CN106366431B - A kind of polypropene composition of high rigidity high tenacity - Google Patents
A kind of polypropene composition of high rigidity high tenacity Download PDFInfo
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- CN106366431B CN106366431B CN201510441682.4A CN201510441682A CN106366431B CN 106366431 B CN106366431 B CN 106366431B CN 201510441682 A CN201510441682 A CN 201510441682A CN 106366431 B CN106366431 B CN 106366431B
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- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 31
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 30
- -1 polypropylene Polymers 0.000 claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008096 xylene Substances 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 150000002220 fluorenes Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000012685 gas phase polymerization Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- NABSNBPOXKZXAJ-UHFFFAOYSA-N 1-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)OC(=O)C1=CC=CC=C1 NABSNBPOXKZXAJ-UHFFFAOYSA-N 0.000 claims description 2
- FUWXYOFDPKHAHV-UHFFFAOYSA-N 2-benzoyloxypropan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(C)OC(=O)C1=CC=CC=C1 FUWXYOFDPKHAHV-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002681 magnesium compounds Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N propyl benzoate Chemical compound CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims 2
- YPKCDSZRXVRQPJ-UHFFFAOYSA-N C(C)(C)C(C(CCC)C(=O)O)(CCCC)CCC(C)C Chemical compound C(C)(C)C(C(CCC)C(=O)O)(CCCC)CCC(C)C YPKCDSZRXVRQPJ-UHFFFAOYSA-N 0.000 claims 1
- HYUCXWDZLOMDPY-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(CC)(OC(C1=CC=CC=C1)=O)OC(C1=CC=CC=C1)=O Chemical compound C(C1=CC=CC=C1)(=O)OC(CC)(OC(C1=CC=CC=C1)=O)OC(C1=CC=CC=C1)=O HYUCXWDZLOMDPY-UHFFFAOYSA-N 0.000 claims 1
- GGNMPXNLPFTNRS-UHFFFAOYSA-N [1-(benzoyloxymethyl)-9h-fluoren-2-yl]methyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCC1=CC=C(C2=CC=CC=C2C2)C2=C1COC(=O)C1=CC=CC=C1 GGNMPXNLPFTNRS-UHFFFAOYSA-N 0.000 claims 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical group C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- VCVPBOSUBOKPNN-UHFFFAOYSA-N butanoic acid prop-1-ene Chemical compound C(CCC)(=O)O.CC=C VCVPBOSUBOKPNN-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- QKNZNUNCDJZTCH-UHFFFAOYSA-N pentyl benzoate Chemical compound CCCCCOC(=O)C1=CC=CC=C1 QKNZNUNCDJZTCH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000000536 complexating effect Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- NZZCFNBAOPZCTJ-UHFFFAOYSA-N 2-pentyl-2-propylheptanoic acid Chemical compound C(CC)C(C(=O)O)(CCCCC)CCCCC NZZCFNBAOPZCTJ-UHFFFAOYSA-N 0.000 description 1
- IYSSNWRZYUDEKK-UHFFFAOYSA-N 3-benzoyloxypentan-3-yl benzoate Chemical compound C(C1=CC=CC=C1)(=O)OC(CC)(CC)OC(C1=CC=CC=C1)=O IYSSNWRZYUDEKK-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YLBUHBKDOKSTES-UHFFFAOYSA-N FC(C(C)N1C(CCCC1)CC)(F)F Chemical compound FC(C(C)N1C(CCCC1)CC)(F)F YLBUHBKDOKSTES-UHFFFAOYSA-N 0.000 description 1
- HIZCTWCPHWUPFU-UHFFFAOYSA-N Glycerol tribenzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(OC(=O)C=1C=CC=CC=1)COC(=O)C1=CC=CC=C1 HIZCTWCPHWUPFU-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- MORKUPFNQOBNGX-UHFFFAOYSA-N [9-(benzoyloxymethyl)fluoren-9-yl]methyl benzoate Chemical group C=1C=CC=CC=1C(=O)OCC1(C2=CC=CC=C2C2=CC=CC=C21)COC(=O)C1=CC=CC=C1 MORKUPFNQOBNGX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-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
- XZFXULUXIPPWEW-UHFFFAOYSA-N dimethoxy-methyl-propan-2-ylsilane Chemical compound CO[Si](C)(OC)C(C)C XZFXULUXIPPWEW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-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
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-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
- 239000000945 filler Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 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
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of polypropene composition with high rigidity and high tenacity, the composition include: the homopolypropylene of (a) 60-90 weight %, and the homopolypropylene is the high isotatic polypropylene of isotactic index >=97%；(b) ethylene-propylene copolymer of 5-20 weight %, the ethylene-propylene copolymer contain the ethylene of 30-60 weight %, and the intrinsic viscosity of room temperature xylene soluble part is 2-5dl/g；And (c) homopolymerisation polyethylene of 5-20 weight %；Wherein the intrinsic viscosity of component (c) is greater than 5dL/g.The present invention also provides the preparation methods of above-mentioned composition, by adjusting the composition of component (b) and the molecular weight of component (c), in the higher situation of molecular weight of crystallizable poly- second component, hence it is evident that improve the toughness of product, while keeping certain rigidity.
Description
Technical field
The present invention relates to the preparation methods of a kind of polypropene composition of high rigidity high tenacity and the composition.
Background technique
Polypropylene is one of with the fastest developing speed, the synthetic resin kind that dosage is maximum, purposes is most wide.With automobile, object
The rapid development of the industries such as stream, there is an urgent need to the high-performance polypropylene compound materials of high bending modulus, high impact.
The toughening of high polymer and enhancing are the important topic of polymer material science always, and the purpose of enhancing is to improve mould
Amount, the purpose of toughening is to improve impact strength, but the two is often conflicting, can not balance.The prior art is mostly by altogether
Mixed method addition rubber and elastomer realize toughening, and realize enhancing by addition inorganic rigid particle, or carry out bullet
Property body/inorganic rigid particle it is composite filled come and meanwhile realize the effect of activeness and quietness.But these method post-processing steps are complicated,
Energy consumption is high.
Summary of the invention
An object of the present invention is to provide a kind of method of high strong and unyielding impact polypropylene of direct polymerization preparation, in homopolymerization
On the basis of polyacrylic, elastomer is obtained by being copolymerized in the first gas-phase reactor, polymerization obtains in the second gas-phase reactor
Poly- polyethylene, homopolymerisation polyethylene crystallization are contained inside rubber phase, and two phase compositions of control, content and molecular weight, Ke Yi are passed through
Higher rigidity is kept while improving toughness.
Another object of the present invention is to provide the polypropene composition for the high rigidity high tenacity that the above method is prepared,
It has the characteristics of high-modulus and high impact strength, can be used for producing automobile component, household items etc..
Specifically, the present invention uses ziegler-natta catalyzed system, continuously prepares in multi-step polymerization reaction high strong and unyielding poly-
Propylene compositions, the continuous phase of acquired composition are the homopolypropylene of high stereoregularity, can keep product rigidity,
Hardness and heat resistance.Dispersed phase is the copolymer of ethylene and propylene or other alpha-olefins with special composed structure, and packet
Ensconce the crystallization homopolymerisation polyethylene inside aforementioned copolymer, that is, rubber phase.By the composition and homopolymerisation polyethylene that adjust rubber phase
Molecular weight, in the higher situation of molecular weight of crystallizable poly- second component, hence it is evident that improve the toughness of product, while keeping centainly
Rigidity.
Present invention eliminates the prior arts phase addition filler (to use be blended as mentioned in the background art after the reaction
Method addition rubber and elastomer realize toughening, and by addition inorganic rigid particle realize enhancing) complicated process, drop
Low energy consumption, solving the problems, such as that polypropene composition is strong and unyielding can not balance.
An object of the present invention is to provide a kind of polypropene composition with high rigidity and high tenacity, the composition
Include:
(a) 60-90 weight %, the preferably homopolypropylene of 65-85 weight %, the homopolypropylene be isotactic index >=
97% high isotatic polypropylene；(b) 5-20 weight %, the preferably ethylene-propylene copolymer of 10-15 weight %, the ethylene-
Propylene copolymer contains 30-60 weight %, the preferably ethylene of 30-50 weight %, and the intrinsic viscosity of room temperature xylene soluble part is
2-5dl/g；And (c) homopolymerisation polyethylene of 5-20 weight %.Wherein, the intrinsic viscosity of the component (c) is greater than 5dL/g.
The flexural modulus values of the polypropene composition are at least 1.4GPa, preferably higher than 1.5GPa；Izod notch shock
(23 DEG C) numerical value is at least 16kJ/m2, preferably 20.0-60kJ/m2。
According to the present invention, fusing point >=160 DEG C of the component (a), the fusing point of component (c) is between 120 DEG C -135 DEG C.Institute
Stating component (a) is continuous phase, and component (b) and component (c) are dispersed phase, and component (c) crystallizes in component (b).
It is yet another object of the invention to provide the preparation methods of the polypropene composition, use Ziegler-Natta
Catalyst is prepared with continuous polymerization.The method includes the polymerization reaction zone that at least three carry out in order, wherein group
(a), (b) and (c) is divided to prepare in different polymerization reaction zones in order, in addition to first segment, other each sections are all poly- in leading portion
It closes and is operated in the presence of reacting established polymer and catalyst used.
Specifically, propylene homo generate component (a) reaction at least carried out in a polymeric segment, then carry out ethylene with
Propylene or other alpha-olefins generate the reaction of elastocopolymer, finally carry out the reaction that ethylene homo generates component (c).
In method of the invention, the Ziegler-Natta catalyst used is largely disclosed, wherein CN02100900.7
Described catalyst especially has advantage for the present invention.
The catalyst includes catalyst activity component, organo-aluminum compound and optional external electron donor.It is described to urge
Agent active component includes titanium compound, magnesium compound and internal electron donor, and the internal electron donor is in the following general formula
At least one polyester compound:
Wherein:
A, B be carbon or selected from nitrogen, oxygen, sulphur, boron hetero atom；
R1-R6、R1-RnGroup is the C of identical or different hydrogen, halogen or substituted or unsubstituted linear chain or branched chain1-
C20Alkyl, naphthenic base, aryl, alkaryl, aralkyl, alkylene, fused ring aryl, ester group, R1And R2It is not hydrogen, R3-R6And R1-Rn
It arbitrarily include substituent of one or several hetero atoms as carbon or hydrogen atom or both on group, the hetero atom is selected from
Nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R3-R6And R1-RnOne or more of group can link up cyclization；
N is the integer of 0-10；
When A or B is oxygen or sulphur, the number of R group connected thereto is 0；When A or B is boron or nitrogen, connect thereon
The number of the R group connect is 1；When A or B is carbon or silicon, the number of R group connected thereto is 2, and when A and B is
It is bonded in the form of carbon-carbon single bond or double or triple bonds between A and B when carbon, when bonded in the form of carbon-carbon single bond between A and B,
The number for the R group that A and B are separately connected is 2, when bonded in the form of carbon-carbon double bond between A and B, R group that A is connected with B
Number 1, when bonded in the form of triple carbon-carbon bonds between A and B, the number 0 for the R group that A is connected with B.
In a specific embodiment of the present invention, the internal electron donor is selected from 9,9- bis- (benzoyloxy methyl) fluorenes, 9,
Bis- (propylene carboxymethyl group) fluorenes of 9-, bis- (the third carboxymethyl group) fluorenes of 9,9-, bis- (cortex cinnamomi carboxymethyl group) fluorenes of 9,9-, 2- isopropyl -2-
Bis- benzoyloxy propane of isopentyl -1,3-, bis- propylene carboxyl propane of 2- isopropyl -2- isopentyl -1,3-, 2- isopropyl -2- are different
Amyl -1,3- dipropyl carboxyl propane, 1,2-, bis- benzoyloxy ethane, 1,3-, bis- benzoyloxy propane,-two benzoyloxy fourth of Isosorbide-5-Nitrae
Alkane, ortho-xylene carboxyl benzene, bis- cortex cinnamomi carboxyl propane of 2- isopropyl -2- isopentyl -1,3-, four (benzoyloxy methyl) methane,
1,2,3- tri- benzoyloxy propane, 2,2,4- trimethyl -1,3-, bis- benzoyloxy pentane and 2,2- diisobutyl -1,3- hexichol first
At least one of carboxyl propane.
As the organo-aluminum compound optimizing alkyl aluminium compound of cocatalyst component, more preferable trialkylaluminium and its derivative
Object, such as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, trioctylaluminum, aluminium diethyl monochloride, a chlorine two are different
Butyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, one aluminium ethide of dichloro, ethyl aluminum dichloride etc..With Ti/Al weight ratio meter,
The weight ratio of the active solid catalyst component and organo-aluminum compound cocatalyst component is 1: (10-500), preferably 1:
(25-100)。
External electron donor as optional catalyst component is preferably organo-silicon compound, general formula RnSi(OR′)4-n,
0≤n≤3 in formula, R and R ' are alkyl, naphthenic base, aryl, halogenated alkyl etc. of the same race or not of the same race, R may be halogen or
Hydrogen atom.It specifically may include but be not limited to tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, trimethyl second
Oxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, methyl tertbutyl two
Methoxy silane, isopropyl methyl dimethoxysilane, two phenoxy group dimethoxysilanes, diphenyl diethoxy silane, benzene
Base trimethoxy silane, phenyl triethoxysilane, vinyltrimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, two
Cyclopenta dimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2- ethyl piperidine base -2-
T-butyldimethoxysilane, (1,1,1- tri- fluoro- 2- propyl) -2- ethyl piperidine base dimethoxysilane and (1,1,1- tri- is fluoro-
2- propyl)-methyl dimethoxysilane etc..With Al/Si weight ratio meter, the alkyl aluminum compound and organo-silicon compound
Weight ratio is (3-100): 1.
Three kinds of catalytic components can be added directly into polymer reactor, can also be known pre- by industry
It complexing and/or prepolymerization and then is added in reactor.It can also be carried out optionally with or without the catalyst being complexed in advance
Ground prepolymerization processing.Prepolymerization can be carried out continuously under the conditions of liquid-phase bulk, can also intermittently be carried out in atent solvent.Prepolymerization
Reactor can be continuous stirred tank, annular-pipe reactor etc..Prepolymerized temperature control is between -10 to 60 DEG C, preferably
Temperature is 0-40 DEG C.At 0.5-1000 times, preferred multiple is 1.0-500 times for prepolymerized multiple control.
The polymerization, which can be, to be carried out continuously, and also may be carried out batchwise.
The continuous polymerization can be used more than two tandem reactors and carry out.Wherein one or several reactor systems
Standby component (a) of the present invention, the reactor for preparing the component (a) can be Liquid-phase reactor or gas-phase reactor, liquid
Phase reaction device can be annular-pipe reactor or stirred tank reactor, and gas-phase reactor can be horizontal type agitated bed reactor or stand
Formula agitated bed reactor or fluidized-bed reactor etc., the above Liquid-phase reactor and gas-phase reactor can also arbitrarily collocation groups
It closes.It is used to prepare component (b) of the present invention preparing the subsequent reactor of the component (a), prepares the component
(b) reactor is gas-phase reactor, and gas-phase reactor can be horizontal type agitated bed reactor, vertical mixing bed reactor or stream
Fluidized bed reactor etc., the above gas-phase reactor can also arbitrarily matched combineds.Preparing the subsequent reactor of the component (b)
For preparing component (c) of the present invention, the reactor for preparing the component (c) is gas-phase reactor, gas phase reaction
Device can be horizontal type agitated bed reactor, vertical mixing bed reactor or fluidized-bed reactor etc., and the above gas-phase reactor can also
With arbitrarily matched combined.
The batchwise polymerization can be sequentially prepared component of the present invention in single-reactor (such as tank reactor)
(a), (b) and (c).It can be polymerize in liquid phase when wherein preparing component (a), can also be polymerize in gas phase.Preparation group
Divide (b) and (c) need to be polymerize in gas phase.
For the polymerization reaction in liquid phase polymerization, polymerization temperature is 0-150 DEG C, preferably 40-100 DEG C；Polymerization pressure is answered
Higher than saturated vapour pressure of the propylene under corresponding polymerization temperature.In gas-phase polymerization, polymerization temperature is 0-150 DEG C, preferably 40-
100℃；It is highly preferred that reaction temperature when preparation component (a) is 50-80 DEG C, and prepare component (b) and reaction temperature when (c)
Degree is 70-100 DEG C.Polymerization pressure can be normal pressure or higher, and preferably pressure is 0.5-3.0MPa (gauge pressure, similarly hereinafter).Using hydrogen
Gas produces the product of different melt index as molecular weight regulator.
The known thermo oxidative aging auxiliary agent of industry can be added in polypropene composition of the present invention and halogen absorption helps
The known antistatic agent of industry, colorant, nucleating agent etc. can also be added to further increase the property of material in some aspects in agent
Energy.
Polypropene composition of the present invention has both high-modulus and good impact resistance, can be used for producing automobile component
With household items etc..
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of 4 gained polypropene composition of embodiment.
Fig. 2 is differential scanning calorimetry (DSC) figure of 4 gained polypropene composition of embodiment.
Specific embodiment
The present invention is further described below with reference to embodiment.The scope of the present invention is not restricted by the embodiments, this hair
Bright range proposes in detail in the claims.
Data in embodiment are obtained according to following test method:
Melt mass flow rate (MFR): GB/T 3682-2000 standard test is pressed.
Isotactic index (II): GB/T 2412-2008 standard test is pressed；
Co-monomer content: it is measured with fourier infrared method.
Gas molar ratio in reactor: it is measured with gas chromatography.
Cold xylene solubles content: it is measured by ASTM D5492-98.
Bending modulus and bending strength: it is measured according to GB/T 9341-2008.
Tensile strength and elongation: it is measured according to GB/T 1040.2-2006.
Izod notched impact strength (23/-20 DEG C): it is measured according to GB/T 1843-2008.
Heat distortion temperature: it is measured according to GB/T 1634.2-2004.
Melting temperature (Tm): it is measured with the DSC7 type differential scanning calorimeter instrument of Perkin Elmer company, test scope
From 50 DEG C to 200 DEG C.Sample is first risen to 200 DEG C by the speed of 10 DEG C/min to eliminate thermal history, then presses the speed of 10 DEG C/min
Degree is down to 50 DEG C, measures its crystallization temperature and crystallization enthalpy, then rise to 200 DEG C by the speed of 10 DEG C/min, measures its fusing point and melts
Melt enthalpy.
Intrinsic viscosity: it is measured according to ASTM D5225-98.Wherein component (a) and component (b) and final composition (a+b
+ c) intrinsic viscosity can directly be measured by instrument, the intrinsic viscosity of component (c) need to be calculated by the following formula to obtain:
IVC component=[IVComposition-(IVA component* a constituent mass percentage composition %+IVB component* b constituent mass percentage composition %)]/c constituent mass
Percentage composition %.
Above each test all carries out under the conditions of room temperature environment, unless otherwise indicated.
Embodiment 1
Polypropene composition in the present invention and embodiment obtains by the following method:
Major catalyst (active solid catalyst component) is recorded using embodiment 24 in Chinese patent CN02100900.7
Method obtains, and wherein Ti content is 2.5wt%, and polyester compound 9, bis- (benzoyloxy methyl) the fluorenes contents of 9- are 15.1wt%.
Polymerization reaction carries out on a set of polypropylene pilot-plant, polymerization and steps are as follows:
Pre-terminated touches prepolymerization
By the above-mentioned major catalyst being prepared, co-catalyst (triethyl aluminum) and external electron donor (methylcyclohexyl two
Methoxy silane, CHMMS) at 10 DEG C pre-contact reaction 20min after, be added continuously prepolymerization reactor carry out prepolymerization it is anti-
It answers.The addition rate of each raw material in pre-polymerization process are as follows: triethyl aluminum (TEA) flow is 6g/hr, methylcyclohexyl dimethoxy
Silane (CHMMS) flow is 1.02g/hr, and major catalyst flow is 0.36g/hr.Prepolymerization under propylene liquid-phase bulk environment into
Row, temperature are 15 DEG C, and the residence time is about 4min.
Polymerization reaction
Pre-polymerization rear catalyst is completed propylene homo in annular-pipe reactor and is closed instead continuously into liquid phase annular-pipe reactor
It answers, prepares component (a).Polymeric reaction condition are as follows: liquid-phase polymerization temperature 70 C, reaction pressure 4.0MPa, ring canal reaction
Hydrogen is added in the charging of device, the density of hydrogen of on-line chromatograph detection is 0.3mol%.
After annular-pipe reactor reaction, resulting material enters the copolymerization that first fluidized bed gas-phase reactor carries out ethylene and propylene
Reaction is prepared component (b).Polymeric reaction condition are as follows: gas phase polymerization temperature is 75 DEG C, reaction pressure 0.8MPa, wherein
Ethylene/(ethylene+propylene)=0.4 (volume ratio), gas-phase reactor charging in plus a certain amount of hydrogen, on-line chromatograph detect gas phase
Density of hydrogen in reactor cycles gas is 0.3mol%.
After first gas-phase reactor, resulting material enters second fluidized bed gas-phase reactor and carries out ethylene homo reaction, system
Standby component (c), obtains polypropene composition of the present invention.Polymeric reaction condition are as follows: gas phase polymerization temperature is 75 DEG C,
Reaction pressure is 0.3MPa.Wherein ethylene/(ethylene+propylene) >=0.99 (volume ratio), gas-phase reactor charging in plus it is a certain amount of
Hydrogen, on-line chromatograph detect gas-phase reactor circulating air in density of hydrogen be 0.4mol%.
The concrete technology condition of above-mentioned prepolymerization and polymerization reaction is shown in Table 1.
It reacts that obtained polymerizate is degassed, after wet nitrogen deactivation processing, is added 0.1wt%'s into powder
168 additive of IRGAFOS, 1010 additive of IRGANOX of 0.1wt%, the calcium stearate of 0.05wt% and 0.2wt%
VP 101B nucleating agent, is granulated with double screw extruder.Injection molding machine prepares the injected sample for meeting GB standard, and tests its physics
Property, test result are as shown in table 2.
Subordinate list and explanation
Table 1 is that embodiment and comparative example prepares the reaction condition of polypropene composition, and obtains polypropene composition
Performance parameter；Table 2 is polypropene composition that embodiment and comparative example is prepared after being granulated and sample is made, and is surveyed
Try obtained performance parameter.
Embodiment 2
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
Density of hydrogen in two gas-phase reactor is 0.2mol%, and concrete technology condition is shown in Table 1.
Embodiment 3
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
Reaction pressure in two gas-phase reactor is 0.6MPa, and concrete technology condition is shown in Table 1.
Embodiment 4
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
Density of hydrogen in two gas-phase reactor is 0.2mol%, reaction pressure 0.6MPa, and concrete technology condition is shown in Table 1, product
Microscopic appearance is as shown in Figure 1, continuous phase therein is component (a), and the spherical discontinuous phase part of white is component (c), in component
(c) component (b) of annular, component (c) crystallization in component (b) are wrapped in outside.The DSC melting curve of product as shown in Fig. 2, its
There are two melting peak, the position between 160 DEG C and 120-135 DEG C respectively.Since polyacrylic fusing point is generally on 160 DEG C of left sides
The right side, so melting peak as we know from the figure >=160 DEG C is the melting peak of component (a), the melting peak between 120-135 DEG C is component
(c) melting peak.
Embodiment 5
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
The ethylene of one gas-phase reactor/(ethylene+propylene)=0.5 (volume ratio), density of hydrogen 0.4mol%, concrete technology condition are shown in
Table 1.
Comparative example 1
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: it is anti-
The first gas-phase reactor should only be proceeded to, no longer carry out the second gas phase reaction, concrete technology condition is shown in Table 1.
Comparative example 2
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
Two gas-phase reactor continue to repeat the reaction in the first gas-phase reactor, do not produce homopolymerisation polyethylene, and are to continue with production second third
Copolymer, concrete technology condition are shown in Table 1.
Comparative example 3
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: the
Density of hydrogen in two gas-phase reactor is 40mol%, reaction pressure 0.6MPa, and concrete technology condition is shown in Table 1.
Comparative example 4
Used catalyst, pre- complexing and polymerization process condition are substantially the same manner as Example 1, the difference is that: ring
Density of hydrogen in pipe reactor is 0.5mol%, ethylene/(ethylene+propylene)=0.2 (volume ratio) in the first gas-phase reactor,
Density of hydrogen is 0.2mol%, and the density of hydrogen in the second gas-phase reactor is 27%, and concrete technology condition is shown in Table 1.
Claims (10)
1. a kind of polypropene composition with high rigidity and high tenacity, the composition include:
(a) homopolypropylene of 67-68 weight %, the homopolypropylene are the polypropylene of isotactic index >=97%；
(b) ethylene-propylene copolymer of 12-14 weight %, the ethylene-propylene copolymer contain the ethylene of 30-60 weight %, room
The intrinsic viscosity of warm xylene soluble part is 2-5dl/g；And
(c) homopolymerisation polyethylene of 19-20 weight %；Wherein the intrinsic viscosity of the component (c) is greater than 9dL/g；
The flexural modulus values of the polypropene composition are at least 1.63GPa；Izod notch shock (23 DEG C) numerical value is at least
37kJ/m2。
2. polypropene composition according to claim 1, which is characterized in that fusing point >=160 DEG C of the component (a), institute
The fusing point of component (c) is stated between 120 DEG C -135 DEG C.
3. polypropene composition according to claim 1 or 2, which is characterized in that the component (a) is continuous phase, described
Component (b) and component (c) are dispersed phase, and the component (c) crystallizes in component (b).
4. the preparation method of polypropene composition described in any one of claims 1 to 3, uses Ziegler-Natta to urge
Agent is prepared with continuous polymerization, the polymerization reaction zone carried out in order including at least three, wherein component (a), (b) and
(c) it is prepared in different polymerization reaction zones in order, in addition to first segment, other each sections have been formed in first-stage polymerization reaction
Polymer and catalyst used in the presence of operated.
5. according to the method described in claim 4, being carried out under liquid phase or gas phase condition when it is characterized in that, preparing component (a)
Polymerization, preparation component (b) and (c) are polymerize under gas phase condition.
6. according to the method described in claim 5, it is characterized in that, polymerization temperature is 0-150 DEG C when liquid phase polymerization, polymerization pressure
Power is higher than saturated vapour pressure of the propylene under corresponding polymerization temperature；When gas-phase polymerization, polymerization temperature is 0-150 DEG C, and pressure is
0.5-3.0MPa。
7. according to the method described in claim 6, it is characterized in that, polymerization temperature is 40-100 DEG C when liquid phase polymerization；Gas phase is poly-
When conjunction, polymerization temperature is 40-100 DEG C.
8. according to the method described in claim 4, catalyst used in it includes titanium compound, magnesium compound and interior electron
Body, the internal electron donor are selected from least one of the following general formula polyester compound:
Wherein:
A, B be carbon or selected from nitrogen, oxygen, sulphur, boron hetero atom；
R1-R6、R1-RnGroup is the C of identical or different hydrogen, halogen or substituted or unsubstituted linear chain or branched chain1-C20Alkane
Base, naphthenic base, aryl, alkaryl, aralkyl, alkylene, fused ring aryl, ester group, and R1And R2It is not hydrogen, R3-R6And R1-RnBase
In group arbitrarily include substituent of one or several hetero atoms as carbon or hydrogen atom or both, the hetero atom selected from nitrogen,
Oxygen, sulphur, silicon, phosphorus or halogen atom, R3-R6And R1-RnOne or more of group can link up cyclization；
N is the integer of 0-10；
When A or B is oxygen or sulphur, the number of R group connected thereto is 0；It is connected thereto when A or B is boron or nitrogen
The number of R group is 1；When A or B is carbon or silicon, the number of R group connected thereto is 2, and when A and B is carbon
When, it is bonded in the form of carbon-carbon single bond or double or triple bonds between A and B, when bonded in the form of carbon-carbon single bond between A and B, A
It is 2 with the number of the B R group being separately connected, when bonded in the form of carbon-carbon double bond between A and B, R group that A is connected with B
Number 1, when bonded in the form of triple carbon-carbon bonds between A and B, the number 0 for the R group that A is connected with B.
9. according to the method described in claim 8, wherein the internal electron donor be selected from bis- (benzoyloxy methyl) fluorenes of 9,9-,
Bis- (propylene carboxymethyl group) fluorenes of 9,9-, bis- (the third carboxymethyl group) fluorenes of 9,9-, bis- (cortex cinnamomi carboxymethyl group) fluorenes of 9,9-, 2- isopropyl-
Two benzoyloxy propane of 2- isopentyl -1,3-, two propylene carboxyl propane of 2- isopropyl -2- isopentyl -1,3-, 2- isopropyl -2-
Isopentyl -1,3- dipropyl carboxyl propane, bis- benzoyloxy ethane of 1,2-, bis- benzoyloxy propane of 1,3-, bis- benzoyloxy of 1,4-
Butane, ortho-xylene carboxyl benzene, two cortex cinnamomi carboxyl propane of 2- isopropyl -2- isopentyl -1,3-, four (benzoyloxy methyl) first
Alkane, tri- benzoyloxy propane of 1,2,3-, two benzoyloxy pentane of 2,2,4- trimethyl -1,3- and 2,2- diisobutyl -1,3- two
At least one of benzoyloxy propane.
10. a kind of product is prepared by composition described in any one of claims 1 to 3.
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| US3487128A (en) * | 1966-01-31 | 1969-12-30 | Sumitomo Chemical Co | Blends comprising polypropylene,polyethylene,and an ethylene-propylene block copolymer |
| US4128606A (en) * | 1976-02-13 | 1978-12-05 | Mitsui Petrochemical Industries, Ltd. | Impact-resistant chemically blended propylene polymer composition and process for preparation thereof |
| CN101180357A (en) * | 2005-05-27 | 2008-05-14 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefinic compositions having good whitening resistance |
| CN103304691A (en) * | 2012-03-08 | 2013-09-18 | 中国石油化工股份有限公司 | Catalyst system used for alkene polymerization |
| CN104250317A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst |
| CN104558822A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Polypropylene composition |
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- 2015-07-24 CN CN201510441682.4A patent/CN106366431B/en active Active
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|---|---|---|---|---|
| US3487128A (en) * | 1966-01-31 | 1969-12-30 | Sumitomo Chemical Co | Blends comprising polypropylene,polyethylene,and an ethylene-propylene block copolymer |
| US4128606A (en) * | 1976-02-13 | 1978-12-05 | Mitsui Petrochemical Industries, Ltd. | Impact-resistant chemically blended propylene polymer composition and process for preparation thereof |
| CN101180357A (en) * | 2005-05-27 | 2008-05-14 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefinic compositions having good whitening resistance |
| CN103304691A (en) * | 2012-03-08 | 2013-09-18 | 中国石油化工股份有限公司 | Catalyst system used for alkene polymerization |
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