CN116731434A - Polypropylene powder for 3D printing and preparation method and application thereof - Google Patents
Polypropylene powder for 3D printing and preparation method and application thereof Download PDFInfo
- Publication number
- CN116731434A CN116731434A CN202210208777.1A CN202210208777A CN116731434A CN 116731434 A CN116731434 A CN 116731434A CN 202210208777 A CN202210208777 A CN 202210208777A CN 116731434 A CN116731434 A CN 116731434A
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- CN
- China
- Prior art keywords
- polypropylene powder
- polypropylene
- antioxidant
- titanium
- powder
- Prior art date
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- -1 Polypropylene Polymers 0.000 title claims abstract description 369
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 322
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 303
- 239000000843 powder Substances 0.000 title claims abstract description 251
- 238000002360 preparation method Methods 0.000 title claims abstract description 90
- 238000010146 3D printing Methods 0.000 title claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 126
- 238000009826 distribution Methods 0.000 claims abstract description 79
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 47
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 47
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 125000005843 halogen group Chemical group 0.000 claims description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 32
- 239000005977 Ethylene Substances 0.000 claims description 32
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 125000001188 haloalkyl group Chemical group 0.000 claims description 18
- 239000004711 α-olefin Substances 0.000 claims description 17
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 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 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Chemical group 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 150000003944 halohydrins Chemical class 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910017718 MgXY Inorganic materials 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052740 iodine Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Chemical group 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- APYCNQFSOVJLPN-UHFFFAOYSA-N 1,4-dichlorobutan-1-ol Chemical compound OC(Cl)CCCCl APYCNQFSOVJLPN-UHFFFAOYSA-N 0.000 claims description 3
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- NUFATYMMMZQQCQ-UHFFFAOYSA-N butan-1-olate;titanium(3+) Chemical compound [Ti+3].CCCC[O-].CCCC[O-].CCCC[O-] NUFATYMMMZQQCQ-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- NNRZFZBJEDXBPK-UHFFFAOYSA-N ethanolate;titanium(3+) Chemical compound [Ti+3].CC[O-].CC[O-].CC[O-] NNRZFZBJEDXBPK-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 claims description 2
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- GSGPUGZLDGHFDO-UHFFFAOYSA-N 2-(chloromethoxy)propane Chemical compound CC(C)OCCl GSGPUGZLDGHFDO-UHFFFAOYSA-N 0.000 claims 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 claims 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 claims 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 238000010094 polymer processing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 38
- 239000000463 material Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 23
- 230000000694 effects Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 239000011859 microparticle Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 239000002685 polymerization catalyst Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QXBDFCZHAAOUBY-UHFFFAOYSA-N 1,2-dichloroethanol Chemical compound OC(Cl)CCl QXBDFCZHAAOUBY-UHFFFAOYSA-N 0.000 description 1
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NYEWDMNOXFGGDX-UHFFFAOYSA-N 2-chlorocyclohexan-1-ol Chemical compound OC1CCCCC1Cl NYEWDMNOXFGGDX-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- QSECPQCFCWVBKM-UHFFFAOYSA-N 2-iodoethanol Chemical compound OCCI QSECPQCFCWVBKM-UHFFFAOYSA-N 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MBMKFKOVXPKXCV-UHFFFAOYSA-N CCO[Ti]OCC Chemical compound CCO[Ti]OCC MBMKFKOVXPKXCV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- CFXDAHURBQNVFG-UHFFFAOYSA-M magnesium;propan-2-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)[O-] CFXDAHURBQNVFG-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of polymer processing, and discloses polypropylene powder for 3D printing, a preparation method and application thereof, a polypropylene composition for 3D printing and application thereof. The polypropylene powder comprises polypropylene and an antioxidant; based on the total weight of the polypropylene powder, 99-99.5 parts of polypropylene and 0.5-1 part of antioxidant are used; the molecular weight distribution index M of the polypropylene powder w /M n 4-8; the particle size distribution of the polypropylene powder is less than 2.5, and the polypropylene powder is regular and uniform spherical particles and has smooth surface and can be used for preparing the polypropylene powderCan be directly used for selective laser sintering 3D printing.
Description
Technical Field
The invention relates to the technical field of polymer processing, in particular to polypropylene powder for 3D printing and a preparation method and application thereof.
Background
The selective laser sintering (Selective Laser Sintering, SLS) technology is a rapid prototyping technology, is the most widely applied technology with the most market prospect in the additive manufacturing technology at present, and has a rapid development trend in recent years. The SLS technology is a technology in which a three-dimensional entity is first scanned by a computer, and then material powder previously laid on a workbench or a part is irradiated by high-intensity laser, and is selectively fused and sintered layer by layer, thereby realizing layer-by-layer molding. The SLS technology has high design flexibility, can manufacture accurate models and prototypes, can form parts which have reliable structures and can be directly used, shortens the production period and simplifies the process, thus being particularly suitable for developing new products.
Theoretically, the types of molding materials that can be used in SLS technology are relatively wide, such as polymers, paraffin waxes, metals, ceramics, and composites thereof. However, the properties and characteristics of the molding material are an important factor for successful sintering by the SLS technology, and directly affect the molding speed and precision of the molded part, as well as the physical and chemical properties and the comprehensive properties thereof. At present, polymer powder raw materials which can be directly applied to the SLS technology and successfully produce molded products with small dimensional errors, regular surfaces and low porosity are quite visible in the market. Accordingly, there is a need to develop and improve the polymer types and their corresponding solid powder materials suitable for SLS technology.
In the prior art, pulverization methods, such as cryogenic pulverization, are commonly employed to prepare powder materials suitable for SLS. For example, CN104031319a discloses a polypropylene powder obtained by a cryogenic pulverizing method; classifying and collecting by an airflow sieving machine, selecting polypropylene powder with the granularity of 200-800 meshes, and returning coarse materials which do not meet the fineness requirement to a storage bin for continuous crushing; adding 100 parts of polypropylene powder, 0.1-1 part of graphite powder, 0.01-0.5 part of antioxidant and 0.5-5 parts of metal soap salt, and uniformly mixing in a high-speed mixer; the particle size of the graphite powder is 1000-5000 meshes; the antioxidant is formed by mixing phenols and phosphite or thioesters according to a mass ratio of 1:1, and a composite antioxidant formed by the components. However, this method requires not only special equipment, but also the prepared powder raw material particles have rough surface, uneven particle size and irregular shape, which is unfavorable for the formation of sintered molded bodies and affects the properties of the molded bodies.
In addition, precipitation processes exist for preparing polymer powder starting materials, such as polyamide powders. In this process, the polyamide is generally dissolved in a suitable solvent, the mass is homogeneously distributed in the solvent by stirring and the powder precipitate is separated off by cooling. For example, CN103374223a discloses a precipitated polymer powder based on an AABB-type polyamide, obtained by reprecipitating a polyamide obtained by polycondensation of a diamine and a dicarboxylic acid. In the process described in this patent, an alcoholic solvent is used during the reprecipitation process. However, this method requires the use of a large amount of organic solvents, and is low in yield and efficiency, and does not have environmental and economical advantages.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polypropylene powder for 3D printing and a preparation method and application thereof. The polypropylene powder has a particle size distribution of less than 2.5 and a relatively narrow molecular weight distribution index, is in the form of regular and uniform spherical particles, has a smooth surface, and can be directly used for selective laser sintering 3D printing.
In order to achieve the above object, a first aspect of the present invention provides a polypropylene powder for 3D printing, characterized in that the polypropylene powder comprises polypropylene and an antioxidant;
Based on the total weight of the polypropylene powder, 99-99.5 parts of polypropylene and 0.5-1 part of antioxidant are used;
the molecular weight distribution index M of the polypropylene powder w /M n 4-8; the particle size distribution of the polypropylene powder is less than 2.5.
The second aspect of the invention provides a preparation method of the polypropylene powder for 3D printing, which is characterized by comprising the following steps:
and (3) carrying out polymerization reaction on olefin containing propylene and ethylene and/or alpha-olefin in the presence of a catalyst and an antioxidant to obtain the polypropylene powder for 3D printing.
The third aspect of the invention provides an application of the polypropylene powder for 3D printing in selective laser sintering 3D printing.
Through the technical scheme, the polypropylene powder for 3D printing, the preparation method and application thereof, the polypropylene composition for 3D printing and the application thereof provided by the invention have the following beneficial effects:
(1) The polypropylene powder for 3D printing provided by the invention has a particle size distribution smaller than 2.5 and a relatively narrow molecular weight distribution index, is regular and uniform in spherical particles, has a smooth surface, and can be directly used for selective laser sintering 3D printing. Compared with the general crushing method in the industry, the polypropylene particles are regular and smooth, which is beneficial to the sintering process; compared with the precipitation method, the direct polymerization method reduces labor intensity and energy consumption, has higher yield and has the advantage of environmental protection.
(2) The polypropylene powder provided by the invention has a small particle size, and the formed body prepared by using the polypropylene powder in selective laser sintering 3D printing has excellent surface quality, and mechanical properties and surface precision are superior to those of the polypropylene powder prepared by the prior art.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides polypropylene powder for 3D printing, which is characterized by comprising polypropylene and an antioxidant;
based on the total weight of the polypropylene powder, 99-99.5 parts of polypropylene and 0.5-1 part of antioxidant are used;
the molecular weight distribution index M of the polypropylene powder w /M n 4-8; the particle size distribution of the polypropylene powder is less than 2.5.
In the invention, the polypropylene powder for 3D printing has a particle size distribution of less than 2.5 and a relatively narrow molecular weight distribution index, and meanwhile, the polypropylene powder is in regular and uniform spherical particles and has a smooth surface, and can be directly used for selective laser sintering 3D printing. Compared with the general crushing method in the industry, the polypropylene particles are regular and smooth, which is beneficial to the sintering process; compared with the precipitation method, the direct polymerization method reduces labor intensity and energy consumption, has higher yield and has the advantage of environmental protection.
In the present invention, the molecular weight distribution index of the polypropylene powder is measured by GPC. In the present invention, the particle size distribution of the polypropylene powder is obtained according to (D90-D10)/D50.
Further, the particle size distribution of the polypropylene powder is less than 2; the molecular weight distribution index M of the polypropylene powder w /M n 4.5-6.
According to the invention, the polypropylene powder has an average particle diameter D50 of 10 to 500. Mu.m, preferably 50 to 200. Mu.m.
In the present invention, the average particle diameter and particle size distribution of the polypropylene powder are measured using a laser particle Sizer such as a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
According to the invention, the polypropylene powder has a melting point T m Is 120-170 ℃.
Further, the method comprises the steps of,the melting point T of the polypropylene powder m 129-160 ℃.
According to the invention, the crystallization temperature T of the polypropylene powder c 80-130 ℃.
Further, the crystallization temperature T of the polypropylene powder c 95-120 ℃.
In the invention, the melting point T of the polypropylene powder m And crystallization temperature T c When the above range is satisfied, it is possible to ensure that the polypropylene powder has a wide processing window.
In the invention, the melting point T of the polypropylene powder m And crystallization temperature T c Measured by DSC.
According to the invention, the polypropylene powder has a melt flow rate MFR of 1-1000g/10min at 230℃and a load of 2.16 kg.
In the invention, when the melt flow rate of the polypropylene powder meets the range, the polypropylene powder has adaptive fluidity, and can ensure that the product is compact and the product has excellent formability.
In the invention, the melt flow rate of the polypropylene powder is tested according to the method specified in ISO 1133-1-2011.
Further, the melt flow rate MFR of the polypropylene powder is 1 to 399g/10min, preferably 10 to 50g/10min.
According to the invention, the bulk density of the polypropylene powder is 0.3-0.5g/cm 3 。
In the present invention, when the bulk density of the polypropylene powder satisfies the above range, the polypropylene powder is easily pulverized, whereby the surface finish of the polypropylene product can be improved.
In the invention, the bulk density of the polyolefin powder is measured by a method specified in GB/T1636-2008.
Further, the bulk density of the polypropylene powder is 0.35-0.45g/cm 3 。
According to the invention, the polypropylene is a copolymer of propylene with ethylene and/or an alpha-olefin.
In the present invention, the α -olefin may be an α -olefin commonly used in the art, such as α -butene, α -pentene, etc.
According to the invention, the content of structural units provided by the ethylene and/or alpha-olefin is from 1 to 5% by weight, based on the total weight of the polypropylene.
Further, the content of structural units provided by the ethylene and/or alpha-olefin is from 1.5 to 3.5wt%, based on the total weight of the polypropylene.
According to the present invention, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
The second aspect of the invention provides a preparation method of the polypropylene powder for 3D printing, which is characterized by comprising the following steps:
and (3) carrying out polymerization reaction on olefin containing propylene and ethylene and/or alpha-olefin in the presence of a catalyst and an antioxidant to obtain the polypropylene powder for 3D printing.
According to the invention, the catalyst comprises a spherical support.
According to the invention, the spherical support has an average particle diameter of 2-100 microns; the particle size distribution is less than 2.
In the invention, in the presence of the catalyst containing the spherical carrier with the average particle diameter and the particle size distribution, polypropylene powder with good spherical morphology, uniform particles and smooth surface and the particle size distribution of 10-500 μm can be prepared, and the polypropylene powder can be directly used for selective laser sintering 3D printing.
In the present invention, the average particle diameter refers to D50.
In the present invention, the size of the particle size distribution is obtained according to (D90-D10)/D50.
In the present invention, the average particle diameter and particle size distribution of the catalyst support are measured using a laser particle Sizer such as a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
Further, the spherical carrier has an average particle diameter of 2 to 19 μm and a particle size distribution of 0.6 to 1.6.
According to the present invention, the spherical support has a structure represented by formula (1);
wherein in formula (1), R 1 Selected from C 1-10 Alkyl of (a);
R 2 and R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
R 4 selected from C substituted by at least one halogen atom 1-10 Haloalkyl groups and C substituted by at least one halogen atom 6-20 Is a halogenated aromatic group;
R 5 selected from C 1-5 Alkyl of (a);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1.
In the invention, in the presence of the catalyst comprising the spherical carrier shown in the formula (1), the polypropylene powder with regular and uniform appearance and smooth surface can be directly polymerized to obtain the polypropylene powder with regular and uniform appearance, and the polypropylene powder can be directly used for selective laser sintering 3D printing.
In the present invention, in the formula (1)Part representation (OC 2 H 2 XR 2 R 3 ) n 。
In the present invention, R 1 Selected from C 1-10 Alkyl of (C), R is 1 Alkyl groups that are straight, branched, or cyclic including, but not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-di-Methylpropyl, and the like.
Herein, regarding R 1 The alkyl substituents of (a) have similar definitions to those described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In order to obtain a spherical support with better properties, R is preferably 1 Selected from C 1-8 Alkyl of (a); more preferably, R 1 Selected from C 1-6 Is a hydrocarbon group.
In the present invention, R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 Is a haloalkyl group of (2).
When said R is 2 And R is 3 Selected from C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 When the alkyl is halogenated, the alkyl is a linear or branched group, the C 1-10 Examples of alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, and the like. The haloalkyl group is a linear or branched group, the C being substituted by 1 to 10 halogen atoms 1-10 Haloalkyl of (C) 1-10 The alkyl group of (2) may have 1 to 10 hydrogen atoms replaced with halogen atoms, and may have a plurality of hydrogen atoms replaced with halogen atoms on the same carbon atom or may have hydrogen atoms replaced with different carbon atoms; when a plurality of halogen atoms are substituted, the halogen atoms may be the same or different, and the halogen atoms are fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. For example including but not limited to-CF 3 、-CH 2 CF 3 、-CH 2 CF 2 H、-CF 2 CF 3 、-CF 2 CH 2 CF 2 H、-CH 2 CF 2 CF 2 H、-CH 2 CH 2 CH 2 Cl、-CH 2 CH 2 CH 2 Br, etc.
Herein, regarding R 2 And R is 3 Alkyl substituent groups and halo groups of (a)Alkyl substituents have similar definitions to those described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In order to obtain a spherical support with better properties, R is preferably 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 Is a haloalkyl group of (2).
In the present invention, R 4 Selected from C substituted by at least one halogen atom 1-10 Haloalkyl groups and C substituted by at least one halogen atom 6-20 Is a halogenated aromatic group. Said C being substituted by at least one halogen atom 1-10 Haloalkyl and at least one halogen atom substituted C 6-20 The halogenated aromatic group of (C) 1-10 Alkyl, C of (2) 6-20 At least one hydrogen atom in the aromatic group is substituted with a halogen atom, which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Wherein the C 1-10 The haloalkyl group of (c) may be a linear, branched or cyclic group, for example including but not limited to CF 3 、-CH 2 CF 3 、-CH 2 CF 2 H、-CF 2 CF 3 、-CF 2 CH 2 CF 2 H、-CH 2 CF 2 CF 2 H、-CH 2 CH 2 CH 2 Cl、-CH 2 CH 2 CH 2 Br, etc. The C is 6-20 The halogenated aromatic group of (2) means a halogenated aromatic group having 6 to 20 carbon atoms.
Herein, regarding R 4 The substituents of (a) have similar definitions to those described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In order to obtain a spherical support with better properties, R is preferably 4 Selected from C substituted by at least two halogen atoms 1-10 Haloalkyl groups and C substituted by at least two halogen atoms 6-20 And the halogen atom is preferably at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom.
In the present invention, the halogen atoms are formed from at least two halogen atomsSub-substitution means C 1-10 Alkyl and C of (C) 6-20 At least two hydrogen atoms in the aromatic group of (a) are substituted with halogen atoms, which may be hydrogen atoms on one carbon or hydrogen atoms on different carbons, and the halogen atoms may be the same or different.
In the present invention, R 5 Selected from C 1-5 Alkyl group of said C 1-5 Alkyl of (a) refers to alkyl groups having 1 to 5 carbon atoms and includes, for example, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, and the like.
Herein, regarding R 5 The substituents of (a) have similar definitions to those described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In order to obtain a spherical support with better properties, R is preferably 5 Selected from C 1-2 Is a hydrocarbon group.
In order to obtain a spherical support with better properties, X is preferably selected from chlorine and bromine.
According to the invention, the volume ratio of propylene to ethylene and/or alpha-olefin is from 12.7 to 80:1.
further, the volume ratio of the propylene to the ethylene and/or alpha-olefin is 20-50:1.
according to the invention, the antioxidant is used in an amount of 0.5 to 1% by weight relative to the total amount of olefins.
Further, the antioxidant is used in an amount of 0.55 to 0.95wt% relative to the total amount of olefins.
According to the present invention, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
In the present invention, in order to be able to obtain a catalyst suitable for olefin polymerization, in particular propylene polymerization, it is preferable that the catalyst contains a spherical support, a titanium halide compound and an electron donor compound. Preferably, the titanium halide is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tri-n-butoxide, titanium di-n-butoxide, titanium tri-chloride, titanium triethoxide, titanium di-ethoxide, titanium tri-monoethoxide and titanium trichloride. Preferably, the electron donor compound is selected from at least one of diisobutyl phthalate, carboxylic acid glycol ester and phosphoric acid ester. Meanwhile, the content of each component in the catalyst is not particularly limited, and a person skilled in the art can reasonably adjust and design according to actual needs.
The preparation method of the catalyst is not particularly limited, and may be prepared by methods of preparing an olefin polymerization catalyst existing in the art, and the present invention is exemplified in the examples hereinafter to be used as a specific procedure, and the person skilled in the art should not be construed as limiting the present invention.
In one embodiment of the invention, the spherical support is prepared according to the following steps:
(1) Sequentially carrying out first contact and emulsification on a component A to obtain a first product, wherein the component A contains magnesium halide with a general formula of MgXY and a general formula of R 1 A first alcohol compound of OH;
(2) Carrying out second contact on the first product and a component B to obtain a second product, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (2);
(3) The second product is subjected to third contact with a component C to obtain a third product, wherein the component C contains a compound with a general formula of R 4 Halogenated alcohols of OH with the general formula R 5 A second glycol compound of OH;
(4) Subjecting the third product to spray drying;
wherein in formula R 1 In OH, R 1 Selected from C 1-10 Alkyl of (a);
in formula (2), R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
in R 4 In OH, R 4 Selected from C substituted by at least one halogen atom 1-10 Haloalkyl groups and C substituted by at least one halogen atom 6-20 Is a halogenated aromatic group;
in R 5 In OH, R 5 Selected from C 1-5 Alkyl of (a);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C of (2) 1-6 Alkoxy, C 6-14 Aryl and C of (2) 6-14 An aryloxy group of (a);
the amounts of the component a, the component B and the component C are such that the resulting spherical support has a structure represented by formula (1):
in formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1;
wherein in the step (3), the amount of the halohydrin is 0.05 to 6.5mol and the amount of the second glycol compound is 5 to 100mol with respect to 1mol of the magnesium halide.
In the preparation method of the spherical carrier, R is as follows 1 、R 2 、R 3 、R 4 And R is 5 The definition of the substituents of (a) is correspondingly the same as that of the spherical support of the present invention, and the present invention will not be described in detail herein.
In the present invention, in the formula MgXY, when Y is selected from C 1-6 Alkyl, C of (2) 1-6 The alkyl and the alkoxy are straight or branched alkyl and alkoxy groups, the C 1-6 Alkyl of (a) refers to an alkyl group having 1 to 6 carbon atoms, including for example but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and the like; the C is 1-6 Alkoxy of (2) refers to an alkoxy group having 1 to 6 carbon atoms, including for example, but not limited to methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and the like.
The C is 6-14 Aryl of (c) refers to aryl groups having 6 to 14 carbon atoms and includes, for example, but is not limited to, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, and the like.
The C is 6-14 Aryloxy of (c) refers to an aryloxy group having 6 to 14 carbon atoms, including, for example, but not limited to, phenoxy, naphthoxy, o-methylphenoxy, o-ethylphenoxy, m-methylphenoxy, and the like.
Herein, in the formula MgXY, substituents such as alkyl, alkoxy, aryl and aryloxy for Y have similar definitions as described above, except for the number of carbon atoms, and the present invention will not be described in detail hereinafter.
According to a preferred embodiment of the invention, in the formula MgXY, X is selected from chlorine and bromine and Y is selected from chlorine, bromine, C 1-5 Alkyl, C of (2) 1-5 Alkoxy, C 6-10 Aryl and C of (2) 6-10 An aryloxy group of (a).
In order to obtain a spherical support having a smaller particle diameter and better performance, more preferably, the magnesium halide is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxy magnesium chloride and n-butoxymagnesium chloride, and still more preferably, magnesium chloride.
According to another preferred embodiment of the invention, in formula R 1 In OH, R 1 Selected from C 1-8 Is a hydrocarbon group.
In order to obtain a spherical carrier with smaller particle size, more uniform particle size distribution and better performance, more preferably, the first alcohol compound is at least one selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
According to yet another preferred embodiment of the present invention, in formula (2), R 2 And R is 3 Each independently selected from H, C 1-5 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-5 Is a haloalkyl group of (2).
In order to obtain a spherical support having a smaller particle diameter, a more uniform particle diameter distribution and a better performance, more preferably, the oxirane compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, bromopropane and oxybutylene oxide.
According to the invention, the halohydrin may be a monohalohydrin or a polyhalogenated alcohol, preferably a chlorohydrin, a bromohydrin or an iodinated alcohol, for example 2, 2-trichloroethanol, 2-dichloroethanol, 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol, 2-chlorocyclohexanol, 1, 2-dichloroethanol, 1, 3-dichloropropanol, 1, 4-dichlorobutanol or 2-iodoethanol, etc.
However, in order to be able to obtain spherical supports with better properties, according to a further preferred embodiment of the invention, a polymer of formula R 4 In OH, R 4 Selected from C substituted by at least two halogen atoms 1-10 Haloalkyl groups and C substituted by at least two halogen atoms 6-20 And the halogen atom is selected from at least one of a chlorine atom, a bromine atom and an iodine atom.
Preferably, the halogenated alcohol is at least one selected from 2, 2-trichloroethanol, 2-dichloroethanol, 1, 3-dichloropropanol and 1, 4-dichlorobutanol.
According to the invention, the second glycol compound is selected from C 1-5 At least one of the alcohol compounds of (a) is, for example, ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol. However, in order to be able to obtain spherical supports with better properties, according to a further preferred embodiment of the invention, a polymer of formula R 5 In OH, R 5 Selected from C 1-2 I.e. the second glycol compound is methanol and/or ethanol.
According to the present invention, the inventors found that when the amounts of the halohydrin compound and the alcohol compound are excessively large, the resultant spherical support is sticky and agglomerated, and thus subsequent operations cannot be performed.
Preferably, the first alcohol compound is used in an amount of 1 to 30mol and the ethylene oxide compound is used in an amount of 1 to 10mol, relative to 1mol of the magnesium halide.
More preferably, the amount of the first alcohol compound is 6 to 22 moles, the amount of the ethylene oxide compound is 2 to 6 moles, the amount of the halohydrin is 1 to 5 moles, and the amount of the second alcohol compound is 8 to 80 moles, more preferably 31 to 50 moles, relative to 1 mole of the magnesium halide.
In the present invention, it should be noted that the trace amount of water carried in each of the above reactants may also participate in the reaction for forming the spherical support, and thus, the spherical support may be prepared to contain trace amounts of water carried from the reaction raw materials and the reaction medium, and those skilled in the art should not understand the limitation of the present invention.
Preferably, in step (1), the first contacting is performed under stirring conditions, and the conditions of the first contacting include: the temperature is 80-120 ℃ and the time is 0.5-5h.
More preferably, in step (1), the conditions of the first contact include: the temperature is 80-100deg.C, and the time is 0.5-3h.
In the step (1), the specific operation method of the emulsification is not particularly limited, and may be carried out by methods known to those skilled in the art. For example, emulsification is performed using low-speed shearing or high-speed shearing. Preferably, when low shear is used, the agitation rate of the low shear is 400-800rpm. Such high speed shearing methods are well known to those skilled in the art, for example, using the high speed agitation speeds disclosed in CN1330086 a. In addition, the emulsification operation may be carried out by referring to the method disclosed in the following patent application, such as the method disclosed in CN1580136a in which a solution containing a liquid magnesium halide compound is subjected to rotary dispersion in a hypergravity bed (the rotation speed is 100 to 3000 rpm); the solution containing the liquid magnesium halide adduct is then discharged in an emulsifying machine at a speed of 1500-8000rpm as disclosed in CN1463990 a; the solution containing the liquid magnesium halide adducts is emulsified by spraying as disclosed in US6020279 a.
Preferably, in step (2), the conditions of the second contact include: the temperature is 50-120deg.C, and the time is 20-60min.
More preferably, in step (2), the conditions of the second contact include: the temperature is 80-100deg.C, and the time is 20-50min.
According to a preferred embodiment of the present invention, step (3) further comprises, after washing the second product with an inert solvent, carrying out the third contact with each of the components C, preferably at least one inert solvent selected from pentane, hexane, heptane, petroleum ether and petrol.
The specific conditions of the third contact in step (3) are not particularly limited in the present invention as long as the component C and the second product can be sufficiently contacted to form a fluid, but in order to enable a catalyst support having better performance, preferably, in step (3), the conditions of the third contact include: the process is carried out under the condition of stirring, the temperature is 0-120 ℃, and the time is 0.5-6h.
The specific mode of the third contact in the step (3) is not particularly limited, and the halohydrin and the second glycol compound may be mixed and simultaneously contacted with the second component, or the halohydrin and the second glycol compound may be sequentially contacted with the second component, respectively.
In the present invention, the spray-drying conditions may employ existing conditions capable of forming spherical supports for olefin polymerization, but in order to be able to obtain spherical supports with better performance, according to a preferred embodiment of the present invention, the spray-drying is carried out in a sprayer having an atomizing nozzle containing a material conduit and a nozzle head, the third product is introduced into the nozzle head through the material conduit and is injected into a column of the sprayer containing an inert medium through the nozzle head for solidification, preferably, the temperature of the third product in the material conduit is between 0 ℃ and 80 ℃ and the temperature of the third product in the nozzle head is 80-180 ℃; more preferably the temperature of the third product in the nozzle head is 120-180 ℃.
In the present invention, in step (4), preferably, the spray-drying conditions include: the temperature is 60-200 ℃, more preferably 90-150 ℃, in the present invention, the spray drying temperature refers to the temperature of the inert medium in the sprayer.
In the present invention, the inert medium may include a protective gas medium and/or an inert liquid medium, and the type of the protective gas medium is not particularly limited, and for example, nitrogen gas may be an inert gas medium such as helium gas, or other suitable gas such as carbon dioxide gas, etc.; the inert liquid medium is a variety of liquid mediums commonly used in the art that do not chemically react with the reactants and reaction products, preferably the inert liquid medium is silicone oil and/or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil, and still more preferably is white oil.
In the present invention, the amount of the inert liquid medium in the spraying machine may be selected according to the amount of magnesium halide of the general formula MgXY, preferably 0.8 to 10L, more preferably 2 to 8L.
The method for producing the spherical support of the present invention further includes post-treatment means such as solid-liquid separation, washing, drying, etc., which are conventional in the art, and the present invention is not particularly limited thereto. The solid-liquid separation may be performed by any of various conventional methods capable of separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation method is a pressure filtration method. The conditions for press filtration are not particularly limited in the present invention, so long as the separation of the solid phase and the liquid phase is achieved as sufficiently as possible. The washing may be performed by methods known to those skilled in the art, and for example, the obtained solid phase product may be washed with an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline. The specific conditions for the drying are not particularly limited in the present invention, and for example, the temperature of the drying may be 20 to 70 ℃, the time of the drying may be 0.5 to 10 hours, and the drying may be performed under normal pressure or reduced pressure.
The inventors found that by using specific kinds and amounts of alcohol compounds and halohydrin compounds in combination with components such as magnesium halides and ethylene oxide compounds, while matching specific spray drying modes, a spherical carrier having a novel composition and having a good particle morphology, which is substantially free of abnormal particles, can be obtained; and the preparation process does not need to add a surfactant, and the process is stable.
Particularly, the spherical carrier with small particle size can be prepared by the method provided by the invention, so that the preparable particle size range of the carrier is greatly expanded; and when the catalyst prepared by the spherical carrier is used for olefin polymerization, the hydrogen regulation sensitivity is higher.
The third aspect of the invention provides polypropylene powder for 3D printing, which is prepared by the preparation method.
In the invention, the polypropylene powder comprises polypropylene and an antioxidant;
based on the total weight of the polypropylene powder, 99-99.5 parts of polypropylene and 0.5-1 part of antioxidant are used;
the molecular weight distribution index M of the polypropylene powder w /M n 4 to 8, preferably 4.5 to 6; the particle size distribution of the polypropylene powder is less than 2.5, preferably less than 2.
In the present invention, the average particle diameter D50 of the polypropylene powder is 10 to 500. Mu.m, preferably 50 to 200. Mu.m.
In the invention, the melting point T of the polypropylene powder m 120-170℃and preferably 129-160 ℃.
In the invention, the crystallization temperature T of the polypropylene powder c 80-130℃and preferably 95-120 ℃.
In the invention, the melt flow rate MFR of the polypropylene powder is 1-1000g/10min at 230 ℃ and under a load of 2.16 kg; preferably 1-399g/10min, more preferably 10-50g/10min.
In the invention, the bulk density of the polypropylene powder is 0.3-0.5g/cm 3 Preferably 0.35-0.45g/cm 3 。
In the present invention, the polypropylene is a copolymer of propylene with ethylene and/or an alpha-olefin.
In the present invention, the α -olefin may be an α -olefin commonly used in the art, such as α -butene, α -pentene, etc.
In the present invention, the content of structural units provided by the ethylene and/or alpha-olefin is 1 to 5wt%, preferably 1.5 to 3.5wt%, based on the total weight of the polypropylene.
In the invention, the antioxidant is at least one selected from the group consisting of antioxidant 1010, antioxidant 168 and antioxidant 1076.
The fourth aspect of the invention provides an application of the polypropylene powder for 3D printing in selective laser sintering 3D printing.
The present invention will be described in detail by examples. In the following examples of the present invention,
1. average particle diameter and particle size distribution of catalyst support: the measurement was carried out by using a Master Sizer 2000 particle Sizer manufactured by Malvern Instruments company;
2. morphology of the catalyst support: observation was performed by an XL-30 type field emission electron microscope manufactured by FEI company of America;
3. structure and composition of the catalyst support: carrying out 1H-NMR test on the carrier by using an AVANCE 300 nuclear magnetic resonance spectrometer of Bruker, switzerland, and carrying out test on the carrier by using a PY-2020iD type cracker of front tellab, a traceGC Ultra type chromatograph of Thermo Fisher and a DSQ II type mass spectrometer;
4. catalyst activity: evaluating the ratio of the weight of the product obtained after polymerization to the weight of the catalyst dosage;
5. bulk density of polyolefin powder: the method specified in GB/T1636-2008 is adopted for measurement;
6. melt flow rate index of polyolefin powder: measured according to ISO1133, 230 ℃,2.16kg load;
7. molecular weight distribution index M of polypropylene powder w /M n Is characterized by comprising the following steps: the method specified in GB/T36214-2018 is adopted for measurement;
8. polypropylene powder Is of the melting point T of (2) m And crystallization temperature T c Heating each sample from-100 ℃ to 250 ℃ on a Perkin Elmer Pyris 1 tester, and carrying out heating scanning twice at a heating rate of 10 ℃/min;
in the examples below, the emulsification was carried out with stirring at 600rpm during the preparation of the catalyst support, unless otherwise specified.
In the following examples and comparative examples, the materials used were as follows:
in the following examples, all the raw materials used were commercially available ones unless otherwise specified.
1, 3-dichloropropanol was purchased from carbofuran corporation;
epichlorohydrin was purchased from belvedere corporation;
diisobutyl phthalate was purchased from belowder company;
titanium tetrachloride was purchased from carbofuran corporation;
triethylaluminum was purchased from belowder company;
methylcyclohexyl dimethoxy silane was purchased from carbofuran corporation;
antioxidant 1010, manufactured by basf vapour ba company, germany;
the polypropylene is B4808 of the company of the petrifaction, the melting point is 138 ℃, and the melt index is 11.1g/10min;
xylenes were purchased from alaa Ding Gongsi.
Preparation example 1 of catalyst microsphere Carrier
(1) Adding 0.08mol of magnesium chloride and 1.7mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, performing constant-temperature reaction for 1h to perform first contact, and then performing emulsification to obtain a first product;
(2) Second contacting the first product with 0.48mol of epichlorohydrin to obtain a second product, wherein the second contacting conditions comprise: the temperature is 90 ℃ and the time is 30min;
(3) After the second product is subjected to filter pressing, the second product is fully mixed and stirred with 2.5mol of ethanol (second glycol compound) and 0.35mol of 1, 3-dichloropropanol (halogenated alcohol) to form fluid, and a third product is obtained;
(4) Spray drying is carried out by spraying the third product into circulating nitrogen at 100 ℃ in a spray tower by using a spray machine B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain a spherical carrier Z1.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z1 are as follows:
the catalyst spherical support Z1 was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst spherical carrier Z1 has regular particle morphology, smooth surface, basically spherical shape, centralized particle size distribution and basically no abnormal particle.
In the process of preparing the catalyst spherical carrier Z1, no clogging phenomenon occurred at the nozzle head of the spraying machine, and 11.8g of carrier Z1 was obtained in total.
Preparation example 2 of catalyst microsphere Carrier
(1) Adding 0.08mol of magnesium chloride and 1.4mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 1.5h for first contact, and emulsifying to obtain a first product;
(2) Second contacting the first product with 0.35mol of epichlorohydrin to obtain a second product, wherein the conditions of the second contact include: the temperature is 90 ℃ and the time is 30min;
(3) After the second product is subjected to filter pressing, the second product is fully mixed and stirred with 2.5mol of ethanol (second glycol compound) and 0.25mol of 1, 3-dichloropropanol (halogenated alcohol) to form fluid, and a third product is obtained;
(4) Spraying and drying the third product into circulating nitrogen with the temperature of 100 ℃ in a sprayer tower by using a sprayer B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain the catalyst spherical carrier Z2.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z2 are as follows:
the catalyst spherical support Z2 was tested to have an average particle diameter (D50) of 4 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The spherical support Z2 for olefin polymerization was observed to have a relatively regular particle morphology, a smooth surface, a relatively concentrated particle size distribution, and substantially no irregular particles.
In the process of preparing the catalyst spherical support Z2, no clogging phenomenon occurred at the nozzle head of the atomizer, and 11.9g of the catalyst spherical support Z2 was obtained in total.
Preparation example 3 of catalyst microsphere Carrier
(1) Adding 0.08mol of magnesium chloride and 1.4mol of ethanol (first alcohol compound) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 1.5h for first contact, and then emulsifying to obtain a first product;
(2) And carrying out second contact on the first product and 0.35mol of epichlorohydrin to obtain a second product, wherein the second contact conditions comprise: the temperature is 90 ℃ and the time is 30min;
(3) Filter-pressing the second product, and stirring the second product with 2.5mol of ethanol (a second glycol compound) and 0.1mol of 1, 3-dichloropropanol (halogenated alcohol) until third contact is carried out to form a fluid, so as to obtain a third product;
(4) Spraying the third product into circulating nitrogen at 100 ℃ in a sprayer tower by using a sprayer B-290 comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain a spherical carrier Z3.
Through testing, the structure and the composition of the obtained catalyst spherical carrier Z3 are as follows:
the catalyst spherical support Z3 was tested to have an average particle diameter (D50) of 5 μm and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst spherical carrier Z3 has regular particle morphology, smooth surface, basically spherical shape, centralized particle size distribution and basically no abnormal particle.
In the process of preparing the catalyst spherical carrier Z3, no clogging phenomenon occurred at the nozzle head of the spraying machine, and 12.0g of the catalyst spherical carrier Z3 was obtained in total.
Comparative example 1 of catalyst microsphere Carrier
(1) Adding 0.08mol of magnesium chloride and 1.4mol of ethanol into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting for 1.5 hours at constant temperature, adding 0.35mol of epichlorohydrin, and reacting for 30 minutes at 90 ℃ to obtain a fluid mixed substance;
(2) Spraying the fluid mixed substance into circulating nitrogen at 100 ℃ by using a sprayer with a nozzle head and a material conduit, wherein the temperature of the fluid mixed substance in the material conduit is 90 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain the catalyst carrier DZ1 for olefin polymerization.
In the spraying process, the fluid mixed material obtained in the step (1) is easy to precipitate, so that spray drying cannot be normally performed, and a spray head is easy to be blocked.
The average particle diameter (D50) of the catalyst carrier DZ1 for olefin polymerization was 15. Mu.m, and the particle size distribution ((D90-D10)/D50) was 1.3.
Comparative example 2 catalyst microsphere Carrier
(1) Adding 0.08mol of magnesium chloride and 1.7mol of ethanol into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting for 1h at constant temperature, adding 0.48mol of epichlorohydrin, and reacting for 30min at 90 ℃ to obtain a first product;
(2) After the first product is subjected to filter pressing, adding 2.5mol of ethanol, and stirring until a fluid mixture is formed;
(3) Spraying the fluid mixture into circulating nitrogen at 100 ℃ by using a sprayer comprising a nozzle head and a material conduit, wherein the temperature of the third product in the material conduit is 15 ℃, and the temperature in the nozzle head is 120 ℃, so as to obtain a catalyst carrier DZ2 for olefin polymerization.
The average particle diameter (D50) of the catalyst carrier DZ2 for olefin polymerization was 3 μm, and the particle size distribution ((D90-D10)/D50) was 0.8.
Comparative example 3 catalyst microsphere Carrier
The catalyst spherical support was prepared in a similar manner to example 1, except that: in the step (3), the third contact was carried out by thoroughly mixing and stirring the second product with only the halohydrin (1, 3-dichloropropanol) without using the second alcohol compound, and the amount of the halohydrin used was the same as in example 1 to obtain the catalyst carrier DZ3.
In the preparation of the catalyst support DZ3, the support was tacky and agglomerated and no subsequent operation was possible.
Preparation example 1 of Polypropylene powder
(1) Preparation of catalyst for olefin polymerization
In a 300mL reaction flask, 100mL of titanium tetrachloride was added, cooled to-20℃and 8 g of the catalyst spherical support Z1 obtained in preparation example 1 of the catalyst microsphere support was added thereto, and stirred at-20℃for 30 minutes. Then, the temperature was slowly raised to 110℃and 1.5mL of diisobutylphthalate was added thereto during the temperature rise, and the solution was filtered off after maintaining the temperature at 110℃for 30 minutes. Then, the catalyst was washed with titanium tetrachloride for 2 times, finally, with hexane for 3 times, and dried to obtain a catalyst C1 for olefin polymerization.
(2) Propylene polymerization
In a 5L stainless steel autoclave, under a nitrogen atmosphere, 1mmol of triethylaluminum in hexane (the concentration of triethylaluminum is 0.5 mmol/mL), 0.05mmol of methylcyclohexyldimethoxy silane, 10mL of anhydrous hexane, 5mg of antioxidant 1010, 10mg of the catalyst C1 for olefin polymerization obtained in the step (1), 1.5L (standard volume) of hydrogen, 2.5L of liquid propylene monomer and 150mL of ethylene monomer are added, the temperature is raised to 70 ℃, the temperature is reacted for 1 hour, and then the temperature is lowered, the pressure is released, the material is discharged and dried, thereby obtaining polypropylene powder.
The activity of the catalyst prepared in the test example is 30.9kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 10.1g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =71.2 μm, and the particle size distribution ((D90-D10)/D50) was 1.65=4.6. Melting point T m At 134.9 ℃and crystallization temperature T c 107.3℃and is shown in Table 1.
Preparation example 2 of Polypropylene powder
Polypropylene was prepared in a similar manner to polypropylene microparticle preparation 1, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in the test example polypropylene microparticle preparation example 1.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The activity of the catalyst prepared in the test example is 30.8kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 40.4g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =85 μm, and the particle size distribution ((D90-D10)/D50) was 1.77. Melting point T m At 129.18 ℃and crystallization temperature T c Is 101.03 ℃and is shown in Table 1.
Preparation example 3 of Polypropylene powder
Polypropylene was prepared in a similar manner to polypropylene microparticle preparation 1, except that: in the step (1), the kind of the catalyst carrier used is different, and in the step (2), the antioxidant 168 is used, and the rest is the same as in the polypropylene microparticle preparation example 1.
Specific: replacing the catalyst spherical carrier Z1 with the catalyst spherical carrier Z2 prepared in the preparation example 2 of the catalyst microsphere carrier with the same weight to obtain an olefin polymerization catalyst C2; then, the polypropylene powder is prepared according to the step (2) of the polypropylene microparticle preparation example 1 by using an olefin polymerization catalyst C2.
The activity of the catalyst prepared in the test example is 31.5kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 9.8g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =4.7, average particle diameter D (50) =74.5 μm, particle size distribution ((D90-D10)/D50) is 1.74. Melting point T m At 137.46 ℃and crystallization temperature T c For 110.03 ℃, see table 1 in particular.
Preparation example 4 of Polypropylene powder
Polypropylene was prepared in a similar manner to polypropylene microparticle preparation 3, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in the polypropylene microparticle preparation example 3.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The activity of the catalyst prepared in the test example is 31.1kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 36.7g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =5.3, average particle diameter D (50) =67.1 μm, particle size distribution ((D90-D10)/D50) is 1.91. Melting point T m At 135.18 ℃and crystallization temperature T c For 107.43 ℃, see table 1 in particular.
Preparation example 5 of Polypropylene powder
Polypropylene was prepared in a similar manner to polypropylene microparticle preparation 1, except that: in the step (1), the type of the catalyst carrier used was different, and in the step (2), the antioxidant 1076 was used, and the remainder was the same as in the polypropylene microparticle preparation example 1.
Specific: replacing the catalyst spherical carrier Z1 with the catalyst spherical carrier Z3 prepared in the preparation example 3 of the catalyst microsphere carrier with the same weight to obtain an olefin polymerization catalyst C3; then, the polypropylene powder is prepared according to the step (2) of the polypropylene microparticle preparation example 1 by using an olefin polymerization catalyst C3.
The activity of the catalyst prepared in the test example is 32.4kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 8.8g/10min, the polypropylene powder has good particle morphology, basically no special-shaped material exists, the average particle diameter D (50) =65.6 mu M, and the molecular weight distribution M w /M n =5.3, the particle size distribution ((D90-D10)/D50) was 1.84. Melting point T m At 139.55 ℃and crystallization temperature T c 113.5℃and is shown in Table 1.
Preparation example 6 of Polypropylene powder
Polypropylene was prepared in a similar manner to polypropylene microparticle preparation 5, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in the test example polypropylene microparticle preparation example 5.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The activity of the catalyst prepared in the test example is 32.1kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 35.8g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =67.3 μm, and the particle size distribution ((D90-D10)/D50) was 1.87=5.7. Melting point T m At 140.2℃and crystallization temperature T c For 117.41 ℃, see table 1 in particular.
Preparation example 7 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: in the step (2), the amount of the antioxidant to be added was varied, and the rest was the same as in the polypropylene powder preparation example 1. Specifically, 5.5mg of antioxidant 1010 was added;
the activity of the catalyst prepared in the test example is 30.3kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder is 99.45 parts and the antioxidant is 0.55 part.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 9.8g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =71.3 μm, and the particle size distribution ((D90-D10)/D50) was 1.70=4.6. Melting point T m At 134.8℃and crystallization temperature T c At 107.0deg.C, see Table 1 for details.
Preparation example 8 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: in the step (2), the amount of the antioxidant to be added was different, and the rest was the same as in the test example polypropylene powder preparation example 1. Specifically, 6.5mg of antioxidant 1010 was added;
The activity of the catalyst prepared in the test example is 29.8kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder is 99.35 parts and the antioxidant is 0.65 part.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 9.6g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =4.6, average particle diameter D (50) =71.5 μm, particle size distribution ((D90-D10)/D50) is 1.72. Melting point T m At 134.6℃and crystallization temperature T c At 106.9℃see Table 1 for details.
Preparation example 9 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: in the step (2), the amount of the antioxidant to be added was different, and the rest was the same as in the test example polypropylene powder preparation example 1. Specifically, 7mg of antioxidant 1010 was added;
the activity of the catalyst prepared in the test example is 29.2kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.3 parts of polypropylene and 0.7 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 9.5g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =4.6, average particle diameter D (50) =71.6 μm, particle size distribution ((D90-D10)/D50) is 1.74. Melting point T m At 134.3℃and crystallization temperature T c 106.8℃and is shown in Table 1.
Preparation example 10 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation example 1 except that antioxidant 264 was used in place of antioxidant 1010.
The activity of the catalyst prepared in the test example is 27.8kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.42g/cm 3 The melt flow rate index is 9.9g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =4.6, average particle diameter D (50) =71.2 μm, particle size distribution ((D90-D10)/D50) is 1.76. Melting point T m At 134.7 ℃and crystallization temperature T c At 107.2℃see in particular Table 1.
Preparation example 11 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: the polymerization temperature was 65 ℃.
The activity of the catalyst prepared in the test example is 31.4kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.42g/cm 3 The melt flow rate index is 9.3g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n =7.1, average particle diameter D (50) =76.3 μm, particle size distribution ((D90-D10)/D50) is 1.97. Melting point T m At 136.8℃and crystallization temperature T c At 107.9℃and is shown in Table 1.
Comparative preparation example 1 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: in the step (1), the kind of the catalyst carrier used was different, and the rest was the same as in the test example polypropylene microparticle preparation example 1.
Specific: the catalyst spherical carrier DZ1 prepared in comparative example 1 was used in place of the catalyst spherical carrier Z1 to obtain an olefin polymerization catalyst DC1, and then the olefin polymerization catalyst DC1 was used to prepare a polypropylene powder according to step (2) of preparation example 1 of polypropylene microparticles.
The activity of the catalyst prepared in the test example is 30.3kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.37g/cm 3 Melt flow Rate index 8.2g/10min, molecular weight distribution M w /M n The average particle diameter D (50) =115 μm, and the particle size distribution ((D90-D10)/D50) was 2.6=8.1. Melting point T m At 135.4℃and crystallization temperature T c 110.6℃and is shown in Table 1.
Comparative preparation example 2 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: in the step (1), the kind of the catalyst carrier used was different, and the rest was the same as in the polypropylene powder preparation example 1.
Specific: the catalyst spherical carrier DZ2 prepared in comparative example 2 was used in place of the catalyst spherical carrier Z1 to obtain an olefin polymerization catalyst DC2, and then the olefin polymerization catalyst DC2 was used to prepare a polypropylene powder according to step (2) of preparation example 1 of polypropylene microparticles.
The activity of the catalyst prepared in the test example is 31.9kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 Melt flow Rate index 7.8g/10min, molecular weight distribution M w /M n 8.3, average particle diameter D (50) =131.5 μm, particle size distribution ((D90-D10)/D50) of 2.71. Melting point T m At 136.4℃and crystallization temperature T c At 109.2℃in particular, seeTable 1.
Comparative preparation example 3 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder comparative example 2, except that: in the step (2), the volume of hydrogen used was different, and the rest was the same as in the polypropylene powder comparative example 2.
Specific: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The activity of the catalyst prepared in the test example is 31.5kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 Melt flow Rate index 35.5g/10min, molecular weight distribution M w /M n 8.2, average particle diameter D (50) =127.6 μm, particle size distribution ((D90-D10)/D50) of 2.75. Melting point T m At 132.5℃and crystallization temperature T c 106.3℃and is shown in Table 1.
Comparative preparation example 4 of Polypropylene powder
1.5kg of PP granules (B4808, purchased from Yanshan petrochemical industry, MFR=11.1 g/10 min) are frozen in liquid nitrogen at low temperature until the embrittlement temperature is below minus 35 ℃, and then the frozen polypropylene material is put into a cavity of a low-temperature pulverizer and is pulverized by high-speed rotation of an impeller; classifying and collecting the obtained polypropylene powder by an airflow screening machine, selecting the polypropylene powder with the granularity within the range of 200-800 meshes, and returning coarse materials which do not reach the fineness requirement to a storage bin for continuous crushing; 9mg of antioxidant 1010 is added into the obtained polypropylene powder, and the mixture is put into a high-speed mixer to be uniformly mixed, so as to obtain polypropylene powder. Wherein, in the PP pellets, the ethylene provides a content of structural units of 1.75wt%. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 Melt flow index of 18.6g/10min, molecular weight distribution M w /M n The average particle diameter D (50) =40 μm, and the particle size distribution ((D90-D10)/D50) was 3.20=9.4. Melting point T m At 132.7deg.C, crystallization temperature T c At 104.3℃see in particular Table 1.
Comparative preparation example 5 of Polypropylene powder
The oil bath was warmed up, an experimental apparatus was installed, and then 1.5kg of polypropylene pellets (same as comparative example 4), 5.2L of xylene, and 7.5mg of antioxidant 1010 were added to the flask, and thoroughly stirred to be sufficiently dissolved. Stopping heating, and dropwise adding 11.4L of absolute ethyl alcohol into the flask at a rate of 2mL/min under natural cooling to carry out stirring precipitation. And cooling the mixed solution to room temperature, vacuum filtering, drying and grinding to obtain the polypropylene powder. Wherein, in the PP pellets, the ethylene provides a content of structural units of 1.75wt%. Based on the total weight of the polypropylene powder, the polypropylene powder comprises 99.5 parts of polypropylene and 0.5 part of antioxidant.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 Melt flow Rate index MFR 9.9g/10min, molecular weight distribution M w /M n 8.8, average particle diameter D (50) =86.4 μm, particle size distribution ((D90-D10)/D50) of 2.89. Melting point T m At 129.8℃and crystallization temperature T c 107.1℃and is shown in Table 1.
Comparative preparation example 6 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: does not contain an antioxidant.
The activity of the catalyst prepared in the test example is 32.5kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, 100 parts of polypropylene are used.
The bulk density of the obtained polypropylene powder was 0.42g/cm 3 The melt flow rate index is 10.2g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =71.1 μm, and the particle size distribution ((D90-D10)/D50) was 1.73. Melting point T m At 135.1℃and crystallization temperature T c At 107.6deg.C, in particularSee table 1.
Comparative preparation example 7 of Polypropylene powder
Polypropylene powder was prepared in a similar manner to polypropylene powder preparation 1 except that: the amount of antioxidant added varies.
Specific: 12mg of antioxidant 1010 was used.
The activity of the catalyst prepared in the test example is 30.2kg PP/g.Cat; the resulting polypropylene powder had an ethylene content of 1.9% by weight of structural units. Based on the total weight of the polypropylene powder, the polypropylene powder is 98.8 parts and the antioxidant is 1.2 parts.
The bulk density of the obtained polypropylene powder was 0.41g/cm 3 The melt flow rate index is 9.1g/10min, the polypropylene powder has good particle morphology, no special material exists basically, and the molecular weight distribution M w /M n The average particle diameter D (50) =71.1 μm, and the particle size distribution ((D90-D10)/D50) was 1.72=4.7. Melting point T m At 134.6℃and crystallization temperature T c 107.1℃and is shown in Table 1.
TABLE 1
Table 1 (subsequent)
As can be seen from the data shown in Table 1, when the polypropylene is polymerized, the particle morphology of the olefin polymerization catalyst carrier is controlled to directly prepare the polypropylene powder with small particle size, narrow particle size distribution, smooth surface, moderate melt fluidity and uniform shape, and the polypropylene powder can be directly used for selective laser sintering 3D printing.
Examples and comparative examples
In a selective laser sintering printer, 1kg of the polypropylene powder preparation example or the comparative example is added, parameters such as the working temperature, the laser power, the scanning speed and the like are adjusted to print sample bars, the sample bars are specifically shown in table 2, and then the mechanical properties of the sample bars are tested, and the specific results are shown in table 3.
TABLE 2
TABLE 3 Table 3
| Examples | Polypropylene powder | Tensile Strength/MPa | Nominal strain/% | Flexural Strength/MPa | Flexural modulus/GPa |
| Example 1 | Preparation example 1 | 28.6 | 19.5 | 31.5 | 1.34 |
| Example 2 | Preparation example 1 | 27.8 | 23.6 | 31.1 | 1.26 |
| Example 3 | Preparation example 2 | 27.4 | 20.1 | 29.5 | 1.19 |
| Example 4 | Preparation example 3 | 26.8 | 23.1 | 29.9 | 1.24 |
| Example 5 | Preparation example 4 | 26.3 | 20.5 | 29.2 | 1.15 |
| Example 6 | Preparation example 5 | 27 | 22.1 | 28.7 | 1.11 |
| Example 7 | Preparation example 6 | 26.2 | 24.3 | 27.8 | 1.06 |
| Example 8 | Preparation example 7 | 28.1 | 20.4 | 30.9 | 1.31 |
| Example 9 | Preparation example 8 | 27.8 | 20.3 | 30.6 | 1.30 |
| Example 10 | Preparation example 9 | 27.5 | 20.4 | 30.3 | 1.28 |
| Example 11 | Preparation example 10 | 24.6 | 20.3 | 25.7 | 1.05 |
| Example 12 | PREPARATION EXAMPLE 11 | 25.3 | 20.7 | 26.9 | 1.08 |
| Comparative example 1 | Comparative preparation example 1 | 22.9 | 15.6 | 25.2 | 1.07 |
| Comparative example 2 | Comparative preparation example 1 | 22.2 | 18.9 | 24.9 | 1.01 |
| Comparative example 3 | Comparative preparation example 2 | 21.9 | 18.5 | 23.9 | 0.99 |
| Comparative example 4 | Comparative preparation example 3 | 21.6 | 17.8 | 23 | 0.89 |
| Comparative example 5 | Comparative preparation example 4 | - | - | - | - |
| Comparative example 6 | Comparative preparation example 5 | 21.4 | 19.4 | 23.4 | 0.92 |
| Comparative example 7 | Comparative preparation example 5 | 21.1 | 16.1 | 22.2 | 0.85 |
| Comparative example 8 | Comparative preparation example 6 | - | - | - | - |
| Comparative example 9 | Comparative preparation example 7 | 21.2 | 17.0 | 22.9 | 0.90 |
When the polypropylene powder provided by the invention is used for selective laser sintering 3D printing, the polypropylene powder has small particle size, the prepared 3D printing spline has smooth surface and excellent surface quality, and more importantly, the mechanical property of the 3D printing spline prepared from the polypropylene powder provided by the invention is obviously higher than that of the polypropylene particles prepared by the prior art, and in addition, the printing operability is stronger.
Whereas the polypropylene powder provided in comparative example 5 was interrupted due to the uneven and uneven particles, which were significantly shifted in size during printing, the polypropylene powder provided in comparative example 8 did not contain an antioxidant, which resulted in the polypropylene powder being significantly sticky and roll-sticking during printing.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. The polypropylene powder for 3D printing is characterized by comprising polypropylene and an antioxidant;
based on the total weight of the polypropylene powder, 99-99.5 parts of polypropylene and 0.5-1 part of antioxidant are used;
the molecular weight distribution index M of the polypropylene powder w /M n 4-8; the particle size distribution of the polypropylene powder is less than 2.5.
2. The polypropylene powder according to claim 1, wherein the polypropylene powder has a particle size distribution of less than 2;
preferably, the polypropylene powder has a molecular weight distribution index M w /M n 4.5-6;
preferably, the polypropylene powder has an average particle diameter D50 of 10-500. Mu.m, preferably 50-200. Mu.m;
preferably, the polypropylene powder has a melting point T m 120-170 ℃, preferably 129-160 ℃;
preferably, the crystallization temperature of the polypropylene powderDegree T c 80-130 ℃, preferably 95-120 ℃;
preferably, the melt flow rate MFR of the polypropylene powder is in the range of 1 to 1000g/10min, preferably 1 to 399g/10min, more preferably 10 to 50g/10min, at 230℃and a load of 2.16 kg;
preferably, the bulk density of the polypropylene powder is 0.3-0.5g/cm 3 Preferably 0.35-0.45g/cm 3 。
3. Polypropylene powder according to claim 1 or 2, wherein the polypropylene is a copolymer of propylene with ethylene and/or an α -olefin;
Preferably, the content of structural units provided by the ethylene and/or alpha-olefin is from 1 to 5wt%, based on the total weight of the polypropylene;
preferably, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
4. A method for preparing the polypropylene powder for 3D printing according to any one of claims 1 to 3, comprising:
in the presence of a catalyst and an antioxidant, carrying out polymerization reaction on olefin containing propylene and ethylene and/or alpha-olefin to obtain the polypropylene powder for 3D printing;
preferably, the catalyst comprises a spherical support;
preferably, the spherical support has an average particle diameter of from 2 to 100 microns, preferably from 2 to 19 microns, and a particle size distribution of less than 2, preferably from 0.6 to 1.6.
5. The process of claim 4, wherein the volume ratio of propylene to ethylene and/or alpha-olefin is from 12.6 to 80:1, a step of;
preferably, the antioxidant is used in an amount of 0.5 to 1wt% relative to the total amount of olefins;
preferably, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
6. The method according to claim 4 or 5, wherein the spherical support has a structure represented by formula (1);
Wherein in formula (1), R 1 Selected from C 1-10 Alkyl of (a);
R 2 and R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
R 4 selected from C substituted by at least one halogen atom 1-10 Haloalkyl groups and C substituted by at least one halogen atom 6-20 Is a halogenated aromatic group;
R 5 selected from C 1-5 Alkyl of (a);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1.
7. The preparation method according to any one of claims 4 to 6, wherein the spherical support is prepared by:
(1) Sequentially carrying out first contact and emulsification on a component A to obtain a first product, wherein the component A contains magnesium halide with a general formula of MgXY and a general formula of R 1 A first alcohol compound of OH;
(2) Carrying out second contact on the first product and a component B to obtain a second product, wherein the component B contains an ethylene oxide compound with a structure shown in a formula (2);
(3) The second product is subjected to third contact with a component C to obtain a third product, wherein the component C contains a compound with a general formula of R 4 Halogenated alcohols of OH with the general formula R 5 A second glycol compound of OH;
(4) Subjecting the third product to spray drying;
wherein in formula R 1 In OH, R 1 Selected from C 1-10 Alkyl of (a);
in formula (2), R 2 And R is 3 Each independently selected from H, C 1-10 Alkyl of (2) and C substituted by 1-10 halogen atoms 1-10 A haloalkyl group of (2);
in R 4 In OH, R 4 Selected from C substituted by at least one halogen atom 1-10 Haloalkyl groups and C substituted by at least one halogen atom 6-20 Is a halogenated aromatic group;
in R 5 In OH, R 5 Selected from C 1-5 Alkyl of (a);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C of (2) 1-6 Alkoxy, C 6-14 Aryl and C of (2) 6-14 An aryloxy group of (a);
the amounts of the component a, the component B and the component C are such that the resulting spherical support has a structure represented by formula (1):
in formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0< q <0.2;0< a <0.1;
wherein in the step (3), the amount of the halohydrin is 0.05 to 6.5mol and the amount of the second glycol compound is 5 to 100mol with respect to 1mol of the magnesium halide.
8. The production method according to claim 7, wherein the magnesium halide is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymethyl chloride and n-butoxymagnesium chloride;
preferably, the first alcohol compound is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, n-octanol and 2-ethylhexanol;
Preferably, the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, propylene oxide and butylene oxide;
preferably, the halogenated alcohol is at least one selected from 2, 2-trichloroethanol, 2-dichloroethanol, 1, 3-dichloropropanol and 1, 4-dichlorobutanol;
preferably, the first alcohol compound is used in an amount of 6 to 22mol, the ethylene oxide compound is used in an amount of 2 to 6mol, the halohydrin is used in an amount of 1 to 5mol, and the second alcohol compound is used in an amount of 8 to 80mol, relative to 1mol of the magnesium halide.
9. The production method according to claim 7 or 8, wherein the first contact is performed under stirring conditions, and the conditions of the first contact include: the temperature is 80-120deg.C, preferably 80-100deg.C, and the time is 0.5-5 hr, preferably 0.5-3 hr;
preferably, the conditions of the second contact include: the temperature is 50-120deg.C, preferably 80-100deg.C, and the time is 20-60min, preferably 20-50min;
preferably, the spray drying conditions include: the temperature is 60-200deg.C, preferably 90-150deg.C.
10. The production method according to any one of claims 4 to 9, wherein the catalyst further comprises: a titanium halide compound and an electron donor compound;
Preferably, the titanium halide compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tri-n-butoxide, titanium di-n-butoxide dichloride, titanium mono-n-butoxide trichloride, titanium tri-ethoxide, titanium di-ethoxide dichloride, titanium mono-ethoxide trichloride, and titanium trichloride;
preferably, the electron donor compound is selected from at least one of diisobutyl phthalate, carboxylic acid glycol esters and phosphoric acid esters.
11. Use of the polypropylene powder for 3D printing according to any one of claims 1 to 3 for selective laser sintering 3D printing.
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