CN104558850B - Polypropylene resin composite and moulding article - Google Patents
Polypropylene resin composite and moulding article Download PDFInfo
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- CN104558850B CN104558850B CN201510043414.7A CN201510043414A CN104558850B CN 104558850 B CN104558850 B CN 104558850B CN 201510043414 A CN201510043414 A CN 201510043414A CN 104558850 B CN104558850 B CN 104558850B
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- -1 Polypropylene Polymers 0.000 title claims abstract description 191
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 64
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 64
- 239000000805 composite resin Substances 0.000 title claims abstract description 38
- 238000000465 moulding Methods 0.000 title description 48
- 229920001971 elastomer Polymers 0.000 claims abstract description 51
- 239000005060 rubber Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- 239000011256 inorganic filler Substances 0.000 claims abstract description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 9
- 229920001400 block copolymer Polymers 0.000 claims description 99
- 239000005977 Ethylene Substances 0.000 claims description 81
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 79
- 229920005604 random copolymer Polymers 0.000 claims description 62
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 48
- 238000005259 measurement Methods 0.000 claims description 16
- 239000000454 talc Substances 0.000 claims description 16
- 235000012222 talc Nutrition 0.000 claims description 16
- 229910052623 talc Inorganic materials 0.000 claims description 16
- 238000011068 load Methods 0.000 claims description 13
- 229920001384 propylene homopolymer Polymers 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 10
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000005712 crystallization Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 119
- 229920000642 polymer Polymers 0.000 description 105
- 239000001257 hydrogen Substances 0.000 description 39
- 229910052739 hydrogen Inorganic materials 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 28
- 239000002002 slurry Substances 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 239000011949 solid catalyst Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 239000004615 ingredient Substances 0.000 description 21
- 150000001336 alkenes Chemical class 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 235000013616 tea Nutrition 0.000 description 17
- 150000002431 hydrogen Chemical class 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000001404 mediated Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000003197 catalytic Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008079 hexane Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L mgso4 Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- 241000282890 Sus Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 229920002521 Macromolecule Polymers 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 230000003078 antioxidant Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- FKHIFSZMMVMEQY-UHFFFAOYSA-N Talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000003550 marker Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000004164 analytical calibration Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-Methyl-2-butene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical class CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MGWAVDBGNNKXQV-UHFFFAOYSA-N Diisobutyl phthalate Chemical class CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N Tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- UUNGXYVLXYGZKH-UHFFFAOYSA-M [Cl-].CCCC[Mg+] Chemical class [Cl-].CCCC[Mg+] UUNGXYVLXYGZKH-UHFFFAOYSA-M 0.000 description 1
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- WEPTUKVCIZSMNO-UHFFFAOYSA-N butyl-dimethoxy-propylsilane Chemical group CCCC[Si](OC)(OC)CCC WEPTUKVCIZSMNO-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- QEPVYYOIYSITJK-UHFFFAOYSA-N cyclohexyl-ethyl-dimethoxysilane Chemical class CC[Si](OC)(OC)C1CCCCC1 QEPVYYOIYSITJK-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention discloses polypropylene resin composite, it includes：The acrylic resin with specific structure of 50 94 weight %；The ethylene-alpha-olefin copolymer rubber of 1 25 weight %, the copolymer rubber are 0.85 0.91g/cm by density3And ethylene-alpha-olefin (the C that melt flow rate (MFR) is 0.9 20g/10 minutes4‑20) copolymer rubber and/or density is 0.85 0.91g/cm3And ethylene-alpha-olefin (C of the melt flow rate (MFR) not less than 0.1 but less than 0.9g/10 minutes5‑20) copolymer rubber composition；With the inorganic filler of 5 25 weight %.
Description
It is on 2 27th, 2008 the applying date that the application, which is, Application No. 200810081395.7 and entitled " poly- third
The divisional application of the application of olefine resin composition and moulding article ".
Technical field
The present invention relates to polypropylene resin composite and moulding articles prepared therefrom.
Background technology
Polypropylene resin composite is in the excellent material of rigidity, impact resistance etc., and they are with mechanograph
Form is used for a variety of applications, such as automotive interior or external component and electric appliance casing.
For example, JP-A 5-51498 disclose a kind of thermoplastic resin composition, which includes 50 to 75 weights
The crystalline polypropylene of % is measured, in the butene-1 content of 15 to 35 weight %, inherent viscosity and each comfortable particular range of Mooney viscosity
- 1 copolymer rubber of Ethylene/Butylene and 5 to 20 weight % talcum of the average grain diameter in particular range.
JP-A 7-157626 disclose a kind of thermoplastic resin composition, which, which includes, passes through multi-step polymerization
The propylene-ethylene block copolymer and polyolefin elastomer of preparation.Document introduction uses a kind of block copolymer as propylene-second
Alkene block copolymer, the block copolymer are made of following block copolymer：Include the embedding of Propylene-ethylene random copolymer phase
Section copolymer, the random copolymer mutually have the ethylene contents and 4.0 to 8.0dl/g inherent viscosity of 5 to 50 weight %；With
The block copolymer of propylene-ethylene block copolymer phase is included, the block copolymer is mutually with more than 50 weight % but less
In 98 weight % ethylene contents and not less than 2.0dl/g but less than 4.0dl/g inherent viscosity.
JP-A 9-157492 disclose a kind of thermoplastic resin composition, which, which includes, passes through multi-step polymerization
Propylene-ethylene block copolymer, ethylene-butene copolymer rubber and the talcum of preparation.Document introduction is total to using a kind of block
Polymers is consisted of following parts as propylene-ethylene block copolymer, the block copolymer：Homo-polypropylene part, melt
Flow rate in a specific range, and its by DSC measure heat of fusion and melt flow rate (MFR) meet specific relation；
Propylene-ethylene copolymers part with relatively low ethylene contents；With the propylene-ethylene copolymers portion with higher ethylene contents
Point.
It is, however, required that in current mark (flow mark) appearance, toughness, low temperature impact strength, high speed impact intensity is particularly,
And improved polypropylene resin composite and moulding article prepared therefrom in terms of the balance between rigidity and case hardness.
The content of the invention
In this case, it is an object of the present invention to provide a kind of acrylic resin combinations that can prepare mechanograph
Object, the mechanograph have improved current mark appearance, are excellent in terms of toughness and low temperature impact strength, and with flat very well
The rigidity and case hardness of weighing apparatus.It is a further object to provide the molding systems prepared by this polypropylene resin composite
Product.
In one aspect, the present invention provides a kind of polypropylene resin composite, it includes：
The acrylic resin (A) of 50 to 94 weight %,
The ethylene-α-olefincopolymerrubber (B) of 1 to 25 weight %, the copolymer rubber (B) include：Ethene-alpha-olefin
Copolymer rubber (B-1), the copolymer rubber (B-1) include C4 to C12 alpha-olefins and ethylene, and with 0.85 to
0.91g/cm3Density and the melt flow rate (MFR) of 0.9 to 20g/10 minute, the melt flow rate (MFR) be at 190 DEG C
It is measured under the load of temperature and 2.16kgf；And/or ethylene-α-olefincopolymerrubber (B-2), the copolymer rubber (B-
2) comprising C5 to C12 alpha-olefins and ethylene, and with 0.85 to 0.91g/cm3Density and not less than 0.01 but be less than
The melt flow rate (MFR) of 0.9g/10 minutes, the melt flow rate (MFR) are surveyed at 190 DEG C of temperature and the load of 2.16kgf
The sum of amount
The inorganic filler (C) of 5 to 25 weight %, wherein the amount of (A), (B) and (C) are each based on polypropylene-base resin
The total weight of composition,
Wherein acrylic resin (A) is to meet the crystalline propylene-ethylene blocks of following requirements (1), (2), (3) and (4) to be total to
Polymers (A-1) or the polymeric blends (A-3) comprising block copolymer (A-1) and crystalline propylene homopolymer (A-2),
It is required that (1)：Block copolymer (A-1) is crystalline propylene-ethylene random copolymer, and the random copolymer includes base
In block copolymer (A-1) total weight be 55 to 85 weight % crystalline polypropylene portion and based on block copolymer (A-1)
Total weight be 15 to 45 weight % Propylene-ethylene random copolymer part,
It is required that (2)：Crystalline polypropylene portion in block copolymer (A-1) is Noblen or propylene with being based on
The total amount of all monomers in the copolymer be equal to or less than the ethylene of 1 mole of % or α containing 4 or more carbon atoms-
The copolymer of alkene,
It is required that (3)：The propylene and ethylene contained in the Propylene-ethylene random copolymer part of block copolymer (A-1)
Weight ratio for 75/25 to 40/60,
It is required that (4)：The Propylene-ethylene random copolymer part of block copolymer (A-1) includes propylene-ethylene random copolymerization
Object component (EP-A) and Propylene-ethylene random copolymer component (EP-B), the copolymer component (EP-A) have 5.5dl/g extremely
The inherent viscosity [η] of 9dl/gEP-AWith the ethylene contents [(C2 ') not less than 20 weight % but less than 50 weight %EP-A], and institute
Stating copolymer component (EP-B) has the inherent viscosity [η] of 0.5dl/g to 4dl/gEP-BWith 30 weight % to the second of 60 weight %
Alkene content [(C2 ')EP-B]。
In another aspect, the present invention provides a kind of moulding article prepared by the polypropylene resin composite.
By the polypropylene resin composite of the injection molding present invention, a kind of moulding article can be prepared, wherein outside current mark
Sight is not significant, and the moulding article is excellent in terms of toughness and low temperature impact strength, and hard in rigidity and surface
It is balanced very well in terms of degree.
Description of the drawings
Attached drawing is for evaluating the schematic plan of the plate moulding article of current mark appearance.
Specific embodiment
The polypropylene resin composite of the present invention is to include the polypropylene resin composite of following component：50 to 94 weight %
Acrylic resin (A)；The ethylene-α-olefincopolymerrubber (B) of 1 to 25 weight %, the copolymer rubber (B) include second
Alkene-alpha olefin copolymer rubber (B-1) and/or (B-2)；With the inorganic filler (C) of 5 to 25 weight %, wherein (A), (B) and
(C) amount is each based on the total weight of polypropylene-base resin composition.
[acrylic resin (A)]
Acrylic resin (A) be crystalline propylene-ethylene block copolymer (A-1) or comprising block copolymer (A-1) and knot
The polymeric blends (A-3) of brilliant Noblen (A-2).
<Crystalline propylene-ethylene block copolymer (A-1)>
Crystalline propylene-ethylene block copolymer (A-1) is the crystalline propylene-ethylene block copolymer for including following part：
Total weight based on the block copolymer is the crystalline polypropylene portion of 55 to 85 weight %；With based on the total of the block copolymer
Weight is the Propylene-ethylene random copolymer part of 15 to 45 weight %.
Fluidity of molten in view of the composition and the moulding article that is prepared by the composition it is rigid, hard
Degree, toughness and impact resistance, preferably crystalline propylene-ethylene block copolymer (A-1) include the crystallization poly- third of 55 to 80 weight %
Alkene part and the Propylene-ethylene random copolymer part of 20 to 45 weight %, and preferably comprise the crystallization of 60 to 75 weight %
The Propylene-ethylene random copolymer part of homopolypropylene portion and 25 to 40 weight %.
In view of the rigidity, heat resistance and hardness of moulding article, the crystalline polypropylene portion of block copolymer (A-1) is third
Polyamino alkenyl object or propylene and the total amount based on all monomers in the copolymer are equal to or less than the ethylene of 1 mole of % or containing 4
The copolymer of the alpha-olefin of a or more carbon atom.
In view of the rigidity, heat resistance or hardness of moulding article, the crystalline polypropylene portion of preferred block copolymer (A-1)
It is to pass through13Isotaxy five-tuple (pentad) fraction of C-NMR measurements is equal to or more than 0.97 Noblen, and more
Preferably isotactic pentad fraction is equal to or more than 0.98 Noblen.
Isotactic pentad fraction is to be present in isotactic chain center with five-tuple unit form, in other words,
In 5 propylene monomer units it is successive in chain of the m- combination (meso-bond) in polypropylene molecular chain center propylene monomer
The fraction of unit, the fraction be by using13C-NMR measurements.It uses13The measuring method of C-NMR is by A.Zambelli etc.
Disclosed in Macromolecules, 6,925 (1973).
The confirmation of NMR absworption peaks be according to Macromolecules, what the content of 8,687 (1975) carried out.Specifically,
With13The form of the area fraction at the mmmm peaks in the entire peak area of the methyl carbon range of C-NMR spectrums determines isotaxy five
First number of components.According to this method, by NPL standard substances, available from NATIONAL PHYSICAL LABORATORY, G.B.'s
The isotactic pentad fraction of CRM No.M19-14 polypropylene PP/MWD/2 is measured as 0.944.
In view of the balance between the fluidity of molten of composition and the toughness of moulding article, preferred block copolymer
(A-1) crystalline polypropylene portion has 0.6 to 1.5dl/g, more preferable 0.7 to 1.2dl/g inherent viscosity [η]p。
The rigidity and toughness of fluidity of molten and the moulding article prepared by said composition in view of composition, preferably such as
Pass through the molecular weight distribution (M for the crystalline polypropylene portion that gel permeation chromatography (GPC) measuresw/Mn) not less than 3 but less than 7, and
And more preferably no less than 3 but less than 5.
Impact strength in view of the moulding article prepared by the composition, in propylene-second of block copolymer (A-1)
The propylene and the weight ratio of ethylene contained in olefinic random copolymer part is 75/25 to 40/60, and preferably 70/30 to 40/
60。
The Propylene-ethylene random copolymer part of block copolymer (A-1) includes Propylene-ethylene random copolymer component
(EP-A) and Propylene-ethylene random copolymer component (EP-B), the copolymer component (EP-A) have 5.5dl/g to 9dl/g
Inherent viscosity [η]EP-AWith the ethylene contents [(C2 ') not less than 20 weight % but less than 50 weight %EP-A], and it is described common
Copolymer component (EP-B) has the inherent viscosity [η] of 0.5dl/g to 4dl/gEP-BContain with the ethylene of 30 weight % to 60 weight %
It measures [(C2 ')EP-B]。
In view of the toughness and impact resistance of the moulding article of acquisition, and in order to inhibit stream in the production of moulding article
The generation of trace, ethylene contents [(C2 ')EP-A] be not less than 20 weight % but be less than 50 weight %, and preferably 25 to 45 weight %,
And more preferable 25 to 35 weight %.
Rigidity, hardness, toughness and the impact resistance of fluidity of molten and moulding article in view of composition, and in order to
Inhibiting the generation of the current mark and hard spot in layered product, copolymer component (EP-A) has 5.5dl/g to 9dl/g, and preferably
Inherent viscosity [η] more than 6dl/g but no more than 8dl/gEP-A。
In view of the impact resistance of moulding article at low temperature, in the propylene-ethylene random copolymerization of block copolymer (A-1)
In object part, the ethylene contents [(C2 ') of preferred copolymer component (EP-B)EP-B] it is not less than the ethylene of copolymer component (EP-A)
Content [(C2 ')EP-A], preferably 30 to 60 weight %, and more preferable 35 to 55 weight %.
The rigidity of fluidity of molten in view of composition and the moulding article prepared by said composition, hardness, toughness and
Impact resistance, copolymer component (EP-B) have 0.5dl/g to 4dl/g, and preferably not less than 1.5dl/g but less than 3.5dl/
The inherent viscosity [η] of gEP-B。
The impact resistance of mouldability and moulding article in view of composition, preferably crystalline propylene-ethylene block copolymerization
Object has 5 to 120g/10 minutes, and the melt flow rate (MFR) (being below MFR) of preferably 10 to 100g/10 minutes, described molten
Body flow rate is to be measured according to JIS K-7120 at 230 DEG C of temperature and the load of 2.16kgf.
By typical polymerization methods crystalline propylene-ethylene block copolymer (A- can be prepared using such as catalyst system
1), the catalyst system is made of following component：(a) comprising solid magnesium, titanium, halogen and electron donor as necessary component
Catalytic component；(b) organo-aluminum compound；Electron component (c).It can be for example, by JP-A 1-319508, JP-A
The method being described in detail in 7-216017, JP-A 10-212319, JP-A 2004-182876 etc. prepares such catalysis
Agent system.
Being used to prepare the example of the method for crystalline propylene-ethylene block copolymer (A-1) includes：
(1) include the method for at least three polymerization procedures, in the method, prepare crystalline polypropylene portion in the first step
Point, Propylene-ethylene random copolymer component (EP-A), the random copolymer component (EP-A) are then prepared in the second step
With 20 weight % to the ethylene contents [(C2 ') of 50 weight %EP-A] and 5.5dl/g to 9dl/g inherent viscosity [η]EP-A, with
Propylene-ethylene random copolymer component (EP-B) is prepared in third step afterwards, the random copolymer component (EP-B) has
The ethylene contents [(C2 ') of 30 weight % to 60 weight %EP-B] and 0.5dl/g to 4dl/g inherent viscosity [η]EP-B；With
(2) following method：Prepare crystalline polypropylene portion in the first step, then prepare in the second step propylene-
Ethylene atactic copolymer component (EP-B), the random copolymer component (EP-B) have the ethylene of 30 weight % to 60 weight %
Content [(C2 ')EP-B] and 0.5dl/g to 4dl/g inherent viscosity [η]EP-B, then prepared in third step propylene-ethylene without
Copolymer component (EP-A) is advised, the random copolymer component (EP-A) has the ethylene contents of 20 weight % to 50 weight %
[(C2′)EP-A] and 5.5dl/g to 9dl/g inherent viscosity [η]EP-A。
The example of polymerization includes bulk polymerization, polymerisation in solution, slurry polymerization, gas-phase polymerization etc..These polymerizations
Can be the form of batch systems or the form of continuous system, and can be carried out with suitable combining form.For work
The viewpoint of industry practicality, the gas-phase polymerization preferably in continuous system and the bulk polymerization in continuous system and gas-phase polymerization
Combination.
The more specific examples of polymerization include：
(3) the continuous preparation method of the device of the polymer reactor comprising three provided in series is used, wherein anti-first
Answer in device, by above-mentioned ingredient of solid catalyst (a), organo-aluminum compound (b) and electron component (c) is made to contact with each other and
In the presence of the catalyst system of preparation, crystalline polypropylene portion is prepared, then product is transferred in second reactor, and
Propylene-ethylene random copolymer component (EP-A) is prepared in the second reactor, and the random copolymer component (EP-A) has
The ethylene contents [(C2 ') of 20 weight % to 50 weight %EP-A] and 5.5dl/g to 9dl/g inherent viscosity [η]EP-A, then will
Product is transferred in the 3rd reactor, and Propylene-ethylene random copolymer component (EP-B), institute are prepared in the 3rd reactor
Stating random copolymer component (EP-B) has the ethylene contents [(C2 ') of 30 weight % to 60 weight %EP-B] and 0.5dl/g is extremely
The inherent viscosity [η] of 4dl/gEP-B；With
(4) the continuous preparation method of the device of the polymer reactor comprising three provided in series is used, wherein anti-first
Answer in device, by above-mentioned ingredient of solid catalyst (a), organo-aluminum compound (b) and electron component (c) is made to contact with each other and
In the presence of the catalyst system of preparation, crystalline polypropylene portion is prepared, then product is transferred in second reactor, and
Propylene-ethylene random copolymer component (EP-B) is prepared in the second reactor, and the random copolymer component (EP-B) has
The ethylene contents [(C2 ') of 30 weight % to 60 weight %EP-B] and 0.5dl/g to 4dl/g inherent viscosity [η]EP-B, then will
Product is transferred in the 3rd reactor, and Propylene-ethylene random copolymer component (EP-A), institute are prepared in the 3rd reactor
Stating random copolymer component (EP-A) has the ethylene contents [(C2 ') of 20 weight % to 50 weight %EP-A] and 5.5dl/g is extremely
The inherent viscosity [η] of 9dl/gEP-A。
Can the ingredient of solid catalyst that used in above-mentioned polymerization suitably be determined according to the type of catalyst
(a), organo-aluminum compound (b) is with the amount of electron component (c) and for each catalytic component to be supplied to polymerization instead
Answer the method in device.
Polymerization temperature is typically -30 to 300 DEG C, and preferably 20 to 180 DEG C.Polymerization pressure is typically normal pressure extremely
10MPa, and preferably 0.2 to 5MPa.As molecular weight regulator, hydrogen can be used.
In the preparation of crystalline propylene-ethylene block copolymer (A-1), preliminary polymerization can be carried out before main polymerization.
Preliminary polymerization can for example, by the presence of ingredient of solid catalyst (a) and organo-aluminum compound (b), by a small amount of propylene with
Slurry state is supplied in solvent and carries out.
Various additives can be added in crystalline propylene-ethylene block copolymer (A-1).The example bag of these additives
Include antioxidant, UV absorbents, lubricant, pigment, antistatic agent, copper deactivator, fire retardant, neutralizer, foaming agent, plasticising
Agent, nucleating agent, antifoaming agent and crosslinking agent etc..Among these additives, antioxidant and UV absorbents are preferably added to improve
Heat resistance, weatherability and inoxidizability.
<Crystalline propylene homopolymer (A-2)>
It is preferred that crystalline propylene homopolymer (A-2) is preferably the homopolymerization that isotactic pentad fraction is equal to or more than 0.97
Object, and more preferably isotactic pentad fraction is equal to or more than 0.98 homopolymer.
It is preferred that crystalline propylene homopolymer (A-2) has 20 to 500g/10 minutes, and preferably 80 to 300g/10 minutes
MFR, the MFR are to be measured according to JIS K-7120 at 230 DEG C of temperature and the load of 2.16kgf.
It can use and catalyst same type used in the preparation of crystalline propylene-ethylene block copolymer (A-1)
Catalyst preparation crystalline propylene homopolymer (A-2).
<Polymeric blends (A-3)>
In the polypropylene resin composite of the present invention acrylic resin (A) that includes can be individual crystalline polypropylene-
Ethylene block copolymer (A-1) or polymeric blends (A-3), the polymeric blends (A-3) include crystalline propylene-ethylene
Block copolymer (A-1) and crystalline propylene homopolymer (A-2).
It is preferred that the content of the crystalline propylene-ethylene block copolymer (A-1) included in polymeric blends (A-3) is 30
To 99 weight %, and the content of crystalline propylene homopolymer (A-2) is 1 to 70 weight %.More preferable Propylene-ethylene block copolymerization
The content of object (A-1) is 50 to 90 weight %, and the content of crystalline propylene homopolymer (A-2) is 10 to 50 weight %.
The rigidity and impact resistance of fluidity of molten and moulding article in view of the composition, based on acrylic resin
The total weight of composition, acrylic resin (A) content included in the polypropylene resin composite of the present invention are 50 to 94 weights
Measure %, preferably 55 to 90 weight %, and more preferably 60 to 85 weight %.
[ethylene-α-olefincopolymerrubber (B)]
The ethylene-α-olefincopolymerrubber (B) being used in the present invention is comprising following ethene-alpha-olefin copolymer
Rubber：Ethylene-α-olefincopolymerrubber (B-1), the copolymer rubber (B-1) include C4 to C12 alpha-olefins and ethylene, and
And with 0.85 to 0.91g/cm3Density and the melt flow rate (MFR) of 0.9 to 20g/10 minute, the melt flow rate (MFR)
It is to be measured according to JIS K-7210 at 190 DEG C of temperature and the load of 2.16kgf；And/or ethene-alpha-olefin copolymer rubber
Glue (B-2), the copolymer rubber (B-2) include C5 to C12 alpha-olefins and ethylene, and with 0.85 to 0.91g/cm3's
Density and the melt flow rate (MFR) not less than 0.01 but less than 0.9g/10 minutes, the melt flow rate (MFR) is according to JIS
What K-7210 was measured at 190 DEG C of temperature and the load of 2.16kgf.
The example of C4 to C12 alpha-olefins includes butene-1, amylene -1, hexene -1, heptene -1, octene-1 and decylene-1.It is excellent
Select butene-1, hexene -1 and octene-1.
For the impact strength of moulding article, the viewpoint of impact strength particularly at low temperature, based on copolymer rubber
(B) total weight, the content of the alpha-olefin included in copolymer rubber (B) are usually 20 to 50 weight %, and preferably 24
To 50 weight %.
The example of ethylene-α-olefincopolymerrubber includes -1 random copolymer rubber of Ethylene/Butylene, polyethylene-hexene -1
Atactic polymer rubber, -1 random copolymer rubber of ethylene-octene etc..Optimal ethylene-octene-1 random copolymer rubber and second
Alkene-butene-1 random copolymer rubber.It can be by two or more ethene-alpha-olefin random copolymer rubbers in combination
It uses.
In view of the impact resistance of moulding article, impact strength particularly at low temperature, ethene-alpha-olefin copolymer rubber
The density of glue (B-1) and ethylene-α-olefincopolymerrubber (B-2) is independently 0.85 to 0.91g/cm3In the range of, and
It is preferred that 0.85 to 0.87g/cm3In the range of.
The melt flow rate (MFR) of ethylene-α-olefincopolymerrubber (B-1) is 0.9 to 20g/10 minute, the melt flow
Dynamic rate is to be measured according to JIS K-7210 at 190 DEG C of temperature and the load of 2.16kgf.In view of the anti-of moulding article
Impact, impact strength particularly at low temperature, it is preferably 0.9 to 15g/10 minute, and more preferably 0.9 to 7g/
10 minutes.The melt flow rate (MFR) of ethylene-α-olefincopolymerrubber (B-2) is not less than 0.01 but less than 0.9g/10 minutes, institute
It is to be measured according to JIS K-7210 at 190 DEG C of temperature and the load of 2.16kgf to state melt flow rate (MFR).In view of molding
The impact resistance of product, impact strength particularly at low temperature, it was preferably not less than 0.05 but less than 0.9g/10 minute, and
And more preferably no less than 0.2 but less than 0.9g/10 minutes.
Conventional catalyst and conventional polymerization can be used, by preparing ethylene and various alpha-olefin copolymers
Ethylene-α-olefincopolymerrubber (B).
The example of conventional catalyst includes the catalyst system comprising vfanadium compound and organo-aluminum compound, Ziegler-receive
Tower catalyst system, metallocene catalyst system.The example of conventional polymerization includes polymerisation in solution, slurry polymerization, high pressure
Ionic polymerization, gas-phase polymerization etc..
Rigidity and impact strength in view of the moulding article prepared by the composition, based on polypropylene resin composite
Total weight, the content of ethylene-α-olefincopolymerrubber (B) included in the polypropylene resin composite of the present invention is 1
To 25 weight %, preferably 3 to 22 weight %, and more preferably 5 to 20 weight %.
[inorganic filler (C)]
The inorganic filler (C) used in the present invention contributes to the rigidity of moulding article, and the example include calcium carbonate,
Barium sulfate, mica, crystallization calcium silicates, talcum, magnesium sulfate fiber etc..Preferably talc or with magnesium sulfate fiber.These inorganic fills
Agent can use in combination.
Talcum as inorganic filler (C) is the hydrous magnesium silicate being ground.The crystal structure of hydrous magnesium silicate
It is Pyrophyllite-Type three-decker.The compound that talcum is made of the layered product of this structure.Preferred talcum be pass through by
The foliated talc that hydrous magnesium silicate crystal is subtly ground to size almost small as elementary layer and prepares.
The average grain diameter of preferably talc is not more than 3 μm.The average grain diameter of talcum refer to by subsieve (sub-sieve) method by
The 50% equivalent grain size D that integral distribution curve determines50, it is by using centrifugal sedimentation type particle size distribution analysis device, makes talcum
Decentralized medium is suspended in as measured in water or alcohol.
Inorganic filler can be used in the case of without any preliminary treatment.It is alternatively possible to by it with
Following various substances handle its surface to improve with the interface adhesiveness of acrylic resin (A) or raising at acrylic resin (A)
In dispersibility after use：Silane coupling agent, titanium coupling agent, higher fatty acids, high-grade aliphatic ester, higher aliphatic acyl
Amine, higher fatty acid salt or other surfactants.
In the case where using magnesium sulfate fiber as inorganic filler (C), preferably average fiber length is 5 to 50 μm,
More preferably 10 to 30 μm.The average diameter of preferably sulfuric acid magnesium fiber is 0.3 to 2 μm, and more preferably 0.5 to 1 μm.
Rigidity and impact strength in view of the moulding article prepared by the composition, based on polypropylene resin composite
Total weight %, the content of inorganic filler (C) included in the polypropylene resin composite of the present invention is 5 to 25 weights
Measure %, preferably 7 to 23 weight %, and more preferably 10 to 20 weight %.
It can be by the way that component melts be mediated to prepare the polypropylene resin composite of the present invention.It, can in melt kneading
To use kneader, such as single screw extrusion machine, double screw extruder, Banbury mixer and heating roller.Tree when mediating
Fat temperature is typically 170 to 250 DEG C, and kneading time is typically 1 to 20 minute.Mediate can be by adding in all groups simultaneously
Divide or carried out by sequentially adding component.
The method (1) to (4) being illustrated below for the example of the method for component to be mediated to include.
(1) wherein by crystalline propylene-ethylene block copolymer (A-1), ethylene-α-olefincopolymerrubber (B) and inorganic
Filler (C) mixes simultaneously, the method then mediated.
(2) wherein by crystalline propylene-ethylene block copolymer (A-1) and crystalline propylene homopolymer (A-2), ethylene-α-alkene
Hydrocarbon copolymer rubber (B) and inorganic filler (A) mix simultaneously, the method then mediated.
(3) wherein crystalline propylene-ethylene block copolymer (A-1) and ethylene-α-olefincopolymerrubber (B) are mediated,
Then inorganic filler (C) and the method further mediated are added in.
(4) wherein crystalline propylene-ethylene block copolymer (A-1) and inorganic filler (C) are mediated, then adds in second
Alkene-alpha olefin copolymer rubber (B) and the method further mediated.
It is mixed when using the polymer containing crystalline propylene-ethylene block copolymer (A-1) and crystalline propylene homopolymer (A-2)
When closing object (A-3) as acrylic resin (A), crystalline propylene homopolymer (A-2) can be added in method (3) or (4).
Various additives can be added in the polypropylene resin composite of the present invention.The example of these additives includes anti-
Oxidant, UV absorbents, lubricant, pigment, antistatic agent, copper deactivator, fire retardant, neutralizer, foaming agent, plasticizer, into
Core agent, antifoaming agent, crosslinking agent etc..In order to improve heat resistance, weatherability and inoxidizability, it is preferably added to antioxidant or UV absorbs
Agent.
In order to further improve the balance between mechanical performance, the rubber containing vinyl aromatic compounds can be added in
In the polypropylene resin composite of the present invention.
The example of rubber containing vinyl aromatic compounds is included by vinyl aromatic compounds polymer blocks, conjugation two
Block copolymer of alkene-based polyalcohol block composition etc..The double bond total weight contained in conjugated diene portion is preferably based on, is conjugated
The hydrogenation degree of the double bond of diene portions is preferably not less than 80 weight %, and preferably not less than 85 weight %.
The molecular weight distribution of the rubber of vinyl aromatic compounds is preferably comprised no more than 2.5, and preferably 1.0 to 2.3,
The molecular weight distribution is measured by gel permeation chromatography (GPC).
The total weight of the rubber containing vinyl aromatic compounds is preferably based on, in the rubber containing vinyl aromatic compounds
The content of the vinyl aromatic compounds contained is 10 to 20 weight %, and more preferably 12 to 19 weight %.
It is preferred that the rubber containing vinyl aromatic compounds has 0.01 to 15g/10 minute, and preferably 0.03 to 13g/10
The MFR of minute, the MFR is according to JIS K-7210, is measured at 230 DEG C of temperature and the load of 2.16kgf.
The example of rubber containing vinyl aromatic compounds includes block copolymer, such as styrene-ethylene-butadiene-benzene second
Alkene rubber (SEBS), styrene ethylene-propylene-styrene rubber (SEPS), SBR styrene butadiene rubbers (SBR), styrene-
Afpol (SBS) and styrene-isoprene-styrene rubber (SIS) and pass through above-mentioned block copolymerization
Hydrogenated block copolymer prepared by the hydrogenation of object.Further, it is also possible to using by make vinyl aromatic compounds such as styrene with
The rubber that ethylene-propylene-non-conjugated diene rubber is reacted and prepared.Two or more can be contained vinyl aromatic compounds
Rubber use in combination.
It can be for example, by vinyl aromatic compounds be connected on alkene-based copolymer rubber or conjugated diene rubber
Prepare the rubber containing vinyl aromatic compounds.
The injection molding product of the present invention is the mould prepared by the polypropylene resin composite of the injection molding present invention
Mould product.The particularly preferred application of injection molding product of the present invention is automobile component, as door decoration (door trims),
Pillar, instrument board, bumper etc..
Embodiment
Below with reference to embodiment and the comparative example description present invention.Described below for measurement in embodiment and comparative example
The polymer material and the method for the physical property of the moulding article prepared used.
(1) inherent viscosity (unit：dl/g)
Reduced viscosity is three measurement of concetrations in 0.1,0.2 and 0.5g/dl using Ubbelohde viscometer.By
" Kobunshi Yoeki (polymer solution (Polymer Solution)), Kobunshi Jikkengaku (polymer experiments
Study (Polymer Experiment Study)) page 11 " 491 (Kyoritsu Shuppan Co., Ltd.s, nineteen eighty-two publish)
Described in computational methods, i.e., by the way that wherein reduced viscosity maps to concentration, and concentration is extrapolated to zero Extrapolation method,
Estimated performance viscosity.Measurement is carried out using tetrahydronaphthalene as solvent at a temperature of 135 DEG C.
The inherent viscosity of (1-1) crystalline propylene-ethylene block copolymer
The inherent viscosity of (1-1a) crystalline polypropylene portion：[η]p
In the preparation process of crystalline propylene-ethylene copolymer, the first step of crystalline polypropylene portion is being used to prepare
Afterwards, polymer powder is taken out from reactor.Using polymer powder, reduced viscosity is measured by the above method (1), and
Inherent viscosity is determined by reduced viscosity.The crystallization that inherent viscosity is defined as containing in crystalline propylene-ethylene block copolymer
The inherent viscosity [η] of homopolypropylene portionp。
The inherent viscosity of (1-1b) Propylene-ethylene random copolymer：[η]Ep
The inherent viscosity [η] of crystalline polypropylene portion is measured by the above method (1)pIt is total to crystalline propylene-ethylene block
The inherent viscosity [η] of polymersT.Using Propylene-ethylene random copolymer part and the weight ratio X of propylene-ethylene block copolymer,
By the characteristic for the Propylene-ethylene random copolymer part that following equalities calculating contains in crystalline propylene-ethylene block copolymer
Viscosity [η]Ep.Weight ratio X is measured by measuring method given below (2).
[η]EP=[η]T/X-(1/X-1)[η]p
[η]p：The inherent viscosity (dl/g) of crystalline polypropylene portion
[η]T：The inherent viscosity (dl/g) of propylene-ethylene block copolymer
It is polymerize by two-stage wherein in the case of preparing Propylene-ethylene random copolymer part, in following method (b-
1) characteristic of the Propylene-ethylene random copolymer component (EP-1) prepared in the first stage, is measured in (b-2) and (b-3) respectively
Viscosity [η]EP-1, the inherent viscosity [η] of Propylene-ethylene random copolymer component (EP-2) for preparing in the second levelEP-2With most
The characteristic of Propylene-ethylene random copolymer part in the propylene-ethylene block copolymer comprising EP-1 and EP-2 obtained eventually
Viscosity [η]EP。
(b-1) inherent viscosity：[η]EP-1
After Propylene-ethylene random copolymer component (EP-1) is prepared, the sample taken out from polymer reactor is measured
Inherent viscosity ([η](1)), Propylene-ethylene random copolymer component (EP- is then measured in a manner of identical with above-mentioned (1-1b)
1) inherent viscosity [η]EP-1。
[η]EP-1=[η](1)/X(1)-(1/X(1)-1)[η]p
[η]p：The inherent viscosity (dl/g) of crystalline polypropylene portion
[η](1)：After the polymerization of EP-1 is used to prepare, the inherent viscosity (dl/g) of propylene-ethylene block copolymer
X(1)：After the polymerization of EP-1 is used to prepare, the weight ratio of EP-1 and propylene-ethylene block copolymer
(b-2) inherent viscosity：[η]EP
It is measured in a manner of identical with above-mentioned (1-1b) in the Propylene-ethylene block for including EP-1 and EP-2 finally obtained
The inherent viscosity [η] of the Propylene-ethylene random copolymer included in copolymerEP。
[η]EP=[η]T/X-(1/X-1)[η]p
[η]p：The inherent viscosity (dl/g) of crystalline polypropylene portion
[η]T：The inherent viscosity (dl/g) of the propylene-ethylene block copolymer finally obtained
X：The Propylene-ethylene random copolymer part that finally obtains and the propylene-ethylene block copolymer finally obtained
Weight ratio
(b-3) inherent viscosity：[η]EP-2
By the inherent viscosity of the Propylene-ethylene random copolymer part in the propylene-ethylene block copolymer that finally obtains
[η]EP, Propylene-ethylene random copolymer component (EP-1) inherent viscosity [η]EP-1And their weight ratio, determine propylene-
The inherent viscosity [η] of ethylene atactic copolymer component (EP-2)EP-2。
[η]EP-2=([η]EP×X-[η]EP-1×X1)/X2
X1：The weight ratio of EP-1 and the propylene-ethylene block copolymer finally obtained
X1=(X(1)-X×X(1))/(1-X(1))
X2：The weight ratio of EP-2 and the propylene-ethylene block copolymer finally obtained
X2=X-X1
(2) weight ratio of Propylene-ethylene random copolymer part and propylene-ethylene block copolymer：X
In propylene-ethylene block copolymer, for each of crystalline polypropylene and block copolymer, measurement crystal melts
Change heat.Based on the measurement, by following equalities calculating Propylene-ethylene random copolymer part and the weight ratio X of block copolymer.
X=1- (Δ Hf) T/ (Δ Hf) P
(ΔHf)T：The heat of fusion (card/g) of block copolymer
(ΔHf)P：The heat of fusion (card/g) of crystalline polypropylene portion
(3) ethylene contents (unit：Weight %)
The tabletting of polymer material is prepared, and measures its infrared absorption spectrum.Use measured methyl (- CH3) and
Methylene (- CH2-) characteristic absorption absorbance, the content of ethylene in the material is determined by calibration curve.
(4) ethylene contents (unit of the Propylene-ethylene random copolymer part in propylene-ethylene block copolymer：Weight
Measure %)：[(C2’)EP]
By using the ethylene contents (weight %) of the block copolymer measured beforehand through infrared absorption spectroscopy, under
Row equation determines the ethylene contents of the Propylene-ethylene random copolymer part in propylene-ethylene block copolymer.
[(C2’)EP]=(C2 ') T/X
(C2’)T：The ethylene contents (weight %) of block copolymer
[(C2’)EP]：The ethylene contents (weight %) of Propylene-ethylene random copolymer
X：Propylene-ethylene random copolymer part and the weight ratio of propylene-ethylene block copolymer
(5) melt flow rate (MFR) (MFR, unit：G/10 minutes)
The MFR of polymer material is measured by the method provided in JIS K7210.Unless stated otherwise, otherwise
Measurement is carried out at 230 DEG C of temperature and the load of 2.16kgf.
(6) flexural modulus (FM, unit：MPa)
The flexural modulus of moulding article is measured by the method provided in JIS K7203.Measurement was at 5mm/ minutes
Load rate and 23 DEG C at a temperature of, using thickness be 3.2mm and span length is 60mm injection-molded test specimens carry out.
(7) Izod impact strength (Ai Zuode, unit：kJ/m2)
The Izod impact strength of moulding article is measured by the method provided in JIS K7110.Measurement is 23
DEG C and -30 DEG C at a temperature of, carried out using the band notched specimen that thickness is 6.4mm, the sample is by injection molding, then
Notch and prepare.
(8) heat distortion temperature (HDT, unit：℃)
The heat distortion temperature of moulding article is measured by the method provided in JIS K7207.Measurement is in 4.6kgf/
cm2Fibre stress under carry out.
(9) Rockwell hardness (R grades)
The Rockwell hardness of moulding article is measured by the method provided in JIS K7202.Measurement by using by
The sample that thickness prepared by injection molding is 3.0mm carries out.Measured value is represented with R classic forms.
(10) tension test (elongation (UE) in fracture, unit：%)
Elongation of the moulding article in fracture is measured by the method provided in ASTM D638.Stretching in fracture
Long rate (UE) is to be measured using the injection-molded test specimens that thickness is 3.2mm under the rate of extension of 50mm/ minutes.
(11) isotactic pentad fraction
Isotactic pentad fraction is by the use disclosed in Macromolecules, 6,925 (1973)13C-
The method measurement of NMR.According to Macromolecules, the content of 8,687 (1975) carries out the confirmation of NMR absworption peaks.
(12) molecular weight distribution (Mw/Mn)
Molecular weight distribution is measured by GPC under conditions of following give：
Instrument：Model 150CV (are manufactured) by Millipore Waters
Pillar：Shodex M/S 80
Measure temperature：145℃
Solvent：O-dichlorohenzene
Sample concentration：5mg/8mL
Calibration curve is generated using polystyrene standard.Standard polystyren (the NBS706 measured under these conditions；
Mw/Mn=2.0 Mw/Mn) is 1.9 to 2.0.
[preparation of injection molding product]
Using the injection molding machine IS150E-V manufactured by Toshiba Machine Co., Ltd.s, by molding temperature
For 220 DEG C, mold cooling temperature be 50 DEG C, injection time is 15 seconds and cooling time be 30 seconds under conditions of injection molding, system
It is ready for use on the sample of the physical property evaluation of (6) shown above to (10).
(13) it is used for the preparation of the injection molding product of the evaluation of current mark appearance
It is prepared via a method which to evaluate the sample of the condition of current mark generation.
Mold (chamber size using injector and in injector：100mm (width) × 200mm (length) ×
3.0mm (thickness), there are one gates for tool), it is molded under 220 DEG C of molding temperature.Plate moulding article is obtained, is being schemed
Its schematic diagram is illustrated in 1.In the figure, reference marker 1 represents gate.Reference marker 2 represents the current mark generated on side.
Reference marker 3 represents the current mark generated in central part.
(14) condition that current mark generates
Using the plate moulding article prepared in above-mentioned (13), current mark is visually observed.In the transverse direction of moulding article
Side and transverse central portion measure in gate end face and (current mark generate distance, with mm closest to the distance between gate end face
Meter), and observe the perceptible degree of current mark.Current mark generation is fewer apart from longer or perceptible current mark, moulding article
Appearance is better.
Description prepares the catalyst (ingredient of solid catalyst for being used to prepare the polymer in embodiment and comparative example below
(I), (II)) method.
(1) ingredient of solid catalyst (I)
With nitrogen purging equipped with the 200L SUS reactors of blender.Afterwards, by 80L hexanes, tetra- butanol of 6.55mmol
Titanium and 98.9mol tetraethoxysilanes are packed into wherein to form uniform solution.Then, it is maintained at by the temperature in reactor
While 20 DEG C, solution of the 2.1mol/L butyl magnesium chlorides of 50L in di-n-butyl ether is slowly added dropwise, last 4 it is small when.It is being added dropwise
After finishing, by mixture 20 DEG C futher stir 1 it is small when, subsequent solid- liquid separation at room temperature.It then, will be obtained solid
Body is washed three times with 70L toluene.Then the solid of washing is dispersed in toluene to form slurries, and remove some toluene with
Concentration of slurry is adjusted to 0.4Kg/L.The mixed solution of 8.9mol di-n-butyl ethers and 274mol titanium tetrachlorides is added in, then also
20.8mol o-phthaloyl chlorides are added in, are then reacted three hours at 110 DEG C.It after the reaction was completed, will using 95 DEG C of toluene
Obtained solid washing is three times.Then, the solid of washing is dispersed in toluene to form slurries, and concentration of slurry is adjusted
To 0.4Kg/L.Then, 3.13mol diisobutyl phthalates, 8.9mol di-n-butyl ethers and 109mol titanium tetrachlorides are added in,
Then when 105 DEG C of reactions 1 are small.After the reaction was completed, separation of solid and liquid is carried out in the temperature, and uses the first of 95 DEG C of 90L
Benzene washes twice obtained solid.Then, the solid of washing is dispersed in toluene to be formed slurries, and by concentration of slurry
Adjust 0.4Kg/L.Then, 8.9mol di-n-butyl ethers and 109mol titanium tetrachlorides are added in, then when 95 DEG C of reactions 1 are small.
After completing reaction, separation of solid and liquid is carried out at such a temperature, and is washed obtained solid in mutually synthermal toluene using 90L
It washs twice.Then, the solid of washing is dispersed in toluene to form slurries, and concentration of slurry is adjusted to 0.4Kg/L.So
Afterwards, 8.9mol di-n-butyl ethers and 109mol titanium tetrachlorides are added in, then when 95 DEG C of reactions 1 are small.After the reaction was completed, at this
Temperature carries out separation of solid and liquid.Obtained solid is washed three times at the same temperature using 90L toluene, and in addition uses 90L
Hexane washs three times, then, is dried under reduced pressure to generate the ingredient of solid catalyst of 12.8Kg.The ingredient of solid catalyst contains
There are the titanium atom of 2.1 weight %, the magnesium atom of 18 weight %, the chlorine atom of 60 weight %, the phthalic acid of 7.15 weight %
The butoxy of ester, the ethyoxyl of 0.05 weight % and 0.26 weight %.It does not contain particulate and with good practicability.
This ingredient of solid catalyst is known as ingredient of solid catalyst (I) below.
(2) ingredient of solid catalyst (II)
To prepare ingredient of solid catalyst (II) with those identical methods disclosed in JP-A 2004-182876.
[preparation of polymer]
(1) preparation of Noblen (HPP)
The preparation of (1-1) HPP-1
(1-1a) preliminary polymerization
In the 3-L SUS autoclaves equipped with blender, using the triethyl aluminum as electron component of 25mmol/L
(hereinafter referred to as TEA) and tertiary butyl-n-propyl dimethoxysilane (hereinafter referred to as tBunPrDMS) are with tBunPrDMS/
The amount and 19.5g/L ingredients of solid catalyst (H) of TEA=0.1 (mol/mol) is added to what is be dehydrated and deaerated completely
In hexane.Then, by continuously supplying propylene until the quantitative change of propylene supplied is 2.5g/1 grams of solid catalyst, protect simultaneously
Temperature is held not higher than 15 DEG C, carries out preliminary polymerization.Obtained preliminary polymer slurries are transferred to 120-L equipped with blender
SUS dilution traps in, diluted by adding in fully refined liquid butane, then preserved at a temperature of not higher than 10 DEG C.
(1-1b) main polymerization
It is 1m in capacity3And equipped in the fluidized-bed reactor of blender, propylene and hydrogen are supplied to be kept for 83 DEG C
Polymerization temperature, the polymerization pressure of 1.8MPa-G and in the gas phase based on propylene be 17.9 volume % density of hydrogen.Continuously supplying
Give cyclohexyl-ethyl dimethoxysilanes (be below CHEDMS) and 1.80g/ of TEA, the 6.3mmol/ of 43mmol/ when small when small
While the preliminary polymerization object slurries prepared as ingredient of solid catalyst hour in (1-1a), progress continuous gas-phase polymerization.
Therefore, polymer when acquisition 18.6kg/ is small.Obtained polymer has the inherent viscosity [η] of 0.78dl/gP, 0.985
Isotactic pentad fraction and 4.3 molecular weight distribution.The analysis result of obtained polymer is shown in Table 1.
The production of (1-2) HPP-2
It is operated in a manner of identical with HPP-1, the difference is that adjusting the hydrogen in gas phase in main polymerization
The amount of gas so that the polymer of needs can be obtained.Obtained polymer has the inherent viscosity [η] of 0.92dl/gP,
0.983 isotactic pentad fraction and 5.4 molecular weight distribution.
The production of (1-3) HPP-3
It is operated with the mode identical with HPP-1, the difference is that adjusting the hydrogen in gas phase in main polymerization
The amount of gas so that the polymer of needs can be obtained.Obtained polymer has the inherent viscosity [η] of 1.36dl/gP,
0.980 isotactic pentad fraction and 4.2 molecular weight distribution.
(2) preparation of propylene-ethylene block copolymer (BCPP)
The preparation of (2-1) BCPP-1
(2-1a) preliminary polymerization
In the 3-L SUS autoclaves equipped with blender, using TEAs of the 25mmol/L as electron component and
CHEDMS is added to the ingredient of solid catalyst (I) of the amount of CHEDMS/TEA=0.1 (mol/mol) and 15.8g/L
In the hexane for being dehydrated and deaerating completely.Then, by continuously supplying propylene until the quantitative change of the propylene supplied is 1.0g/1 grams
Solid catalyst, while temperature is kept to carry out preliminary polymerization not higher than 15 DEG C.Obtained preliminary polymer slurries are transferred to
200-L is diluted, then not higher than 10 equipped in the SUS dilution traps of blender by adding in fully refined liquid butane
It is preserved at a temperature of DEG C.
(2-1b) main polymerization
It is being 300L comprising a capacity and vessel type reactor equipped with blender and respective capacity are 1m3And match somebody with somebody
It has in the device of two gas fluidized bed reactors (three reactors are series connection) of blender, leads in the first reactor
It crosses continuous polymerization and prepares propylene homopolymer portion, and in the case where not deactivating, the polymer of generation is transferred to
In two reactors.Propylene-ethylene copolymers part is prepared by continuous polymerization in the second reactor, and is not being deactivated
In the case of, the polymer of generation is transferred in the 3rd reactor.In the 3rd reactor by continuous polymerization prepare propylene-
Ethylene copolymer fraction.
In the first reactor, be 65 DEG C including polymerization temperature, polymerization pressure 3.06MPa, 45Kg/ it is small when propylene
Delivery rate and hydrogen during 239NL/ small delivery rate under conditions of, TEA, the 5.264mmol/ for introducing 27.3mmol are small
When CHEDMS and the preliminary polymer slurries prepared as ingredient of solid catalyst in (2-1a) during 1.28g/ small.Cause
This, polymer is obtained with rates of 16.84kg/ when small.The inherent viscosity [η] of this polymerPFor 1.17dl/g.
In the second reactor, in the presence of the polymer continuously received from first reactor, including following item
Continuous polymerization (following, EP-1 polymerizations) is carried out under part：Polymerization temperature is 65 DEG C, polymerization pressure 1.6MPa, and is continually introduced into
Propylene, ethylene and hydrogen allow to respectively by the gas phase hydrogen, the concentration of ethylene and propylene be maintained at 6.02 volume %,
22.58 volume % and 64.99 volume %.Therefore, polymer is obtained with the rate of 19.83kg//hour.By a part of polymer
It samples from second reactor, then analyzes.It was found that inherent viscosity [η]TFor 1.30dl/g, and generate in the second reactor
Polymer content (EP1 contents) be 15 weight %.Therefore, the polymer generated in the second reactor (is below EP-1
Part) there is the inherent viscosity [η] of 2.0dl/gEP-1.Ethylene contents in EP-1 parts are 41 weight %.
In addition, in the 3rd reactor, while polymer is received from second reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 65 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 0.278 volume %,
25.01 volume % and 73.95 volume %.Therefore, polymer is obtained with rates of 22.25kg/ when small.Point of the polymer of collection
Analysis shows inherent viscosity [η]TContent (EP2 contents) for 1.87dl/g, and the polymer generated in the 3rd reactor is
10 weight %.Therefore, the polymer (following for EP-2 parts) generated in the 3rd reactor has the inherent viscosity of 6.8dl/g
[η]EP-2.Ethylene contents in EP-2 parts are 30 weight %.
The production of (2-2) BCPP-2
(2-2a) preliminary polymerization
It is polymerize in a manner of identical with the preliminary polymerization in the preparation of BCPP-1.
(2-2b) main polymerization
The device comprising a vessel type reactor and two gas fluidized bed reactors in the preparation of such as BCPP-1
In, the propylene-ethylene block copolymer with structure P- (EP-1)-(EP-2) is prepared by continuous polymerization.
In the first reactor, be 65 DEG C including polymerization temperature, polymerization pressure 3.07MPa, 45Kg/ it is small when propylene
Delivery rate and hydrogen during 238NL/ small delivery rate under conditions of, introduce 26mmol TEA, 6.4mmol/ it is small when
The preliminary polymer slurries prepared as ingredient of solid catalyst in (2-2a) during CHEDMS and 1.27g/ small.Therefore,
Polymer is obtained with rates of 16.98kg/ when small.The inherent viscosity [η] of this polymerPFor 1.16dl/g.
In the second reactor, while continuously polymer is received from first reactor, including under conditions of following
Carry out continuous polymerization (following, EP-1 polymerizations)：Polymerization temperature be 65 DEG C, polymerization pressure 1.6MPa, and be continually introduced into propylene,
Ethylene and hydrogen allow to respectively by the gas phase hydrogen, the concentration of ethylene and propylene be maintained at 3.63 volume %, 21.15
Volume % and 66.8 volume %.Therefore, polymer is obtained with rates of 20.21kg/ when small.A part of polymer is anti-from second
It answers in device and samples, then analyze.It was found that inherent viscosity [η]TFor 1.36dl/g, and the polymer generated in the second reactor
Content (EP1 contents) be 16 weight %.Therefore, the polymer (being below EP-1 parts) generated in the second reactor has
The inherent viscosity [η] of 2.5dl/gEP-1.Ethylene contents in EP-1 parts are 39 weight %.
In addition, in the 3rd reactor, while polymer is received from second reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 65 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 15.91 volume %,
31.89 volume % and 50.0 volume %.Therefore, polymer is obtained with rates of 22.9kg/ when small.The analysis of the polymer of collection
Show inherent viscosity [η]TFor 1.43dl/g, and the content (EP2 contents) of the polymer generated in the 3rd reactor is 12
Weight %.Therefore, the polymer (following for EP-2 parts) generated in the 3rd reactor has the inherent viscosity of 1.9dl/g
[η]EP-2.Ethylene contents in EP-2 parts are 59 weight %.The analysis result of obtained polymer is shown in Table 1.
The production of (2-3) BCPP-3
(2-3a) preliminary polymerization
Using the autoclave equipped with blender, using TEA, tBunPrDMS as electron component of 20mmol/L with
The amount of tBunPrDMS/TEA=0.1 (mol/mol) and the amount of the titanium contained in catalytic component are TEA/Ti=3.8's
Ingredient of solid catalyst (II) is sequentially introduced into this in the hexane for being dehydrated and deaerating completely.By being continually introduced into third
Alkene, while ratio (the following letter so that the polymer based on ingredient of solid catalyst is kept the temperature in the range of 5 to 15 DEG C
Referred to as PP/Cat) become 1.0 (g/g), obtain preliminary polymerization object slurries.By obtained preliminary polymerization object slurries be transferred to equipped with
In the autoclave of blender, and after fully refined liquid butane is added in, it is protected at a temperature of not higher than 10 DEG C
It deposits.
(2-3b) main polymerization
Continuous polymerization is carried out using the device comprising 5 polymer reactors of provided in series.The first, second of upstream and
The bulk polymerization of propylene is carried out in three reactors.It, will when the slurries with predetermined powder concn are formed in the 3rd reactor
The slurries discharged from the 3rd reactor are transferred in the 4th gas-phase polymerization reactor, and the 4th gas-phase polymerization reactor accommodates
The gas phase of the ratio of predetermined propylene and ethylene is had been adjusted to, and prepares Propylene-ethylene random copolymer (EP-1).This
Outside, the polymer powder discharged when forming the polymer of needs in the 4th reactor from the 4th reactor is transferred to the 5th
In gas-phase polymerization reactor, the 5th gas-phase polymerization reactor receiving has been adjusted to the ratio of predetermined propylene and ethylene
Gas phase, then prepare propylene-ethylene copolymers (EP-2).Therefore, third with structure P- (EP-1)-(EP-2) is obtained
Alkene-ethylene block copolymer.
In first, second, and third reactor, the temperature in each reactor is adjusted respectively to 70 DEG C, 70 DEG C and
67 DEG C, and polymerization pressure is adjusted respectively to 4.55MPa, 3.99MPa and 3.75MPa.By propylene of 25kg/ when small,
Solid is used as during tBunPrDMS and 1.03g/ small when hydrogen, 42.2mmol TEA, 6.13mmol/ when 300NL/ is small are small
Preliminary polymerization object slurries that catalytic component is prepared in (2-3a) are introduced into first reactor, and by 15kg/ when small third
Alkene and hydrogen during 70NL/ small are introduced into second reactor.Wherein by the residence time in first, second, and third reactor
Adjust respectively to 0.3 it is small when, 0.5 it is small when and 0.5 it is small when under conditions of carry out continuous polymerization.Therefore, the speed with 13.1kg/ when small
Rate obtains polymer.The inherent viscosity [η] of this polymerpFor 0.9dl/g.
In the 4th reactor, while polymer is received from the 3rd reactor, including carrying out under conditions of following
Continuous polymerization (polymerize) for EP-1 below：Polymerization temperature is 70 DEG C, polymerization pressure 1.6MPa, and is continually introduced into propylene, second
Alkene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 6.8 volume %, 46.4 bodies
Product % and 46.8 volume %.Therefore, polymer is obtained with rates of 17.1kg/ when small.A part of polymer is reacted from the 4th
It samples in device, then analyzes.It was found that inherent viscosity [η]TFor 1.32dl/g, and the polymer generated in the 4th reactor
Content (EP1 contents) is 23 weight %.Therefore, the polymer (being below EP-1 parts) generated in the 4th reactor has
The inherent viscosity [η] of 2.7dl/gEP-1.Ethylene contents in EP-1 parts are 59 weight %.
In addition, in the 5th reactor, while polymer is received from the 4th reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 70 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 0.4 volume %,
28.2 volume % and 71.4 volume %.Therefore, polymer is obtained with rates of 18.9kg/ when small.The analysis of the polymer of collection
Show inherent viscosity [η]TContent for 1.74dl/g, and the polymer generated in the 5th reactor (contains for EP2 below
Amount) it is 10 weight %.Therefore, the polymer (following for EP-2 parts) generated in the 5th reactor has the spy of 5.6dl/g
Property viscosity [η]EP-2.Ethylene contents in EP2 parts are 33 weight %.The analysis result of obtained polymer is shown in table 1
In.
The preparation of (2-4) BCPP-4
(2-4a) preliminary polymerization
By with BCPP-3 prepare it is identical in a manner of carry out preliminary polymerization.
(2-4b) main polymerization
In the preparation with BCPP-3 in the device of identical five comprising provided in series reactor, pass through continuous polymerization
Prepare the propylene-ethylene block copolymer with structure P- (EP-1)-(EP-2).
In first, second, and third reactor, the temperature in each reactor is adjusted respectively to 70 DEG C, 70 DEG C and
67 DEG C, and polymerization pressure is adjusted respectively to 4.50MPa, 3.97MPa and 3.75MPa.By propylene of 25kg/ when small,
Solid is used as during tBunPrDMS and 1.08g/ small when TEA, 6.22mmol/ of hydrogen, 42.4mmol when 300NL/ is small are small
Preliminary polymerization object slurries that catalytic component is prepared in (2-4a) are introduced into first reactor, and by 15kg/ when small third
Alkene and hydrogen during 70NL/ small are introduced into second reactor.Wherein by the residence time in first, second, and third reactor
Adjust respectively to 0.3 it is small when, 0.5 it is small when and 0.5 it is small when under conditions of carry out continuous polymerization.It is obtained with rates of 14.2kg/ when small
Obtain polymer, and the inherent viscosity [η] of this polymerpFor 0.90dl/g.
In the 4th reactor, while polymer is received from the 3rd reactor, including carrying out under conditions of following
Continuous polymerization (polymerize) for EP-1 below：Polymerization temperature is 70 DEG C, polymerization pressure 1.6MPa, and is continually introduced into propylene, second
Alkene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 6.5 volume %, 39.4 bodies
Product % and 54.1 volume %.Therefore, polymer is obtained with rates of 19.0kg/ when small.A part of polymer is reacted from the 4th
It samples in device, then analyzes.It was found that inherent viscosity [η]TFor 1.32dl/g, and the polymer generated in the 4th reactor
Content (EP1 contents) is 25 weight %.Therefore, the polymer (being below EP-1 parts) generated in the 4th reactor has
The inherent viscosity [η] of 2.6dl/gEP-1.Ethylene contents in EP-1 parts are 52 weight %.
In addition, in the 5th reactor, while polymer is received from the 4th reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 70 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 1.6 volume %,
27.6 volume % and 70.8 volume %.Therefore, polymer is obtained with rates of 21.2kg/ when small.The analysis of the polymer of collection
Show inherent viscosity [η]TContent for 1.54dl/g, and the polymer generated in the 5th reactor (contains for EP2 below
Amount) it is 10 weight %.Therefore, the polymer (following for EP-2 parts) generated in the 5th reactor has the spy of 3.4dl/g
Property viscosity [η]EP-2.Ethylene contents in EP-2 parts are 34 weight %.The analysis result of obtained polymer is shown in table 1
In.
The preparation of (2-5) BCPP-5
(2-5a) preliminary polymerization
Using the autoclave equipped with blender, by TEA, tBunPrDMS of 25mmol/L with tBunPrDMS/TEA=
The amount of 0.1 (mol/mol) and the ingredient of solid catalyst that the amount of the titanium contained in catalytic component is TEA/Ti=3
(II) it is sequentially introduced into this in the hexane for being dehydrated and deaerating completely.It is protected by being continually introduced into propylene, while by temperature
It holds in the range of 5 to 15 DEG C so that the ratio (hereinafter referred to as PP/Cat) of the polymer based on ingredient of solid catalyst becomes
1.0 (g/g) obtain preliminary polymerization object slurries.Obtained preliminary polymerization object slurries are transferred to the autoclave equipped with blender
In, and after fully refined liquid butane is added in, it is preserved at a temperature of not higher than 10 DEG C.
(2-5b) main polymerization
In the device of five comprising provided in series reactor in the preparation of such as BCPP-3, prepared by continuous polymerization
Propylene-ethylene block copolymer with structure P- (EP-1)-(EP-2).
In first, second, and third reactor, the temperature in each reactor is adjusted respectively to 70 DEG C, 70 DEG C and
65 DEG C, and polymerization pressure is adjusted respectively to 4.51MPa, 3.97MPa and 3.56MPa.By propylene of 30kg/ when small,
Conduct during tBunPrDMS and 0.843g/ small when TEA, 10.3mmol/ of hydrogen, 68.2mmol when 320NL/ is small are small is consolidated
Preliminary polymerization object slurries that body catalyst component is prepared in (2-5a) are introduced into first reactor, and by 15kg/ when small
Propylene and hydrogen during 120NL/ small are introduced into second reactor.Wherein by the stop in first, second, and third reactor
Time adjust respectively to 0.2 it is small when, 0.4 it is small when and 0.5 it is small when under conditions of carry out continuous polymerization.With speed of 14.2kg/ when small
Rate obtains polymer, and the inherent viscosity [η] of this polymerpFor 0.91dl/g.
In the 4th reactor, while polymer is received from the 3rd reactor, including carrying out under conditions of following
Continuous polymerization (polymerize) for EP-1 below：Polymerization temperature is 70 DEG C, polymerization pressure 1.6MPa, and is continually introduced into propylene, second
Alkene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 4.5 volume %, 41.7 bodies
Product % and 53.8 volume %.Therefore, polymer is obtained with rates of 21.8kg/ when small.A part of polymer is reacted from the 4th
It samples in device, then analyzes.It was found that inherent viscosity [η]TFor 1.48dl/g, and the polymer generated in the 4th reactor
Content (EP1 contents) is 34.7 weight %.Therefore, the polymer (being below EP-1 parts) generated in the 4th reactor has
The inherent viscosity [η] of 2.6dl/gEP-1.Ethylene contents in EP-1 parts are 56 weight %.
In addition, in the 5th reactor, while polymer is received from the 4th reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 70 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 0.25 volume %,
22.6 volume % and 77.15 volume %.Finally, polymer is obtained with rates of 23.1kg/ when small.The analysis of the polymer of collection
Show inherent viscosity [η]TContent for 1.83dl/g, and the polymer generated in the 5th reactor (contains for EP2 below
Amount) it is 6 weight %.Therefore, the polymer (following for EP-2 parts) generated in the 5th reactor has the characteristic of 7.9dl/g
Viscosity [η]EP-2.Ethylene contents in EP-2 parts are 41 weight %.The analysis result of obtained polymer is shown in table 1
In.
The preparation of (2-6) BCPP-6
(2-6a) preliminary polymerization
By with BCPP-5 prepare it is identical in a manner of polymerize.
(2-6b) main polymerization
In the preparation with BCPP-3 in the device of identical five comprising provided in series reactor, pass through continuous polymerization
Prepare the propylene-ethylene block copolymer with structure P- (EP-1)-(EP-2).
In first, second, and third reactor, the temperature in each reactor is adjusted respectively to 75 DEG C, 70 DEG C and
65 DEG C, and polymerization pressure is adjusted respectively to 4.41MPa, 3.88MPa and 3.67MPa.By propylene of 30kg/ when small,
Conduct during tBunPrDMS and 0.870g/ small when TEA, 10.2mmol/ of hydrogen, 66.1mmol when 320NL/ is small are small is consolidated
Preliminary polymerization object slurries that body catalyst component is prepared in (2-5a) are introduced into first reactor, and by 15kg/ when small
Propylene and hydrogen during 120NL/ small are introduced into second reactor.Wherein by the stop in first, second, and third reactor
Time adjust respectively to 0.2 it is small when, 0.4 it is small when and 0.5 it is small when under conditions of carry out continuous polymerization.With speed of 16.7kg/ when small
Rate obtains polymer, and the inherent viscosity [η] of this polymerpFor 0.91dl/g.
In the 4th reactor, while polymer is received from the 3rd reactor, including carrying out under conditions of following
Continuous polymerization (polymerize) for EP-1 below：Polymerization temperature is 70 DEG C, polymerization pressure 1.6MPa, and is continually introduced into propylene, second
Alkene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 4.4 volume %, 42.5 bodies
Product % and 53.1 volume %.Therefore, polymer is obtained with rates of 25.0kg/ when small.A part of polymer is reacted from the 4th
It samples in device, then analyzes.It was found that inherent viscosity [η]TFor 1.51dl/g, and the polymer generated in the 4th reactor
Content (EP1 contents) is 33 weight %.Therefore, the polymer (being below EP-1 parts) generated in the 4th reactor has
The inherent viscosity [η] of 2.7dl/gEP-1.Ethylene contents in EP-1 parts are 57 weight %.
In addition, in the 5th reactor, while polymer is received from the 4th reactor, including under conditions of following
Carry out continuous polymerization (polymerizeing below for EP-2)：Polymerization temperature is 70 DEG C, polymerization pressure 1.2MPa, and is continually introduced into third
Alkene, ethylene and hydrogen allow to by the gas phase hydrogen, the concentration of ethylene and propylene be kept at 2.4 volume %,
29.0 volume % and 68.6 volume %.Therefore, polymer is obtained with rates of 26.2kg/ when small.The analysis of the polymer of collection
Show inherent viscosity [η]TContent for 1.56dl/g, and the polymer generated in the 5th reactor (contains for EP2 below
Amount) it is 5 weight %.Therefore, the polymer (following for EP-2 parts) generated in the 5th reactor has the characteristic of 2.6dl/g
Viscosity [η]EP-2.Ethylene contents in EP-2 parts are 50 weight %.The analysis result of obtained polymer is shown in table 1
In.
Embodiment 1
To 100 parts by weight propylene-ethylene block copolymer (BCPP-1) powder add in 0.05 parts by weight of calcium stearate (by
NOF companies produce), 0.05 parts by weight 3, the double [2- { 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy } -1,1- of 9-
Dimethyl ethyl] (Sumilizer GA80, are given birth to -2,4,8,10- tetra- oxaspiro [5.5] hendecanes by Sumitomo Chemical Co
Production) and double (2,4- di-t-butyl phenyl) pentaerythritol diphosphites (the Ultranox U626, by GE of 0.05 parts by weight
Specialty Chemicals are produced) it is used as stabilizer, and dry-mixing.By 40-mm φ single screw extrusion machines (at 220 DEG C
Under) be granulated obtained blend to generate the pellet of BCPP-1.
Following substance is tentatively equably mixed in roller：The BCPP-1 pellets of 68 weight %；The propylene of 5 weight % is equal
The powder of polymers (HPP-1)；Ethylene/Butylene -1 random copolymers of the 11 weight % as ethylene-α-olefincopolymerrubber (B)
Rubber EBR-1 (the TAFMER A6050 produced by Mitsui Chemicals Inc., density=0.864g/cm3, MFR (190
DEG C)=6.5g/10 minutes)；And 16 weight % as the average grain diameter of inorganic filler (C) be 2.7 μm of talcum (commodity
Name：MWHST is produced by Hayashi Kasei Co., Ltd.s).Then, using twin-screw kneading extruder (by The Japan
The TEX44SS-30BW-2V of Steel Works, Ltd. production) extruded velocity when 50kg/ is small, the spiral shell of 230 DEG C and 350rpm
Mixture is mediated and squeezed out under bar speed.
In table 2, it is shown that the recombination rate of component, the MFR of obtained polypropylene resin composite and by said composition
The physical property of the moulding article of preparation.
Embodiment 2
In addition to propylene-ethylene block copolymer (BCPP-1) is changed into propylene-ethylene block copolymer (BCPP-3), lead to
It crosses and is operated in the same manner as example 1, prepare BCPP-3 pellets.Following substance is compound：The BCPP- of 70 weight %
3 pellets；The powder of the Noblen (HPP-2) of 5 weight %；9 weight % are as ethylene-α-olefincopolymerrubber (B)
- 1 random copolymer rubber EBR-2 of Ethylene/Butylene (is produced by dongle Chemical Co., Ltd. (Dow Chemical Co., Ltd.s)
ENGAGE 7467, density=0.862g/cm3, MFR (190 DEG C)=1.2g/10 minutes)；And 16 weight % as inorganic
The average grain diameter of filler (C) is 2.7 μm of talcum (trade name：MWHST is produced by Hayashi Kasei Co., Ltd.s).
Then, mixture is subjected to processing same as Example 1 to generate polypropylene resin composite.
In table 2, it is shown that the recombination rate of component, the MFR of obtained polypropylene resin composite and by said composition
The physical property of the moulding article of preparation.
Embodiment 3
In addition to propylene-ethylene block copolymer (BCPP-1) is changed into propylene-ethylene block copolymer (BCPP-5), lead to
It crosses and is operated in the same manner as example 1, prepare BCPP-5 pellets.Following substance is compound：The BCPP- of 29 weight %
5 pellets；The powder of the Noblen (HPP-1) of 15 weight %；The powder of the Noblen (HPP-3) of 26 weight %；10
Weight % is (chemical by dongle as -1 random copolymer rubber EOR-2 of ethylene-octene of ethylene-α-olefincopolymerrubber (B)
The ENGAGE 8150 of Co., Ltd's production, density=0.868g/cm3, MFR (190 DEG C)=0.5g/10 minutes)；And 20 weight
Measure the talcum (trade name that % is 2.7 μm as the average grain diameter of inorganic filler (C)：MWHST, by Hayashi Kasei
Co., Ltd. produces).Then, mixture is subjected to processing same as Example 1 to generate polypropylene resin composite.
In table 2, it is shown that the recombination rate of component, the MFR of obtained polypropylene resin composite and by said composition
The physical property of the moulding article of preparation.
Comparative example 1
In addition to propylene-ethylene block copolymer (BCPP-1) is changed into propylene-ethylene block copolymer (BCPP-2), with
Mode same as Example 1 prepares polypropylene resin composite.In table 2, it is shown that the recombination rate of component, obtain it is poly-
The physical property of the MFR of propylene resin composition and the moulding article prepared by said composition.
Comparative example 2
In addition to propylene-ethylene block copolymer (BCPP-3) is changed into propylene-ethylene block copolymer (BCPP-4), with
Mode same as Example 2 prepares polypropylene resin composite.In table 2, it is shown that the recombination rate of component, obtain it is poly-
The physical property of the MFR of propylene resin composition and the moulding article prepared by said composition.
Comparative example 3
In addition to propylene-ethylene block copolymer (BCPP-1) is changed into propylene-ethylene block copolymer (BCPP-6), lead to
It crosses and is operated in the same manner as example 1, prepare the pellet of BCPP-6.Following substance is compound：31 weight %'s
BCPP-6 pellets；The powder of the Noblen (HPP-1) of 15 weight %；The powder of the Noblen (HPP-3) of 24 weight %
End；10 weight % as ethylene-α-olefincopolymerrubber (B) -1 random copolymer rubber EOR-2 of ethylene-octene (by road
The ENGAGE 8150 of your Chemical Co., Ltd.'s production, density=0.868g/cm3, MFR (190 DEG C)=0.5g/10 minutes)；With
And 20 weight % as the average grain diameter of inorganic filler (C) be 2.7 μm of talcum (trade name：MWHST, by Hayashi
Kasei Co., Ltd.s produce).Then, mixture is subjected to processing same as Example 1 to generate acrylic resin combination
Object.In table 2, it is shown that the recombination rate of component, obtained polypropylene resin composite MFR and by said composition prepare
The physical property of moulding article.
Table 1
Table 2
* 1) measurement is in 18.6kg/cm2Fibre stress under carry out.
* 2) measurement is carried out under the tensile speed of 10mm/ minutes.
* 3) degree of the perceptibility of current mark is observed by visual observation.
○：Current mark is not perceptible.
△：Current mark is slightly perceptible.
×：Current mark is perceptible.
Industrial feasibility
The polypropylene resin composite of the present invention can be used for the field for wherein needing high quality, such as automotive interior or outside
Component.
Claims (7)
1. a kind of polypropylene resin composite, it includes：
The acrylic resin (A) of 50 to 94 weight %,
The ethylene-α-olefincopolymerrubber (B) of 1 to 25 weight %, the copolymer rubber (B) include：
Ethylene-α-olefincopolymerrubber (B-1), the copolymer rubber (B-1) include C4 to C12 alpha-olefins and ethylene, and
And with 0.85 to 0.91g/cm3Density and the melt flow rate (MFR) of 0.9 to 20g/10 minute, the melt flow rate (MFR)
It is to be measured at 190 DEG C of temperature and the load of 2.16kgf；And/or
Ethylene-α-olefincopolymerrubber (B-2), the copolymer rubber (B-2) include C5 to C12 alpha-olefins and ethylene, and
And with 0.85 to 0.91g/cm3Density and not less than 0.01 but less than the melt flow rate (MFR) of 0.9g/10 minutes, it is described
Melt flow rate (MFR) is the sum measured at 190 DEG C of temperature and the load of 2.16kgf
The inorganic filler (C) of 5 to 25 weight %, wherein the amount of (A), (B) and (C) are each based on the polypropylene-base resin
The total weight of composition,
Wherein acrylic resin (A) is the crystalline propylene-ethylene block copolymer for meeting following requirements (1), (2), (3) and (4)
(A-1) or the polymeric blends (A-3) comprising the block copolymer (A-1) and crystalline propylene homopolymer (A-2),
It is required that (1)：The block copolymer (A-1) is crystalline propylene-ethylene block copolymer, and the block copolymer includes base
In the block copolymer (A-1) total weight be 55 to 85 weight % crystalline polypropylene portion and based on the block copolymerization
The total weight of object (A-1) is the Propylene-ethylene random copolymer part of 15 to 45 weight %,
It is required that (2)：The crystalline polypropylene portion in the block copolymer (A-1) be Noblen or propylene with
Total amount based on all monomers in the copolymer is equal to or less than the ethylene of 1 mole of % or containing 4 or more carbon atom
Alpha-olefin copolymer,
It is required that (3)：The propylene that contains in the Propylene-ethylene random copolymer part of the block copolymer (A-1) with
The weight ratio of ethylene is 75/25 to 40/60,
It is required that (4)：It is random that the Propylene-ethylene random copolymer part of the block copolymer (A-1) includes propylene-ethylene
Copolymer component (EP-A) and Propylene-ethylene random copolymer component (EP-B), the copolymer component (EP-A), which has, to be more than
6dl/g but the inherent viscosity [η] no more than 8dl/gEP-AWith the ethylene contents [(C2 ') of 25 weight % to 45 weight %EP-A], and
And the copolymer component (EP-B) has the inherent viscosity [η] of 0.5dl/g to 4dl/gEP-BWith 30 weight % to 60 weight %
Ethylene contents [(C2 ')EP-B]。
2. polypropylene resin composite according to claim 1, wherein the ethylene contents [(C2 ')EP-B] not less than described
Ethylene contents [(C2 ')EP-A]。
3. polypropylene resin composite according to claim 1, wherein the inherent viscosity [η]EP-BFor 1.5dl/g extremely
3.5dl/g。
4. polypropylene resin composite according to claim 1, wherein the crystallization of the block copolymer (A-1) gathers
Propylene fraction has the inherent viscosity [η] of 0.6dl/g to 1.5dl/gPWith the molecule by gpc measurement not less than 3 but less than 7
Amount distribution.
5. polypropylene resin composite according to claim 1, wherein the crystallization of the block copolymer (A-1) gathers
Propylene fraction has the isotactic pentad fraction equal to or more than 0.97.
6. polypropylene resin composite according to any one of claim 1 to 5, wherein the inorganic filler (C) is
Talcum.
7. a kind of injection-molded item, it includes polypropylene resin composites according to any one of claim 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007048926 | 2007-02-28 | ||
| JP2007-048926 | 2007-02-28 |
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|---|---|---|---|
| CNA2008100813957A Division CN101255255A (en) | 2007-02-28 | 2008-02-27 | Polypropylene resin composition and molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789320A (en) * | 2004-12-17 | 2006-06-21 | 住友化学株式会社 | Polypropylene resin composition |
| CN1803909A (en) * | 2005-01-14 | 2006-07-19 | 住友化学株式会社 | Polypropylene resin composition |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789320A (en) * | 2004-12-17 | 2006-06-21 | 住友化学株式会社 | Polypropylene resin composition |
| CN1803909A (en) * | 2005-01-14 | 2006-07-19 | 住友化学株式会社 | Polypropylene resin composition |
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