WO2016004325A1 - Mélanges de carbonate revêtu d'acide gras avec du carbonate non traité destiné à être utilisé dans le traitement en fusion de polymères chargés de carbonate - Google Patents
Mélanges de carbonate revêtu d'acide gras avec du carbonate non traité destiné à être utilisé dans le traitement en fusion de polymères chargés de carbonate Download PDFInfo
- Publication number
- WO2016004325A1 WO2016004325A1 PCT/US2015/039015 US2015039015W WO2016004325A1 WO 2016004325 A1 WO2016004325 A1 WO 2016004325A1 US 2015039015 W US2015039015 W US 2015039015W WO 2016004325 A1 WO2016004325 A1 WO 2016004325A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- earth metal
- alkali earth
- metal carbonate
- treated
- Prior art date
Links
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 9
- 239000000194 fatty acid Substances 0.000 title claims description 9
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- 150000004665 fatty acids Chemical class 0.000 title claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 206
- 238000004381 surface treatment Methods 0.000 claims abstract description 99
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- 238000002156 mixing Methods 0.000 claims abstract description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 131
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 229940088990 ammonium stearate Drugs 0.000 description 2
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910001748 carbonate mineral Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920001279 poly(ester amides) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000002166 wet spinning Methods 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
- 229910052726 zirconium Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- 206010016275 Fear Diseases 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 1
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- OZOJSEUUJMZMCQ-UHFFFAOYSA-L barium(2+);pentanoate Chemical compound [Ba+2].CCCCC([O-])=O.CCCCC([O-])=O OZOJSEUUJMZMCQ-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002902 bimodal effect Effects 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
- YZLMERHFSCVBKZ-UHFFFAOYSA-L calcium;pentanoate Chemical compound [Ca+2].CCCCC([O-])=O.CCCCC([O-])=O YZLMERHFSCVBKZ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- BXDNFAXUAQVKRQ-UHFFFAOYSA-L cobalt(2+);pentanoate Chemical compound [Co+2].CCCCC([O-])=O.CCCCC([O-])=O BXDNFAXUAQVKRQ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MCJLRTHYUFIPCD-UHFFFAOYSA-K di(pentanoyloxy)alumanyl pentanoate Chemical compound [Al+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O MCJLRTHYUFIPCD-UHFFFAOYSA-K 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- YXCWHISSFUSKMR-UHFFFAOYSA-N docosa-4,7,10,13,18,19-hexaenoic acid Chemical compound CCC=C=CCCCC=CCC=CCC=CCC=CCCC(O)=O YXCWHISSFUSKMR-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- PWDTYUOSZRLLEV-UHFFFAOYSA-L magnesium;pentanoate Chemical compound [Mg+2].CCCCC([O-])=O.CCCCC([O-])=O PWDTYUOSZRLLEV-UHFFFAOYSA-L 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- IFJYVNTXUVQYOU-UHFFFAOYSA-J pentanoate zirconium(4+) Chemical compound [Zr+4].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O IFJYVNTXUVQYOU-UHFFFAOYSA-J 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LLOLUUSIFMACRO-UHFFFAOYSA-L strontium;pentanoate Chemical compound [Sr+2].CCCCC([O-])=O.CCCCC([O-])=O LLOLUUSIFMACRO-UHFFFAOYSA-L 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
Definitions
- compositions for use in melt-processing of filled polymer products including polymer fibers, polymer nonwovens, and polymer films.
- Nonwoven fabrics and monofilament fibers can be made by melt spinning, dry spinning, or wet spinning. In particular, nonwoven fabrics and
- monofilament fibers may be produced by spinning a polymeric resin into the shape of a fiber, such as by heating the resin to at least its softening temperature and extruding the resin through a spinneret. Monofilament fibers may also be produced by extruding the resin and attenuating the streams of resin by hot air to form fibers with a fine diameter. Commercial products can also be formed from polymeric films, such as for packaging or protective layers.
- thermoplastic polymeric resin each year, about 300 million pounds of monofilament fiber.
- These fibers may incorporate various mineral fillers, such as calcium carbonate and kaolin, during production of non-woven products, polymeric films, and molded parts.
- mineral fillers such as calcium carbonate and kaolin
- increasing polymeric resin prices have created cost-benefits associated with increasing the quantity of mineral fillers and decreasing the quantity of resin in many products.
- the required amount of virgin polymer resin material decreases while the end product may have comparable quality in areas such as fiber strength, texture, and appearance.
- a surface treatment can be added to the filler material.
- Calcium carbonate (CaC0 3 ) is a commonly used filler/extender for the polymer industry. Due to its hydrophilic nature and having a high surface energy, it may be incompatible with the most common hydrophobic polymers, such as, for example, polyethylene (PE) and polypropylene (PP), which may exhibit a tow surface energy. Moreover, moisture pick-up by calcium carbonate may pose additional problems during handling and processing. As a result, surface treatments, such as stearic acid, have been used to render the calcium carbonate surface hydrophobic, making the calcium carbonate more compatible with various polymers.
- stearic acid may interfere with downstream processes. Unreacted stearic acid may lead to, for example, smoke generation, difficulties in printing, undesirable emissions to the environment, and/or extruder die-buildup in polymer processing applications.
- stearic acid may sublime during processing and deposit as a build-up on processing equipment, thereby contaminating processing equipment. In fiber formation, sublimed stearic acid at the spinneret can cause fiber breakage. In film processing, the
- sublimated stearic acid may cause pores, voids, or tears in the polymer film, thereby potentially adversely affecting the film's properties.
- product performance may be adversely affected due to surface aesthetics and adhesion.
- a blended functional filler composition may include a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate, wherein a surface treatment of the treated alkali earth metal carbonate may include a monolayer concentration of the surface treatment.
- a polymer filler composition may include a surface-treated alkali earth metal carbonate, wherein a surface treatment of the alkali earth metal carbonate includes less than a monolayer concentration.
- a method of forming a filled polymer article may include mixing a polymeric resin with a filler composition and extruding the mixture to form a polymer article, wherein the filler composition includes a blend of a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate.
- a method of forming a filled polymer article may include mixing a polymeric resin with a filler composition and extruding the mixture to form a polymer article, wherein the filler composition may include a treated alkali earth metal carbonate having a surface treatment having less than a monolayer concentration of the surface treatment.
- a method of mitigating effects of mechano-oxidative degradation products during melt processing of filled polymer articles may include mixing a polymeric resin with a filler composition, and
- the filler composition may include a blend of treated alkali earth metal carbonate and an untreated alkali earth metal carbonate.
- a blended functional fsiler composition may include a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate, wherein a surface treatment of the treated alkali earth metal carbonate may include a monolayer concentration of the surface treatment.
- a polymer filler composition may include a surface-treated alkali earth metal carbonate, wherein a surface treatment of the alkali earth metal carbonate includes less than a monolayer concentration.
- a method of forming a filled polymer article may include mixing a polymeric resin with a filler composition and extruding the mixture to form a polymer article, wherein the filler composition includes a blend of a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate.
- a method of forming filled polymer article may include mixing a polymeric resin with a filler composition and extruding the mixture to form a polymer article, wherein the filler composition may include a treated alkali earth metal carbonate having a surface treatment having less than a monolayer concentration of the surface treatment.
- a method of mitigating effects of mechano-oxidative degradation products during melt processing of filled polymer articles may include mixing a polymeric resin with a filler composition, and
- the filler composition may include a blend of treated alkali earth metal carbonate and an untreated alkali earth metal carbonate.
- the method may include mitigating detrimental effects of mechano-oxidative degradation products during melt processing by immobilizing the degradation products.
- a filler material may include an alkali earth metal carbonate.
- the alkali earth metal carbonate may include a carbonate of calcium, magnesium, barium, or strontium, or a carbonate of two or more alkaline earth metals, e.g., obtained from dolomite.
- certain embodiments may tend to be discussed in terms of calcium carbonate, and/or in relation to aspects where the calcium carbonate is processed and/or treated. The invention should not be construed as being limited to such embodiments and may be applicable to any alkali earth metal carbonate.
- a calcium carbonate-containing material may be produced in a known way from marble, chalk, limestone, dolomite, ca!cite, aragonite, precipitated calcium carbonate (PCC), or ground calcium carbonate (GCC).
- a magnesium carbonate may be produced from, for example, magnesite.
- the alkali earth metal carbonate may also include a synthetic alkali earth metal carbonate, such as, for example, synthetic calcium carbonate produced as a precipitate by a reaction of calcium hydroxide and carbon dioxide in a known way.
- the treated alkali earth metal carbonate may have a low moisture pick up susceptibility.
- the treated alkali earth metal carbonate may have a moisture pick up susceptibility such that its total surface moisture level is below about 2.0 mg/g, such as, for example, below about 1.0 mg/g, below about 0.5 mg/g, or below about 0.4 mg/g of the dry treated mineral filler product, after exposure to an atmosphere of 50% of relative humidity for 48 hours at a temperature of about 23 °C.
- the alkali earth metal carbonate filler may have a moisture content of in the range from about 0.01 wt% to about 0.15 wt% based on the dry weight of the alkali earth metal carbonate, such as, for example, in the range from about 0.02 wt% to about 0.1 wt%, in the range from about 0.03 wt% to about 0.08 wt%, or in the range from about 0.03 wt% to about 0.06 wt% based on the dry weight of the alkali earth metal carbonate.
- the alkali earth metal carbonate may be prepared by attrition grinding.
- Attrition grinding refers to a process of wearing down particle surfaces resulting from grinding and shearing stress between the moving grinding particles. Attrition can be accomplished by rubbing particles together under pressure, such as by a gas flow.
- the attrition grinding may be performed autogenously, where the alkali earth metal carbonate particles are ground only by other alkali earth metal carbonate particles of the same type (e.g., calcium carbonate being ground only by calcium carbonate).
- the alkali earth metal carbonate may be ground by the addition of a grinding media other than calcium carbonate.
- a grinding media can include ceramic particles (e.g., silica, alumina, zirconia, and aluminum silicate), plastic particles, or rubber particles.
- the calcium carbonate is ground in a mill.
- Exemplary mills include those described in U.S. Patent Nos. 5,238,193 and 8,634,224, the disclosures of which are incorporated herein by reference.
- the mill may comprise a grinding chamber, a conduit for introducing the calcium carbonate into the grinding chamber, and an impeller that rotates in the grinding chamber, thereby agitating the calcium carbonate.
- the calcium carbonate is dry ground, where the atmosphere in the mill is ambient air. In some embodiments, the calcium carbonate may be wet ground.
- the ground calcium carbonate may be further subjected to an air sifter or hydrocyclone.
- the air sifter or hydrocyclone can function to classify the ground calcium carbonate and remove a portion of residual particles greater than, for example, 20 microns.
- the classification can be used to remove residual particles greater than 50 microns, greater than 40 microns, greater than 30 microns, greater than 10 microns, or greater than 5 microns.
- the ground calcium carbonate may be classified using a centrifuge, hydraulic classifier, or elutriator.
- calcium carbonate may be subjected to size selection using a rotary or centrifugal sifter.
- sifters include rotary sifters, such as the "K range" of centrifugal (rotary) sifters commercially available from Kek-Gardner (Kek ⁇ Gardner Ltd, Springwood Way, Macclesfield, Cheshire SK10 2 nd ; www.kekgardner.com).
- the K650C is a small pilot machine with a 850 mm length of drum and the K1350 possesses a drum length of 1350 mm.
- the sifter may be fitted with a screen possessing a suitable mesh size.
- the screen may be a fine woven screen or a laser ablated screen.
- the screen may be made from nylon or stainless steel.
- Other suitable rotary (or centrifugal) sifters may be obtained from Kek-Gardner (Kek ⁇ Gardner Ltd, Springwood Way, Macclesfield, Cheshire SK10 2
- KASON KASON Corporation, 67-71 East Willow Street, Millburn, New Jersey, USA; www.kason.com
- SWECO SWECO, PO Box 1509, Florence, KY 41022, USA; www.sweco.com
- centrifugal sifter In a typical centrifugal sifter, material is fed into the feed inlet and redirected into the cylindrical sifting chamber by means of a feed screw. Rotating, helical paddles within the chamber continuously propel the material against a mesh screen, while the resultant, centrifugal force on the particles accelerates them through the apertures. These rotating paddles, which do not make contact with the screen, also serve to breakup soft agglomerates. Most over-sized particles and trash are ejected via the oversize discharge spout.
- centrifugal sifters are designed for gravity-fed applications, and for sifting in-line with pneumatic conveying systems. Suitable sifters include single and twin models and those available with belt drive or direct drive. The units may be freestanding or adapted for easy mounting on new or existing process equipment. Removable end housings allow for rapid cleaning and screen changes.
- the amount of coarse material present in the particulate filler may be reduced to very low values or zero by the use of a mill classifier, for example a dynamic mill classifier or a cell mill fitted with a classifier.
- a mill classifier may comprise block rotors, blade rotors, and/or a blade classifier.
- Suitable examples of mill classifiers include dynamic mill classifiers and cell mills fitted with a classifier, such as those commercially available from Atritor (Atritor Limited, Coventry, West Midlands, England; www.atritor.com), a suitable example being the multirotor cell mill.
- the ground calcium carbonate disclosed herein may be free of dispersant, such as a polyacrylate.
- a dispersant may be present in a sufficient amount to prevent or effectively restrict floccuiation or agglomeration of the ground calcium carbonate to a desired extent, according to normal processing requirements.
- the dispersant may be present, for example, in levels up to about 1 % by weight relative to the dry weight of the alkali earth metal carbonate.
- dispersants include polyelectrolytes such as po!yacrylates and copolymers containing polyacrylate species, including polyacrylate salts (e.g., sodium and
- aluminium optionally with a Group ⁇ metal salt
- sodium hexametaphosphates sodium hexametaphosphates, non-ionic polyol, po!yphosphoric acid, condensed sodium phosphate, non-ionic surfactants, a!kanolamine, and other reagents commonly used for this function.
- a dispersant may be selected from conventional dispersant materials commonly used in the processing and grinding of alkali earth metal carbonate, such as calcium carbonate. Such dispersants will be recognized by those skilled in this art. Dispersants are generally water-soluble salts capable of supplying anionic species, which in their effective amounts may adsorb on the surface of the alkali earth metal carbonate particles and thereby inhibit aggregation of the particles.
- the unsolvated salts suitably include alkali metal cations, such as sodium. Solvation may in some cases be assisted by making the aqueous suspension slightly alkaline.
- Suitable dispersants also include water soluble condensed phosphates, for example, polymetaphosphate salts (general form of the sodium salts: (NaP0 3 ) x ), such as tetrasodium metaphosphate or so-called "sodium hexametaphosphate” (Graham's salt); water-soluble salts of polysilicic acids; polyelectrolytes; salts of homopolymers or copolymers of acrylic acid or methacrylic acid; or salts of polymers of other derivatives of acrylic acid, suitably having a weight average molecular mass of less than about 20,000.
- Sodium hexametaphosphate and sodium polyacrylate the latter suitably having a weight average molecular mass in the range of about 1 ,500 to about 10,000, are preferred.
- the production of the ground calcium carbonate includes using a grinding aid, such as propylene glycol, or any grinding aid known to those skilled in the art.
- a grinding aid such as propylene glycol, or any grinding aid known to those skilled in the art.
- the alkali earth metal carbonate may be treated to include a treatment layer located on the surface of the alkali earth metal carbonate mineral.
- a surface-treatment may include a fatty-acid coating.
- a surface treatment may include, for example, a treatment with an organic carboxylic acid.
- the organic carboxylic acid may have the following general structure:
- R is a carbon-containing compound having from 8 to 40 carbon atoms, such as, for example from 8 to 40 carbon atoms.
- organic carboxylic acid may include an aliphatic carboxylic acid, such as, for example, caproic acid.
- the aliphatic carboxylic acid may be a saturated or unsaturated aliphatic carboxylic ac d.
- the aliphatic carboxylic acid may include a mixture of two or more aliphatic carboxylic acids, such as, for example, a mixture of two or more of caproic acid, 2-ethylhexanoic acid, caprylic acid, neodecanoic acid, capric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, tall oil fatty acid, napthenic acid, montanic acid, coronaric acid, linoleic acid, linolenic acid, 4,7,10,13,16,19-docosahexaenoic acid, 5,8,1 1 ,14,17- eicosapeniaenoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and isononanoic acid,
- aliphatic carboxylic acids such as, for example, a
- the weight ratio of a mixed aliphatic carboxy!ic acid may range from about 90:10 to about 10:90 by weight, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40:60 by weight. According to some embodiments, the weight ratio of aliphatic carboxylic acids in a mixture may be about 50:50 by weight.
- the aliphatic carboxylic acid may include one or more of a linear, branched, substituted, or non-substituted carboxylic acid.
- the aliphatic carboxylic acid may be chosen from aliphatic monocarboxylic acids. Alternatively or additionally, the aliphatic carboxylic acid may be chosen from branched aliphatic monocarboxylic acids.
- the surface treatment may include an aromatic carboxylic acid, such as, for example, alkylbenzoic acid, hydroxybenzoic acid, aminobenzoic acid, protocatechuic acid, or combinations thereof.
- aromatic carboxylic acid such as, for example, alkylbenzoic acid, hydroxybenzoic acid, aminobenzoic acid, protocatechuic acid, or combinations thereof.
- the surface treatment may include a Rosin acid, such as, for example, palustrinic acid, neoabietic acid, abietic acid, or levopimaric acid.
- Rosin acid such as, for example, palustrinic acid, neoabietic acid, abietic acid, or levopimaric acid.
- R may include one or more of a straight chain or branched alkyi, phenyl, substituted phenyi, C6-40 alkyl substituted with up to four OH groups, C6-40 alkyl, amido, maleimido, amino or acetyl substituted hydrocarbon radicals.
- the surface treatment may include a combination of one or more of an aliphatic carboxylic acid, an aromatic carboxylic acid, or a Rosin acid.
- the organic carboxylic acid may be a liquid at room temperature, such as, for example, an organic carboxylic acid having a viscosity of less than 500 mPa-s at 23 °C when measured in a DV III Ultra model Brookfield viscometer equipped with the disc spindle 3 at a rotation speed of 100 rpm and room temperature (23 ⁇ 1 °C).
- the alkali earth metal carbonate may be treated by forming a treatment layer including at least one organic carboxylic acid and/or one or more reaction products of at least one organic carboxylic acid on the surface of the alkali earth metal carbonate filler resulting in a treated alkali earth metal carbonate filler.
- the treated alkali earth metal carbonate may include a stearate treatment, such as, for example ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
- a stearate treatment such as, for example ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
- the treated alkali earth metal carbonate may include a salt of at least one of a valerate, stearate, iaurate, palmitate, caprylate, neodecanoate, caproate, myristate, behenate, lignocerate, napthenate, montanate, coronarate, iinoleate,
- the surface treatment may include a blend of a carboxylic acid and a salt of a carboxySic acid.
- the weight ratio of a mixed carboxylic acid and salt thereof may range from about 90:10 to about 10:90 by weight (acid:salt), from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 80:40 to about 40:60 by weight
- the weight ratio of carboxylic acid and salt in a mixture may be about 50:50 by weight (acid:sait).
- the treated alkali earth metal carbonate filler may have a volatile onset temperature of greater than or equal to about 100 °C. According to some embodiments, the treated alkali earth metal carbonate filler may have a volatile onset temperature of greater than or equal to about 130 °C, greater than or equal to about 150 °C, greater than or equal to about 160 °C, greater than or equal to about 170 °C, greater than or equal to about 200 °C, greater than or equal to about 220 °C, greater than or equal to about 250 °C, greater than or equal to about 260 °C, such as, for example, greater than or equal to 270 °C, greater than or equal to 280 °C, greater than or equal to 290 °C, greater than or equal to 300 °C, greater than or equal to 310 °C, or greater than or equal to 320 °C.
- the terms "polymer,” “resin,” “polymeric resin,” and derivations of these terms may be used interchangeably.
- the polymeric resin is chosen from conventional polymeric resins that provide the properties desired for any particular yarn, woven product, non-woven product, film, moid, or other applications.
- the polymeric resin may be a thermoplastic polymer, including but not limited to, a polyolefin, such as, for example, polypropylene and polyethylene homopolymers and copolymers, including copolymers with 1-butene, 4-methyl ⁇ 1-pentene, and 1-hexane; po!yamides, such as nylon;
- a polyolefin such as, for example, polypropylene and polyethylene homopolymers and copolymers, including copolymers with 1-butene, 4-methyl ⁇ 1-pentene, and 1-hexane
- po!yamides such as nylon
- thermoplastic polymers may also include polyolefin homopolymers or copolymers (e.g., low density or high density polyethy!enes, linear poiyethylenes, polypropy!enes, ethylene-propylene copolymers, ethylene(vinyl acetate) copolymers, and ethylene- (acrylic acid) copolymers, halogenated poiyethylenes (such as chlorinated
- polyethylene polyethylene
- polybutene polymethylbutene
- polyisobutylene polystyrenes and polystyrene derivatives (e.g., SB, ABS, SA, and SBS rubbers)
- PVCs polycarbonates
- polysulphones polyether sulphones
- PEEK saturated polyesters
- saturated polyesters e.g., polyethylene terephthalates and/or polybutylene terephthalates
- polyphenylene oxides and blends, mixtures or copolymers containing these species e.g., polyethylene terephthalates and/or polybutylene terephthalates
- the polymeric resin may include an isotropic semi-crystalline polymer.
- An isotropic semi-crystalline polymer may be melt- processable, melting in a temperature range that makes it possible to spin the polymer into fibers in the melt phase without significant decomposition.
- Exemplary isotropic semi-crystalline polymers may include, but are not limited to, poly(alkylene
- terephthalates poly(aikylene naphthalates), poly(arylene sulfides), aliphatic and aliphatic-aromatic poiyamicles, polyesters comprising monomer units derived from cyclohexanedimethanol and terephtha!ic acid, poly ⁇ ethy!ene terephthalate),
- the polymeric resin may include a semi-crystalline polymer polyolefin, including but not limited to, semi-crysta!line polyethylene and polypropylene.
- the polymeric resin may include an extended chain polyethylene having a high tensile modulus, made by the gel spinning or the melt spinning of very or ultrahigh molecular weight polyethylene.
- isotropic polymers that cannot be processed in the melt may also be used as the polymeric resin.
- the isotropic polymer may include RAYON® , cellulose acetate, poiybenzimidazole, poly[2,2 , -(m ⁇ phenyiene)-5,5' ⁇ bibenzimidazole].
- isotropic polymers may be dry spun using acetone; N.N'-dimethylacetamide; or polar aprotic solvents, including but not limited to N-methylpyrrolidinone as a solvent.
- the polymeric resin may include a liquid crystalline polymer (LCP).
- LCPs may generally produce fibers with high tensile strength and/or modulus.
- the LCP may be
- LCPs that exhibit liquid crystalline behavior in solution may be blended with a hard filler, and then wet or dry spun to yield monofilament fibers.
- the liquid crystalline polymer may include any aromatic polyamide that is soluble in polar aprotic solvents, including, but not limited to, N-methy!pyrrolidinone, and that can be spun into monofilament fibers.
- an aromatic polyamide made from p-phenylenediamine and terephthalic acid can be filled and wet spun to yield monofilament fibers.
- the liquid crystalline polymer may not be liquid crystalline under some or all of a given condition or set of conditions, but may still yield high modulus fibers. According to some embodiments, the liquid crystalline polymer may exhibit lyotropic liquid crystalline phases at some concentrations and in some solvents, but isotropic solutions at other concentrations and/or in other solvents.
- the liquid crystalline polymers may include thermotropic LCPs.
- thermotropic LCPs include, but are not limited to, aromatic polyesters, aliphatic-aromatic polyesters, aromatic hydrocarbons, and the like.
- thermotropic LCPs are aromatic polyesters and poly(esteramides) that form liquid crystalline melt phases at temperatures less than about 360 °C and include one or more monomer units derived from the group consisting of terephthalic acid, isophthaiic acid, 1 ,4-hydroquinone, resorcinol, 4,4 -dihydroxybiphenyl, 4,4'-biphenyldicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2,6- dihydroxynaphthalene, 4-aminophenol, and 4 ⁇ aminobenzoic acid.
- the aromatic groups may include substituent
- the LCPs may have monomer repeat units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in a ratio in the range from about 15:85 to about 85:15 on a mole basis, such as, for example, in the range from about 27:73 to about 73:27 on a mole basis, or from about 40:80 to about 80:40 on a mold basis.
- alkali earth metal carbonate fillers such as, for example, calcium carbonate-containing mineral fillers, may be associated with the presence of volatiles evolving at
- Exemplary volatiles include:
- inherent volatiles volatiles inherently associated with the mineral filler (inherent volatiles"), and may be especially associated with the presence of water;
- volatiles generated by the reaction of inherent and/or added organic materials with the mineral filler which may be induced or enhanced by temperatures reached during the introduction and/or processing of the polymeric resin that includes a mineral filler, such as during the extrusion or compounding process;
- a first category of surface treatment molecules includes "free" surface treatment molecules (such as "free” stearic acid). Free surface treatment molecules result from having surface treatments amounts in excess of a monolayer concentration. The excess surface treatment (e.g., stearic acid) may not be bound, either chemically or physically, to the alkali earth metal carbonate.
- the free surface treatment molecules may sublime, which may adversely affect the properties of the filled polymer product by creating voids, tears, fiber breakage, dripping, "dog-legging" of fibers, clumps, or knots. Sublimated surface treatments may also contaminate processing equipment.
- a second category of surface treatment molecules includes "reacted" surface treatment molecules (such as "reacted” stearic acid).
- the reacted stearic acid reacts with the surface of the alkali earth metal carbonate to chemisorb or physisorb to the surface.
- the reacted stearic acid does not readily sublimate during processing.
- a third category of surface treatment molecules includes "loosely bound” surface treatment molecules (such as loosely bound” stearic acid).
- Loosely bound stearic acid (or other surface treatment) is bound to the surface of the alkali earth metal carbonate to a lesser degree than "reacted" stearic acid, such as, for example, through physisorption to the surface of the alkali earth metal carbonate.
- loosely bound stearic acid is not “free” stearic acid, but the loose binding may result in the stearic acid sublimating during processing, which may result in adverse effects on the resulting polymer product and processing equipment, such as the adverse effects described above.
- loosely bound stearic acid may contribute to sublimated stearic acid even in monolayer concentrations of surface treatments.
- the adverse effects resulting from sublimation of the surface treatment may be mitigated or reduced by providing less than a monolayer concentration of the surface treatment. Providing less than a monolayer concentration can be achieved through severai methods, either alone or in combination. [0087] According to some embodiments, adverse effects sometimes associated with processing polymers (e.g., polyolefins) in the presence of heat and/or mechanical input, for example, during melt-processing such as, for example, extrusion (e.g., of a polymer film), spinning a spunlaid fiber, and melt spinning a spunlaid fiber, may result in mechano-oxidative degradation products.
- processing polymers e.g., polyolefins
- melt-processing such as, for example, extrusion (e.g., of a polymer film), spinning a spunlaid fiber, and melt spinning a spunlaid fiber
- Such mechano-oxidative degradation products may have a significant fraction of organic acid end groups, and may have undesirable effects on the polymer article, for example, as mentioned above (e.g., defects, recondensation onto processing equipment). Without wishing to be bound by theory, it is believed that such undesirable effects resulting from the mechano-oxidative degradation products may be mitigated or reduced by providing less than a monolayer concentration of the surface treatment of alkali earth metal carbonate fillers, which may retain reactive surfaces that may react with and/or immobilize the mechano-oxidative degradation products.
- a blended functional filler composition may include a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate, wherein a surface treatment of the treated alkali earth metal carbonate may include a monolayer concentration of the surface treatment.
- the alkali earth metal carbonate fillers having less than a monolayer concentration of the surface treatment and the blended functional filler composition including a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate includes reactive surfaces that can react with and immobilize mechano-oxidatsve degradation products (e.g., organic acids).
- mechano-oxidatsve degradation products e.g., organic acids
- an alkali earth metal carbonate filler composition may include a blend of a treated alkali earth metal carbonate and an untreated alkali earth metal carbonate.
- the blend of treated and untreated alkali earth metal carbonates may be referred to herein as a "blended" composition or "blended filler" composition.
- the treated alkali earth metal carbonate may be treated as described above, such as, for example with stearic acid and/or stearate.
- the ratio of treated to untreated alkali earth metal carbonate in the blended filler composition may range from about 99:1 to about 60:40 (treated:untreated) by weight.
- the ratio of treated to untreated alkali earth metal carbonate may range from about 98:2 to about 80:20 (treated: untreated) by weight, from about 98:2 to about 90:10 (treated: untreated) by weight, from about 98:2 to about 94:6 (treated:untreated) by weight, or from about 98:4 to about 94:6 (treated:untreated) by weight.
- the sublimated loosely bound or free surface treatment may react with the untreated alkali earth metal carbonate material rather than forming voids, blemishes, or other defects in the polymer product. It is also believed that the reaction of the sublimated surface treatment with the untreated alkali earth metal carbonate may prevent the treatment from building up and contaminating the processing equipment,
- the treated alkali earth metal carbonate may be treated with a monolayer concentration of the surface treatment.
- the alkali earth metal carbonate may be surface treated in a treatment vessel containing a water-dry atmosphere in which the surface treatment is in a liquid (e.g., droplet) and/or vapor form.
- calcium carbonate may be treated by exposing the calcium carbonate to a carboxylic acid, such as stearic acid, vapor or liquid. The amount of vapor or liquid in the reaction vessel should be controlled so as not to exceed a monolayer concentration of the surface treatment.
- the mixture may be blended at a temperature sufficient for at least a portion of the carboxylic acid to react (e.g., sufficient for a majority of the carboxylic acid to react) with at least a portion of the calcium carbonate.
- the mixture may be blended at a temperature sufficient such that at least a portion of the carboxylic acid may coat at least a portion of the calcium carbonate (e.g., the surface of the calcium carbonate).
- the alkali earth metal carbonate may be treated by exposing the surface of the alkali earth metal carbonate to the surface treatment agent in the reaction vessel at a temperature at which surface treatment is in a fluid or vaporized state.
- the temperature may be in the range from about 20 °C to about 300 °C, such as, for example, from about 25 °C to 100 °C, from about 50 °C to 150 °C, from about 100 °C to 200 °C, or from about 100 °C to 150 °C.
- the temperature selected in the atmosphere of the treatment vesse! should provide sufficient heat to ensure melting and good mobility of the molecules of the surface treatment agent, and therefore, good contacting of and reaction with the surface of the alkali earth metal carbonate particles.
- a mixture of the alkali earth metal carbonate and carboxy!ic acid, such as stearic acid may be blended at a temperature high enough to melt the carboxylic acid.
- the alkali earth metal carbonate may be blended at a temperature in the range from about 65 °C to about 200 °C.
- the mixture may be blended at a temperature in the range from about 65 °C to about 150 °C, for example, at about 120 °C.
- the mixture may be blended at a temperature in the range from about 65 °C to about 100 °C.
- the mixture may be blended at a temperature in the range from about 65 °C to about 90 °C.
- the mixture may be blended at a temperature in the range from about 70 °C to about 90 °C.
- Surface treating the alkali earth metal carbonate may be carried out in a heated vessel in which a rapid agitation or stirring motion is applied to the atmosphere during the reaction of the surface treatment and with the alkali earth metal carbonate, such that the surface treatment agent is well dispersed in the treatment atmosphere.
- the agitation should not be sufficient to alter the surface area of the alkali earth metal carbonate because such an alteration may change the required surface treatment agent concentration to create, for example, a monolayer concentration.
- the treatment vessel may include, for example, one or more rotating paddles, including a rotating shaft having laterally extending blades including one or more propellers to promote agitation
- a treated calcium carbonate may be prepared by combining (e.g., blending) the carbonate with stearic acid and water at room temperature in an amount greater than about 0.1 % by weight relative to the total weight of the mixture (e.g., in the form of a cake-mix).
- the mixture may be blended at a temperature sufficient for at least a portion of the stearic acid to react (e.g., sufficient for a majority of the stearic acid to react) with at least a portion of the surface of the calcium carbonate.
- the mixture may be blended at a temperature sufficient such that at least a portion of the stearic acid may coat the surface of the calcium carbonate in a monolayer concentration.
- an alkali earth metal carbonate such as calcium carbonate
- stearic acid or other carboxy!ic acid
- water in an amount greater than about 1 % by weight relative to the total weight of the mixture (e.g., in the form of a cake-mix) to inhibit the formation of free stearic acid.
- the mixture may be blended at a temperature sufficient for at least a portion of the stearic acid to react (e.g., sufficient for a majority of the acid to react, for example, with at least a portion of the calcium carbonate).
- the mixture may be blended at a temperature sufficient such that at least a portion of the stearic acid may coat at least a portion of the calcium carbonate (e.g., the surface of the calcium carbonate).
- Treatment of an alkali earth metal carbonate with stearic acid and water is described U.S. Patent No. 8,580,141 to Khanna et al. [0079] After treatment of the alkali earth metal carbonate, the treated alkali earth metal carbonate may be blended with an untreated alkali earth metal carbonate to form a blended composition.
- the treated and untreated alkals earth metal carbonates may be mixed (e.g., blended) together to promote dispersion of the untreated alkali earth metal carbonate throughout the treated alkali earth metal carbonate.
- the mixing of the treated and untreated alkali earth metal carbonates may occur at room temperature or at an elevated temperature.
- Particle sizes, and other particle size properties, of the treated and untreated alkali earth metal carbonate may be measured using a SED GRAPH 5100 instrument, as supplied by Micromeritics Corporation.
- the size of a given particle is expressed in terms of the diameter of a sphere of equivalent diameter, which sediments through the suspension, i.e., an equivalent spherica! diameter or esd.
- the particle size of the treated alkali earth metal carbonate is expressed in terms of the particle size prior to the surface treatment.
- the treated alkali earth metal carbonate may be characterized by a mean particle size (d 50 ) value, defined as the size at which 50 percent of the calcium carbonate particles have a diameter less than or equal to the stated value, in some embodiments, the treated alkali earth metal carbonate may have a d 5 o in the range from about 0.1 micron to about 50 microns, such as, for example, in the range from about 0.1 micron to about 30 microns, from about 0.1 micron to about 20 microns, from about 0.1 micron to about 10 microns, from about 0.1 micron to about 5 microns, from about 0.1 micron to about 3 microns, from about 0.1 micron to about 2 microns, from about 0.1 micron to about 1 micron, from about 0.5 microns to about 2 microns, from about 1 micron to about 5 microns, from about 5 microns to about 20 microns, or from about 5 microns to about 10 microns.
- d 50 mean particle size
- the untreated alkali earth metal carbonate may be characterized by a mean particle size (d 50 ) value in the range from about 0.1 micron to about 50 microns, such as, for example, in the range from about 0.1 micron to about 30 microns, from about 0.1 micron to about 20 microns, from about 0.1 micron to about 10 microns, from about 0.1 micron to about 5 microns, from about 0.1 micron to about 3 microns, from about 0.1 micron to about 2 microns, from about 0.1 micron to about 1 micron, from about 0.5 microns to about 2 microns, from about 1 micron to about 5 microns, from about 5 microns to about 20 microns, or from about 5 microns to about 10 microns.
- d 50 mean particle size
- the treated alkali earth metal carbonate may be characterized by a top cut size (d 98 ) value, defined as the size at which 98 percent of the calcium carbonate particles have a diameter less than or equal to the stated value.
- the treated alkali earth metal carbonate may have a da 8 in the range from about 2 microns to about 100 microns, such as, for example, in the range from about 5 microns to about 50 microns, from about 2 micron to about 20 microns, or from about 5 microns to about 20 microns.
- the untreated alkali earth metal carbonate may be characterized by a top cut size (dg 8 ) value in the range from about 2 microns to about 100 microns, such as, for example, in the range from about 2 microns to about 100 microns, such as, for example, from about 5 microns to about 50 microns, from about 2 micron to about 20 microns, or from about 5 microns to about 20 microns.
- the treated alkali earth metal carbonate and the untreated alkali earth metal carbonate may have the same, substantially the same, or similar particle size distributions.
- the treated alkali earth metal carbonate and the untreated alkali earth metal carbonate may have different particle size distributions.
- the treated alkali earth metal carbonate may have a larger particle size distribution that the untreated alkali earth metal carbonate, such as, for example, a larger median or mean particle size and/or a broader overall size distribution.
- the treated alkali earth metal carbonate may have a smaller particle size distribution that the untreated alkali earth metal carbonate, such as, for example, a smaller median or mean particle size and/or a narrower overall size distribution.
- the blended filler material may have, for example, a bimodal or multimodal distribution of particle sizes.
- the ratio of the coarse component of the blend to the fine component of the blend may range from about 10:1 to about 1 : 10 by weight (coarseiine), such as, for example, from about 8:1 to about 1 :1 by weight, from about 8:1 to about 4:1 by weight, from about 8:1 to about 8:1 by weight, from about 5:1 to about 1 : 1 by weight, from about 4: 1 to about 2: 1 by weight, from about 2: 1 to about 1 :2 by weight, from about 1 :2 to about 1 :4 by weight, from about 1 :1 to about 1 :5 by weight, from about 1 :4 to about 1 :8 by weight, from about 1 :6 to about 1 :8 by weight, or from about 1 :1 to about 1 :8 by weight (coarse:fine).
- a treated alkali earth metal carbonate may be undercoated with a surface treatment.
- the term "undercoated” or “undercoating” refers to a surface treatment that includes less than a monolayer concentration of the surface treatment of a treated alkali earth metal carbonate.
- the undercoated alkali earth metal carbonate may include a surface treatment that includes from about 50% to about 95% of a monolayer concentration, such that from about 5% to about 50% of the surface of the alkali earth metal carbonate is not reacted with the surface treatment.
- the undercoating may range from about 50% to about 95% of a monolayer concentration, such as, for example, from about 70% to about 95%, from about 80% to about 95%, from about 85% to about 95%, from about 90 to about 95%, from about 80% to about 90%, or from about 85% to about 90% of a monolayer concentration.
- the undercoated alkali earth metal carbonate may be prepared by the same methods as a treated alkali earth metal carbonate, except that the concentration of surface treatment is reduced to create the desired level of undercoating.
- an undercoated alkali earth metal carbonate may reduce or mitigate the effects of sublimated surface treatments during processing of a polymer containing the
- the sublimated treatment may be prevented from creating voids, blemishes, tears, or clumps in fibers or films, causing dog-legging of fibers, or causing contaminant buildup in the processing equipment.
- an undercoated alkali earth metal carbonate may be used as a filler for a polymeric resin.
- an undercoated alkali earth metal carbonate may be blended with an uncoated alkali earth metal carbonate, as described above.
- a monolayer concentration-treated alkali earth metal carbonate may be blended with an undercoated alkali earth metal carbonate.
- two different undercoated alkali earth metal carbonates may be blended together. Blended alkali earth metal carbonates may include the properties, treatments ratios, and mixtures described above, except that they vary in the amount of surface treatment.
- the treated or undercoated alkali earth metal carbonate may be treated with an organic carboxylic acid or salt thereof, or a mixture of an organic carboxylic acid and salt of an organic carboxylic acid.
- some or all of the stearic acid may be replaced by ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
- salts may include, for example, calcium valerate, barium valerate, magnesium valerate, strontium valerate, zinc valerate, aluminum valerate, zirconium valerate, or cobalt valerate, which may replace some or all of valeric acid.
- some or all of the organic carboxylic acid may be replaced with a salt of the organic carboxylic acid.
- some or all of the carbolxylic acid may be replaced by a salt of at least one of a valerate, stearate, laurate, palmitate, caprylate, neodecanoate, caproate, myristate, behenate, lignocerate, napthenate, montanate, coronarate, linoleate, docosahexaenoate, eicosapentaenoate, bexanoate, heptanoate, octanoate, nonanoate, isononanoate, or mixtures thereof, such as, for example, ammonium, calcium, barium, magnesium, strontium, zinc, aluminum, zirconium, or cobalt forms of the aforementioned salts.
- the ratio of acid to salt may range from about 5:95 to about 95:5 (acid:salt) by weight, from about 10:90 to about 90:10 by weight, from about 80:20 to about 20:80 by weight, from about 70:30 to about 30:70 by weight, from about 80:40 to about 40:60 by weight, or from about 45:55 to about 55:45 by weight.
- all of the stearic acid (or other surface treatment) may be replaced by a salt, such as stearate, which may be used to create a monolayer concentration or an undercoated alkali earth metal carbonate.
- undertreated, blended, unblended, or any combination thereof, may be further subjected to an air sifter or hydrocyclone.
- the air sifter or hydrocyclone can function to classify the ground calcium carbonate and remove a portion of residual particles greater than 20 microns.
- the classification can be used to remove residual particles greater than 40 microns, greater than 30 microns, greater than 15 microns, greater than 10 microns, or greater than 5 microns.
- the ground calcium carbonate may be classified using a centrifuge, hydraulic classifier, or elutriator.
- an undercoated alkali earth metal carbonate may be used as a filler for a polymeric resin.
- the undercoated alkali earth metal carbonate may be blended with an untreated alkali earth metal carbonate in some embodiments.
- a treated or undercoated alkali earth metal carbonate may have some or ail of an organic carboxylic acid replaced with a salt of the carboxylic acid, and may, in some embodiments, be optionally blended with an untreated alkali earth metal carbonate.
- the treated, undercoated, and/or blended alkali earth metal carbonates may be used as a filler for a polymer product, such as, for example, a filler for a polymer fiber or film.
- monofiliment fibers may be produced according to any appropriate process or processes now known to the skilled artisan or hereafter discovered.
- a monofilament fiber may include the production of a continuous monofilament fiber of at least one polymeric resin and at least one filler.
- Exemplary techniques include, but are not limited to, melt spinning, dry spinning, wet spinning, spinbonding, or meltblowing processes.
- Melt spinning may include an extrusion process to provide molten polymer mixtures to spinneret dies.
- monofilament fibers may be produced by heating the polymeric resin to at least about its melting point as it passes through the spinneret dies.
- the treated, undercoated, or blended alkali earth metal carbonate filler may be incorporated into the polymeric resin using any method conventionally known in the art or hereafter discovered.
- alkali earth metal carbonate may be added to the polymeric resin during any step prior to extrusion, for example, during or prior to the heating step or as a "masterbatch" in which the polymeric resin and the filler are premixed and optionally formed into granulates or pellets, and melted or mixed with additional virgin polymeric resin before extrusion of the fibers.
- the virgin polymeric resin may be the same or different from the polymeric resin containing the filler.
- the molten polymer may then be continuously extruded through at least one spinneret to produce long filaments.
- the extrusion rate may vary according to the desired application, and appropriate extrusion rates will be known to the skilled artisan. Extrusion of the filled polymer from the spinnerets may be used to create, for example, a non-woven fabric.
- the a polymeric film may be created from the molten filled polymer according to methods known in the art or hereinafter discovered.
- melt compounding may also be used to extrude films, tubes, shapes, strips, and coatings onto other materials, injection moulding, blow moulding, or casting, and thermoforming and formation of tubes or pipes(such as where the polymer is a PVC polymer).
- the melt compounding may for example be carried out in a suitable compounder or screw extruder.
- a thermoplastic material to be compounded may suitably be in a granular or pelletized form. The temperature of the compounding and moulding, shaping or extrusion processes will depend upon the thermoplastic material being processed and materials incorporated therein. The temperature will be above the softening point of the thermoplastic material.
- Calcium carbonate filler samples A ⁇ E were prepared as calcium- carbonate-filled polymeric resins.
- Sample A was prepared by adding 1.0% by weight stearic acid to a ground caScium carbonate having a median particle diameter (d 5 o) of 1.8 microns to provide a monolayer concentration of stearic acid.
- Sample B was prepared by mixing one part untreated ground calcium carbonate having a d 50 of 1.1 micron with nine parts of monolayer-treated calcium carbonate prepared in sample A. The mixture was blended for 10 minutes in a Henschel mixer at 1000 rpm at room temperature.
- Sample C was prepared by mixing 0.8% by weight (45 g) stearic acid with 4.5 kg of ground calcium carbonate having a d 50 of 1 .1 micron in a Henschel mixer for at 1000 rpm for 10 minutes at 93.3 °C. Without wishing to be bound by a particular theory, it is believed that sample C is an undercoated treatment of stearic acid (e.g., less than a monolayer concentration).
- Sample D was prepared as described for sample C, except that 1.0% by weight of stearic acid was added to the filler, representing a monolayer concentration of stearic acid.
- Sample E was prepared in the same way as sample C, except that 1.2% by weight of stearic acid was added to the carbonate, representing stearic acid in excess of the monolayer concentration.
- Filled polymer samples A-E were prepared by loading a 35 melt polypropylene homopolymer with 50% by weight of each of filler samples A-E, respectively.
- the filled polymer samples were each prepared using a Werner and Pfleiderer ZSK-30 twin screw extruder having the temperature profile shown in Table 1 with the screws rotating at 230 rpm.
- the polymeric resin was fed into the mouth of the extruder at a rate of 1 1.3 kg/hr using a Hardy C2 feeder.
- Filler samples A-E separately fed into the extruder at zone 5 at 11.3 kg/hr using a Ktron feeder for each of polymer samples A-e, respectively.
- each filled polymer sample was passed through the extruder at the temperature profile shown in Table 1 to determine the amount of subiimable stearic acid in the sample.
- the screw speeds were reduced to 150 rpm to form a vacuum seal in the barrel of the extruder.
- Each resin sample was fed into the mouth of the extruder at a rate of 13.6 kg/hr for 20 minutes using a Hardy C2 feeder.
- a Greenburg-Smith high- velocity impinge was connected to zone 7 of the extruder.
- the vacuum pressure at the extruder was maintained between 254 and 381 mm-Hg using a vacuum pump at 835 mm-Hg.
- the lower half of the impinge was submerged in an insulated ice bath at 10 °C, Between samples, virgin (i.e.. unfilled) 35 melt polypropylene was used to flush the extruder by passing the virgin polymer resin through the extruder until the exudate was clear.
- sample C resulted in significantly less sublimated stearic acid than the polymer resins containing a monolayer concentration of stearic acid (samples A and D) and containing greater than a monolayer concentration (sample E).
- the polymer containing the undercoated filler contains less loosely bound and/or free stearic acid than samples A, B, D, and E.
- the sublimated acid reacts with the unreacted surface of the calcium carbonate, thereby resulting in less overall sublimated (e.g.. liberated" or volatile) stearic acid in the sample.
- the further increase in liberated stearic acid in sample E may result from the further increase in free stearic acid at a concentration greater than the monolayer concentration.
- the use of a blended functional filler composition having treated and untreated carbonate materials, or the use of an undercoated filler carbonate material may result in decreased amounts of sublimed or liberated stearic acid.
- This reduction in sublimed stearic acid may reduce the formation of voids, blemishes, holes, or fears in the film or fibers, may mitigate dog-legging of fibers, or may prevent the buildup of contaminants in the processing equipment when processing filled polymer resins.
- sample B is discussed with respect to a monolayer concentration of stearic acid on the treated carbonate, it is understood that the treated carbonate may contain less than a monolayer concentration (e.g., an undercoated carbonate). It is also understood that the untreated carbonate in sample B may be replaced by an undercoated carbonate.
- the blended filler may contain two undercoated carbonates having different levels of undercoating.
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Abstract
L'invention concerne une composition de charge mélangée qui peut comprendre un carbonate de métal de terre alcalino-terreux traité et un carbonate de métal alcalino-terreux non traité. Un traitement de surface du carbonate de métal alcalino-terreux traité peut comprendre une concentration de monocouche du traitement de surface. Une composition de charge polymère peut comprendre un carbonate de métal alcalino-terreux traité en surface, un traitement de surface du carbonate de métal alcalino-terreux comprenant moins d'une concentration de monocouche. Un procédé de formation d'un article polymère chargé peut comprendre le mélange d'une résine polymère avec une composition de charge et l'extrusion du mélange pour former un article polymère. La composition de charge peut comprendre un mélange d'un carbonate de métal alcalino-terreux traité et d'un carbonate de métal alcalino-terreux non traité. La composition de charge peut comprendre un carbonate de métal alcalino-terreux traité ayant un traitement de surface ayant moins d'une concentration de monocouche de traitement de surface.
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PCT/US2015/038964 WO2016004291A1 (fr) | 2014-07-02 | 2015-07-02 | Carbonates modifiés pour transport de poudre, stabilité de mélange à sec et charge de polymère améliorés |
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US4560712A (en) * | 1984-12-27 | 1985-12-24 | Mobil Oil Company | Polypropylene compositions containing bimodal calcium carbonate and a polysiloxane |
US4889878A (en) * | 1988-04-15 | 1989-12-26 | Dow Corning Corporation | Flowable joint sealant for concrete highway |
US20090234055A1 (en) * | 2006-09-28 | 2009-09-17 | Takahiro Kawashima | Calcium carbonate treated with curing active ingredient |
US20100249308A1 (en) * | 2007-12-11 | 2010-09-30 | Toshio Oba | Room-temperature-curable polyorganosiloxane composition |
Family Cites Families (4)
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JPS61266438A (ja) * | 1985-05-21 | 1986-11-26 | Shin Etsu Chem Co Ltd | 表面特性の改質された塩化ビニル系樹脂成形品の製造方法 |
DE19738481C2 (de) * | 1997-09-03 | 1999-08-12 | Solvay Alkali Gmbh | In Wässrigen Systemen mit oberflächenaktiven Stoffen gecoatetes Calciumcarbonat sowie Verfahren zur gesteuerten bimolekularen Beschichtung von Calciumcarbonat - Teichen |
EP1557442A1 (fr) * | 2004-01-23 | 2005-07-27 | SOLVAY (Société Anonyme) | Méthode pour le traitement de surface de carbonate de calcium précipité |
SI2390280T1 (sl) * | 2010-05-28 | 2015-06-30 | Omya International Ag | Obdelani proizvodi mineralnega polnila, postopek in priprava le-teh in njihova uporaba |
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2015
- 2015-07-02 WO PCT/US2015/039015 patent/WO2016004325A1/fr active Application Filing
- 2015-07-02 WO PCT/US2015/038964 patent/WO2016004291A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4560712A (en) * | 1984-12-27 | 1985-12-24 | Mobil Oil Company | Polypropylene compositions containing bimodal calcium carbonate and a polysiloxane |
US4889878A (en) * | 1988-04-15 | 1989-12-26 | Dow Corning Corporation | Flowable joint sealant for concrete highway |
US20090234055A1 (en) * | 2006-09-28 | 2009-09-17 | Takahiro Kawashima | Calcium carbonate treated with curing active ingredient |
US20100249308A1 (en) * | 2007-12-11 | 2010-09-30 | Toshio Oba | Room-temperature-curable polyorganosiloxane composition |
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