CN106279484A - A kind of high fondant-strength impact polypropylene foaming plate and preparation method thereof - Google Patents
A kind of high fondant-strength impact polypropylene foaming plate and preparation method thereof Download PDFInfo
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- CN106279484A CN106279484A CN201510359349.9A CN201510359349A CN106279484A CN 106279484 A CN106279484 A CN 106279484A CN 201510359349 A CN201510359349 A CN 201510359349A CN 106279484 A CN106279484 A CN 106279484A
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- China
- Prior art keywords
- polypropylene
- random
- propylene
- ethylene
- foaming
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- -1 polypropylene Polymers 0.000 title claims abstract description 260
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 243
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 241
- 238000005187 foaming Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 15
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008096 xylene Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 64
- 238000007334 copolymerization reaction Methods 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 36
- 239000004088 foaming agent Substances 0.000 claims description 32
- 229920005604 random copolymer Polymers 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 15
- 210000004027 cell Anatomy 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 210000000497 foam cell Anatomy 0.000 claims description 4
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 4
- 239000002667 nucleating agent Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005604 azodicarboxylate group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000005034 decoration Methods 0.000 abstract description 3
- 238000004100 electronic packaging Methods 0.000 abstract description 3
- 206010000269 abscess Diseases 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 71
- 238000006116 polymerization reaction Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 19
- 239000006260 foam Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000012565 NMR experiment Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011903 deuterated solvents Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical compound COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 description 1
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 1
- QQQXNLBGXGXTHL-UHFFFAOYSA-N 2,4-diethoxybutylcyclohexane Chemical compound C1(CCCCC1)CC(CCOCC)OCC QQQXNLBGXGXTHL-UHFFFAOYSA-N 0.000 description 1
- JUJMPCLNRKYKRA-UHFFFAOYSA-N 2,4-dimethoxybutylcyclohexane Chemical compound COCCC(OC)CC1CCCCC1 JUJMPCLNRKYKRA-UHFFFAOYSA-N 0.000 description 1
- HBHVBOUUMCIGMG-UHFFFAOYSA-N 2,6-Dibutyl-p-cresol Natural products CCCCC1=CC(O)=CC(CCCC)=C1O HBHVBOUUMCIGMG-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- DBCCDXWGWMPKBB-UHFFFAOYSA-N 2,6-dimethyl-3,3-bis(propoxymethyl)heptane Chemical compound C(C)(C)C(COCCC)(COCCC)CCC(C)C DBCCDXWGWMPKBB-UHFFFAOYSA-N 0.000 description 1
- HEUKEUVOQISEPV-UHFFFAOYSA-N 3,3-bis(ethoxymethyl)-2,6-dimethylheptane Chemical compound CCOCC(CCC(C)C)(COCC)C(C)C HEUKEUVOQISEPV-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HLXKHZZBHUAIQI-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]cyclohexane Chemical compound COCC(COC)(C(C)C)CC1CCCCC1 HLXKHZZBHUAIQI-UHFFFAOYSA-N 0.000 description 1
- GVVHLVYPTGVRPW-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)propyl]benzene Chemical compound C(C1=CC=CC=C1)C(COC)COC GVVHLVYPTGVRPW-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JOUWRCGZMOSOCD-UHFFFAOYSA-N cyclopentyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C1CCCC1 JOUWRCGZMOSOCD-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- XFAOZKNGVLIXLC-UHFFFAOYSA-N dimethoxy-(2-methylpropyl)-propan-2-ylsilane Chemical compound CO[Si](C(C)C)(OC)CC(C)C XFAOZKNGVLIXLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides polypropylene foamed plate and preparation method thereof, described foaming plate is resin based on high fondant-strength impact polypropylene, foamed, roll-in and prepare；Described high fondant-strength impact polypropylene includes atactic copolymerized polypropene continuous phase and propylene-ethylene copolymers rubber domain, and its room temperature xylene soluble content is more than or equal to 10 weight %, and less than or equal to 35 weight %；And the M of its room temperature trichloro-benzenes soluble substancewM with room temperature trichloro-benzenes insoluble matterwRatio more than 0.4, less than or equal to 1.The polypropylene foamed plate that the present invention provides have surfacing, abscess and size distribution uniformly, high/low temperature erosion-resisting characteristics is good, melt strength advantages of higher, can be widely applied to automobile component, food and the field such as electronic packaging and building decoration；Its preparation method is simple, it is easy to operation, low cost.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-melt-strength impact-resistant polypropylene foamed sheet and a preparation method thereof.
Background
Foamed sheets are widely used for containers, building materials, automobile parts, impact energy absorbing materials, and the like. Polypropylene (PP) -based foamed sheets have excellent rigidity and thermal stability compared to polystyrene-based foamed sheets, and the demand for it has been increasing in recent years. The method for forming polypropylene extrusion foaming sheet is also widely regarded. The polypropylene foaming sheet and the polypropylene board are mainly obtained by an extrusion foaming method, and specifically, the mixing and melting of foaming components are directly completed in an extruder, and the foaming process is completed through the decomposition and overflow of the foaming agent in the extruder. The direct extrusion foaming method is a method in which the mixing, melting and foaming processes of foaming components are directly completed in an extruder, and can be called a one-step extrusion foaming molding method. Direct extrusion foam molding methods can be further classified into physical foam and chemical foam methods according to the foaming agent used, and the common control factor in either method is to establish a sufficiently high head pressure to suppress premature foaming of the foam system near the extrusion die, and to release the pressure for foam molding once the foam system enters the die. The specific extrusion process, energy consumption and equipment requirements vary according to the published patent.
Compared with the polystyrene series resin foaming plate forming products, the polypropylene foaming forming body obtained by molding the polypropylene foaming plate has excellent performances such as corrosion resistance, toughness, heat resistance, compression rebound resilience and the like. However, polypropylene has poor low temperature impact properties, especially propylene homopolymer. The impact polypropylene can be prepared through process adjustment. The impact-resistant polypropylene has excellent high and low temperature impact strength, higher rigidity such as tensile strength, flexural modulus and the like and higher heat-resistant temperature, and is widely applied in many fields. The foamed sheet prepared from the impact-resistant polypropylene also has good low-temperature resistance, and has wide prospects in the fields of cold chain transportation and packaging, sports equipment, building heat preservation, aerospace and the like. However, the conventional general-purpose impact polypropylene has low melt strength, and when the conventional general-purpose impact polypropylene is used for preparing foamed sheets, the problems of merging and breaking of cells, poor molding forming capability and the like exist.
The homo-polypropylene or random co-polypropylene prepared in the prior art often cannot have high melt strength and impact resistance, and has poor performances such as rigidity and toughness, so that the performance exertion and application of the polypropylene foamed sheet prepared on the basis of the polypropylene material are still limited. Therefore, the polypropylene foam board with high melt strength and impact resistance, which is prepared by using the high-melt strength and impact resistance polypropylene as a base material and combining an optimized foaming process, and has good high-low-temperature impact resistance and high closed cell ratio is still widely demanded by the current market.
Disclosure of Invention
The invention aims to provide a high-melt-strength impact-resistant polypropylene foam material and a preparation method thereof. The polypropylene foaming plate is prepared by taking an impact-resistant polypropylene material with high melt strength as a base material through a foaming process, and has the characteristics of meeting the requirement of environmental protection, being degradable, uniform in foam pores, smooth in surface, high in physical heat resistance, low in production cost, suitable for continuous mass production, good in high and low temperature impact property and the like.
The invention also provides a preparation method of the polypropylene foamed sheet, which is characterized in that a polypropylene material with high melt strength, impact resistance, rigidity and toughness is used as a base resin, a foaming agent is added, and the polypropylene foamed sheet with compact and uniformly distributed foam holes is prepared by a chemical extrusion foaming method. The method has simple process, and the foamed sheet has high closed cell rate and controllable density.
According to the invention, the polypropylene foaming plate is prepared by foaming and rolling the high-melt-strength impact-resistant polypropylene serving as a base resin; the high melt strength impact polypropylene comprises a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, wherein the random copolymerized polypropylene continuous phase comprises at least a first random copolymerized polypropylene and a second random copolymerized polypropylene, and the first random copolymerized polypropylene and the second random copolymerized polypropylene are independently selected from propylene-ethylene random copolymer or propylene-1-butylene random copolymer or ethylene-propylene-1-butylene terpolymer; the high melt strength impact polypropylene has a room temperature xylene solubles content of greater than or equal to 10 wt% and less than or equal to 35 wt%; and M of room temperature trichlorobenzene soluble matter of the high melt strength impact resistant polypropylenewM of (weight average molecular weight) and trichlorobenzene insolubles at room temperaturewThe ratio of (d) is greater than 0.4, less than or equal to 1, such as greater than 0.4, and less than or equal to 0.8. The above high melt strength impact resistanceThe polypropylene has excellent rigidity and toughness and higher melt strength, and the foamed sheet prepared by using the polypropylene as the base resin has high melt strength, rigidity and toughness. Therefore, the invention provides the high-melt-strength impact-resistant polypropylene foamed sheet.
In the present invention, the high melt strength impact polypropylene refers to polypropylene comprising the above-described features.
In the present invention, high melt strength means a melt strength of more than 0.1N, especially 0.15-0.25N.
The Izod notched impact (23 ℃) of the impact-resistant polypropylene foamed sheet provided by the invention is generally 25-50KJ/m2. The notched Izod impact (23 ℃) of the base resin is generally 70 to 100KJ/m2。
In the present invention, the content of the rubber phase of the base resin, in terms of the xylene solubles content at room temperature, can be determined according to the CRYSTEX method. For ease of characterization, the molecular weight of the rubber phase is based on the molecular weight of the trichlorobenzene solubles.
In the base resin used in the invention, the random copolymerization polypropylene is used as a continuous phase to provide certain rigidity for the polypropylene base resin, and the propylene-ethylene copolymer rubber is used as a disperse phase to improve the toughness of the polypropylene base resin. In order to ensure that the product of the invention has better rigidity-toughness balance, the invention adopts ethylene-propylene copolymer as the rubber component, and the inventor of the invention finds that in the high melt strength impact polypropylene material used in the invention, when the ethylene content in the xylene soluble content at room temperature of the material is more than or equal to 28 wt% and less than 45 wt%, the impact polypropylene material has better rigidity and toughness. In particular, in the present invention, by arranging the random copolymer polypropylene continuous phase to include at least a first random copolymer polypropylene and a second random copolymer polypropylene, and the first random copolymer polypropylene and the second random copolymer polypropylene are each independently selected from a propylene-ethylene random copolymer or a propylene-1-butene random copolymer or an ethylene-propylene-1-butene terpolymer, the continuous phase and the dispersed phase are better compounded with each other, resulting in an impact polypropylene material with high melt strength and high toughness, which is advantageous as a base resin for polypropylene foamed sheets. It is to be understood that the term "ethylene content" as used herein means the weight content of the portion of ethylene monomer in the polymer in which the ethylene monomer is present. In this context, the other means the "butene content" in the polymer, which is synonymous therewith.
In order to obtain higher melt strength, the melt index of the high melt strength impact polypropylene material used in the present invention is preferably controlled in the range of 0.1 to 15g/10min, and more preferably 0.1 to 6.0g/10 min. The melt index was measured at 230 ℃ under a load of 2.16 kg. The base resin with higher melt strength can effectively solve the problems of combination and breakage of foam holes in the rapid pressure relief expansion process in the preparation process of the foamed sheet, and can effectively improve the closed porosity of the sheet.
For high melt strength impact polypropylene, the factors affecting melt strength become more complex due to the material being of multi-phase structure. The present inventors have found that in order to secure high melt strength of a base resin and a foamed sheet product, a molecular weight distribution M of an impact polypropylene material as a base resinw/Mn(weight average molecular weight/number average molecular weight) is preferably less than or equal to 10 and greater than or equal to 4, for example 4, 5, 6, 7, 8, 9 or 10; and/or Mz+1/MwPreferably greater than or equal to 10 and preferably less than 20.
In some preferred embodiments, the high melt strength impact polypropylene material used in the present invention has an ethylene content of from 8 to 20 weight percent; and/or a butene content of 0 to 10% by weight.
The base resins used according to the invention have a molecular weight Polydispersity Index (PI) of from 4 to 10, preferably from 4.5 to 6.
According to the present invention, there is provided a base resin for polypropylene foamed sheets, which is prepared by subjecting a random copolymerization reaction of propylene groups to a first random copolymerization polypropylene to obtain a random copolymerization polypropylene continuous phase comprising the first random copolymerization polypropylene and a second random copolymerization polypropylene, and then subjecting a propylene-ethylene copolymerization reaction to a propylene-ethylene copolymerization reaction in the presence of the random copolymerization polypropylene continuous phase to obtain a polypropylene material comprising a propylene-ethylene copolymer rubber phase. It can be seen that the base resin used in the present invention, i.e., the high melt strength impact polypropylene material, is not simply a mixture of a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, but is a unitary polypropylene material comprising a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase obtained after further propylene-ethylene copolymerization is performed on the basis of the random copolymerized polypropylene continuous phase.
The base resin used in the invention also has better heat resistance and better heat sealing performance, and the melting peak temperature T of the final polypropylene resin is measured by DSCm145 ℃ or higher and 158 ℃ or lower.
Based on the high-melt-strength impact-resistant polypropylene as a base resin, the closed-cell rate of the polypropylene foamed sheet provided by the invention is more than 82%, preferably 82-95%; and/or the notched Izod impact (23 ℃) is 25 to 50KJ/m2。
According to the present invention, there is also provided a method for preparing the polypropylene foamed sheet as described above, comprising the steps of: a. mixing the base resin with a foaming agent and a processing aid to obtain a polypropylene foaming premix; b. adding the polypropylene foaming premix into an extruding machine, stirring, and heating to melt the polypropylene foaming premix; c. the melted polypropylene foaming premix is extruded to a die of an extruding machine, flows to a plate extruding machine and is rolled into plates.
The foaming agent is added into the polypropylene resin matrix to produce the foamed polypropylene. The added foaming agent decomposes at a specific temperature and pressure to release gas, and forms a porous bubble-like structure in an expandable material such as resin.
According to the invention, the foaming agent is selected from chemical organic foaming agents and can be at least one of azo foaming agents, nitroso foaming agents and hydrazide foaming agents. Specifically, the azo-based foaming agent is preferably at least one of Azodicarbonamide (AC), Azobisisobutyronitrile (AIBN), barium azodicarboxylate (BaAC), and azodicarboxylate; the nitroso foaming agent is preferably at least one of dinitrosopentamethylene tetramine (DPT), N '-dinitrosopentamethylene tetramine, N' -dimethyl-N, N-dinitrosoterephthalamide (NTA) and trinitrotrimethylenetriamine; the hydrazide-based foaming agent is preferably at least one selected from 4, 4' -oxybis-benzenesulfonyl hydrazide (OBSH), Tosylsemicarbazide (TSSC), triphosphonyltriazine (CTHT) and 5-phenyltetrazole.
In the present invention, the blowing agent is more preferably azodicarbonamide.
The chemical foaming agent is used for preparing the foaming sheet material, so that the foaming sheet material has the characteristics of smooth surface, compact and uniform foam holes, low foaming multiplying power, controllability and the like, and is widely applied to automobile interior decoration, food, household appliances, electronic packaging and the like.
According to the invention, the foam cell nucleating agent is selected from at least one of talc, aluminium hydroxide, silica, zeolite and borax. The addition of the foam cell nucleating agent can control foaming, so that the foam cell distribution, the pore diameter and the like of the foamed sheet are more uniform, and the closed pore rate is high.
In the present invention, processing aids commonly used in polypropylene foaming, such as antioxidants, secondary antioxidants, lubricants, pigments, etc., may also be added to the formulation according to specific processing requirements. The dosage is conventional dosage or adjusted according to the requirement of actual situation.
According to a preferred embodiment of the present invention, the blowing agent is added in an amount of 1 to 15 parts by weight, preferably 1 to 10 parts by weight, and more preferably 5 to 7 parts by weight, based on 100 parts by weight of the base resin; and/or the cell control agent is added in an amount of 5 to 20 parts by weight, preferably 5 to 15 parts by weight.
In summary, the present invention provides a method for preparing a high melt strength polypropylene foam, comprising: the components are melted, blended, foamed and rolled according to the using amount to obtain the product. In a specific embodiment, the following preparation process may be included:
mixing high melt strength polypropylene (base resin), a foaming agent, a cell control agent and various processing aids (if needed) according to the weight ratio of the formula by adopting a high-speed stirrer to obtain a premix of the polypropylene foaming plate; adding the premix into a hopper of an extruder, and heating the temperature of the extruder to 150-280 ℃, preferably 160-180 ℃ to smelt the polypropylene foaming material; the rotating speed of the screw can be adjusted to 15-180 rpm; then, extruding the plasticized polypropylene resin to a neck mold (such as a T-shaped head) at the temperature of 150-280 ℃, preferably 160-180 ℃, flowing to a gap between two rollers of a plate extruding machine, and rolling into a sheet material; naturally cooling to room temperature, and cutting into plates with certain specifications as required, namely the finished polypropylene foamed plate.
The extruder adopted in the preparation method can be one of a single-screw extruder, two single-screw extruders in series connection, a co-rotating double-screw extruder in series connection with the single-screw extruder, a counter-rotating double-screw extruder, a conical double-screw extruder and a three-screw extruder. In order to better control the operation of the extruder, the extruders currently on the market divide the interior of the extruder into sections and control the temperature of each section.
The neck ring mold can be a flat neck ring mold, a T-shaped neck ring mold, a round hole neck ring mold or a circular ring neck ring mold and the like according to actual needs. For example, the molten polypropylene resin composition is discharged from a flat die, expanded, and subjected to a three-roll calender with the roll gap adjusted to control the die size, thereby obtaining a polypropylene foamed sheet or plate having a desired thickness. Or, the melted polypropylene composition is discharged from a circular ring-shaped die, expanded, blown, cooled inside and outside, cut along the axial direction, and rolled to obtain a polypropylene foamed sheet with a desired thickness.
In the process of extruding and foaming the polypropylene material, the melting and blending temperature of the material is usually selected within the range of ensuring that the base resin is completely melted and can not be decomposed, and is usually 160-280 ℃. However, this temperature can be suitably adjusted depending on the conditions, for example, the decomposition temperature of the industrial AC foaming agent is 150-.
Therefore, according to a preferred embodiment of the present invention, the temperature in step b is raised to 150-280 ℃, preferably 160-180 ℃; and/or in step c the temperature of the extruder die is 140-.
In another embodiment, the polypropylene foamed sheet provided by the invention can also be prepared by using the base resin and performing a foaming reaction under the action of an inorganic foaming agent. The inorganic blowing agent may be, for example, at least one of air, nitrogen, carbon dioxide, oxygen, and water.
The preparation method of the polypropylene foamed sheet further comprises the step of preparing a base resin, namely the high-melt-strength impact polypropylene, and comprises the following steps:
the first step is as follows: random copolymerization of propylene groups comprising:
the first stage is as follows: carrying out random copolymerization of propylene and ethylene and/or 1-butene in the presence or absence of hydrogen under the action of a Ziegler-Natta catalyst containing a first external electron donor to obtain a reaction stream containing first random copolymerized polypropylene;
and a second stage: adding a second external electron donor to perform a complex reaction with a catalyst in the reactant flow, and then performing a random copolymerization reaction of propylene and ethylene and/or 1-butene in the presence of the first random copolymerization polypropylene and hydrogen to generate second random copolymerization polypropylene, so as to obtain a random copolymerization polypropylene continuous phase containing the first random copolymerization polypropylene and the second random copolymerization polypropylene;
wherein,
the first random copolymerized polypropylene and the random copolymerized polypropylene continuous phase containing the first random copolymerized polypropylene and the second random copolymerized polypropylene respectively have melt indexes of 0.001-0.4g/10min and 0.1-15g/10min at 230 ℃ and under the load of 2.16 kg; and the weight ratio of the first random copolymerized polypropylene to the second random copolymerized polypropylene is 40: 60-60: 40;
the second step is that: propylene-ethylene copolymerization, which is carried out in the presence of the random copolymerization polypropylene continuous phase and hydrogen to produce a propylene-ethylene copolymer rubber dispersed phase, to obtain the base resin comprising the random copolymerization polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase. It is to be understood that the reaction stream comprises unreacted catalyst in the first stage.
In a preferred embodiment of the present invention, the first random copolymer polypropylene has a melt index of 0.001 to 0.4g/10min measured at 230 ℃ under a load of 2.16 kg. Preferably, the first random copolymer polypropylene has a melt index less than that of the second random copolymer polypropylene. Also preferably, the random copolymer polypropylene comprising the first random copolymer polypropylene has a melt index of 0.1 to 15g/10min, preferably 0.1 to 6g/10min, measured at 230 ℃ under a load of 2.16 kg.
According to a preferred embodiment of the present invention, the ratio of the melt index of the random copolymerized polypropylene continuous phase to the melt index of the polypropylene base resin comprising the random copolymerized polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase obtained in the second step is 0.6 or more and less than 1.
Preferably, the weight ratio of the propylene-ethylene copolymer rubber dispersed phase to the random copolymerized polypropylene continuous phase is 11-80: 100.
In the base resin production step of the present invention, by setting the random copolymerized polypropylene continuous phase of the base resin to include a combination of at least two kinds of random copolymerized polypropylenes having different melt indexes and having a specific ratio relationship, particularly under the condition that the first random copolymerized polypropylene and the random copolymerized polypropylene including the first random copolymerized polypropylene and the second random copolymerized polypropylene respectively have specific different molecular weights and molecular weight distributions, the polypropylene material used to constitute the present invention has a specific continuous phase, and in the further combination of the continuous phase and a specific dispersed phase, i.e., rubber phase, an impact polypropylene material having both high melt strength and good rigidity and toughness is produced, and thus a foamed polypropylene sheet having good properties can be produced using this as the base resin.
According to a preferred embodiment of the present invention, the random copolymerized polypropylene continuous phase constituting the base resin of the present invention has the following features: a melt index, measured at 230 ℃ under a load of 2.16kg, of 0.1 to 10g/10min, preferably 0.1 to 6g/10 min; molecular weight distribution Mw/Mn6-20, preferably Mw/Mn10-16; the fraction having a molecular weight of more than 500 ten thousand is present in an amount of more than or equal to 1.5% by weight and less than or equal to 5% by weight; the content of fractions having a molecular weight of less than 5 ten thousand is greater than or equal to 15.0% by weight and less than or equal to 40% by weight; mz+1/MnGreater than or equal to 70 and preferably less than 150. Wherein, the molecular weight of more than 500 ten thousand and less than 5 ten thousand refers to the part with the molecular weight of more than 500 ten thousand and the part with the molecular weight of less than 5 ten thousand in the molecular weight distribution curve, which is known and easily understood by those skilled in the art, and is not described herein again.
According to the present invention, it is preferred that the ethylene content in the random copolymerized polypropylene continuous phase is from 0 to 6% by weight; and/or a butene content of 0 to 10% by weight.
In the first stage, the amount of hydrogen used may be, for example, from 0 to 200 ppm. In the second stage, the amount of hydrogen used was 2000-. The process provided by the present invention is preferably carried out in two or more reactors operated in series.
The process according to the invention is a Ziegler-Natta catalyst direct catalysed polymerisation process. The method comprises the steps of respectively using two or more different types of external electron donors in a plurality of reactors connected in series, selecting a proper amount of the external electron donors, combining different amounts of chain transfer agent hydrogen, reaction monomer compositions and the like in the reaction to prepare a random copolymerization polypropylene continuous phase with a specific melt index and a large amount of ultrahigh molecular weight components and extremely wide molecular weight distribution, further carrying out copolymerization of propylene and ethylene on the basis to obtain a rubber phase dispersed in the continuous phase, and controlling the composition, structure, content and the like of the rubber phase by controlling the reaction conditions of the copolymerization reaction to obtain the impact polypropylene with high melt strength effect.
In the process provided by the present invention, the catalyst used is a Ziegler-Natta catalyst, preferably a catalyst with high stereoselectivity. The Ziegler-Natta catalyst having high stereoselectivity as used herein means a catalyst which can be used for the preparation of a propylene homopolymer having an isotactic index of more than 95%. Such catalysts generally comprise (1) a titanium-containing solid catalyst active component, the main components of which are magnesium, titanium, halogen and an internal electron donor; (2) an organoaluminum compound co-catalyst component; (3) an external electron donor component.
The solid catalyst active component (which may also be referred to as a procatalyst) of the Ziegler-Natta catalyst used in the process of the present invention may be well known in the art. Specific examples of such active solid catalyst component (1) containing that can be used are, for example, described in patent documents CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN 02100900.7. These patent documents are incorporated by reference herein in their entirety.
The organoaluminum compound in the Ziegler-Natta catalyst used in the process of the present invention is preferably an alkylaluminum compound, more preferably a trialkylaluminum, for example, at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, trihexylaluminum and the like.
The molar ratio of the titanium-containing active solid catalyst component and the organoaluminum compound in the Ziegler-Natta catalyst employed in the process of the present invention is from 10: 1 to 500: 1, preferably from 25: 1 to 100: 1, based on aluminum/titanium.
According to the invention, said first external electron donor is preferably selected from those of formula R1R2Si(OR3)2At least one of the compounds of (a); wherein R is2And R1Each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl of (A), R3Is C1-C3A straight chain aliphatic group. Specific examples include, but are not limited to, dicyclopentyldimethoxysilane, isopropylcyclopentyldimethoxysilane, isopropylisobutyldimethoxysilane, dipyridyldimethoxysilane, diisopropyldimethoxysilane, and the like.
The molar ratio of the organic aluminum compound to the first external electron donor is 1: 1-100: 1, preferably 10: 1-60: 1, calculated as aluminum/silicon.
In the process according to the invention, the catalyst comprising the first external electron donor may be fed directly to the first random copolymerization reactor or may be fed to the first random copolymerization reactor after pre-contacting and/or pre-polymerization as known in the art. The prepolymerization refers to that the catalyst is prepolymerized at a certain ratio at a lower temperature to obtain the ideal particle shape and dynamic behavior control. The prepolymerization can be liquid phase bulk continuous prepolymerization, and can also be batch prepolymerization in the presence of an inert solvent. The temperature of the prepolymerization is usually-10 to 50 ℃ and preferably 5 to 30 ℃. A precontacting step may optionally be provided before the prepolymerization process. The pre-contact step refers to the complex reaction of a cocatalyst, an external electron donor and a main catalyst (solid active center component) in the catalyst system to obtain the catalyst system with polymerization activity. The temperature of the precontacting step is usually controlled to be-10 to 50 ℃ and preferably 5 to 30 ℃.
According to the invention, the second external electron donor is selected from at least one of the compounds shown in the chemical general formulas (I), (II) and (III);
wherein R is1And R2Each independently selected from C1-C20One of linear, branched or cyclic aliphatic radicals, R3、R4、R5、R6、R7And R8Each independently selected from a hydrogen atom, a halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl, and R3、R4、R5、R6、R7And R8Optionally linked to form a ring between any two of them; r9、R10And R11Each independently is C1-C3Straight-chain aliphatic radical, R12Is C1-C6Straight or branched alkyl or C3-C8A cycloalkyl group. Specific examples of the second external electron donor include, but are not limited to, 2-diisobutyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isopropyl-2-3, 7-dimethyloctyl-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-diethoxypropane, 2-diisobutyl-1, 3-dipropoxypropane, 2-isopropyl-2-isopentyl-1, 3-diethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dipropoxypropane, 2-bis (cyclohexylmethyl) -1, 3-diethoxypropane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isopropyltriethoxysilane, tetraethoxysilane and the like.
The molar ratio of the organic aluminum compound to the second external electron donor is 1: 1-60: 1 in terms of aluminum/silicon or aluminum/oxygen, preferably 5: 1-30: 1.
According to some embodiments of the present invention, the molar ratio of the second external electron donor to the first external electron donor is from 1 to 30, and preferably from 5 to 30.
In the process of the present invention, it is preferred that the second external electron donor is brought into sufficient contact with the catalyst component in the first-stage reaction product before the second-stage random copolymerization reaction. In some preferred embodiments, the second external electron donor may be added in the feed line after the first stage reactor and before the second stage reactor, or at the front end of the feed line of the second stage reactor, in order to first perform a precontacting reaction with the catalyst in the reaction product of the first stage before the second stage reaction.
Preferably, in the second step, the amount of ethylene is 20-60% of the total volume of ethylene and propylene. In the second step, the volume ratio of hydrogen to the total amount of ethylene and propylene is 0.02 to 1. Meanwhile, as described above, in the first stage, the amount of hydrogen used may be, for example, 0 to 200 ppm. In the second stage, the amount of hydrogen used may be 2000-20000 ppm. In the present invention, control of the composition, structure or properties of the dispersed and continuous phases is important in order to obtain an impact-resistant polypropylene material having high melt strength, as well as high stiffness and toughness. The present invention can prepare the impact polypropylene material with molecular weight distribution, ethylene content of rubber phase and thus better performance.
In a preferred embodiment of the present invention, the yields of the first random copolymerized polypropylene and the second random copolymerized polypropylene are 40: 60 to 60: 40. The yield ratio of the propylene-ethylene copolymer rubber dispersed phase to the random copolymerization polypropylene continuous phase is 11-80: 100.
The polymerization reaction of the first step may be carried out in liquid-liquid phase, or in gas-gas phase, or using a combination of liquid-gas techniques. In the liquid phase polymerization, the polymerization temperature is 0 to 150 ℃, preferably 60 to 100 ℃; the polymerization pressure should be higher than the saturation vapor pressure of propylene at the corresponding polymerization temperature. The polymerization temperature in the gas phase polymerization is 0 to 150 ℃, preferably 60 to 100 ℃; the polymerization pressure may be normal pressure or higher, and preferably the pressure is from 1.0 to 3.0MPa (gauge pressure, the same applies hereinafter).
The polymerization reaction of the second step is carried out in the gas phase. The gas phase reactor may be a gas phase fluidized bed, a gas phase moving bed, or a gas phase stirred bed reactor. The polymerization temperature is preferably from 0 to 150 ℃ and more preferably from 60 to 100 ℃. The polymerization pressure is any pressure below the partial pressure of the propylene at which it liquefies.
According to a preferred embodiment of the invention, the reaction temperature in the first stage is between 50 and 100 ℃, preferably between 60 and 85 ℃; the reaction temperature of the second stage is 55-100 ℃, preferably 60-85 ℃; the reaction temperature in the second step is 55-100 deg.C, preferably 60-85 deg.C.
In a preferred embodiment of the present invention, the method of the present invention further comprises further modifying the prepared impact polypropylene material with an alpha or beta crystal nucleating agent to increase the rigidity or toughness of the polypropylene resin material. Suitable alpha crystal and beta crystal nucleating agent modification is well known in the art. The nucleating agent is generally present in a ratio by weight of (0.005-3) to 100 based on the total weight of the polypropylene.
According to the process of the present invention, the polymerization reaction may be carried out continuously or batchwise.
In the preparation step of the base resin, the added second external electron donor can react with the catalytic activity center in the copolymerization product material of the propylene and the ethylene and/or the butylene in the first stage to generate a new catalytic activity center, and the propylene and the ethylene and/or the butylene are continuously initiated to polymerize into a random copolymerization polymer with a molecular weight which is greatly different from that of the product obtained in the first stage in the second stage. The second external electron donor has higher hydrogen response than the first external electron donor, and can prepare a high melt index polymer in the presence of a small amount of hydrogen. And then controlling the molecular weight of the obtained polymer by controlling the reaction conditions of the second-step polymerization reaction, wherein the step is very important, and the second external electron donor with good hydrogen regulation sensitivity added in the second step in the first step is utilized to obtain the rubber phase molecular weight matched with the continuous phase under the specific hydrogen concentration, so that the polypropylene material with good performance is obtained, and the polypropylene foamed sheet with excellent performance is further prepared, which is one of the outstanding advantages of the invention. The composition and structure control of the rubber phase component ensures that the rubber phase component has high melt strength, the specific content of the rubber component ensures that the rubber phase component has higher impact resistance, and in addition, the proper molecular weight distribution also ensures that the polymer has good processability. That is, the invention obtains the polypropylene material with excellent performance by setting a plurality of propylene random copolymerization reaction stages to prepare the continuous phase and selecting the appropriate reaction parameters and reaction conditions of the preparation steps of the continuous phase and the rubber dispersed phase to regulate and control the structure and the performance of the generated continuous phase and the rubber dispersed phase and the combination relationship of the continuous phase and the rubber dispersed phase. The polypropylene foamed sheet prepared by using the polypropylene as the base resin and through a foaming process also has corresponding excellent performance.
According to the polypropylene foaming sheet provided by the invention, the polypropylene foaming sheet is prepared by foaming an anti-impact polypropylene material with high melt strength as a base material, has the advantages of smooth and flat surface self-skinning, compact pores, uniform pore size distribution, uniform pore diameter, closed pore hard structure, good high and low temperature impact performance, low cost and the like; the density of the foamed sheet can be controlled at 0.2-0.9g cm-3The thickness can be 0.1-100 mm; the method can be applied to occasions with high requirements on light weight of plastic products, such as automobile parts, food, electronic packaging, architectural decoration and the like.
In addition, the preparation method of the polypropylene foaming sheet material provided by the invention is simple and effective, easy to operate and low in cost, and can realize the stabilization of the polypropylene raw material, so that the foaming window is effectively enlarged, and the process is easy to adjust.
The method preferably adopts azo foaming agent such as AC, and has the advantages of environmental protection, no damage to atmosphere and the like compared with the prior art which uses fluorine-containing foaming agent.
The foamed polypropylene board manufactured according to the invention is of a non-crosslinked structure, can be recycled according to common polypropylene modified materials, does not cause secondary pollution, and meets the requirement of circular economy.
The relevant contents of the base resins of the present invention are described in patent application 201410602224X and patent application 2014106023083, which are incorporated herein by reference in their entirety.
Drawings
FIG. 1 is a cross-sectional electron micrograph of a high melt strength polypropylene foamed sheet of example 1;
FIG. 2 is a cross-sectional electron micrograph of the polypropylene foamed sheet of comparative example 1.
Detailed Description
The invention will now be further described by way of specific examples, which are not to be construed as limiting the invention in any way.
The starting materials in the following examples and comparative examples include:
ordinary random copolymer polypropylene: yanshan division of petrochemical, Inc., China, No. 4908;
high melt strength copolymerized polypropylene: northern european chemical, trade mark WB260 HMS;
azodicarbonamide: industrial grade, Shenzhen Jitian chemical Co., Ltd, foaming temperature 160-;
dinitroso pentamethylene tetramine: Sigma-Aldrich;
4, 4' -oxybis-benzenesulfonylhydrazide: Sigma-Aldrich;
high molecular weight polysiloxane MB 50-002: dow Corning, USA;
all other raw materials are commercially available.
The data relating to the polymers in the examples and comparative examples were obtained according to the following test methods:
① content of xylene soluble at room temperature and ethylene content in xylene soluble at room temperature (i.e. characterizing the content of rubber phase and ethylene content of rubber phase), were measured by CRYSTEX method using CRYST-EX instrument (CRYST-EX EQUIPMENT, IR 4) manufactured by the company Cambridge Polymer Char+Detector) and a series of samples with different room temperature xylene soluble content are selected as standard samples for calibration, and the room temperature xylene soluble content of the standard samples is measured by ASTM D5492. The infrared detector carried by the instrument can detect the weight content of the propylene in the soluble substance and is used for representing the ethylene content (ethylene content in a rubber phase) in the xylene soluble substance at room temperature, namely 100 percent to the weight content of the propylene.
② tensile Strength of the resin was measured according to GB/T1040.2 using Rheotens from Goettfert, GermanyTM97 melt tensile tester.
③ melt mass flow rate (also known as melt index, MFR): the measurement was carried out at 230 ℃ under a load of 2.16kg using a melt index apparatus of type 7026 from CEAST, according to the method described in ASTM D1238.
Bending modulus: measured according to the method described in GB/T9341.
Impact strength of the simply supported beam notch: measured according to the method described in GB/T1043.1.
Sixthly, the content of ethylene: measuring by infrared spectroscopy (IR) method, and calibrating with standard sample measured by nuclear magnetic resonance method. The NMR method was carried out using an AVANCE III 400MHz NMR spectrometer (NMR), 10 mm probe, from Bruker, Switzerland. The solvent is deuterated o-dichlorobenzene, about 250mg of the sample is placed in 2.5ml of deuterated solvent, and the sample is dissolved by heating in an oil bath at 140 ℃ to form a uniform solution. And (3) acquiring 13C-NMR (nuclear magnetic resonance), wherein the probe temperature is 125 ℃, 90-degree pulses are adopted, the sampling time AQ is 5 seconds, the delay time D1 is 10 seconds, and the scanning times are more than 5000 times. Other manipulations, spectral peak identification, etc. were performed as required for commonly used NMR experiments.
Content of butylene: measuring by infrared spectroscopy (IR) method, and calibrating with standard sample measured by nuclear magnetic resonance method. The NMR method was carried out using an AVANCE III 400MHz NMR spectrometer (NMR), 10 mm probe, from Bruker, Switzerland. The solvent is deuterated o-dichlorobenzene, about 250mg of the sample is placed in 2.5ml of deuterated solvent, and the sample is dissolved by heating in an oil bath at 140 ℃ to form a uniform solution. And (3) acquiring 13C-NMR (nuclear magnetic resonance), wherein the probe temperature is 125 ℃, 90-degree pulses are adopted, the sampling time AQ is 5 seconds, the delay time D1 is 10 seconds, and the scanning times are more than 5000 times. Other manipulations, spectral peak identification, etc. were performed as required for commonly used NMR experiments. References include Eric T.Hsieh, and James C.Randall, Ethylene-1-Butene copolymers.1. Commonomer sequence Distribution, Macromolecules, 15, 353-.
⑧ molecular weight Polydispersity Index (PI) resin samples were molded into 2mm sheets at 200 deg.C, subjected to dynamic frequency scanning at 190 deg.C under nitrogen using an ARES (advanced rheometer extended system) rheometer from Rheometric Scientific Inc, parallel plate clamps were selected, appropriate strain amplitude was determined to ensure that the experiment was performed in the linear region, and the change in storage modulus (G '), dissipation modulus (G') and the like with frequency was measured for the samples, the molecular weight polydispersity index PI was 105/GcWherein G isc(unit: Pa) is the modulus value at the intersection of the G' -frequency curve and the G "-frequency curve.
⑨ molecular weight (M)w、Mn) And molecular weight distribution (M)w/Mn，Mz+1/Mw): the molecular weight and molecular weight distribution of the sample were measured by using a PL-GPC 220 gel permeation chromatograph manufactured by Polymer laboratories, UK, or a GPCIR apparatus manufactured by Polymer Char, Spanish (IR5 concentration Detector), the chromatographic columns were 3 PLgel 13um Olexis columns connected in series, the solvent and mobile phase were 1, 2, 4-trichlorobenzene (containing 250ppm of antioxidant 2, 6-dibutyl-p-cresol), the column temperature was 150 ℃, the flow rate was 1.0ml/min, and the general calibration was performed by using an EasiCal PS-1 narrow distribution polystyrene standard manufactured by PL. The preparation process of the room temperature trichlorobenzene soluble substance comprises the following steps: accurately weighing samples anddissolving chlorobenzene solvent at 150 deg.C for 5 hr, standing at 25 deg.C for 15 hr, and filtering with quantitative glass fiber filter paper to obtain solution of trichlorobenzene soluble substance at room temperature for determination. The content of trichlorobenzene solubles at room temperature was determined by correcting the GPC curve area with polypropylene of known concentration, and the molecular weight data of trichlorobenzene insolubles at room temperature was calculated from the GPC data of the original sample and the GPC data of trichlorobenzene solubles at room temperature.
Other production and test equipment includes:
density tester: CPA225D, density annex YDK01, Satorius, germany. Referring to GB/T1033.1-2008, the test method is as follows: the densities of the polypropylene base resin and the polypropylene foamed sheet were obtained by draining using a density attachment of a Satorius balance. The foaming ratio of the obtained polypropylene foaming material is calculated by a formula: where b is the expansion ratio ρ 1/ρ 2, ρ 1 is the density of the polypropylene base resin, and ρ 2 is the apparent density of the foam.
Open-close porosity tester: ULTRAFOAM 1200e, Quantachrome instruments, USA.
Scanning electron microscope: FEI XL-30 environmental Scanning Electron Microscope (SEM).
Preparation of polypropylene base resin HMSPP 801:
the propylene polymerization reaction is carried out on a polypropylene device, and the main equipment of the device comprises a prepolymerization reactor, a first loop reactor, a second loop reactor and a third gas-phase reactor. The polymerization method and the steps are as follows.
(1) Prepolymerization reaction
The main catalyst (DQC-401 catalyst, supplied by Oda, Beijing, China petrochemical catalyst Co., Ltd.), the cocatalyst (triethylaluminum) and the first external electron donor (diisopropyldimethoxysilane, DIPMS) were precontacted at 6 ℃ for 20min, and then continuously added into a continuous stirred tank type prepolymerization reactor to perform a prepolymerization reactor. The Triethylaluminum (TEA) flow into the prepolymerization reactor was 6.33g/hr, the diisopropyldimethoxysilane flow was 0.3g/hr, the procatalyst flow was 0.6g/hr, and the TEA/DIPMS ratio was 50 (mol/mol). The prepolymerization is carried out in a propylene liquid phase bulk environment, the temperature is 15 ℃, the residence time is about 4min, and the prepolymerization multiple of the catalyst under the condition is about 80-120 times.
(2) The first step is as follows: random copolymerization of propylene and ethylene
The first stage is as follows: the prepolymerized catalyst continuously enters a first loop reactor to complete the random copolymerization reaction of propylene and a small amount of ethylene in the first loop reactor, wherein the ethylene addition amount of the first loop is 10000 ppm. The polymerization temperature of the first loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; and adding no hydrogen into the feed of the first loop reactor, wherein the concentration of the hydrogen detected by online chromatography is less than 10ppm, and obtaining the first random copolymer polypropylene A.
And a second stage: 0.63g/hr of 2, 2-diisobutyl-1, 3-Dimethoxypropane (DIBMP) was added to the second loop reactor connected in series with the first loop reactor and mixed with the reactant stream from the first loop reactor, the TEA/DIBMP ratio was 5(mol/mol), where DIBMP was the second external electron donor. The polymerization temperature of the second loop reactor is 70 ℃, and the reaction pressure is 4.0 MPa; and adding a certain amount of hydrogen along with the propylene feeding, detecting the hydrogen concentration in the feeding to be 1000ppm by using an online chromatographic method, and generating a second random copolymer polypropylene B in the second loop reactor to obtain a random copolymer polypropylene continuous phase containing the first random copolymer polypropylene and the second random copolymer polypropylene.
(3) The second step is that: copolymerization of ethylene-propylene
A certain amount of hydrogen and H is added into the third reactor2/(C2+C3)＝0.06(mol/mol)，C2/(C2+C3)＝0.4(mol/mol)(C2And C3Respectively referring to ethylene and propylene), and continuously initiating ethylene/propylene copolymerization reaction in a third reactor, wherein the reaction temperature is 75 ℃, and a propylene-ethylene copolymer rubber disperse phase C is generated.
The final product contains the first random copolymerization polypropylene, the second random copolymerization polypropylene and the propylene-ethylene copolymer rubber disperse phase, and the polymer powder is obtained by removing the activity of the unreacted catalyst by wet nitrogen and heating and drying. The powder obtained by polymerization was added with 0.1 wt% of IRGAFOS 168 additive, 0.1 wt% of IRGANOX1010 additive and 0.05 wt% of calcium stearate, and pelletized with a twin-screw extruder. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Preparation of polypropylene base resin HMSPP 802:
the used catalyst, pre-complexing and polymerization process conditions, the formula of the auxiliary agent and the addition amount are the same as those of the HMSPP 801. The difference from the HMSPP801 is that: the comonomer ethylene addition in the first and second stages of the first step was changed to 30000 ppm. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Preparation of polypropylene base resin HMSPP 803:
the used catalyst, pre-complexing and polymerization process conditions, the formula of the auxiliary agent and the addition amount are the same as those of the HMSPP 801. The difference from the HMSPP801 is that: the comonomer ethylene in the first and second stages of the first step was changed to 1-butene, the amount of addition in the first and second loop was 10 mol% each. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
Preparation of polypropylene base resin HMSPP 804:
the used catalyst, pre-complexing and polymerization process conditions, the formula of the auxiliary agent and the addition amount are the same as those of the HMSPP 801. The difference from the HMSPP801 is that: in the first step, the comonomer ethylene in the first stage and the comonomer ethylene in the second stage are changed into ethylene + 1-butylene, the ethylene addition amount of the first loop and the ethylene addition amount of the second loop are both 6000ppm, and the 1-butylene addition amount is both 5 mol%. The analysis results of the obtained polymer and the physical properties of the polymer are shown in tables 1 and 2.
As can be seen from the results shown in tables 1 and 2, the polypropylene material prepared according to the method of the present invention has high melt strength, tensile strength and flexural modulus, and high notched impact strength. The polypropylene material is an excellent base resin for polypropylene foamed sheets.
Examples 1 to 12
Preparation of Polypropylene base resin
High melt strength impact polypropylene HMSPP801, HMSPP802, HMSPP803 and HMSPP804 as base resins are prepared according to the preparation methods of HMSPP801, HMSPP802, HMSPP803 and HMSPP804, respectively.
Foaming and rolling process
The base resin, the foaming agent, the cell controlling agent and the processing aid were added to a high-speed mixer according to the formulation shown in Table 3 and mixed at high speed for 1 minute to obtain a premix for polypropylene foamed sheets. Wherein the foam control agent is talcum powder; the antioxidant adopts calcium stearate: antioxidant 1010 (basf corporation): antioxidant 168 (basf corporation) is a compounded mixture of 1: 2 (by weight); MB50-002 (high molecular weight polysiloxane) was used as the lubricant.
The temperature of the extruder was adjusted to the foaming temperature shown in Table 3, and then the premix was fed to the middle twin-screw of the extruder, with the torque controlled at about 65% and the screw rotation speed adjusted to 15-170rpm, so that the premix was melted in the extruder.
Extruding the molten polypropylene resin to a T-shaped head die at a foaming temperature, flowing to a gap between two rollers of a plate extruding machine set, rolling to form a plate-shaped polypropylene foaming material, and naturally cooling to room temperature.
The surface and cell morphology of the article of the polypropylene foam obtained were visually observed, and the density thereof was measured using a densitometer. The results are shown in Table 3 and FIG. 1.
Comparative examples 1 to 3
Referring to the procedure for preparing the polypropylene foamed sheets of examples 1 to 12, tests were carried out using ordinary random copolymer polypropylene 4908 instead of HMSPP801, HMSPP802, HMSPP803 and HMSPP804, and the specific formulation and process conditions and properties of the prepared polypropylene foamed sheets were shown in table 3 and fig. 2.
Comparative examples 4 to 6
Referring to the procedure for preparing the polypropylene foamed sheets of examples 1 to 12, the tests were carried out using the high melt strength copolymerized polypropylene WB260HMS instead of HMSPP801, HMSPP802, HMSPP803 and HMSPP804, and the specific formulation and process conditions and properties of the prepared polypropylene foamed sheets are shown in table 3.
It can be seen from examples 1-12 that the HMSPP801, HMSPP802, HMSPP803 and HMSPP804 prepared by the present invention have high melt strength and impact strength, high tensile strength and flexural modulus, and high notched impact strength, and the foamed sheet with dense and uniform cells and smooth surface can be obtained by using the organic foaming agent provided by the present invention as a base resin and foaming the sheet by a method of foaming and rolling the sheet with the organic foaming agent (as shown in fig. 1). By adjusting the type and amount of the foaming agent, the foaming temperature, etc., a density of, for example, 0.2 to 0.9g cm can be obtained-3The foamed sheet of (1).
As can be seen from comparative examples 1-6, the foamed sheet products obtained by using conventional random copolymer polypropylene 4908 or high melt strength copolymer polypropylene WB260HMS as the base resin have non-uniform cells and uneven sheet surface (as shown in FIG. 2) compared with the high melt strength impact polypropylene HMSPP801, HMSPP802, HMSPP803 and HMSPP 804.
It can be seen from comparative examples 1-3 that the foamed sheet prepared from the high melt strength polypropylene HMSPP prepared by the method of the invention has a wider foaming temperature window compared with the foamed sheet prepared from the general random copolymerization polypropylene 4908, and the HMSPP product has a smoother surface and more uniform cells under the same addition amount. It can be seen from comparative examples 4-6 that the density of the foamed sheet product obtained with WB260HMS is higher than that of the high melt strength polypropylene HMSPP, and the surface is not smooth and the cells are not uniform. It is speculated that the product is unstable due primarily to WB260HMS being a high melt strength polypropylene obtained by the addition of peroxide during the synthesis.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Moreover, it should be understood that the various aspects recited, portions of different embodiments (aspects), and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (15)
1. A polypropylene foaming plate is prepared by using high-melt-strength impact-resistant polypropylene as a base resin through foaming and rolling;
the high melt strength impact polypropylene comprises a random copolymerized polypropylene continuous phase and a propylene-ethylene copolymer rubber dispersed phase, wherein the random copolymerized polypropylene continuous phase comprises at least a first random copolymerized polypropylene and a second random copolymerized polypropylene, and the first random copolymerized polypropylene and the second random copolymerized polypropylene are independently selected from propylene-ethylene random copolymer, propylene-1-butylene random copolymer or ethylene-propylene-1-butylene terpolymer;
the high melt strength impact polypropylene has a room temperature xylene solubles content of greater than or equal to 10 wt% and less than or equal to 35 wt%; and is
M of room temperature trichlorobenzene soluble matter of the high melt strength impact resistant polypropylenewM with trichlorobenzene insolubles at room temperaturewThe ratio of (A) to (B) is greater than 0.4 and less than or equal to 1.
2. The polypropylene foamed sheet according to claim 1, wherein the ethylene content of the base resin is 8 to 20% by weight; and/or a butene content of 0 to 10% by weight.
3. The polypropylene foamed sheet according to claim 1 or 2, wherein the base resin has a melt index of 0.1 to 15g/10min, preferably 0.1 to 6g/10min, measured at 230 ℃ under a load of 2.16 kg.
4. The polypropylene foamed sheet according to any one of claims 1 to 3, wherein the molecular weight distribution M of the base resin isw/MnLess than or equal to 10 and greater than or equal to 4; and/or Mz+1/MwGreater than or equal to 10 and less than 20.
5. The polypropylene foamed sheet according to any one of claims 1 to 4, wherein the base resin is prepared by copolymerizing propylene groups in the presence of a first random copolymer polypropylene to obtain a random copolymer polypropylene continuous phase comprising the first random copolymer polypropylene and a second random copolymer polypropylene, and then copolymerizing propylene and ethylene in the presence of the random copolymer polypropylene continuous phase to obtain a polypropylene material comprising a propylene-ethylene copolymer rubber dispersed phase.
6. The polypropylene foamed sheet according to any one of claims 1 to 5, wherein the polypropylene foamed sheet has a closed cell ratio of 82% or more; and/or the notched Izod impact (23 ℃) is 25 to 50KJ/m2。
7. A method for preparing the polypropylene foamed sheet according to any one of claims 1 to 6, comprising the steps of:
a. mixing the base resin, the foaming agent and the cell control agent to obtain a polypropylene foaming premix;
b. adding the polypropylene foaming premix into an extruding machine, stirring, and heating to melt the polypropylene foaming premix;
c. the melted polypropylene foaming premix is extruded to a die of an extruding machine, flows to a plate extruding machine and is rolled into plates.
8. The method of claim 7,
the foaming agent is at least one of an azo foaming agent, a nitroso foaming agent and a hydrazide foaming agent;
the azo foaming agent is preferably at least one of azodicarbonamide, azodiisobutyronitrile, barium azodicarboxylate and azodicarboxylate;
the nitroso foaming agent is preferably at least one of dinitrosopentamethylene tetramine, N' -dimethyl-N, N-dinitrosoterephthalamide and trinitrotritrimethylenetriamine;
the hydrazide foaming agent is preferably at least one of 4, 4' -oxybis-benzenesulfonyl hydrazide, tosylsemicarbazide, triphosphonyltriazine and 5-phenyltetrazole;
the blowing agent is more preferably azodicarbonamide;
the foam cell nucleating agent is at least one selected from talcum powder, aluminum hydroxide, silicon dioxide, zeolite and borax.
9. The method as claimed in claim 7 or 8, wherein in the step a, at least one processing aid is further added and mixed, wherein the processing aid comprises an antioxidant, an antioxidant aid, a lubricant and a pigment.
10. A method according to any of claims 7-9, characterised in that the blowing agent is added in an amount of 1-15 parts by weight, preferably 5-7 parts by weight, based on 100 parts by weight of base resin; and/or the cell control agent is added in an amount of 5 to 20 parts by weight, preferably 5 to 15 parts by weight.
11. The method according to any one of claims 7-10, wherein the temperature in step b is raised to 150-280 ℃, preferably 160-180 ℃; and/or in step c the temperature of the extruder die is 140-.
12. The method according to any one of claims 7 to 11, further comprising a step of preparing a base resin comprising:
the first step is as follows: random copolymerization of propylene groups comprising:
the first stage is as follows: carrying out random copolymerization of propylene and ethylene and/or 1-butene in the presence or absence of hydrogen under the action of a Ziegler-Natta catalyst containing a first external electron donor to obtain a reaction stream containing first random copolymerized polypropylene;
and a second stage: adding a second external electron donor to perform a complex reaction with a catalyst in the reactant flow, and then performing a random copolymerization reaction of propylene and ethylene and/or 1-butene in the presence of the first random copolymerization polypropylene and hydrogen to generate second random copolymerization polypropylene, so as to obtain a random copolymerization polypropylene continuous phase containing the first random copolymerization polypropylene and the second random copolymerization polypropylene;
wherein,
the melt indices of the first random copolymerized polypropylene and the random copolymerized polypropylene continuous phase are respectively 0.001-0.4g/10min and 0.1-15g/10min measured at 230 ℃ under the load of 2.16 kg; and the weight ratio of the first random copolymerized polypropylene to the second random copolymerized polypropylene is 40: 60-60: 40;
the second step is that: propylene-ethylene copolymerization comprising carrying out propylene-ethylene gas phase copolymerization in the presence of the random copolymerized polypropylene continuous phase and hydrogen to produce a propylene-ethylene copolymer rubber dispersed phase, to obtain the base resin comprising the random copolymerized polypropylene continuous phase and the propylene-ethylene copolymer rubber dispersed phase.
13. The method of claim 12,
the first external electron donor is selected from the general formula R1R2Si(OR3)2At least one of the compounds of (a); wherein R is2And R1Each independently selected from C1-C6Straight or branched alkyl, C3-C8Cycloalkyl and C5-C12Heteroaryl of (A), R3Is C1-C3A linear aliphatic group;
the second external electron donor is selected from at least one of compounds shown as chemical general formulas (I), (II) and (III);
wherein R is1And R2Each independently selected from C1-C20One of linear, branched or cyclic aliphatic radicals, R3、R4、R5、R6、R7And R8Each independently selected from a hydrogen atom, a halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl groups; r9、R10And R11Each independently is C1-C3Straight-chain aliphatic radical, R12Is C1-C6Straight or branched alkyl or C3-C8A cycloalkyl group;
and the molar ratio of the second external electron donor to the first external electron donor is 5-30.
14. The process according to claim 12 or 13, wherein the ratio of the melt index of the continuous phase of random copolymerized polypropylene obtained in the first step to that of the matrix resin obtained in the second step is greater than or equal to 0.6 and less than 1.
15. The process of any of claims 12-14, wherein the random polypropylene continuous phase has an ethylene content of 0-6 wt%; and/or a butene content of 0 to 10% by weight.
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