JP6430643B2 - ポリプロピレンを押出す方法 - Google Patents
ポリプロピレンを押出す方法 Download PDFInfo
- Publication number
- JP6430643B2 JP6430643B2 JP2017528114A JP2017528114A JP6430643B2 JP 6430643 B2 JP6430643 B2 JP 6430643B2 JP 2017528114 A JP2017528114 A JP 2017528114A JP 2017528114 A JP2017528114 A JP 2017528114A JP 6430643 B2 JP6430643 B2 JP 6430643B2
- Authority
- JP
- Japan
- Prior art keywords
- nucleating agent
- ppm
- polypropylene
- extrudate
- acid scavenger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 polypropylene Polymers 0.000 title claims description 135
- 239000004743 Polypropylene Substances 0.000 title claims description 132
- 229920001155 polypropylene Polymers 0.000 title claims description 132
- 239000002667 nucleating agent Substances 0.000 claims description 156
- 239000000203 mixture Substances 0.000 claims description 127
- 239000002253 acid Substances 0.000 claims description 87
- 239000002516 radical scavenger Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229940114930 potassium stearate Drugs 0.000 claims description 16
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 16
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000008116 calcium stearate Substances 0.000 claims description 13
- 235000013539 calcium stearate Nutrition 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000002892 organic cations Chemical class 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002837 carbocyclic group Chemical group 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000002619 bicyclic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000001767 cationic compounds Chemical class 0.000 claims description 3
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 description 41
- 230000008025 crystallization Effects 0.000 description 41
- 239000004615 ingredient Substances 0.000 description 35
- FXDGCBFGSXNGQD-FAESFXMKSA-L disodium;(1s,2s,3r,4r)-bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C[C@H]2[C@@H](C([O-])=O)[C@@H](C(=O)[O-])[C@@H]1C2 FXDGCBFGSXNGQD-FAESFXMKSA-L 0.000 description 31
- 238000009472 formulation Methods 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 26
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 description 24
- 229920001519 homopolymer Polymers 0.000 description 20
- 238000001125 extrusion Methods 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- 238000010899 nucleation Methods 0.000 description 12
- 230000006911 nucleation Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 10
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 8
- 235000010234 sodium benzoate Nutrition 0.000 description 8
- 239000004299 sodium benzoate Substances 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229940031993 lithium benzoate Drugs 0.000 description 4
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 4
- 235000019359 magnesium stearate Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000000159 acid neutralizing agent Substances 0.000 description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 3
- 229940063655 aluminum stearate Drugs 0.000 description 3
- YDIVFMQLYNSNFM-UHFFFAOYSA-K aluminum;4-tert-butylbenzoic acid;trihydroxide Chemical group [OH-].[OH-].[OH-].[Al+3].CC(C)(C)C1=CC=C(C(O)=O)C=C1.CC(C)(C)C1=CC=C(C(O)=O)C=C1 YDIVFMQLYNSNFM-UHFFFAOYSA-K 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- OEUVSBXAMBLPES-UHFFFAOYSA-L calcium stearoyl-2-lactylate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C([O-])=O.CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C([O-])=O OEUVSBXAMBLPES-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- FXDGCBFGSXNGQD-UHFFFAOYSA-L disodium;bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1CC2C(C([O-])=O)C(C(=O)[O-])C1C2 FXDGCBFGSXNGQD-UHFFFAOYSA-L 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229940114069 12-hydroxystearate Drugs 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- KHICUSAUSRBPJT-UHFFFAOYSA-N 2-(2-octadecanoyloxypropanoyloxy)propanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C(O)=O KHICUSAUSRBPJT-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- FDKAAIFOPLCYAM-UHFFFAOYSA-M C(C(O)C)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[Ca+] Chemical compound C(C(O)C)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[Ca+] FDKAAIFOPLCYAM-UHFFFAOYSA-M 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004596 additive masterbatch Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 description 1
- 229940007076 aluminum cation Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000010957 calcium stearoyl-2-lactylate Nutrition 0.000 description 1
- MIHDGSOYBPAAHC-UHFFFAOYSA-L calcium;bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical class [Ca+2].C1CC2C(C([O-])=O)C(C(=O)[O-])C1C2 MIHDGSOYBPAAHC-UHFFFAOYSA-L 0.000 description 1
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229920006379 extruded polypropylene Polymers 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010103 injection stretch blow moulding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- KJSPVJJOPONRTK-UHFFFAOYSA-M lithium;tetradecanoate Chemical compound [Li+].CCCCCCCCCCCCCC([O-])=O KJSPVJJOPONRTK-UHFFFAOYSA-M 0.000 description 1
- 229940096405 magnesium cation Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VIALJPAGUCTUBQ-UHFFFAOYSA-L magnesium;12-hydroxyoctadecanoate Chemical compound [Mg+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O VIALJPAGUCTUBQ-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- FRZSCIVUSFMNBX-UHFFFAOYSA-L zinc;12-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O FRZSCIVUSFMNBX-UHFFFAOYSA-L 0.000 description 1
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- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- C08J5/18—Manufacture of films or sheets
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
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Description
の構造に適合する。
試験方法
[0044]ピーク結晶化温度(Tc)− 20℃/分の速度で50℃から220℃まで加熱し、2分間保持し、20℃/分の速度で冷却して50℃に戻すプロファイルで修正した、ASTM D3418−08に従って、すべての例のピーク結晶化温度(Tc)を決定した。これらの条件下で、次いでピークTcを結晶化発熱から決定した。Mettler Toledo DSC822およびMettler Toledo DSC 1Starの2台の計器が、試料の測定に関与した。2台の計器間のTcバイアスは約1℃であった。
[0046]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量の成核剤を有する無核等級のポリプロピレンおよびポリプロピレン組成物のTcに対する様々な酸スカベンジャーの影響をシミュレートする。
[0052]好ましい酸中和剤が、残留核形成による不要な影響をいかに早く低減できたかを例示するために、MADDOCKS(商標)ミキサー(約6kg/時の典型的な出力)を備えたDELTAPLAST(商標)25mm一軸スクリュー押出機(30:1l/d)での実験を計画した。バレル温度プロファイルを、最大ゾーン設定の約230℃で設定した。溶融したポリマーを60メッシュのスクリーンパックから濾過し、次いで、ストランドダイから押出した。次いで、ストランドを水浴でクエンチし、乾燥し、ペレット化した。
[0060]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量の様々な市販の成核剤を有する無核等級のポリプロピレンおよび様々な好ましい酸スカベンジャーのポリプロピレン組成物のTcに対する影響をシミュレートする。
[0066]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量のHPN−20Eを有する無核等級のポリプロピレンおよびステアリン酸の金属塩を含むクラスからの様々な酸スカベンジャーの影響をシミュレートする。
[0072]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量のHPN−68Lを有する無核等級のポリプロピレンおよび金属脂肪酸塩を含むクラスからの様々な酸スカベンジャーの影響をシミュレートする。
[0081]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量のHPN−20Eを有する無核等級のポリプロピレン、ならびに様々な無機添加剤および酸スカベンジャーの影響をシミュレートする。
[0087]いくつかのポリプロピレン押出システムは、最初に成核剤(50ppm超の量)を有するポリプロピレンを押出し、次いで無核等級のポリプロピレンに切り替える。無核等級のポリプロピレンもやはり残留量(1ppm)の成核剤を含有し得る。この例は、残留量のHPN−68Lを有する無核等級のポリプロピレン、ならびに様々な無機添加剤および酸スカベンジャーの影響をシミュレートする。
[0093]先の試験は、ステアリン酸カリウムにより、残留量のHPN−20EとHPN−68Lの両方の存在下で、好ましい低いピーク結晶化温度になることを示している。一方で、ステアリン酸カルシウムでは、残留量のHPN−20EとHPN−68Lの両方の存在下で、一貫して不必要に高いピーク結晶化温度になった。この試験は、炭素鎖長が、カリウムまたはカルシウム脂肪酸塩のいずれかの作用に影響を及ぼすかどうかを理解するために行われた。
[00100]先の試験はすべて、ある種の酸中和剤により、1ppm以下の残留量の成核剤を含有するポリプロピレン系において、いかに所望の低いまたはベースライン結晶化温度にすることができるのかを例示している。この実験は、ステアリン酸カリウムが、10ppmから従来の使用量(usage loading)の500ppmおよび1000ppmまでの濃度の成核剤を有するPP系における核形成にいかに影響を与えるのかを評価する。ステアリン酸カリウムよりもステアリン酸カルシウムを含有する同様の有核系についても比較した。
[00107]先の試験は、残留量の成核剤との相互作用を理解するために、典型的な商業的配合量の約500ppmで脂肪酸塩を評価した。この実験は、所望の低い結晶化温度が、より高い配合量の酸スカベンジャーを使用することにより、強化され得るかどうかを決定することを試みる。
以下に、本発明の実施態様を付記する。
1. a)第1の組成物を押出して第1の押出物を形成することであり、第1の組成物が、第1のポリプロピレン、成核剤および第1の酸スカベンジャーを含み、成核剤が少なくとも約50ppmの量である、第1の押出物を形成することと、
b)第2の組成物を押出して第2の押出物を形成することであり、第2の組成物が、第2のポリプロピレンおよび第2の酸スカベンジャーを含み、第2の酸スカベンジャーが、第2の押出物を形成する脂肪酸のカリウム塩であり、第2の押出物が、成核剤を約10ppm未満含有する、第2の押出物を形成することと
を順番に含む、ポリプロピレンを押出す方法。
2. 第1の酸スカベンジャーが、ステアリン酸カルシウムおよびハイドロタルサイトからなる群から選択される、1に記載の方法。
3. 成核剤が、脂環式金属塩を含む、1に記載の方法。
4. 成核剤が、式(I)
の構造に適合する、少なくとも1種の金属塩を含む、1に記載の方法。
5. R 1 〜R 10 が水素であり、M 1 がカルシウムカチオンである、4に記載の方法。
6. 成核剤が、式(II)
7. R 20 〜R 29 が水素であり、M 11 およびM 12 がナトリウムカチオンである、6に記載の方法。
8. 第2の押出物が、成核剤を約1ppm未満の量で含む、1に記載の方法。
9. 第2の押出物が、ペレット化された樹脂を形成する、1に記載の方法。
10.
第2の酸スカベンジャーが、カリウムカチオンおよびC 3 〜C 22 脂肪酸アニオンを含む、1に記載の方法。
11. 第2の酸スカベンジャーが、ステアリン酸カリウムを含む、1に記載の方法。
12. 第2の押出物中の全成核剤の含有量が、10ppm未満である、1に記載の方法。
13. 第1の押出物のT c と第2の押出物のT c との差異が約5℃超である、1に記載の方法。
14. 少なくとも1層を含む二軸延伸ポリプロピレンフィルムであって、フィルムの少なくとも1層が、成核剤、脂肪酸のカリウム塩およびポリプロピレンから本質的になる熱可塑性物質を含み、フィルム中の全成核剤の含有量が、10ppm未満であり、フィルム層中の熱可塑性物質すべてが、ポリプロピレンから本質的になり、成核剤が、式(I)
または式(II)
15. 第2の酸スカベンジャーが、カリウムカチオンおよびC 3 〜C 22 脂肪酸アニオンを含む、14に記載のフィルム。
Claims (11)
- a)押出機により、第1の組成物を押出して第1の押出物を形成し、第1の押出組成物をペレット化することであり、第1の組成物が、第1の反応器フレークポリプロピレン、成核剤および第1の酸スカベンジャーを含み、成核剤が少なくとも50ppmの量である、第1の押出物を形成することと、
b)工程a)に続く直後に、押出機により、第2の組成物を押出して第2の押出物を形成し、第2の押出組成物をペレット化することであり、第2の組成物が、第2の反応器フレークポリプロピレンおよび第2の酸スカベンジャーを含み、第2の酸スカベンジャーが、第2の押出物を形成する脂肪酸のカリウム塩であり、第2の押出物が、0.01ppm〜1ppm成核剤を含有し、第2の押出物中の全成核剤の量は、10ppm未満である、第2の押出物を形成することを順番に含む、ポリプロピレンを押出す方法。 - 第1の酸スカベンジャーが、ステアリン酸カルシウムおよびハイドロタルサイトからなる群から選択される、請求項1に記載の方法。
- 第1の酸スカベンジャーとが第2の酸スカベンジャーが同じ組成物である、請求項1に記載の方法。
- 成核剤が、脂環式金属塩を含む、請求項1に記載の方法。
- 成核剤が、式(I)
の構造に適合する、少なくとも1種の金属塩を含む、請求項1に記載の方法。 - R1〜R10が水素であり、M1がカルシウムカチオンである、請求項5に記載の方法。
- R20〜R29が水素であり、M11およびM12がナトリウムカチオンである、請求項7に記載の方法。
- 第2の酸スカベンジャーが、カリウムカチオンおよびC3〜C22脂肪酸アニオンを含む、請求項1に記載の方法。
- 第2の酸スカベンジャーが、ステアリン酸カリウムを含む、請求項1に記載の方法。
- 第1の押出物のTcと第2の押出物のTcとの差異が5℃超である、請求項1に記載の方法。
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US201462084125P | 2014-11-25 | 2014-11-25 | |
US62/084,125 | 2014-11-25 | ||
PCT/US2015/059404 WO2016085634A1 (en) | 2014-11-25 | 2015-11-06 | Process for extruding polypropylene |
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EP (1) | EP3224302A1 (ja) |
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CN113773550B (zh) * | 2020-06-09 | 2022-10-11 | 中国科学院化学研究所 | 一种热塑性塑料用纳米复合成核剂、制备方法及其在聚丙烯中的应用 |
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WO2022101683A1 (en) * | 2020-11-13 | 2022-05-19 | Braskem S.A. | Processing of polypropylene and products therefrom |
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US20180265670A1 (en) | 2018-09-20 |
US10711115B2 (en) | 2020-07-14 |
WO2016085634A1 (en) | 2016-06-02 |
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