WO2011072346A1 - Process for modifying vegetable oils and primary plasticizer for vinyl polymers - Google Patents
Process for modifying vegetable oils and primary plasticizer for vinyl polymers Download PDFInfo
- Publication number
- WO2011072346A1 WO2011072346A1 PCT/BR2009/000428 BR2009000428W WO2011072346A1 WO 2011072346 A1 WO2011072346 A1 WO 2011072346A1 BR 2009000428 W BR2009000428 W BR 2009000428W WO 2011072346 A1 WO2011072346 A1 WO 2011072346A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fact
- vegetable oil
- transesterification
- alcohol
- alkaline metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000008569 process Effects 0.000 title claims abstract description 71
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 61
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 59
- 239000004014 plasticizer Substances 0.000 title claims description 41
- 229920002554 vinyl polymer Polymers 0.000 title claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 53
- 150000001298 alcohols Chemical class 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000006735 epoxidation reaction Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 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 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 3
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 claims description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 claims description 2
- 240000002791 Brassica napus Species 0.000 claims description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000020551 Helianthus annuus Species 0.000 claims description 2
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 235000004426 flaxseed Nutrition 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 235000009973 maize Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 31
- 239000000194 fatty acid Substances 0.000 abstract description 31
- 229930195729 fatty acid Natural products 0.000 abstract description 31
- 239000000047 product Substances 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 20
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- 229920000915 polyvinyl chloride Polymers 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 15
- -1 fatty acid esters Chemical class 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000032050 esterification Effects 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 8
- 229920001944 Plastisol Polymers 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004999 plastisol Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002924 oxiranes Chemical group 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000008037 PVC plasticizer Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002194 fatty esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001550224 Apha Species 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000005498 phthalate group Chemical class 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 239000001195 (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid Substances 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
Definitions
- This invention refers to a process for modifying vegetable oils. More specifically, it refers to a process through which vegetable oils and alcohols are converted into epoxidized fatty acid alkyl esters.
- the present invention also refers to the products obtained through the process disclosed herein. Said products may be used as primary plasticizers for vinyl polymers, particularly for halogenated plastics, especially polyvinyl chloride (PVC).
- PVC polyvinyl chloride
- Polyvinyl chloride is the best known and most widely used vinyl polymer. It is used mainly in two forms: (i) rigid PVC; and (ii) flexible PVC.
- the rigid form of PVC known as non-plasticized PVC, is generally used to produce pipes, connections, profiles and frames, as well as applications where chemical resistance is necessary.
- the flexible form of PVC also known as plasticized PVC, is used in films, blankets, electrical insulators, flooring, toys, wallpapers, synthetic leather used for clothes, footwear and coatings, among many other end products.
- Malleability and flexibility are physical characteristics that may be modulated by formulating a specific polymeric resin with one or more materials that can serve as plasticizers.
- a plasticizer may be understood as a substance with a high boiling point that when included in a polymeric matrix confers and preserves the flexibility of the material. The plasticizer become an integral part of the polymer and must provide the benefits of plastification throughout the entire useful life of the product.
- the primary plasticizers are highly compatible with the polymer and may be included to it in large amounts, with no exudation. In addition to the above-mentioned malleability and flexibility, these additives may provide better coloring, easier processing and broader range of applications.
- the primary PVC plasticizers are generally petroleum derivatives, among which are phthalates, adipates, trimellitates, benzoates, azelates and polymers.
- the secondary plasticizers are moderately compatible with the polymeric resin and are generally used together with a primary plasticizer in order to reduce costs or to obtain specific properties.
- the chlorinated paraffins (PCs) are the most common examples of secondary plasticizers for PVC resins, widely used as they present low flammability and low cost.
- Other examples of secondary plasticizers are the poly-alpha methyl styrene derivatives and vegetable oils derivatives.
- plasticizers that may be obtained from precursors generated through microbiological processes or from renewable sources, such as citrates and modified vegetable oils.
- epoxidized vegetable oils have been used in small proportions as secondary plasticizers and thermo-costabilizers in the production of flexible, semi-rigid and rigid PVCs.
- epoxidized triglycerides as primary plasticizers results in exudation due to the limited compatibility with the polymeric matrix.
- esterified GB 1020866
- interesterified acetylated derivatives were suggested as primary plasticizers for PVC resins.
- the methods for production of epoxidized fatty acid alkyl esters generally involve two steps.
- the first step is to transform fatty acids or a vegetable oil into fatty acid alkyl esters. This transformation may be conducted through esterification (when the precursors are fatty acids) or transesterification (when the precursors are vegetable oils or fatty esters with short alkyl chain).
- the esterification is a reaction between carboxylic acids and alcohols that generates esters and water as products. As this is a balance reaction, the water produced is generally removed from the system in order to favor the formation of the ester.
- Fatty acids esterification is normally conducted in the presence of an acid catalyst (for example, H 3 P0 4 , H 2 SO 4 , CH 3 C 6 H 4 SO3H, CH 3 SO 3 H, among others), at temperatures higher than 120 °C. Titanates may also be used as catalysts in esterification, however higher temperatures are required (> 200 °C) in order to the reaction be effective.
- an acid catalyst for example, H 3 P0 4 , H 2 SO 4 , CH 3 C 6 H 4 SO3H, CH 3 SO 3 H, among others
- Titanates may also be used as catalysts in esterification, however higher temperatures are required (> 200 °C) in order to the reaction be effective.
- temperatures of over 230 °C allow esterification to be achieved with no catalyst, however, the end product is dark
- the transesterification is a process through which an ester is reacted with an alcohol in order to form a new ester and an alcohol resulted from the initial ester.
- This reaction may be used when the precursors are low acidity vegetable oils or fatty acid esters with short alkyl chain - typically methyl or ethyl esters.
- the transesterification is normally conducted at moderate temperatures (below 130 °C), requires anhydrous conditions and may be catalyzed by an acid or a base, generally in the homogenous phase.
- the acid catalyst may be H2S0 4 , HCI, H3PO 4 , CH3C 6 H 4 SO 3 H, among others.
- the basic catalysts most commonly used for transesterification are alkaline metals hydroxides or alcoxides, such as NaOH, KOH, LiOH, NaOCH 3 and KOCH 2 CH 3 .
- the other required step to obtain epoxidized fatty acid alkyl esters is epoxidation.
- the double bounds presented in the different fatty acid alkyl ester chains are converted into epoxide groups (or oxirane).
- This reaction must take place after an esterification step, or may be conducted before or after a base-catalyzed transesterification step.
- the epoxide groups may be incorporated by using any appropriate technique.
- the most widely used procedure is the reaction with a percarboxylic acid, pre-formed or generated in situ through hydrogen peroxide and an aliphatic organic acid, usually formic acid or acetic acid. Said epoxidation techniques are well known in the science.
- the presence of oxirane rings in the fatty acid esters chains significantly contributes to the photo-thermal stability of the end material.
- esterification of carboxylic acids is usually catalyzed by acids and the transesterification may be catalyzed by bases or by acids.
- BR 0602925-6 describes a process for the preparation of fatty acid esters and their subsequent epoxidation in order to produce plasticizers and the resulting product.
- the invention describes the preparation of methyl or ethyl esters through transesterification catalyzed by methoxide or ethoxide of an alkaline metal.
- esters with short alkyl chain were used as precursors in order to produce other fatty acid alkyl esters from polyols and alcohols with medium and long chains, in transesterification reactions catalyzed by acids, preferably methane sulfonic acid, with the catalyst not varying as a function of the alcohol used.
- acids preferably methane sulfonic acid
- titanates were the preferred catalysts.
- the obtained esters were subsequently epoxidized with peracid.
- the catalyst used to obtain the alkyl esters is an acid
- it is not possible to directly convert the raw materials containing epoxide groups in cases where the catalyst used to obtain the alkyl esters is an acid
- the epoxide groups present in these precursors are partially or fully converted into hydroxy ethers.
- the epoxidation stage must always be conducted after the esterification step (or transesterification catalyzed by an acid).
- the epoxidized vegetable oils, as well as epoxidized fatty acid methyl or ethyl esters, may be directly converted into epoxidized alkyl esters by base-catalyzed transesterification.
- the base catalyst is a hydroxide (LiOH, NaOH, KOH, etc.)
- its reaction with the alcohol forms water.
- the water results in the formation of soap, occurring reduction in the alkalinity of the catalyst and greater difficulty during the subsequent purification step, due to formation of emulsions.
- Another problem related to the hydroxides is that when alcohols with medium or long chains are used in transesterification catalyzed by these bases, a good conversion is achieved only with two or more transesterification stages, required to ensure satisfactory conversion of the vegetable oil into fatty acid alkyl esters.
- alkaline metal alcoxides such as sodium methoxide or ethoxide
- alcoxides are effective catalysts and do not form water in the reaction mixture during vegetable oils transesterification.
- alcoxides are commercially available in the form of solutions; for example, sodium methoxide is sold as a 30 % in methanol solution.
- sodium methoxide is sold as a 30 % in methanol solution.
- the use of these catalysts in an alcohol solution results in an end product with appreciable quantities of fatty esters with short alkyl chain in its composition.
- Epoxidized fatty acids methyl or ethyl esters may satisfactorily serve as PVC plasticizers in less sensitive applications, such as the production of certain calendered and extruded materials.
- alkaline metals are highly reactive and require special care when being handled and used. They react with water, forming hydrogen and hydroxide, and there is the possibility of explosion, depending on the quantity involved.
- alkaline metals may be used in transesterification processes, the teachings of the state of the art do not suggest said use for producing PVC plasticizers from vegetable oils. This possibly occurs due to the difficulties and risks involved in the use of alkaline metals in their elementary forms, in addition to a false impression of high costs.
- Another objective of the present invention is to provide a new and improved process for modifying vegetable oil in order to obtain products that serve as high grade primary plasticizers in vinyl polymer formulations that may be used in high concentrations, providing to the polymer the desired qualitative aspects, maintaining the fundamental qualities of the end material. Further characteristics, aspects and advantages of the present invention will become more clearly apparent through reading the following descriptions.
- the present invention refers to a process for modifying vegetable oils in order to obtain primary plasticizers for vinyl polymers.
- the present invention also refers to the products obtained through the process described herein, which are epoxidized fatty acid alkyi esters. Said products may be used as primary plasticizers for vinyl polymers, presenting performances identical or superior to those of traditional plasticizers.
- the process for modifying vegetable oil of the present invention comprises, more specifically, the transesterification of at least one vegetable oil with at least one monohydric alcohol, with a chain size longer than 3 carbon atoms, and/or with at least one polyhydric alcohol of any type, being catalyzed by an alcoxide generated by the reaction of the said alcohol (or alcohols) with an alkaline metal.
- the process of the present invention comprises, preferably, a single transesterification stage. However, two or more transesterification stages may be carried out.
- the process of the present invention may be conducted with epoxidized vegetable oils as well as with non-modified vegetable oils.
- a fatty acid ester with short alkyi chain is understood as presenting up to 3 carbon atoms in its alkyi portion; medium chains are those presenting 4 to 7 carbon atoms in the alkyi portion; with long chain are those presenting 8 or more carbon atoms in the alkyi portion.
- This nomenclature extends to the alcohols used in the preparations of these esters, in other words, alcohols with short chain contain up to 3 carbon atoms; alcohols with medium chain are those with 4 to 7 carbon atoms, and alcohols with long chain are those with 8 or more carbon atoms.
- the polyols that may be used in the process are not encompassed by these definitions.
- At least one epoxidized vegetable oil is reacted with at least one monohydric alcohol, with a chain size of more than 3 carbon atoms, and/or with at least a polyhydric alcohol of any type, with this transformation being catalyzed by an alcoxide generated by the reaction of the said alcohol (or alcohols) with an alkaline metal.
- the primary plasticizer derived from vegetable oils is obtained in a single step, in a simple manner and with a high purity level.
- the precursor is a non- modified vegetable oil.
- At least one oil non-modified is reacted with at least one monohydric alcohol, with a chain size longer than 3 carbon atoms, and/or with at least one polyhydric alcohol of any type, with this transformation being catalyzed by an alcoxide generated by the reaction of the said alcohol (or alcohols) with an alkaline metal.
- This reaction produces fatty acid alkyl esters that, in a second step, must be epoxidized in order to obtain the primary plasticizers.
- Examples of epoxidized vegetable oils available on the market are Drapex 6,8, Vikoflex 7170, Vikoflex 7190, Soyflex 6330, etc.
- Non-modified vegetable oils useful as precursors for the present process are those presenting high unsaturated fatty acid contents in their composition (more than 80 % of unsaturated fatty acids), preferably oleic, linoleic and linolenic acids.
- suitable non-modified vegetable oils include soya, sunflower, maize, flaxseed, rapeseed, rubbertree seed or peanut oils, among other vegetable oils with more than 80 % of unsaturated fatty acids in their composition. Blends of these vegetable oils are also encompassed by this application.
- Examples of monohydric alcohols useful in the present invention are n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, sec-pentanol, isopentanol, hexanol, cyclohexanol, 1-octanol, 2-ethyl-hexanol, isononanoi, isodecanol, tridecanol, fatty alcohols, among others, whose chain size is longer than 3 carbon atoms, preferably from 4 to 16 carbon atoms.
- Polyhydric alcohols (polyols) useful in the present invention are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, pentaerythritol, among other alcohols with more than one hydroxyl, preferably from 2 to 4 hydroxyls, with no restriction on the size of the carbon chain. Said alcohols may be used alone or in combination.
- Any alkaline metal may be used in the process of the present invention.
- metallic lithium, sodium or potassium are used, with metallic sodium being the most preferred.
- the production of the catalyst through the reaction between an alkaline metal and alcohols with medium and long chain sizes allowed, in a surprisingly way, solving several of the problems mentioned in the background of the invention.
- the alkaline metal may be reacted with alcohols with medium or long chain during moderate periods (less than 2 hours), obtaining exclusive alcoxides from the alcohols used. These alcoxides present high efficiency as transesterification catalysts.
- the production of the catalyst in this manner is a comparative advantage of the present invention, and the application of the method was possible even using alcohols with chain size up to 16 carbon atoms. No process known in the state of the art involving transesterification, has used this methodology to produce epoxidized fatty acid esters with medium or long alkyl chains.
- the process of the present invention uses an alkaline metal as a precursor for a catalyst, generating a superior quality product, in contrast to the processes using alcoxides in solution available on the market. Even with a single transesterification stage, the epoxidized fatty acid alkyl esters are produced with high purity levels, excellent yield and without the formation of undesirably by-products, in addition to presenting excellent performance in application tests.
- the quantity of alkaline metal for the preparation of the alcoxide varies, depending on the alcohol used in the process, ranging from 0.03 to 3.0 % of the total reaction mass, preferably 0.06 to 2.5 %.
- the quantity of alcohol used may vary from the stoichiometric up to 300 % above this amount, in relation to the vegetable oil, most frequently in the range of 20 to 200 % of excess.
- the reaction of the alkaline metal with the alcohol preferably occurs before the transesterification.
- the pre-heated vegetable oil preferably up to the temperature at which the transesterification will occur
- the alkaline metal may be added to the reaction mixture (oil and alcohol).
- the preparation of the alcoxide and the transesterification take place under inert atmosphere (nitrogen or argon) or under low pressure (> 600 mmHg).
- the transesterification temperature may vary from 25 to 220 °C depending on the type of alcohol used, preferably from 50 to 160 °C.
- the time needed for the transesterification may vary from 10 to 300 minutes, depending on the type of oil and alcohol used, preferably from 20 to 240 minutes.
- a purification step occurs through which the formed glycerin is decanted and separated.
- the reaction mixture is then neutralized with acid, washed and stripped (alcohol removal process), with steam and under a discreet vacuum (up to about 600 mmHg), at temperatures varying from 120 to 220 °C, depending on the type of alcohol which is retrieved and re-used in subsequent production.
- the product is filtered.
- the precursor is an epoxidized vegetable oil
- the primary plasticizer derived from vegetable oils is ready.
- triglycerides and/or partial glycerides may be present in the end product.
- these glycerides represent less than 4 % of the total mass of the products, preferably less than 3 %, with these compounds in these quantities causing no problems in the application of the plasticizers.
- an epoxidation step is required. This procedure is conducted with performic acid, generated in situ by the reaction between hydrogen peroxide and formic acid.
- the hydrogen peroxide employed in this stage may be in the form of an aqueous solution at concentrations between 30 and 70 % (m/m), preferably at concentrations between 40 and 70 %.
- An acid catalyst H 2 S0 4 , H 3 PO 4 or a suitable acid resin such as Amberlite IR-120H
- the epoxidized esters are washed with water and diluted alkali in order to remove the acid reagent. After drying and filtration, the product is finished, as shown in Figure 2.
- the glycerin generated during transesterification begins to decant during the reaction, and is separated very easily. This allows the reaction mixture to be washed with small volumes of water (20 to 30 % of the total reaction mass).
- the process of eliminating the excess of alcohol may be conducted with steam and a discreet vacuum (up to about 600 mmHg), at temperatures between 120 and 220 °C, not being required the use of high vacuums, independently of the adopted route (epoxidation followed by transesterification or transesterification followed by epoxidation).
- the alkaline transesterification and the purification process of the epoxidized fatty esters keep the oxirane rings intact.
- the differences noted in the epoxy indexes of the precursors and the products obtained from different alcohols are due, b asically, t o differences in the molar masses of the alkyl fragments used in the synthesis of the epoxidized fatty esters.
- the Figure 1 illustrates a diagram of the process of producing fatty acid alkyl esters from epoxidized vegetable oils as described in Examples 1 and 2: (1) represents the reactor for the preparation of the catalyst; (2) represents the recycled alcohol storage tank; (3) represents the transesterification reactor; (4) represents a recipient used for the glycerin separation, neutralization and washing of the reaction mixture; (5) represents the stripper in which the alcohol is removed from the product; (6) represents an alcohol dehydration column; (7) represents a press filter; (8) represents the holding tank; and (9) represents the product storage tank.
- the Figure 2 illustrates a diagram of the process of epoxidation of fatty acid alkyl ester, as described in Example 3: (10) represents the peroxide dosing tank; (11) represents the formic acid dosing tank; (12) represents the epoxidation reactor; (13) represents the recipient used for neutralization, washing and drying of the epoxidized product; (14) represents a press filter; (15) represents the holding tank; (16) represents the product storage tank; and (17) represents the condensates recipient tank.
- PVC formulations were prepared in compliance with the values described in Table 1.
- the quantity of each component in the formulation is expressed in "per" - parts per hundred parts of resin - an indication of quantity by mass of a specific component in relation to hundred PVC resin mass units.
- the products obtained in Examples 1 , 2 and 3 were used as primary plasticizers, and were compared with the following petrochemical plasticizers DEHP (di-2-ethyl- hexyl phthalate) and DINP (di-isononyl phthalate).
- Solvin 265 PY obtained through polymerization in suspension, Solvay Indupa do Brasil S/A.
- Markstab IBZ-580 Ba/Zn-based concentrated liquid stabilizer, Inbra Industries Quimicas Ltda.
- the ingredients were processed for 5 minutes in a laboratory calander (Mecanoplast C 400), with rollers heated at 160 °C and adjusted to produce sheets with a thickness of 0.5 mm.
- the plasticized PVC obtained through the calander was then rolled and pressed in molds (200 °C; 110 bar; 200 seconds) in order to produce sheets with a uniform thickness.
- the sheets obtained in this manner were cut into test bodies that were used to determine their physical properties through conventional test methods (ASTM D 638-08, D 4703-07, D 792-08, D 2115-04 and D 2240-05 Standards).
- the properties of the plasticized PVC resins are described in Table 2.
- the presented data show that the plasticizers derived from vegetable oil of the present invention can serve as primary PVC plasticizers, and that excellent physical characteristics may be obtained.
- the test bodies prepared with the alternative plasticizers performed just as well as those prepared with traditional petrochemical plasticizers. In some critical trials, such as the extraction tests, the alternative plasticizers have superior performance comparing to phthalates.
- Table 3 presents the components used to prepare the plastisols in order to obtain the flattened test bodies.
- the viscosity results for the prepared plastisols are described in Table 4.
- Plasticizer 6 Component Quantity (per)
- Soivin 367 NK obtained through polymerization in microemulsion, Solvay Indupa do Brasil S/A.
- Plastabil K-219 Zn/K-based expansion auxiliary, Inbra Industrias Quimicas Ltda.
- the plastisols obtained from the product in Example 2 and with DINP were spread on paper in order to obtain films with approximately 1.0 mm thick, which were then heated in an LTE-S hot box (Mathis AG) under different time and temperature conditions. Results of thickness and gram weight of the prepared films are illustrated in Table 5.
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/BR2009/000428 WO2011072346A1 (en) | 2009-12-17 | 2009-12-17 | Process for modifying vegetable oils and primary plasticizer for vinyl polymers |
EP09852146.1A EP2513276A4 (en) | 2009-12-17 | 2009-12-17 | Process for modifying vegetable oils and primary plasticizer for vinyl polymers |
BR112012014253-4A BR112012014253B1 (en) | 2009-12-17 | 2009-12-17 | vegetable oil modification processes |
CN200980162941.2A CN102762707B (en) | 2009-12-17 | 2009-12-17 | Method for modifying vegetable oils and primary plasticizer for vinyl polymers |
US13/516,410 US8802877B2 (en) | 2009-12-17 | 2009-12-17 | Process for modifying vegetable oils and primary plasticizer for vinyl polymers |
UY0001033065A UY33065A (en) | 2009-12-17 | 2010-11-29 | PROCESS TO MODIFY VEGETABLE OILS AND PRIMARY PLASTIFICANT FOR VINYL POLYMERS |
ARP100104634A AR079616A1 (en) | 2009-12-17 | 2010-12-14 | PROCESS TO MODIFY VEGETABLE OILS AND PRIMARY PLASTIFICANT FOR VINYL POLYMERS |
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PCT/BR2009/000428 WO2011072346A1 (en) | 2009-12-17 | 2009-12-17 | Process for modifying vegetable oils and primary plasticizer for vinyl polymers |
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US (1) | US8802877B2 (en) |
EP (1) | EP2513276A4 (en) |
CN (1) | CN102762707B (en) |
AR (1) | AR079616A1 (en) |
BR (1) | BR112012014253B1 (en) |
UY (1) | UY33065A (en) |
WO (1) | WO2011072346A1 (en) |
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WO2012016674A3 (en) * | 2010-08-02 | 2012-04-12 | Emery Oleochemicals Gmbh | Lubricant combination for thermoplastics processing |
KR101288437B1 (en) * | 2011-11-29 | 2013-07-26 | 동구산업(주) | Environment-friendly plasticizers prepared with vegetable oil and preparation method thereof |
WO2014135366A1 (en) * | 2013-03-08 | 2014-09-12 | Evonik Industries Ag | Isononyl esters on the basis of fatty acid mixtures consisting of vegetable oils |
EP2990470A1 (en) | 2014-08-26 | 2016-03-02 | Evonik Degussa GmbH | Mixed epoxidised fatty acid esters |
US9499681B2 (en) * | 2012-11-12 | 2016-11-22 | Dow Global Technologies Llc | Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers |
EP2768818B1 (en) * | 2011-10-19 | 2018-12-19 | Archer Daniels Midland Co. | Making epoxidized esters from epoxidized natural fats and oils |
CN111148741A (en) * | 2017-09-27 | 2020-05-12 | 普罗维隆控股股份有限公司 | Process for preparing epoxidized fatty acid ester mixtures |
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DE102013203972A1 (en) * | 2013-03-08 | 2014-09-11 | Evonik Industries Ag | Isononyl esters based on fatty acids or fatty acid mixtures of tall oil or linseed oil |
US10113051B2 (en) | 2013-06-03 | 2018-10-30 | Regents Of The University Of Minnesota | Epoxy estolide fatty acid alkyl esters useful as biorenewable plasticizers |
CN104877170A (en) * | 2015-04-29 | 2015-09-02 | 苏州乔布注塑工业有限公司 | PVC (polyvinyl chloride) internal lubricant |
CN105085982A (en) * | 2015-09-07 | 2015-11-25 | 四川大学 | Environment-friendly migration-resistant epoxy fatty acid cyclohexyl plasticizer and preparation method thereof |
US10144812B2 (en) | 2015-10-05 | 2018-12-04 | Regents Of The University Of Minnesota | Multi-functional fatty acid ester derivatives useful as biorenewable plasticizers |
CN106519081B (en) * | 2016-09-22 | 2018-06-26 | 深圳立山环保材料有限公司 | A kind of epoxy plasticiser and preparation method thereof |
BE1026295B9 (en) | 2018-05-22 | 2020-01-14 | Proviron Holding N V | Use of an epoxidized fatty acid ester as a plasticizer in halogenated resins |
CN109369574A (en) * | 2018-09-14 | 2019-02-22 | 许昌鑫瑞德化工科技有限公司 | A kind of processing method of modified vegetable and animals oils |
CN110128755A (en) * | 2019-05-24 | 2019-08-16 | 烟台鑫汇包装有限公司 | A kind of aerosol valves door system EPT rubber packing gasket |
KR102669652B1 (en) | 2019-09-19 | 2024-05-28 | 주식회사 엘지화학 | The Apparatus For Neutralizing/Water Separating Esterification Products And The Method For Thereof |
CN110804029B (en) * | 2019-11-08 | 2022-04-29 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
CN113817226B (en) * | 2021-10-12 | 2022-05-10 | 南京工业大学 | Polymer composite material additive and application thereof |
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WO2012016674A3 (en) * | 2010-08-02 | 2012-04-12 | Emery Oleochemicals Gmbh | Lubricant combination for thermoplastics processing |
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KR101288437B1 (en) * | 2011-11-29 | 2013-07-26 | 동구산업(주) | Environment-friendly plasticizers prepared with vegetable oil and preparation method thereof |
US9499681B2 (en) * | 2012-11-12 | 2016-11-22 | Dow Global Technologies Llc | Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers |
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EP2990470A1 (en) | 2014-08-26 | 2016-03-02 | Evonik Degussa GmbH | Mixed epoxidised fatty acid esters |
CN111148741A (en) * | 2017-09-27 | 2020-05-12 | 普罗维隆控股股份有限公司 | Process for preparing epoxidized fatty acid ester mixtures |
CN111148741B (en) * | 2017-09-27 | 2023-04-28 | 普罗维隆控股股份有限公司 | Process for preparing epoxidized fatty acid ester mixtures |
Also Published As
Publication number | Publication date |
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US20120289727A1 (en) | 2012-11-15 |
BR112012014253B1 (en) | 2019-11-19 |
BR112012014253A2 (en) | 2017-07-25 |
EP2513276A4 (en) | 2016-09-07 |
US8802877B2 (en) | 2014-08-12 |
AR079616A1 (en) | 2012-02-08 |
CN102762707B (en) | 2014-09-24 |
EP2513276A1 (en) | 2012-10-24 |
UY33065A (en) | 2011-07-29 |
CN102762707A (en) | 2012-10-31 |
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