CN1152323A - 全同立构聚丙烯的用途、制备方法和其产品 - Google Patents
全同立构聚丙烯的用途、制备方法和其产品 Download PDFInfo
- Publication number
- CN1152323A CN1152323A CN95192923.2A CN95192923A CN1152323A CN 1152323 A CN1152323 A CN 1152323A CN 95192923 A CN95192923 A CN 95192923A CN 1152323 A CN1152323 A CN 1152323A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- temperature
- film
- acrylic resin
- metallocenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 83
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims description 42
- 230000008569 process Effects 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 28
- 229920005989 resin Polymers 0.000 abstract description 28
- 239000012968 metallocene catalyst Substances 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 29
- 238000012360 testing method Methods 0.000 description 23
- 238000012545 processing Methods 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- UPFLRGQIBJZJFH-UHFFFAOYSA-N C[SiH2]C.Cl.Cl Chemical compound C[SiH2]C.Cl.Cl UPFLRGQIBJZJFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- LXZGARSEFLNFFB-UHFFFAOYSA-N 2-methyl-3-naphthalen-1-ylpropanoic acid Chemical compound C1=CC=C2C(CC(C)C(O)=O)=CC=CC2=C1 LXZGARSEFLNFFB-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000002650 habitual effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 208000011117 substance-related disease Diseases 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
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
公开了由金属茂催化剂生产的全同立构聚丙烯树脂的应用,其中该树脂可制备具有类似于常规聚丙烯树脂制品的剪切模量和热畸变温度值的制品,但制备该制品可在温度远低于常规聚丙烯可用的温度下进行。
Description
本发明涉及金属茂聚丙烯树脂组合物的用途。本发明更特别涉及形成劲度和使用温度等于用常规聚丙烯通过常规方法形成的制品的劲度和使用温度的制品的方法,但本发明方法可在较低温度下进行。
全同立构聚丙烯树脂有很多用途。聚烯烃中,材料的相对高使用温度和高模量是对其应用特别有用的两个特点。模量是指根据ASTM D4065通过动态力学试验测得的给定树脂的剪切模量。对于本发明,使用温度定义为由聚丙烯树脂生产的制品、薄膜、片材或纤维的使用温度。热畸变试验(HDT)(又称为热变形试验或热挠曲试验)广泛用于定义热塑性塑料的使用温度。该试验中,将重物悬挂在固定于室中的悬臂成型棒上,将室的温度以设定速率升高至棒下垂给定量为止。此试验根据ASTM D648在455kPa(66psi)或1820kPa(264psi)单位荷载下进行。HDT值是材料在高温时在应力作用下耐形变的测量值。HDT值是塑料在工业应用中保持可接受的完整性的最高温度。本文提及的HDT值是相对于455kPa(66psi)单位荷载的试验值。
为了最大限度地使用聚丙烯,需要设计具有尽可能高模量和HDT值的树脂。对于常规聚丙烯树脂,最大限度地提高模量和HDT值一般将最大限度地提高树脂的熔点。在熔体加工中,如制备注塑制品,加工聚丙烯在温度高于其熔点下进行。聚丙烯的性能可通过在温度略低于晶体熔点温度下取向增强。纺织纤维、单轴和双轴取向薄膜是得益于这种取向加工的产品的例子。在取向加工中,将聚丙烯保持在温度稍低于其熔点温度下。通常,在任何加工中,高熔点的树脂需要使用温度高的加工设备。这是不可取的,因为加工前须将树脂加热至高温,然后再耗费额外的时间将其冷却,这将影响生产效率和经济效益。此外,由于这种方法要消耗大量能量,因此也是不可取的。
根据Spalek等人在Metallocene Conference(Houston,Texas,1993年5月)上的发言,对于金属茂和常规聚丙烯,其熔化温度与室温模量的关系是不同的。Spalek等人披露金属茂聚丙烯均聚物与具有类似熔体流动速率(MFR)和熔点(MP)值的常规聚丙烯相比,具有较高的室温模量值。在耐用品和高性能包装品领域中,人们不仅对室温模量感兴趣,而且对此模量与高温的联系怎样感兴趣。
人们特别需要一种具有高模量和HDT值的聚丙烯,而该聚丙烯又可在温度低于具有类似模量和HDT值的常规聚丙烯所需的加工温度下加工。通常,这意味着具有模量和HDT值高,但熔点低的树脂。对于常规全同立构丙烯均聚物,其晶体熔点温度范围为约160-165℃,HDT值范围为约90-105℃。对于这些常规全同立构均聚物,取向加工一般在约135-155℃温度范围内进行。因此,常规聚丙烯的取向温度高于其HDT值约40-50℃或更多。在温度低于目前已知的温度且不损害所得产品的HDT值、模量或其它重要性能下加工全同立构聚丙烯是特别需要的。
我们以令人吃惊地发现,由金属茂基催化剂体系生产的全同立构聚丙烯树脂与具有类似模量和使用温度(由HDT衡量)的常规聚丙烯相比,具有令人吃惊的低熔点。本发明涉及在温度低于常规聚丙烯加工温度下由金属茂聚丙烯形成取向结构或制品,优选取向薄膜的方法。
根据本发明,提供一种形成取向结构的方法,包括步骤:
(a)由聚丙烯树脂形成结构,所述聚丙烯树脂由金属茂催化剂生产;
(b)在温度范围高于聚丙烯HDT约20℃至低于聚丙烯熔点温度约2℃下施加应力使结构取向。
此外,该取向结构可在温度范围高于聚丙烯的HDT约20℃至约35℃下加工或取向。加工优选在温度范围高于聚丙烯的HDT约20℃至约30℃下进行。
金属茂催化剂体系通常用于生产聚丙烯聚合物。金属茂可用助催化剂如铝氧丙环或能够与金属茂反应形成催化剂体系的离子化合物反应活化
金属茂可以均相形式使用,或载在惰性载体上和非必要地与烯烃单体预聚。在优选的实施方案中,将金属茂载在二氧化硅载体上。
由金属茂催化剂生产的聚丙烯可作为均聚物或共聚物使用。丙烯与具有2至约20个碳原子的共聚单体的共聚物和聚丙烯共混物组合物也适合本发明方法。
本发明的取向结构可以是薄膜,纤维,热或压力成型、或拉伸成型制品。可用常规方法由本发明所述的树脂取向或熔融形成制品。
图1为金属茂全同立构聚丙烯和常规聚丙烯的弹性剪切模量与温度的关系图。
已发现金属茂催化剂可生产熔点低于具有类似模量和热挠曲试验值的常规聚丙烯熔点的聚丙烯树脂组合物。这些树脂通常为丙烯均聚物或用丙烯与一种或多种共聚单体,优选具有2至约20个碳原子的α-烯烃或环烯烃制得的丙烯统计共聚物。金属茂生产的聚丙烯可以是聚丙烯与具有不同性质的另一种聚合物的共混物。
本发明涉及由金属茂催化剂制备的这些聚丙烯组合物的用途,和由这些树脂生产取向结构的方法。取向结构一般定义为本文所述的薄膜、纤维、片材或成型制品。取向或成型加工在温度低于目前常规聚丙烯能使用的加工温度下进行。本发明中,常规聚丙烯是由Ziegler-Natta催化剂生产的聚合物;金属茂聚丙烯是由单点或环戊二烯基衍生物过渡金属催化剂生产的聚合物。聚丙烯是指全同立构聚丙烯均聚物或共聚物或其共混物。共聚物是指由丙烯与一种或多种其它单体制备的丙烯基聚合物。
本发明中包括的原理适用于大多数降低取向或成型温度很重要的方法。在熔体加工操作中,形成制品前熔化的聚合物的温度由两个因素确定。第一,该温度必须足够高于聚合物的熔点以确保分子的无规化。第二,该温度必须足够高,这样熔体流动性足以使熔体注入模具中,或形成所需的形状。由于本发明的材料具有令人吃惊的低熔点,因此第一个关于熔体温度的限制可被解除。这样可使能量消耗较低、设备的加工速度更快。几乎所有热塑性加工方法都可受益于这些发现。除了薄膜和纤维取向工艺(其中低取向温度有利)外,加工方法的例子包括在低于材料熔点温度下进行成型的拉坯吹塑、拉伸注塑、固相压力成型或任何热成型加工。同样受益于低温的熔体成型方法的例子包括型材挤出、片材挤出(非必要地接着热成型)、薄膜挤塑、单丝挤出、无纺织物挤出等。作为一个例子,现在常规丙烯均聚物的热成型加工在温度约155-160℃下进行。对于本发明的金属茂,热成型可在温度范围约140-145℃下进行。
根据本发明制备的取向薄膜产品的用途例子包括用于快餐包装或其它食品包装的取向薄膜产品、用于热消毒或用作烹饪袋的薄膜产品。根据本发明制得的熔体吹塑制品的用途例子包括蒸汽消毒硬质包装、用于重要设备和汽车内外的注塑制件。在优选的实施方案中使用的金属茂
在最优选的实施方案中,所用的聚丙烯是由至少一种包括桥连双环戊二烯基,4、5、或6族过渡金属,二卤化物或二烷基衍生物的金属茂生产的。更优选的金属茂包括桥连双茚基、4族二卤化物衍生物。已知的可用作生产全同立构聚丙烯的具体金属茂催化剂公开于EP-A485,820、485,821、485,822、485,823、518,092和519,237;USP5,145,819、5,296,434中(这里所有这些文献作为用于实施US专利的参考引入)。
本发明使用的优选金属茂是手性的并用作制备全同聚-1-烯烃的外消旋体。金属茂的说明性但非限制的例子包括:二氯化二甲基甲硅烷基·双(2-甲基茚基)合锆、二氯化二甲基甲硅烷基·双(2-乙基-4-苯基茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-4-苯基茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-5-异丁基茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-4,5-苯并茚基)合锆和二氯化二甲基甲硅烷基·双(2-甲基-4,6-二异丙基茚基)合锆。最优选的具体金属茂是二氯化二甲基甲硅烷基·双(2-甲基-4,5-苯并茚基)合锆。虽然甲硅烷基桥和锆过渡金属是具体公开的,但本领域熟练技术人员将会想到可以使用其它类型的桥体系和过渡金属。
所用的金属茂优选载在惰性载体上并非必要地进行预聚。各种载体技术是本领域已知的。最优选的是用于USP5,240,894中的技术(这里作为参考引入)。载在载体上的金属茂优选按预聚方式使用。预聚物可以是任何α-烯烃,优选乙烯、丙烯或丁烯,最优选乙烯预聚物。
金属茂优选以金属茂与活化剂的络合物形式使用。活化剂可以是本领域公知的铝氧丙环,或公开于USP5,198,401或5,278,119中的离子活化剂。据信可将金属茂活化至催化状态的任何化合物都可用于本发明。本发明的聚丙烯
用于本发明的聚丙烯可以是使用金属茂催化剂通过气相、淤浆、本体、溶液或高压聚合方法生产的丙烯均聚物或共聚物或共混物。该聚合物优选为丙烯均聚物,其熔点低于由常规催化剂生产的具有类似模量和热挠曲温度的聚丙烯的熔点。聚合物可在流化或搅拌床气相反应器、淤浆或本体的罐式或环形管式反应器中或其它进行丙烯聚合的反应器中生产。载体催化剂体系(金属茂加上某些活化剂组分)优选用于淤浆或气相反应器中生产丙烯聚合物。
共聚物包括丙烯和至少一种共聚单体(或α-烯烃),其中共聚单体具有2至约20个碳原子。聚合物按常规方法使用金属茂催化剂制备。共聚单体的例子包括乙烯、丁烯-1、己烯-1和4-甲基-1-戊烯。所用的丙烯共聚物具有的共聚单体含量范围优选为约0.5至约10wt%。可以使用其它具有3种或更多种聚合物的聚合物混合物或共混物。共混物的例子包括聚丙烯均聚物与聚乙烯、丁烯-1共聚物和乙烯-丙烯-弹性体的共混物。
其它组分也可包括于聚合物组合物中。这些组分可选自惯用于塑料中的常规用量的添加剂,例如填料和/或增强剂、增强纤维、增塑剂、着色剂、染料、阻燃剂、抗氧剂、颜料、脱模剂、防滴剂等。选用的有效用量范围对于每100重量份聚合物通常为约0.1至约100份。
适合在本发明中使用的并且已发现具有意想不到的优异性质的聚丙烯树脂,是模量和HDT值与常规聚丙烯相似但可在较低温度下加工(通过其HDT值证明)的那些聚合物。这些聚合物一般具有窄分子量分布(MWD=Mw/Mn=约1-5,优选1-3,最优选1-2.5)。它们一般具有窄的组成分布和立构规整度分布。共聚物一般具有的熔点范围为约100℃至约145℃,更优选约110℃至约135℃,最优选约120℃至约135℃。均聚物通常具有的熔点范围为约140℃至约160℃。根据本发明制备的薄膜通常呈现低正己烷萃取量,一般低于10wt%,优选低于4wt%,因此适合作为在食品和医药领域中使用的产品。
本发明聚合物适用的熔体流动速率(MFR)(按照ASTM D-1238测量)范围为约0.1至约5000。在优选的实施方案中,熔体流动速率范围为约0.5至约200。对于薄膜和模塑用途,优选的MFR范围为约1至约10,最优选约1至约5。通过取向薄膜原纤化或纵切生产的取向纤维具有的MFR范围优选为约1至约10,最优选为约1至约5。由常规纺丝方法生产的纤维具有的MFR优选为10约至约200,最优选约30至约125。薄膜和片材
薄膜可按本领域熟练技术人员已知的工艺生产。例如,生产吹膜所用的环形口模和空气冷却,或生产流延薄膜所用的缝口模头和冷却用骤冷辊都是可用的工艺。薄膜的厚度范围一般为5至254μm(约0.2至约10mil),然而总厚度可根据所需的用途变化。片材可按常规工艺(例如经模头挤出基本上扁平的型材)制备。片材具有的厚度一般为254-1905μm(约10至约75mil),尽管它们基本上可以是更厚的。
在本发明范围内生产的薄膜或片材可在温度低于目前已知的常规聚丙烯所用的温度下取向。取向薄膜可通过挤出机后控制吹膜经加热和取向,或通过后挤出机拉辐工艺制得。根据所需的拉伸程度,薄膜或片材可以是这里所述的取向薄膜制品的前体。
作为薄膜取向的一个例子,目前HDT值约95℃、熔点约160℃的常规聚丙烯一般在约或大于135℃下对纵向(MD),在155℃下对横向(TD)进行取向。根据本发明用金属茂生产的基本上具有类似使用温度和模量的树脂,一般可在125℃和140℃下对MD和TD分别取向。
本发明的取向薄膜可以为单层或多层(复合)形式。复合物将包括至少一个第一表皮层和至少一个其它层。它们可通过(1)共挤出然后取向,(2)对薄膜取向然后层压,或(3)对薄膜取向然后挤出贴面形成。取向温度较低具有的优点在于共挤出薄膜中,表皮层由熔点低于其它层包括的金属茂聚丙烯的熔点的聚合物形成。首先,在较低温度下熔化的金属茂均聚物层可使人们采用非常低的热合温度的表皮树脂,而无对薄膜进行MD取向时经常遇到的阴模粘模问题。此外,这种薄膜的光学性能损失归因于极低熔点热合层树脂在加工温度下的熔化。在本发明中,加工温度明显较低,因此可最大限度地减少热合层熔化并保持薄膜的良好光学性能。
由金属茂催化剂生产的树脂制得的取向薄膜或制品预期具有类似于由常规催化剂生产的树脂形成的制品的透湿(水)气率(MVTR)。透湿气率是薄膜能用作水或湿气阻挡层的指标。对于目前由常规树脂形成薄膜的方法,随着树脂的熔点降低,因此将损害MVTR。对于本发明,在不损害最终薄膜的湿气阻挡性能下可使树脂熔点降低并降低加工温度。纤维
纤维可使用熔融聚合物通过常规方法如惯用的熔体纺丝、取向片材纵切和薄膜原纤化形成。随后可将纤维用于织造或非织造织物中。将纤维或前体薄膜通过以不同速率运转的顺序加热的辊进行所需的取向。对于本发明方法,这些辊基本上可在温度低于目前工业实际温度下运转。成型制品
成型制品可按常规工艺,例如注塑、注坯吹塑、挤坯吹塑、滚塑成型或发泡成型制备。发现成型部件具有多种厚度,通常为约500μm(20mil)或更大。重要之处在于将树脂加热至远高于其熔点以使分子无规化。本发明的树脂可使这种加热处理的温度低于常规树脂。热挠曲试验、动态力学试验和图1:
正如前面讨论的,热挠曲温度是材料在高温及应力下耐形变的指标。材料形变至预定程度的温度即为热挠曲温度(或热致形变温度),它对于生产厂家决定树脂的加工参数和最终制品的使用温度是重要的。
动态力学试验测量塑料对周期形变或变化形变的响应。通常施加的形变与时间呈正弦曲线变化,使样品形变所需的合力也呈正弦曲线。动态试验可使人们容易测量作为温度和时间函数的聚合物的弹性模量和阻尼或粘度性能。
图1为常规聚丙烯和金属茂全同聚丙烯均聚物的弹性剪切模量与温度的动态力学图。通常,本领域熟练技术人员会想到即使低熔点金属茂聚丙烯具有高的室温弹性模量,但该材料具有低的HDT值。相反,高熔点材料预期具有高HDT值。图1消除了这种概念。
图1的金属茂均聚丙烯的熔点为约145℃,而常规均聚丙烯的熔点为约162℃。根据以前的报道,金属茂聚丙烯在30℃的模量稍高一些。令人意想不到的是,这两种聚合物在100℃(常规聚丙烯通常的热致形变温度)时的模量证明是相同的。在130℃时,该两种聚合物具有不同的模量。同时金属茂树脂实际上具有比常规聚合物高的HDT值。按常理这一结果使人们想到采用已成熟的金属茂催化剂工艺可得到较高模量和使用温度的聚丙烯,并且其熔点接近160℃。
为估算聚合物的取向加工温度,可用图1的数据。我们可从图1中测得,为充分拉伸要求模量约为2×108dyn/cm2。金属茂聚丙烯在约135℃时达到此所需模量,而常规聚丙烯在约150℃时达到此所需模量。本发明利用金属茂树脂的这些特性,可在温度低于目前常规树脂的加工温度下进行加工,而得到的制品基本上相当于目前最好的薄膜制品。生产取向结构:
根据本发明的优选实施方案,提供一种形成取向结构的方法,包括步骤:
(a)由聚丙烯树脂形成结构,所述聚丙烯树脂由至少一种金属茂催化剂生产;
(b)在温度范围高于聚丙烯HDT值约20℃至约35℃下施加应力使结构取向。更优选的取向温度范围为高于聚丙烯HDT值约20℃至约30℃,最优选的取向温度范围为高于聚丙烯HDT值约25℃至约30℃。此外,人们认为较高的取向温度范围值可高于聚丙烯HDT值约35℃、30℃和25℃,较低的取向温度可高于聚丙烯HDT值约20℃和25℃。
另一实施方案涉及形成取向复合薄膜的方法,其中将包括(a)至少一由金属茂催化剂生产的聚丙烯聚合物的第一层和(b)至少一熔点低于第一层(a)熔点的某些聚合物的其它层的薄膜或片材,在温度范围高于金属茂催化制得的聚丙烯HDT值约20℃至约35℃下施加应力进行拉伸或取向。在复合薄膜中的金属茂聚丙烯优选为均聚物,但这不是必须的,取决于所需最终薄膜的用途。
本发明进一步的实施方案涉及在取向期间采取的最大温度,取向中该最大温度不超过聚丙烯HDT值约35℃。
实施例
下列说明性但非限制性的实施例将进一步描述本发明。它们不被认为是以各种方式对权利要求的限制。
合成用于生产实施例的全同立构聚丙烯均聚物的金属茂为下面给出的多步骤方法。合成外消旋二氯化二甲基硅烷二基·双(2-甲基-4,5-苯并茚基)合锆甲基(2-萘甲基)丙二酸二乙酯(1)
在加热下将5.15g(224mmol)钠溶于150ml无水乙醇中,并在室温下加入37.3ml(217mmol)甲基丙二酸二乙酯。在0℃下慢慢滴加50g(217mmol)2-溴甲基萘(纯度96%)在270ml乙醇中的溶液,并将此混合物进一步加热回流4至5小时。然后将其倒在冰水上并用乙酸乙酯萃取。将合并的有机相用硫酸钠干燥后蒸发。在油泵抽真空下干燥后,将油状残余物在0℃下在己烷中搅拌,如此结晶出55g(81%)化合物1。合成2-甲基-3-萘基丙酸(2)
将23.7g(422mmol)氢氧化钾在50ml水中的溶液加入33.2g(105mmol)化合物1在70ml乙醇中的溶液中,并将此混合物加热回流4小时。当汽提除去溶剂后,将固体残余物溶于乙酸乙酯中,加水并用盐酸将pH值调至1。将水相用乙酸乙酯萃取数次。将合并的有机相用硫酸镁干燥后彻底蒸发。然后将残余物在己烷中搅拌结晶。为进行脱羧,将此米黄色固体在175℃加热至释放气体结束为止。得到21g(94%)的米黄色固体产品2。合成2-甲基-6,7-苯并-2,3-二氢-1-茚酮(2-Methyl-6,7-benzoindo-1-one)(3)
在排除水分下,将22ml亚硫酰(二)氯加入21g(98mmoll)化合物2中,并将此混合物加热回流30分钟。然后蒸出过量的亚硫酰(二)氯。将残余物在油泵抽真空下很快除去挥发性化合物,然后在Ar作为惰性气体下将其溶于25ml二氯甲烷中。将此溶液慢慢滴加入26g(196mmol)三氯化铝在60ml二氯甲烷中的悬浮液中,并将此混合物再加热回流30分钟。将其倒在冰上并用二氯甲烷萃取。将合并的有机相用硫酸钠干燥后蒸发。将此黑色油状残余物在600g硅胶60色谱分离。用己烷/乙酸乙酯(9∶3)流动相混合物可洗脱出8.6g(45%)化合物3(黄色固体)。合成2-甲基-4,5-苯并茚(4)
在室温下将2.2g(59.5mmol)氢硼化钠分批加入7.8g(39.7mmol)2,3-二氢-1-茚酮(化合物3)在400ml四氢呋喃/甲醇混合物(2∶1)的溶液中,将此混合物搅拌14小时。将此溶液倒在盐酸冰上并用乙醚萃取。将合并的有机相用水洗涤数次并用硫酸钠干燥。将汽提除去溶剂后残余的橙色油溶于240ml甲苯中,并将此溶液与570mg(3.15mmol)对甲苯磺酸在80℃下加热15分钟。将其在室温下用水洗涤数次后用硫酸钠干燥,然后蒸发。将此残余物在300g硅胶60色谱上进行分离。用己烷/二异丙醚(20∶1)流动相混合物可洗脱出4.7g(65%)茚4(无色油)。1H-NMR光谱(360MHz,CDCL3):8.02(1,d),7.84(1,m),7.59(1,d),7.52(1,d),7.38-7.48(2,m),7.06(1,m),3.42(2,s),2.25(3,d)。
于室温下将10.2ml(25.5mmol)在己烷中的2.5M丁基锂溶液加入4.6g(25.5mmol)化合物4在50ml四氢呋喃中的溶液中,将此混合物加热回流1小时。然后在室温下将此红色溶液滴加入1.55g(12mmol)二甲基二氯硅烷在10ml四氢呋喃中的溶液中,将此混合物加热回流5至6小时。将此反应溶液倒在冰水上并用乙醚萃取数次,将合并的有机相用硫酸钠干燥,接着蒸发,并将残余物在油泵抽真空下干燥。将残余物在300g硅胶60色谱上分离。开始用己烷/3%乙酸乙酯流动相混合物可洗脱出500mg未反应的化合物4。接着用相同的流动相洗脱出配位体体系(化合物5)。汽提除去溶剂后,在己烷中结晶出此配位体体系(同分异构体)。产量为1.7g(34%,或按茚(已反应的化合物4)计44%)。合成外消旋二氯化二甲基硅烷二基·双(2-甲基-4,5-苯并茚基)合锆(6)
在室温下在作为惰性气体的Ar中将4.0ml(10.2mmol)在己烷中的2.5M丁基锂溶液加入1.7g(4.1mmol)化合物5在20ml四氢呋喃中的溶液中,将此混合物在室温下搅拌14小时。将汽提除去溶剂后的剩余的残余物用油泵抽真空干燥并用己烷洗涤。将制得的浅棕色粉末在40至50℃下用油泵抽真空干燥数小时,然后在-78℃下将其加入1.0g(4.0mmol)四氯化锆在25ml二氯甲烷中的悬浮液中。将混合物加热至室温后,汽提除去溶剂并用20ml甲苯萃取残余物以移走内消旋型金属茂(化合物6)。然后将甲苯萃取的残余物用40ml二氯甲烷萃取。将此溶液浓缩使体积变小并在-35℃结晶。经数次分馏分离出总共970mg(42%)纯外消旋体形式的锆茂(化合物6)。外消旋体的1H-NMR光谱(300MHz,CDCL3):7.96(2,m),7.78(2,m),7.60(2,d),7.48-7.56(4,m),7.36(2,d),7.27(2,s,b-Ind-H),2.37(6,s,Ind-CH3),1.36(6,s,Si-CH3)。质谱:574 M+通常的裂解,标准的同位素图形。载体催化剂化合物(6)
在装有冷却夹套和有效架空搅拌器的8升反应器中加入甲基铝氧丙环(在甲苯中30wt%,925ml)。在搅拌下,在N2下经双头针加入化合物6(5.0g)在甲苯(700ml)中的悬浮液。搅拌10分钟后,将脱水二氧化硅(Davison 948,在800℃下干燥,200g)在20分钟内加入溶液中。将此淤浆搅拌10分钟,然后在从反应器顶部施加真空下,将少量N2流经反应器底加入。将此混合物加热至70℃使溶剂在9小时内蒸出。将干燥的固体冷却至室温过夜。加入异戊烷(5升)使固体变为淤浆并将此混合物冷至0℃。在搅拌下将乙烯通过浸管以速率0.03-0.06 SCF/min加入该搅拌的混合物中至总共加入491升乙烯为止。停止搅拌使固体沉降。从固体中滗去液体,并每次用1.5升异戊烷洗涤两次。在N2下将湿固体送入干燥箱中并经#14目筛子过滤。将细颗粒过滤出来,用戊烷(4升)洗涤并在真空下干燥。产量:326g用载体化合物6进行聚合聚合物的大规模生产:
在单个反应器中按照连续本体液相聚合法生产图1中的均聚物。反应器装有搅拌器和用于除去反应热的夹套。反应器温度设定为65℃,将有载体的预聚催化剂(化合物6)以1.3g催化剂/小时的速率加入反应器中。将丙烯以60kg丙烯/小时的速率加入反应器中。用氢气连续流(0.75g氢气/小时)控制产品的分子量。催化剂在反应器中的平均停留时间为4.0小时,聚合物以9.1kg聚合物/小时的速率生产。产品具有7MFR(230℃/2.16kg,按ASTM D1238),其熔点峰值为约145℃。
将上面制得的均聚物树脂与用于抗氧化稳定作用的0.05wt%Irganox1076混合并在聚丙烯使用的通常条件下在1英寸直径的实验室挤出机中造粒。为按ASTM D4101进行测试制备样品。在Van Dorn75吨成型机上进行注塑。在成型操作中使用标准的聚丙烯条件。比较例
选用购自Exxon Chemical Company,Baytown,Texas的常规聚丙烯PP-1024作为与上述由金属茂制备的聚丙烯样品的对比标准。PP-1024具有12MFR,其MP为162℃。为按ASTM D4101进行测试制备样品。在Van Dorn75吨成型机上进行注塑。在成型操作中使用标准的聚丙烯条件。为进行热畸变和动态力学试验制备样品
按相同方式制备进行热畸变和动态力学试验的样品。对于聚丙烯,将样品熔化并按 ASTM D4101注塑。进行热畸变试验的样品尺寸为6″×0.5″×0.125″,进行动态力学试验的样品尺寸为2″×0.5″×0.125″。惯用的做法是将热畸变样品切割为2″长以进行动态试验。动态力学试验/热畸变试验
将上述样品按照ASTM D648在455kPa(66psi)单位荷载下进行热畸变试验(HDT)。发现金属茂聚丙烯样品的热畸变温度为约101℃;发现PP-1024的HDT值为约93℃。
动态力学试验通过经任意挠曲角振荡一端固定的实心矩形板测定。测量使样品挠曲所需的力。挠曲力和角度分别用于计算应力和应变。应力与应变之比即为模量。在试验过程中变化温度得到有关作为温度的函数的材料性能的信息。金属茂聚丙烯和对比样品PP 1024的动态力学试验结果如图1所示。同时将代表性的说明性数据列于下表中。
表:Met PP*和PP 1024的模量与温度关系说明性数据
模量(dyn/cm2) 温 度(℃) 温度(℃)
金属茂PP PP 1024
2×107 150 170
1×108 147 165
2×108 135 150
4×108 125 135
8×108 100 100表1中的数据为近似值×=金属茂催化剂
本领域熟练技术人员将知道可以根据前面的教导在不超出本发明范围和实质内对本发明进行变化和改进。因此,将知道可在所述本发明特定实施方案内进行变化,而这些变化完全在所附权利要求的范围内。
Claims (17)
1.一种形成取向结构的方法,包括步骤:
(a)由聚丙烯树脂形成结构,所述聚丙烯树脂由金属茂催化剂生产;和
(b)在温度范围高于聚丙烯HDT值20℃至35℃下施加应力使结构取向。
2.权利要求1的方法,其中温度范围为高于聚丙烯的HDT值20℃至30℃,优选高于25℃至30℃。
3.权利要求1或2的方法,其中聚丙烯为均聚物。
4.前述权利要求任何一项的方法,其中聚丙烯为丙烯与至少一种具有2至20个碳原子的共聚单体,优选乙烯、丁烯或己烯的共聚物。
5.权利要求4的方法,其中丙烯共聚物的共聚单体含量范围为0.5至10%重量。
6.前述权利要求任何一项的方法,其中聚丙烯为聚丙烯与另一种聚合物的共混物。
7.前述权利要求任何一项的方法,其中金属茂包括硅桥连双(取代茚基)4、5、或6族过渡金属二卤化物。
8.权利要求7的方法,其中金属茂优选自二氯化二甲基甲硅烷基·双(2-甲茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-4,5-苯并茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-4,6-二异丙基茚基)合锆、二氯化二甲基甲硅烷基·双(2-甲基-4-苯基茚基)合锆。
9.前述权利要求任何一项的方法,其中金属茂载在一种载体上。
10.一种形成取向薄膜的方法,包括步骤:
(a)形成包括至少一层第一聚丙烯树脂层的薄膜或片材,所述聚丙烯树脂由金属茂催化剂生产;
(b)在温度范围高于聚丙烯树脂HDT值20℃至35℃下施加应力使薄膜或片材取向。
11.权利要求10的方法,其中拉伸前的薄膜或片材还包括至少一层熔点低于第一聚丙烯层熔点的某些聚合物的其它层。
12.一种形成取向结构的方法,包括步骤:
(a)由聚丙烯树脂形成结构,所述聚丙烯由金属茂催化剂生产;和
(b)在温度范围不超过高于聚丙烯HDT值35℃下施加应力使结构取向。
13.权利要求1的方法,其中取向结构是纤维。
14.权利要求1的方法,其中取向结构是成型制品。
15.由权利要求1的方法生产的取向结构。
16.由权利要求10的方法生产的取向薄膜。
17.由权利要求12的方法生产的取向结构。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08239150 US5468440B1 (en) | 1994-05-06 | 1994-05-06 | Process of making oriented film or structure |
US08/239,150 | 1994-05-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1152323A true CN1152323A (zh) | 1997-06-18 |
CN1073589C CN1073589C (zh) | 2001-10-24 |
Family
ID=22900827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95192923A Expired - Fee Related CN1073589C (zh) | 1994-05-06 | 1995-04-27 | 全同立构聚丙烯的用途、制备方法和其产品 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5468440B1 (zh) |
EP (1) | EP0758355B1 (zh) |
JP (1) | JP3339864B2 (zh) |
CN (1) | CN1073589C (zh) |
CA (1) | CA2187668A1 (zh) |
DE (1) | DE69506539T2 (zh) |
ES (1) | ES2125016T3 (zh) |
WO (1) | WO1995030708A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101679552B (zh) * | 2007-05-08 | 2012-09-05 | 博里利斯技术有限公司 | 电绝缘膜 |
CN106604951A (zh) * | 2014-03-27 | 2017-04-26 | 拉伯拉菲喜安有限公司 | 双轴延展聚合物膜、包括其的簇绒地毯及它们的制造方法 |
Families Citing this family (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2199966T3 (es) * | 1994-02-21 | 2004-03-01 | Basell Polyolefine Gmbh | Lamina de varias capas poliolefinica sellable, un procedimiento para su obtencion y su empleo. |
DE4436113A1 (de) * | 1994-10-10 | 1996-04-11 | Hoechst Ag | Metallocenverbindung |
DE59605702D1 (de) * | 1995-05-31 | 2000-09-14 | Hoechst Ag | Biaxial orientierte Polypropylenfolie mit verbesserten Eigenschaften hinsichtlich Mechanik und Barriere |
EP0745638A1 (de) * | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit verbessertem Weiterreisswiderstand |
DE59605705D1 (de) * | 1995-05-31 | 2000-09-14 | Hoechst Ag | Biaxial orientierte Polypropylenfolie mit erhöhter Dimensionsstabilität |
EP0745477A1 (de) * | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit verbessertem Migrationswiderstand |
EP0745639A1 (de) * | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit guten optischen Eigenschaften |
EP0745637A1 (de) * | 1995-05-31 | 1996-12-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit hohem Flächenmodul |
EP0747212A1 (de) * | 1995-05-31 | 1996-12-11 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie mit verbesserten Eigenschaften hinsichtlich Wasserdampf- und Sauerstoffbarriere |
DE69631600T2 (de) * | 1995-09-18 | 2004-12-23 | Exxonmobil Chemical Patents Inc., Baytown | Polypropylene zusammensetzung mit hohe barrierewirkung und ihre verwendung als verpackungen |
US6156845A (en) | 1995-10-18 | 2000-12-05 | Chisso Corporation | Polyolefin composition and method of making |
DE19544709A1 (de) * | 1995-11-30 | 1997-06-05 | Basf Ag | Biaxial orientierte Polypropylenfolie aus Metallocen-Polypropylen |
US5858515A (en) * | 1995-12-29 | 1999-01-12 | Kimberly-Clark Worldwide, Inc. | Pattern-unbonded nonwoven web and process for making the same |
AU6344098A (en) | 1997-02-28 | 1998-09-18 | Shaw Industries, Inc. | Carpet, carpet backings and methods |
US20030211280A1 (en) | 1997-02-28 | 2003-11-13 | Shaw Industries, Inc. | Carpet, carpet backings and methods |
US7338698B1 (en) | 1997-02-28 | 2008-03-04 | Columbia Insurance Company | Homogeneously branched ethylene polymer carpet, carpet backing and method for making same |
WO1998044042A1 (fr) | 1997-04-02 | 1998-10-08 | Chisso Corporation | Composition (co)polymere d'olefine modifiee, procede pour preparer cette composition et produit moule de cette composition (co)polymere |
US6303696B1 (en) * | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
US6372344B1 (en) * | 1997-07-23 | 2002-04-16 | Pirelli Cavi E Sistemi S.P.A. | Cables with a halogen-free recyclable coating comprising polypropylene and an ethylene copolymer having high elastic recovery |
US6017615A (en) * | 1997-08-25 | 2000-01-25 | Huntsman Polymers Corporation | Film product comprising novel polyolefins |
US6159612A (en) * | 1997-08-25 | 2000-12-12 | Mobil Oil Corporation | Multi-layer films with syndiotactic barrier layer containing a wax |
US6090325A (en) * | 1997-09-24 | 2000-07-18 | Fina Technology, Inc. | Biaxially-oriented metallocene-based polypropylene films |
US5908594A (en) * | 1997-09-24 | 1999-06-01 | Fina Technology, Inc. | Process of making polypropylene fiber |
US6444774B1 (en) * | 1997-10-10 | 2002-09-03 | Exxonmobil Chemical Patents, Inc. | Propylene polymers for fibers and fabrics |
US5972061A (en) * | 1998-04-08 | 1999-10-26 | Nykyforuk; Craig | Wellhead separation system |
US6461706B1 (en) | 1998-04-17 | 2002-10-08 | Avery Dennison Corporation | Multilayer films and labels |
DE19827327A1 (de) * | 1998-06-19 | 1999-12-30 | Targor Gmbh | Siegelbare Mehrschichtfolie aus einem Propen-Terpolymeren |
US6037417A (en) * | 1998-08-18 | 2000-03-14 | Montell Technology Company Bv | Polypropylene composition useful for making solid state oriented film |
US6649548B1 (en) | 1998-10-02 | 2003-11-18 | Kimberly-Clark Worldwide, Inc. | Nonwoven web and film laminate with improved strength and method of making the same |
US6270912B1 (en) * | 1999-02-25 | 2001-08-07 | Mobil Oil Corporation | Multi-layer films with core layer of metallocene-catalyzed polypropylene |
JP3405269B2 (ja) * | 1999-04-26 | 2003-05-12 | ソニーケミカル株式会社 | 実装方法 |
US6391467B1 (en) | 1999-07-08 | 2002-05-21 | Exxonmobil Oil Corporation | Cast film made from metallocene-catalyzed polypropylene |
US6458470B1 (en) | 1999-07-08 | 2002-10-01 | Exxonmobil Oil Corporation | High barrier multilayer film |
CA2369349A1 (en) * | 2000-01-19 | 2001-07-26 | Mitsui Chemicals, Inc. | Spunbonded non-woven fabric and laminate thereof |
US6573344B1 (en) | 2000-06-22 | 2003-06-03 | Phillips Petroleum Company | Propylene polymerization process |
US6869686B1 (en) | 2000-08-30 | 2005-03-22 | Curwood, Inc. | Irradiated biaxially oriented film |
MXPA04000612A (es) | 2001-07-31 | 2004-04-20 | Avery Dennison Corp | ETIQUETAS HOLOGRaFICAS CONFORMABLES. |
US6893722B2 (en) * | 2002-04-29 | 2005-05-17 | Exxonmobil Oil Corporation | Cationic, amino-functional, adhesion-promoting polymer for curable inks and other plastic film coatings, and plastic film comprising such polymer |
US7195818B2 (en) | 2002-05-01 | 2007-03-27 | Exxonmobil Oil Corporation | Sealable multi-layer opaque film |
ES2305371T3 (es) | 2002-06-26 | 2008-11-01 | Avery Dennison Corporation | Peliculas polimericas orientadas en la direccion de mecanizado. |
US6773818B2 (en) | 2002-09-06 | 2004-08-10 | Exxonmobil Oil Corporation | Metallized, metallocene-catalyzed, polypropylene films |
US7524910B2 (en) | 2002-10-15 | 2009-04-28 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US20040105994A1 (en) | 2002-12-03 | 2004-06-03 | Pang-Chia Lu | Thermoplastic film structures with a low melting point outer layer |
US7643734B2 (en) | 2005-03-31 | 2010-01-05 | S.C. Johnson & Son, Inc. | Bottle eject mechanism |
EP1967343A4 (en) * | 2005-12-26 | 2013-05-15 | Konica Minolta Opto Inc | METHOD OF PRODUCING CELLULOSE FOIL, DEVICE FOR PRODUCING CELLULOSE FOIL, OPTICAL FOIL MANUFACTURED BY THE MANUFACTURING DEVICE, THE OPTICAL FILM USING POLARIZATION PLATE AND LIQUID CRYSTAL DISPLAY DEVICE |
ES2398725T3 (es) | 2006-06-14 | 2013-03-21 | Avery Dennison Corporation | Material para etiquetas orientado en la dirección longitudinal que se puede conformar y cortar con troquel y etiquetas y proceso para su preparación |
AU2007261011B2 (en) | 2006-06-20 | 2012-04-05 | Avery Dennison Corporation | Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof |
ATE421760T1 (de) | 2006-07-10 | 2009-02-15 | Borealis Tech Oy | Elektrischer isolierfilm |
ATE487755T1 (de) | 2006-07-10 | 2010-11-15 | Borealis Tech Oy | Biaxial orientierte polypropylenfolie |
JP5579436B2 (ja) | 2006-07-17 | 2014-08-27 | エーブリー デニソン コーポレイション | 非対称の多層高分子フィルム、並びにラベルストック及びそのラベル |
DE602006008470D1 (de) * | 2006-08-25 | 2009-09-24 | Borealis Tech Oy | Geblasene Polypropylenfolie |
EP1892264A1 (en) | 2006-08-25 | 2008-02-27 | Borealis Technology Oy | Extrusion coated substrate |
EP1900764B1 (en) | 2006-08-25 | 2009-04-01 | Borealis Technology Oy | Polypropylene foam |
EP1903579B1 (en) | 2006-09-25 | 2010-03-24 | Borealis Technology Oy | Coaxial cable |
ATE424424T1 (de) | 2006-12-28 | 2009-03-15 | Borealis Tech Oy | Verfahren zur herstellung von verzweigtem polypropylen |
US7473751B2 (en) | 2007-01-22 | 2009-01-06 | Fina Technology, Inc. | Biaxially-oriented metallocene-based polypropylene films having reduced thickness |
US20120077889A1 (en) * | 2010-09-28 | 2012-03-29 | Evans Neal A | Apparatus and method for producing thermoplastic elastomer, elastomers produced thereby and articles produced from the elastomers |
US9272795B2 (en) | 2012-05-17 | 2016-03-01 | Henkel IP & Holding GmbH | Integral hot melt adhesive packaging films and use thereof |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
PL2716435T3 (pl) * | 2012-10-02 | 2018-01-31 | Reifenhaeuser Masch | Sposób wytwarzania zespolonej części kształtowej, w szczególności włóknistej zespolonej części kształtowej oraz zespolona część kształtowa, w szczególności włóknista zespolona część kształtowa |
US11459488B2 (en) | 2014-06-02 | 2022-10-04 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
DE102017004111A1 (de) * | 2017-04-27 | 2018-10-31 | Topas Advanced Polymers Gmbh | Polyolefinfolie und deren Verwendung |
ES2926234T3 (es) * | 2018-01-18 | 2022-10-24 | Borealis Ag | Composición de polipropileno heterofásico de alta flexibilidad y suavidad |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS578118A (en) * | 1980-06-20 | 1982-01-16 | Mitsubishi Petrochem Co Ltd | Biaxially oriented polypropylene film and manufacture thereof |
US5198401A (en) * | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
PL276385A1 (en) * | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
CN1033961C (zh) * | 1990-04-09 | 1997-02-05 | 三井东压化学株式会社 | 间同立构聚丙烯模制法及模制品 |
US5200131A (en) * | 1990-04-09 | 1993-04-06 | Mitsui Toatsu Chemicals, Inc. | Method for molding syndiotactic polypropylene |
EP0485823B1 (de) * | 1990-11-12 | 1995-03-08 | Hoechst Aktiengesellschaft | 2-Substituierte Bisindenylmetallocene, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren bei der Olefinpolymerisation |
EP0722956B1 (de) * | 1990-11-12 | 2001-08-16 | Basell Polyolefine GmbH | Verfahren zur Herstellung eines Olefinpolymers |
DE59107973D1 (de) * | 1990-11-12 | 1996-08-08 | Hoechst Ag | Verfahren zur Herstellung eines hochmolekularen Olefinpolymers |
DE59107926D1 (de) * | 1990-11-12 | 1996-07-18 | Hoechst Ag | Metallocene mit Liganden aus 2-substituierten Indenylderivaten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren |
DE4119343A1 (de) * | 1991-06-12 | 1992-12-17 | Basf Ag | Isolierbares, getraegertes katalysatorsystem zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alk-1-enen |
DE4120009A1 (de) * | 1991-06-18 | 1992-12-24 | Basf Ag | Loesliche katalysatorsysteme zur herstellung von polyalk-1-enen mit hohen molmassen |
EP0538749B1 (en) * | 1991-10-21 | 1995-01-11 | Mitsubishi Petrochemical Co., Ltd. | Propylene copolymer composition |
US5393599A (en) * | 1992-01-24 | 1995-02-28 | Fiberweb North America, Inc. | Composite nonwoven fabrics |
US5241031A (en) * | 1992-02-19 | 1993-08-31 | Exxon Chemical Patents Inc. | Elastic articles having improved unload power and a process for their production |
US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
US5322728A (en) * | 1992-11-24 | 1994-06-21 | Exxon Chemical Patents, Inc. | Fibers of polyolefin polymers |
JPH07118396A (ja) * | 1993-10-27 | 1995-05-09 | Mitsui Toatsu Chem Inc | ポリプロピレンの成形体 |
-
1994
- 1994-05-06 US US08239150 patent/US5468440B1/en not_active Expired - Lifetime
-
1995
- 1995-04-27 JP JP52900695A patent/JP3339864B2/ja not_active Expired - Fee Related
- 1995-04-27 EP EP95918309A patent/EP0758355B1/en not_active Expired - Lifetime
- 1995-04-27 CA CA002187668A patent/CA2187668A1/en not_active Abandoned
- 1995-04-27 ES ES95918309T patent/ES2125016T3/es not_active Expired - Lifetime
- 1995-04-27 WO PCT/US1995/005192 patent/WO1995030708A1/en active IP Right Grant
- 1995-04-27 DE DE69506539T patent/DE69506539T2/de not_active Expired - Fee Related
- 1995-04-27 CN CN95192923A patent/CN1073589C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101679552B (zh) * | 2007-05-08 | 2012-09-05 | 博里利斯技术有限公司 | 电绝缘膜 |
CN106604951A (zh) * | 2014-03-27 | 2017-04-26 | 拉伯拉菲喜安有限公司 | 双轴延展聚合物膜、包括其的簇绒地毯及它们的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69506539D1 (de) | 1999-01-21 |
EP0758355B1 (en) | 1998-12-09 |
CA2187668A1 (en) | 1995-11-16 |
WO1995030708A1 (en) | 1995-11-16 |
US5468440B1 (en) | 1997-04-08 |
DE69506539T2 (de) | 1999-05-06 |
EP0758355A1 (en) | 1997-02-19 |
JPH10503537A (ja) | 1998-03-31 |
ES2125016T3 (es) | 1999-02-16 |
JP3339864B2 (ja) | 2002-10-28 |
US5468440A (en) | 1995-11-21 |
CN1073589C (zh) | 2001-10-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1073589C (zh) | 全同立构聚丙烯的用途、制备方法和其产品 | |
CN1326888C (zh) | 在超临界条件生产聚合物的方法 | |
CN101010705B (zh) | 在超临界条件下生产聚合物 | |
CN100349929C (zh) | 透明和柔性的丙烯聚合物组合物 | |
DE69518922T2 (de) | Katalysatorsysteme für die polymerisation, ihre herstellung und verwendung | |
CN1110518C (zh) | 由环烯烃聚合物制成的双轴定向箔、其制备方法和其用途 | |
CN105142777B (zh) | 长桥Salen催化剂 | |
US20020013440A1 (en) | Propylene diene copolymers | |
US20060025545A1 (en) | Polymer production at supercritical conditions | |
CN1404499A (zh) | 热成型聚烯烃板 | |
EP2094743A1 (en) | Polymer production at supercritical conditions | |
CN1131270C (zh) | 着色聚丙烯组合物、其制备方法及其应用 | |
CN1285851A (zh) | 新型丙烯聚合物及其产品 | |
AU2002244631A1 (en) | Bioriented polypropylene films | |
EP1358252A2 (en) | Bioriented polypropylene films | |
JP2021511403A (ja) | ペレット型ポリプロピレン樹脂およびその製造方法 | |
JP2017101229A (ja) | 二軸延伸ポリプロピレンシート | |
JPH11302474A (ja) | プロピレン系樹脂並びにそれを用いたフィルム及び積層体 | |
JP2009299024A (ja) | プロピレン系複合樹脂組成物およびそれを用いた押出成形体 | |
CN100392010C (zh) | 聚烯烃树脂改性剂,聚烯烃树脂组合物和取向聚烯烃膜 | |
CN1478109A (zh) | 高分子量聚烯烃和催化剂以及所述聚烯烃的聚合方法 | |
CN1266212C (zh) | 无规丙烯共聚物基组合物、它们的制造方法及包含它们的热封多层板 | |
Mülhaupt | Metallocene catalysts and tailor-made polyolefins | |
DE4425787A1 (de) | Verfahren zur Herstellung von kammartigen Polypropylenen | |
MXPA96005445A (es) | Aplicaciones de polipropileno isotactico, procesos y productos del mismo |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |