiment and comparative example, carry out various mensuration projects as follows.
[resin analysis]
(1) melt flow rate (MFR) (MFR)
Undertaken by ASTM D-790 standard.
(2) isotactic five minutes rate (ペ Application ッ De divides rate) (Iso), alpha-olefin content (ethylene content (E%))
The JNM-GSX-270 that use NEC society makes (
13C-nmr frequency 67.8MHz), measure by following condition.
The mensuration mode:
1The complete decoupling of H-
Pulse width: 7.0 microseconds
Pulse repetition time: 3 seconds
Cumulative frequency: 10000 times
Solvent: orthodichlorobenzene/heavy benzol mixed solvent (90/10 capacity %)
Sample solution concentration: 120mg/2.5ml solvent
Measure temperature: 120 ℃
At this moment, by five fens rates of isotactic
13The mensuration at the division peak in the methyl zone of C-NMR spectrum is obtained.In addition, the ownership at the peak in methyl zone is pressed A.Zambelli et al (Macromolecules, 13,267 (1980)) and is determined.
(3) with intensification precipitation staging (TREF) measure below 20 ℃ and 20-70 ℃ one-tenth component, peak temperature (Tp), distribution of crystallizability (σ)
Use the セ ソ シ automatic TREF device SSC-7300ATREF that コ-science society makes, measure by following condition.
Solvent: orthodichlorobenzene
Flow velocity: 150ml/ hour
Heat-up rate: 4 ℃/hour
Detecting instrument: infrared radiation detection apparatus
Measure wavelength: 3.41 μ m
Post: φ 30mm * 300mm
Weighting agent: Chromosorb P (trade(brand)name)
Concentration: 1g/120ml
Injection rate: 100ml
This occasion, under 145 ℃, sample solution is imported in the post, slowly cool to 10 ℃ with 2 ℃/hour speed then sample polymer is adsorbed on the weighting agent surface, post is heated up by above-mentioned condition, be determined at the polymer concentration of separating out at each temperature with infrared radiation detection apparatus, obtain stripping curve.Obtain below 20 ℃ and 20-70 ℃ one-tenth component, peak temperature (Tp), distribution of crystallizability (σ) by this curve.
(4) ratio of expansion
When pressing ASTM D-790 standard test solution flow rate,, measure the external diameter of this resin flow from the about 5cm of molten resin flow sampling that extrudes by MI meter bottom nib, with this numerical value divided by die throat diameter, with institute's value as ratio of expansion.
(5) total ash content
Full-automatic fluorescent x-ray analysis equipment System3080E2 with motor manufacturing of science measures.
Sample: the shaping sheet material stamping-out of being extruded by T pattern head when film shaped becomes the circle of thick 3mm, diameter 45mm.
Element (voltage 50KV, electric current 50mA) beyond condition determination: the Mg
Mg (voltage 35KV, electric current 80mA)
Detection elements: the element of measuring with above-mentioned fluorescent X-ray analysis, be that the element summation (ppm) of the representational Al of being, Ti, Ca, P, Fe, Cl, Si, Mg is as total ash content.
[evaluation when making film at a high speed]
(1) the sheet material end curls
The curling situation of sheet material end is that the sheet material end is estimated from the degree that roller floats by will be cooled off on cooling roller by the sheet material that T pattern head is extruded the time.Evaluation is divided into 4 grades, and promptly to float 1mm from roller be ◎ when following to sheet material, and 1mm is above, be zero when 2mm is following, more than the 2mm, be △ when 3mm is following, when 3mm is above be *.
(2) thickness precision
The thickness precision of gained polypropylene film uses the β ray thickness measuring instrument that is arranged between tenter machine and the reeling machine to measure, and estimates by the thickness pattern.Divide 4 grades to estimate according to the thickness pattern, promptly the thickness precision is ◎ 1% with in, is to be △ more than zero, 2%, below 3% more than 1%, below 2%, more than 3% be *.
[evaluation of film]
(1) film thickness
Undertaken by JIS K 7105 standards.
(2) transparency (haze value)
Undertaken by JIS K7105 standard.
(3) percent thermal shrinkage
Cut the rectangle of wide 15mm, long 300mm in the vertical, heating is 15 minutes in 120 ℃ baking oven, obtains percent thermal shrinkage by the dimensional change after the heating.
(4) press viscosity value
Vertical (MD) at film cuts 300mm, and (TD) cuts 40mm at width, obtains the rectangle sample, with its overlapping 3mm, makes sample.
This sample was placed 24 hours under 30 ℃, the atmosphere of humidity 70%, with pressing machine this film sample is applied 20kg/cm then
2Pressure continued for 30 seconds.With anchor clamps the two ends of film sample are fixed, used the stretching test machine determination flexural strength.
(5) static electricity resistance (surface resistivity)
Press the surface resistivity of JIS K6911 standard test film.
(6) evaluation of heat sealer
With the heat seal bar of 5 * 200mm, at design temperature (80-155 ℃) arbitrarily, with 1kg/cm
2Heat seal pressure with the face of the low-melting-point resin lamination of film 1.0 seconds of heat seal each other, cut the wide sample of 15mm by resulting test portion, measure with the draw speed that 500mm/ divides with tensile testing machine.
With the mean value of 5 samples as measurement result.With individual setting speed is that transverse axis, tensile strength are that the longitudinal axis is depicted as the heat seal curve.According to this curve, the heat seal bar design temperature when tensile strength is 300g is as the heat seal starting temperature.
(preparation of titanium compound)
The method described in the embodiment 1 of clear 58-83006 of opening by the spy prepares solid titanium catalyst component.Promptly, with Magnesium Chloride Anhydrous 9.5g, decane 100ml and 2-Ethylhexyl Alcohol 47ml (300mm0l) 125 ℃ of following heated and stirred 2 hours, in this solvent, add Tetra hydro Phthalic anhydride 5.5g (37.5mmol) then, under 125 ℃, further mixed 1 hour, obtain homogeneous solution.
Behind the cool to room temperature, its full dose is added drop-wise among the titanium tetrachloride 400ml (3.6mmol) that remains on-20 ℃ with 1 hour.With 2 hours this mixed solution is warming up to 110 ℃, adds diisobutyl phthalate 5.4ml (25mmol) when reaching 110 ℃, under this temperature, stir maintenance 2 hours then.
After 2 hours reaction finishes, collect solid part by heat filtering, this solid part is suspended in the titanium tetrachloride of 2000ml, then 110 ℃ of reacting by heating 2 hours, after reaction finished, heat filtering was collected solid part once more, fully clean with decane and hexane, in washing lotion, detect less than the free titanium compound.With the solid titanium catalyst component of method for preparing, preserve as the heptane slurry.The composition of solid titanium catalyst component is titanium 2.1% (weight), chlorine 57.0% (weight), magnesium 18.0% (weight) and diisobutyl phthalate 21.9% (weight).
(prepolymerization)
Refined hexane 6000ml, triethyl aluminum 100mmol, solid titanium catalyst component (being converted into titanium atom) 10mmol pack in the 10L polymerization reactor of replacing with nitrogen, in reactor, imported propylene 1 hour continuously then, make that the propylene total amount is 50g with respect to the 10g solid titanium catalyst component.Temperature keeps 10 ℃ in this process.Stop to import propylene after 1 hour, with the abundant metathesis reactor of nitrogen.Wash the solid part of resulting slurry with refined hexane, wash altogether 5 times, obtain containing the polypropylene of solid titanium catalyst component.
(this polymerization)
Propylene 500kg packs in the inner capacities of replacing with nitrogen is the polymerization reactor of 2000L, reinstall triethyl aluminum 1.64mol, ethyl triethoxysilane 0.164mol, cyclohexyl methyl dimethoxy silane 0.0082mol and hydrogen 10L, will be warming up to 65 ℃ in the polymerization reactor then.Polypropylene (the being converted into titanium atom) 0.00656mol that packs into and contain solid titanium catalyst component will be warming up to 70 ℃ in the polymerization reactor, carry out 1 hour propylene polymerization.Remove unreacted propylene after 1 hour, obtain the white particle shaped polymer.With resulting polymers at 70 ℃ of following drying under reduced pressure.All polymkeric substance receipts amount is 166kg.
The peak temperature (Tp) of the stripping curve that the polyacrylic melt flow rate (MFR) of gained shown in the table 1 (MER), weight-average molecular weight, rate, copolymerization in five minutes form, measure with intensification precipitation staging (TREF), distribution of crystallizability (σ), accumulate temperature (T (90)) that stripping quantity is 90% (weight), stripping temperature measurement result in the stripping quantity below 20 ℃ (a), ratio of expansion and total ash content.In addition, the stripping temperature of expression shown in Fig. 1 (℃) with the stripping curve of the relation of stripping quantity (weight %), the stripping of expression shown in Fig. 2 temperature (℃) with the stripping curve of the relation of accumulation stripping quantity (weight %).
(adjustment of granulation and total ash content)
Add 2 in 100 parts of weight of the polypropylene powder that in by polymerization reactor, obtains; each 0.1 part of weight of 6-two-tertiary butyl hydroxytoluene and calcium stearate; mix with the Henschel mixing tank, the extruding granulator that with screw diameter is 65mm obtains the film raw material at 230 ℃ of following extruding pelletizations.At this moment, be the screen cloth of 60 μ m in the screw tip clamping eyelet size of extruding granulator, be the screen cloth of 150 μ m at this screen cloth both sides configuration eyelet, the total ash content in the pellet is adjusted to the scope shown in the table 1.
(system film)
Use the gained polypropylene granules, carry out the system film test of biaxially oriented film as follows.Use is extruded polypropylene granules by the 3 synusia material forcing machines that 1 main extruder and 2 satellite forcing machines constitute under 280 ℃, be configured as the sheet stock of thick 1mm with 30 ℃ cooling rollers.In the satellite forcing machine, infeed the raw material of the anti that contains amorphous silicon oxide 0.1% (weight), in main extruder, infeed following raw material, described raw material contains octadecyldiethanol amine 0.1%, octadecyl monostearate 0.2%, Zerol 0.3% (total amount 0.6%) as antistatic agent, contain erucicamide 0.05% (weight) as lubricant, the ratio of the extrusion capacity of each forcing machine is, with respect to satellite forcing machine 1 main extruder is 8, is extruded by T pattern head.
Subsequently, the roller speed of dividing with 55.5m/ is fitted in this fusion sheet material on the cooling roller that is called chilled roll (チ Le ロ-Le), and its surface cool that contacts with roller is solidified, and then sheet material is imported in the tank, make its another side cooling curing, obtain the not stretched sheet that 3 layers of total thickness are 0.9mm.With the device of two-way stretch one by one of tentering mode, under 140 ℃ of preheating temperatures with 4.5 times of this sheet material longitudinal stretchings, then 10 times of cross directional stretchs in 170 ℃ tenter machine are that to make thickness (T) be the biaxially oriented film of 20 μ m for film speed that 250m/ divides with V 〉=2000/T.The thickness of gained film depends on the extrusion capacity ratio of forcing machine, because extrusion capacity is than for being 8 with respect to each 1 main extruder of satellite forcing machine, thereby obtains 3 layer films of each outer 2 μ m, central core 16 μ m.In addition, the film of making wore out 3 days down at 40 ℃.
To reaching the polypropylene film that obtains at last in the manufacturing processed, measure the batching of sheet material end, thickness precision, move 12 hours film breaks number of times, the transparency, percent thermal shrinkage, pressure viscosity value and surface resistivity after making continuously, the results are shown in table 1 and the table 2.
Embodiment 2 and 3
In this polymerization, use cyclohexyl methyl dimethoxy silane 0.035mol and tetraethoxysilane 0.35mol (embodiment 2) as silicoorganic compound, perhaps use cyclohexyl methyl methyl dimethoxysilane 0.0175mol and tetraethoxysilane 0.525mol (embodiment 3), in addition granulation similarly to Example 1, obtain the film raw material shown in the table 1, make polypropylene film with this raw material.
Resulting polypropylene film is carried out various projects measure, the results are shown in the table 2.
Embodiment 4
In this polymerization, use dicyclopentyl dimethoxyl silane 0.0164mol to replace cyclohexyl methyl dimethoxy silane as silicoorganic compound, in addition granulation similarly to Example 1 obtains the film raw material shown in the table 1, makes polypropylene film with this raw material.
Resulting polypropylene film is carried out various projects measure, the results are shown in the table 2.
Embodiment 5
In this polymerization, carry out the random copolymerization of ethene and propylene, in addition granulation similarly to Example 1 obtains the film raw material shown in the table 1, makes polypropylene film with this raw material.
Resulting polypropylene film is carried out various projects measure, the results are shown in the table 2.
Ethylene content in the above-mentioned polypropylene that obtains is 0.28% (mole).
Embodiment 6
In embodiment 1, with respect to each satellite forcing machine 1 main extruder to be the sheet material of 18 extrusion capacity ratio, the 26m/ sharp cooling roll speed of dividing by T pattern head extrusion molding 2mm, 5 times of longitudinal stretchings, 10 times of cross directional stretchs, film speed is the 130m/ branch during cross directional stretch, obtain the film of thick 40 μ m, in addition estimate similarly to Example 1.The results are shown in the table 2.
Embodiment 7
The polypropylene granules that uses method similarly to Example 1 to obtain, the extrusion capacity of forcing machine is identical with embodiment 1, sharp cooling roll speed is the 31.3m/ branch, obtain the sheet material of thick 1.6mm, the longitudinal stretching multiplying power is 8 times, and in addition polypropylene film is made in operation similarly to Example 1, various mensuration projects are measured, be the results are shown in the table 2.
Embodiment 8
The polypropylene granules that uses method similarly to Example 1 to obtain, the extrusion capacity of forcing machine is identical with embodiment 1, sharp cooling roll speed is the 65.8m/ branch, obtain the sheet material of thick 0.76mm, the longitudinal stretching multiplying power is 3.8 times, and in addition polypropylene film is made in operation similarly to Example 1, various mensuration projects are measured, be the results are shown in the table 2.
Comparative example 1
The polypropylene that uses method similarly to Example 1 to obtain, using the eyelet size separately is the screen cloth of 150 μ m, does not adjust total ash content, granulation similarly to Example 1, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film.Measurement result is shown in Table 2.
Comparative example 2
In this polymerization, silicoorganic compound use ethyl triethoxysilane 0.5mol, cyclohexyl methyl dimethoxy silane 0.002mol, obtain polypropylene powder, granulation similarly to Example 1, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film, various mensuration projects are measured, be the results are shown in the table 2.
Comparative example 3
In this polymerization, use dicyclopentyl dimethoxyl silane 0.005mol to replace cyclohexyl methyl dimethoxy silane, obtain polypropylene powder, granulation similarly to Example 1, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film, various mensuration projects are measured, be the results are shown in the table 2.
Comparative example 4
In this polymerization, use cyclohexyl methyl dimethoxy silane 0.350mol separately as silicoorganic compound, obtain polypropylene powder as ethylene atactic copolymer, granulation similarly to Example 1, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film, various mensuration projects are measured, be the results are shown in the table 2.
Comparative example 5
In this polymerization, use tetraethoxysilane 0.35mol separately as silicoorganic compound, obtain polypropylene powder as ethylene atactic copolymer, granulation similarly to Example 1, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film, various mensuration projects are measured, be the results are shown in the table 2.
Comparative example 6
(preparation of solid titanium catalyst)
Reduce titanium tetrachloride with diethylaluminum chloride, resulting brown titanous chloride is handled with equimolar isoamyl ether at normal temperatures, uses this brown titanous chloride of 65 ℃ of hexane solvent chemical treatments of titanium tetrachloride then, obtains highly active titanous chloride.
(prepolymerization)
The normal heptane 3.5L that packs in the 10L polymerization reactor of replacing with nitrogen adds the above-mentioned high reactivity titanous chloride of 50g and is the diethylaluminum chloride of 1 times of mole with respect to this titanous chloride.Be warming up to 50 ℃, supply with propylene gas with certain speed and certain hour then, make polymerization velocity be 10g-polymkeric substance/g-catalyzer/hour.Stop polymerization, remove unreacted propylene.With resulting pre-polymerized catalyst (titaniferous polypropylene) slurry as this polymeric catalyzer.
(this polymerization)
Liquid propene 1000L and hydrogen 1000NL pack in the polymerization reactor of the inner capacities 2000L that replaced with propylene gas, with respect to pack into the diethylaluminum chloride of 10 times of moles of highly active titanous chloride, be warming up to 65 ℃, add the pre-polymerized catalyst slurry that is equivalent to 35g-titanous chloride amount and cause this polymerization.
After carrying out this polymerization in 3 hours, remove unreacted propylene, stop polymerization.The polymkeric substance and the methyl alcohol 50L that generate were mixed under 65 ℃ 1 hour, make catalyst decomposes.Filtration drying then.Obtain polymeric powder.
With the granulation similarly to Example 1 of the above-mentioned polypropylene powder that obtains, obtain the film raw material shown in the table 1, in addition operation similarly to Example 1 obtains polypropylene film, and various mensuration projects are measured, and the results are shown in the table 2.
Comparative example 7
Down washed the powder that obtain in the comparative example 6 30 minutes at 60 ℃, fully remove ash content, then complete drying with the 500L normal heptane, obtain polypropylene powder,, obtain the film raw material shown in the table 1 with comparative example 1 same granulation, in addition operate equally with comparative example 1, the results are shown in the table 2.
Comparative example 8
In the polypropylene powder that method makes similarly to Example 1, add 0.1% amorphous silicon oxide, use the polypropylene granules of total ash content as 1000ppm, it is supplied with main extruder as the sandwich layer raw material, in addition operate equally, make polypropylene film with comparative example 1.Various mensuration projects are measured, be the results are shown in the table 2.
Table 1
| MFR g/10 branch | Co-monomer content mole % | The TREF measured value | Ratio of expansion | Total percent of ash amount content ppm | Iso | ||||
| The % of stripping quantity weight below 20 ℃ | 20-70 ℃ of composition stripping quantity weight % | Tp ℃ | σ ℃ | ||||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 comparative examples 7 comparative examples 8 | 2.8 3.1 2.6 2.8 3.0 2.8 2.8 2.8 2.8 2.8 2.8 2.6 3.8 2.8 2.8 2.8 | (0.0 homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.28 (ethene) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) 0.24 (ethene) 0.23 (ethene) 0.0 (homopolymers) 0.0 (homopolymers) 0.0 (homopolymers) | 2.5 2.5 2.6 2.8 3.0 2.5 2.5 2.5 2.5 5.1 0.5 0.4 5.1 5.6 5.1 2.5 | 3.1 2.4 3.1 3.1 3.5 3.1 3.1 3.1 3.1 4.7 0.8 1.5 4.6 4.4 4.3 3.1 | 121.1 121.5 120.6 119.6 118.5 121.1 121.1 121.1 121.1 110.1 127.0 120.1 119.2 120.5 120.6 121.1 | 10.4 9.8 10.9 10.5 11.6 10.4 10.4 10.4 10.4 20.0 4.4 6.6 8.6 12.1 12.1 10.4 | 1.39 1.32 1.43 1.50 1.53 1.39 1.39 1.39 1.39 1.81 1.01 1.21 1.40 1.46 1.40 1.39 | 200 170 280 200 240 200 200 200 400 700 100 300 750 600 100 1000 | 0.930 0.940 0.926 0.910 0.930 0.930 0.930 0.930 0.930 0.870 0.980 0.970 0.890 0.925 0.910 0.930 |
Table 2
| Film thickness μ m | Film speed m/ branch | The longitudinal stretching multiplying power doubly | Curling of sheet material end | The thickness precision | The transparency (mist degree) % | MD percent thermal shrinkage % | Press viscosity value g | Static resistance surface resistivity values Ω | Film breaks number of times number of times/12 hours | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 comparative examples 7 comparative examples 8 | 20 20 20 20 20 40 20 20 20 20 20 20 20 20 20 20 | 250 250 250 250 250 130 250 250 250 250 250 250 250 90 250 250 | 4.5 4.5 4.5 4.5 4.5 4.5 8.0 3.8 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 | ◎ ○ ◎ ◎ ◎ ○ ○ ◎ ◎ ◎ × × ◎ △ ○ △ | ◎ ○ ◎ ○ ◎ ○ ○ ○ ◎ ◎ × × ◎ △ × △ | 1.2 1.2 1.1 1.2 1.1 1.6 1.3 1.5 1.5 2.3 1.0 1.2 1.3 1.4 1.3 3.5 | 0.6 2.2 2.7 2.3 2.9 2.3 2.9 2.0 2.5 4.7 2.0 2.6 3.5 3.0 2.4 2.6 | 200 100 300 ＜100 100 200 300 100 200 700 150 200 650 550 250 ＜100 | 2.0×10 123.0×10 121.0×10 125.0×10 122.0×10 120.8×10 124.0×10 122.0×10 122.0×10 120.5×10 121.0×10 121.0×10 120.7×10 120.7×10 121.0×10 121.0×10 12 | 0 1 0 0 0 0 3 0 10 21 15 6 13 10 6 38 |
Embodiment 9
In embodiment 1, change the addition of the employed anti of skin into 0.5% (weight), in addition make polypropylene film equally.Various mensuration projects are measured, be the results are shown in the table 3.
In embodiment 1, the melamine that the employed anti of skin is changed into the particle diameter 1.3 μ m of 0.05% (weight) is a spherical resin, in addition makes polypropylene film equally.Various mensuration projects are measured, be the results are shown in the table 3.
Embodiment 11
In embodiment 1, the employed anti of skin is changed into the calcium carbonate particles of cubic calcite structure of the particle diameter 2.0 μ m of 0.1% (weight), in addition make polypropylene film equally.Various mensuration projects are measured, be the results are shown in the table 3.
Embodiment 12
In embodiment 1, change the employed antistatic agent of central core into dodecyl diethanolamine 0.1% (weight), dodecyl monostearate 0.2% (weight), glyceryl monolaurate 0.3% (weight), amount to 0.6% (weight), in addition make polypropylene film equally.Various mensuration projects are measured, be the results are shown in the table 3.
Table 3
| Film thickness μ m | Film speed m/ branch | Anti addition/(kind) weight % | Antistatic agent total addition level weight % | Press viscosity value g | The static resistance surface resistivity | Film is disrumpent feelings number of times number of times/12 hour | The transparency (mist degree) % | |
| Embodiment 9 | 20 20 20 20 | 250 250 250 250 | (0.5/ silicon-dioxide) 0.05/ (melamine) 0.1/ (lime carbonate) 0.1/ (silicon-dioxide) | 0.6 0.6 0.6 0.6 1) | ＜100 100 ＜100 200 | 8.4×10 125.5×10 125.5×10 126.5×10 12 | 2 0 1 0 | 2.9 1.1 1.3 1.2 |
1) antistatic agent: use dodecyl diethanolamine, dodecyl monostearate, Zerol
Embodiment 13
In embodiment 1, for the skin of a side, the soft silica of allocating 0.01% (weight) in the propylene-ethylene random copolymers of 90 ℃ of fusing points into forms masterbatch, as the heat seal resin, supplies with the satellite forcing machine.In the satellite forcing machine of opposite side and main extruder, supply with polypropylene granules similarly to Example 1.As the extrusion capacity ratio, be respectively 1 with respect to the satellite forcing machine of supplying with the heat seal resin and the satellite forcing machine of opposite side, main extruder is 8.Then, press embodiment 1 described method system film, each skin of gained film is 2 μ m, and central core is 16 μ m, amounts to 20 μ m.
Various mensuration projects are measured, be the results are shown in the table 4.
Embodiment 14
In embodiment 13, the propylene-ethylene random copolymers that uses 60 ℃ of fusing points is as the heat seal resin, and in addition polypropylene film is made in operation similarly to Example 13, and various mensuration projects are measured, and the results are shown in the table 4.
Embodiment 15
In embodiment 13, the propylene-ethylene random copolymers that uses 145 ℃ of fusing points is as the heat seal resin, and in addition polypropylene film is made in operation similarly to Example 13, and various mensuration projects are measured, and the results are shown in the table 4.
Embodiment 16
In embodiment 13, the propylene-ethylene random copolymers that uses 90 ℃ of fusing points is as two outer heat seal resins, and in addition polypropylene film is made in operation similarly to Example 13, and various mensuration projects are measured, and the results are shown in the table 4.
Embodiment 17
In embodiment 13, with respect to the satellite forcing machine 2 of supplying with the heat seal resin, the satellite forcing machine 1 of opposite side, the central core main extruder is 7, helps out by this extrusion capacity ratio, obtaining thermal synthesis layer is 4 μ m, the opposite side skin is 2 μ m, and central core is 14 μ m, the film of aggregate thickness 20 μ m, in addition operation similarly to Example 13, make polypropylene film, various mensuration projects are measured, the results are shown in the table 4.
Table 4
| Heat seal melting point resin ℃ | Film thickness μ m | Heat seal resin thickness μ m | Laminated of heat seal resin | The heat seal resin begins temperature ℃ | The transparency (mist degree) % | MD percent thermal shrinkage % | Film breaks number of times number of times/12 hours | |
| Embodiment 13 embodiment 14 embodiment 15 embodiment 16 embodiment 17 | 90 60 145 90 90 | 20 20 20 20 20 | 2 2 2 2 4 | One side one side one side two sides one side | 85 60 125 85 83 | 0.3 2.9 1.2 1.8 2.4 | 1.9 3.2 2.7 3.2 2.1 | 0 0 0 0 0 |
Brief description of drawings Fig. 1 is that the polyacrylic TREF stripping curve Fig. 2 that obtains among the embodiment 1 is the polyacrylic TREF accumulation stripping quantity curve that obtains among the embodiment 1
Claims (4)
1, polypropylene for films, it is characterized in that, in the stripping curve of obtaining with intensification precipitation staging, the stripping temperature is 0.5-3.5% (weight) at the stripping composition below 20 ℃, the stripping temperature is 1.5-3.5% (weight) at 20-70 ℃ stripping composition, and peak temperature is 114-124 ℃, and distribution of crystallizability is 5-18 ℃, ratio of expansion is 1.1-1.6, and total ash content is below the 300ppm.
2, the manufacture method of polypropylene film is characterized in that, the described polypropylene for films of claim 1 is melt extruded slabbing, this flap is carried out longitudinal stretching at least with 3-10 stretching ratio doubly, and when carrying out above-mentioned stretching, the coiling speed V of film is in following ranges
V≥2000/T
V: the coiling speed of film (m/ branch)
T: resulting film thickness (μ m).
3, the manufacture method of the described polypropylene film of claim 2, it is characterized in that, this flap is by central core and the outer polylayer forest that constitutes, described central core is to be made of the described polypropylene for films of claim 1, and described skin is to be made of the polyolefin-based resins that contains 0.01-0.5% (weight) anti at least one side surface.
4, the manufacture method of the described polypropylene film of claim 3 is characterized in that, the low melting point polyolefin that constitutes outer field polyolefin-based resins and be fusing point and be 60-150 ℃ is a resin.
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| JP9636198 | 1998-04-08 | ||
| JP96361/1998 | 1998-04-08 | ||
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| US20030039826A1 (en) * | 2000-03-20 | 2003-02-27 | Sun Edward I. | Conformable and die-cuttable biaxially oriented films and labelstocks |
| CN104070757A (en) * | 2014-06-19 | 2014-10-01 | 晋江市新合发塑胶印刷有限公司 | CPP (casting polypropylene) matt film and preparation method thereof |
| CN111100225B (en) * | 2018-10-29 | 2022-08-19 | 中国石油化工股份有限公司 | Propylene polymerization method and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4916498A (en) * | 1985-09-15 | 1990-04-10 | Trw Inc. | High electron mobility power transistor |
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| US4916498A (en) * | 1985-09-15 | 1990-04-10 | Trw Inc. | High electron mobility power transistor |
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