MXPA00009330A - Synthesis of higher polyol fatty acid polyesters by transesterification - Google Patents
Synthesis of higher polyol fatty acid polyesters by transesterificationInfo
- Publication number
- MXPA00009330A MXPA00009330A MXPA/A/2000/009330A MXPA00009330A MXPA00009330A MX PA00009330 A MXPA00009330 A MX PA00009330A MX PA00009330 A MXPA00009330 A MX PA00009330A MX PA00009330 A MXPA00009330 A MX PA00009330A
- Authority
- MX
- Mexico
- Prior art keywords
- polyol
- ingredients
- products
- mixture
- sucrose
- Prior art date
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 130
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 78
- 239000000194 fatty acid Substances 0.000 title claims abstract description 78
- 229920000728 polyester Polymers 0.000 title claims abstract description 64
- -1 polyol fatty acid Chemical class 0.000 title claims abstract description 50
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 39
- 230000002194 synthesizing Effects 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title description 19
- 238000003786 synthesis reaction Methods 0.000 title description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 115
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000004615 ingredient Substances 0.000 claims abstract description 52
- 239000006227 byproduct Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 239000011541 reaction mixture Substances 0.000 claims abstract description 25
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 claims description 83
- 239000005720 sucrose Substances 0.000 claims description 83
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 79
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 47
- 150000003626 triacylglycerols Chemical class 0.000 claims description 35
- 235000011187 glycerol Nutrition 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000004676 glycans Polymers 0.000 claims description 14
- 229920001282 polysaccharide Polymers 0.000 claims description 14
- 239000005017 polysaccharide Substances 0.000 claims description 14
- 150000004804 polysaccharides Polymers 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 150000002314 glycerols Chemical class 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 150000002118 epoxides Chemical class 0.000 claims description 9
- 229920000223 polyglycerol Polymers 0.000 claims description 8
- 150000002772 monosaccharides Chemical class 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000002016 disaccharides Chemical class 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- DPUOLQHDNGRHBS-KTKRTIGZSA-N Erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 235000019486 Sunflower oil Nutrition 0.000 claims description 4
- 239000002285 corn oil Substances 0.000 claims description 4
- 235000012343 cottonseed oil Nutrition 0.000 claims description 4
- 239000002385 cottonseed oil Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000002600 sunflower oil Substances 0.000 claims description 4
- 235000019485 Safflower oil Nutrition 0.000 claims description 3
- 239000000828 canola oil Substances 0.000 claims description 3
- 235000005687 corn oil Nutrition 0.000 claims description 3
- 229920001542 oligosaccharide Polymers 0.000 claims description 3
- 150000002482 oligosaccharides Polymers 0.000 claims description 3
- 235000005713 safflower oil Nutrition 0.000 claims description 3
- 239000003813 safflower oil Substances 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 235000019519 canola oil Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003346 palm kernel oil Substances 0.000 claims description 2
- 235000019865 palm kernel oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 229910000573 alkali metal alloy Inorganic materials 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 238000010923 batch production Methods 0.000 claims 1
- 238000010924 continuous production Methods 0.000 claims 1
- 239000000344 soap Substances 0.000 description 17
- 239000003925 fat Substances 0.000 description 12
- 235000019197 fats Nutrition 0.000 description 12
- 238000005755 formation reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 125000005907 alkyl ester group Chemical group 0.000 description 10
- 125000005233 alkylalcohol group Chemical group 0.000 description 9
- 150000003445 sucroses Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 229920005628 alkoxylated polyol Polymers 0.000 description 7
- 125000004432 carbon atoms Chemical group C* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-Methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- BJHIKXHVCXFQLS-UYFOZJQFSA-N Fructose Natural products OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000005313 fatty acid group Chemical group 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000010356 sorbitol Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- XCOBLONWWXQEBS-KPKJPENVSA-N BSTFA Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L Barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 210000001736 Capillaries Anatomy 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- GUBGYTABKSRVRQ-YOLKTULGSA-N Maltose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)O[C@H]1CO)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 GUBGYTABKSRVRQ-YOLKTULGSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N Potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 2
- 241000277331 Salmonidae Species 0.000 description 2
- SRBFZHDQGSBBOR-SQOUGZDYSA-N Xylose Natural products O[C@@H]1CO[C@@H](O)[C@@H](O)[C@@H]1O SRBFZHDQGSBBOR-SQOUGZDYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SRTHRWZAMDZJOS-UHFFFAOYSA-N lithium hydride Inorganic materials [H-].[Li+] SRTHRWZAMDZJOS-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000001184 potassium carbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 238000000526 short-path distillation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Inorganic materials [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004808 supercritical fluid chromatography Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000002588 toxic Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N α-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- RZYHXKLKJRGJGP-UHFFFAOYSA-N 2,2,2-trifluoro-N,N-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)N([Si](C)(C)C)C(=O)C(F)(F)F RZYHXKLKJRGJGP-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- BVDRUCCQKHGCRX-UHFFFAOYSA-N 2,3-dihydroxypropyl formate Chemical compound OCC(O)COC=O BVDRUCCQKHGCRX-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N Behenic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- DJHJJVWPFGHIPH-OODMECLYSA-N Chitin Chemical compound O[C@@H]1C(NC(=O)C)[C@H](O)OC(CO)[C@H]1COC[C@H]1C(NC(C)=O)[C@@H](O)[C@H](COC[C@H]2C([C@@H](O)[C@H](O)C(CO)O2)NC(C)=O)C(CO)O1 DJHJJVWPFGHIPH-OODMECLYSA-N 0.000 description 1
- RKHQGWMMUURILY-UHRZLXHJSA-N Cortivazol Chemical compound C([C@H]1[C@@H]2C[C@H]([C@]([C@@]2(C)C[C@H](O)[C@@H]1[C@@]1(C)C2)(O)C(=O)COC(C)=O)C)=C(C)C1=CC1=C2C=NN1C1=CC=CC=C1 RKHQGWMMUURILY-UHRZLXHJSA-N 0.000 description 1
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- FBPFZTCFMRRESA-KAZBKCHUSA-N D-Mannitol Natural products OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KAZBKCHUSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
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- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- BJHIKXHVCXFQLS-PYWDMBMJSA-N keto-D-sorbose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(=O)CO BJHIKXHVCXFQLS-PYWDMBMJSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
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- 235000004213 low-fat Nutrition 0.000 description 1
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- 239000000594 mannitol Substances 0.000 description 1
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- OCFVSFVLVRNXFJ-UHFFFAOYSA-N potassium hydride Inorganic materials [H-].[K+] OCFVSFVLVRNXFJ-UHFFFAOYSA-N 0.000 description 1
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- DLRVVLDZNNYCBX-ZZFZYMBESA-N β-melibiose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 DLRVVLDZNNYCBX-ZZFZYMBESA-N 0.000 description 1
Abstract
A process for synthesizing polyol fatty acid polyesters comprising the steps of (1) mixing ingredients comprising (a) unesterified first polyol having hydroxyl groups, (b) second polyol esterified with fatty acids, (c) basic catalyst, and (d) emulsifying agent to form a mixture of ingredients;(2) reacting the mixture of ingredients at a temperature sufficient to obtain a transesterification reaction products and by-products;and (3) removing at least a portion of the by-products from the transesterification reaction mixture;and (4) further heating the transesterification reaction products and ingredients from step (3) at a temperature and for a time sufficient to esterify at least about 50%of the hydroxyl groups of the first polyol.
Description
SYNTHESIS OF SUPERIOR POLYESTERS OF FATTY ACID AND POLYOL BY TRANSESTERIFICATION
• CROSS REFERENCE WITH RELATED APPLICATIONS This patent application is related to the co-pending patent applications, which are incorporated as a reference: "Improved Processes for Synthesis and Purification of Nondigestible Fats", presented in the name of Trout and collaborators, and "Improved
Processes for Synthesis and Purification of Nondigestible
• Fats Using Lipase ", presented on behalf of Trout and collaborators, both applications were submitted on the same date as this application.
TECHNICAL FIELD This application relates to processes for the production of polyesters of fatty acid and polyol, this process eliminates the need to synthesize and purify intermediate compounds of lower alkyl ester. From
More particularly, this invention relates to processes for synthesizing higher polyesters of fatty acid and polyol by the reaction of non-esterified polyol, preferably selected from the group consisting of monosaccharides, disaccharides, polysaccharides,
sugar alcohols, sugar ethers, polyglycerols and polyalkoxylated glycerols and a second polyol esterified with fatty acids and selected from monoglycerides, diglycerides and triglycerides.
BACKGROUND OF THE INVENTION The food industry has recently turned its attention to polyol polyesters for use in food products as low calorie fats. Triglycerides (triacylglycerols) make up approximately 90% of the total fat consumed in the average diet. One method by which the caloric value of edible fat can be reduced is to reduce the amount of triglycerides that are consumed, since normal edible triglyceride fats are almost always completely absorbed by the human system.
(see Lipids, 2, H.J. Deuel, Interscience Publisher, Inc.,
New York, 1955, page 215). Low-calorie fats, referred to below as low-fat fats, which can replace triglycerides are described in U.S. Patent No. 3,600,186 to Mattson et al. Mattson et al. Disclose fat-containing, low-calorie food compositions in which at least a portion of the triglyceride content was replaced with a fatty acid ester and polyol having at least four fatty acid ester groups and, where each fatty acid has eight to twenty-two carbon atoms. Rizzi and Taylor, in U.S. Patent No. 3,963,699, describe a solvent-free transesterification process, in which a mixture of a polyol (such as sucrose), a lower alkyl ester of fatty acid (such as a methyl ester) of fatty acid), an alkali metal fatty acid soap and a basic catalyst, is heated to form a homogeneous melt, to which an excess of lower alkyl ester of fatty acid is added to form the higher fatty acid polyesters and polyol. The polyesters are then separated from the reaction mixture. This process for preparing sucrose polyesters includes two discrete steps of synthesis: (1) the reaction of the triglyceride and the lower alkyl alcohol to form lower alkyl esters with glycerin (glycerol) as a by-product and (2) the reaction of sucrose and esters of lower alkyl to form sucrose polyesters with a lower alkyl alcohol as a by-product. Unfortunately, the need to synthesize intermediates fatty acid lower alkyl ester compounds increases the operating costs of the synthetic polyol polyester process and the reaction of the polyol and the lower alkyl ester of fatty acid results in the
P1109 production of lower alkyl alcohol as a by-product. Systems are required for the capture of the lower alkyl alcohol and the need to separate and handle the lower alkyl alcohol increases the risk of alcohol discharges into the environment. Consequently, there is a need to develop a transesterification process that does not use intermediate compounds of the lower alkyl ester of fatty acid. Feuge et al., In the Patent of the
United States No. 3,714,144, and Feuge et al., In J. Amer. Oil Chem. Soc. , 1970, 47 (2), 56-60, discloses a process of transesterification without solvents, which comprises mixing sucrose melted with esters of fatty acids and sodium or potassium soaps without alkali in a partial vacuum. The teachings of Feuge and collaborators, are directed mainly to the formation of inferior esters; the only specific teaching by Feuge et al., with respect to a method in which the percentage of sucrose esters having three or more fatty acid chains is greater than 35% of the total sucrose esters formed, uses methylcarbitol palmitate as source of the fatty acid. Unfortunately, methylcarbitol is relatively toxic and would not be suitable for use in the production of food grade polyol polyester. Article
P1109 by Feuge et al. Also teaches that triglycerides perform poorly as intermediates. Osipow et al., In U.S. Patent No. 4,380,616, disclose the preparation of sucrose mono- and diesters by forming a clear emulsion containing immiscible reagents and by keeping the emulsions transparent under the appropriate conditions to allow the reaction. The sucrose mono and diesters are formed using emulsions containing methyl fatty acid ester and sucrose. Osipow et al. Also disclose the formation of mono and diglycerides using emulsions containing glycerin and methyl fatty acid esters or glycerol triesters. Parker et al., In U.S. Patent No. 3,996,206 teach that sucrose mono- and diesters are valuable surfactants, while sucrose octaesters are not satisfactory surfactants. Parker et al. Disclose a process for preparing lower polyester surfactants of sucrose by reacting solid particulate sucrose with triglyceride in the presence of a basic transesterification catalyst, the triglyceride and sucrose being used in practically equimolar amounts.
P1109 Gally ore et al., In U.S. Patent No. 4,298,730, disclose a process for preparing a surfactant mixture containing sucrose mono- and diesters by reacting solid particulate sucrose with a triglyceride of fatty acid, a di and / or monoglyceride and a basic transesterification catalyst in the presence of a fatty acid soap. Gallymore et al. Teach that sucrose octaesters are unsatisfactory surfactants and, therefore, octaesters were not prepared in the process. Cooper et al., In U.S. Patent No. 5,304,665, disclose a method for obtaining highly esterified alkoxylated polyols from triglycerides by contacting an epoxide, an aliphatic polyalcohol and a triglyceride in the presence of a basic catalyst to achieve the opening of the epoxide ring and the formation of a partially esterified alkoxylated polyol, followed by contacting the partially esterified alkoxylated polyol with fatty acids. Thus, many methods of the prior art that react triglycerides and polyol are limited to the synthesis of lower esters and higher polyesters of polyhydric compounds, such as sucrose, are not obtained or can not be obtained.
P1109 Additionally, many two step methods of the prior art require that a basic transesterification catalyst be used in both steps. The use of these catalysts in the two steps increases the losses in performance and increases the color formation in the product. Other methods of the prior art require the addition of fatty acids in the second step.
SUMMARY OF THE INVENTION In accordance with the foregoing, it is an object of this invention to avoid the various problems of the prior art. Another object of this invention is to provide novel batch and continuous processes for the production of polyol polyesters, in particular of polyol polyesters in which at least 50%, preferably at least about 70%, more preferably at least about 75% and most preferably at least about 95% of the hydroxyl of the polyol are esterified. The preferred products of the sucrose polyester are higher sucrose polyesters in which an average of at least 4 and preferably an average of about 5 to about 8 hydroxyls per ester of polyol is esterified. It is also an object of this invention
P1109 provide novel processes for the production of polyol fatty acid polyesters, these processes eliminate the need to synthesize and purify fatty acid lower alkyl ester intermediates. Processes can be continuous or batch processes. It is a further object of this invention to provide novel processes for the production of fatty acid and polyol polyesters that eliminate the need to ship, handle, capture and / or recycle lower alkyl alcohol. It is also an object of this invention to provide novel processes for the production of fatty acid and polyol polyesters that eliminate discharging into the environment lower alkyl alcohol. It is yet another object of this invention to provide processes that provide superior performance and reduce undesirable color formation. In accordance with one aspect of the present invention, both batch and continuous processes are provided for synthesizing polyol fatty acid polyesters, comprising the steps of: (1) mixing ingredients comprising: (a) a first non-esterified polyol which has hydroxyl groups, (b) a second polyol esterified with fatty acids, (c) a basic catalyst and (d) an emulsifying agent selected from the group consisting of partially esterified solvents, soaps and polyols, to form a mixture of ingredients; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a reaction mixture of the ingredients, the reaction products and the by-products; (3) removing from the reaction mixtures at least a portion of the by-products; and (4) further reacting the reaction products and the ingredients of step (3) at a temperature and for a time sufficient to esterify at least 50%, preferably at least about 70%, more preferably at least about 75 % and most preferably at least about 95% of the hydroxyl groups of the first polyol. The reaction can be continuous or batch. The basic catalyst, the solvent and / or the soap can be removed or eliminated at the end of the second step. In accordance with another aspect of the present invention, there are provided processes for synthesizing polyesters of fatty acid and polyol, comprising the steps of: (1) mixing ingredients comprising: (a) a first non-esterified polyol, preferably selected from the group consists of monosaccharides, disaccharides, polysaccharides, sugar alcohols, sugar ethers, polyglycerols and polyalkoxylated glycerols, (b) a second polyol esterified with chains of fatty acids, (c) a basic catalyst and (d) a solvent to form a mixture of ingredients; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a reaction mixture of the ingredients, reaction products and by-products; and (3) removing at least a portion of the by-products from the reaction mixture; and (4) further reacting the reaction products and the ingredients of step (3) at a temperature and for a time sufficient to esterify at least about 50%, preferably at least about 70%, more preferably at least about 75 % and most preferably at least about 95% of the hydroxyl groups of the first polyol. In accordance with another aspect of the present invention, processes are provided for synthesizing higher sucrose polyesters (sucrose polyesters having more than four fatty acids), comprising the steps of: (1) mixing the ingredients comprising sucrose, triglyceride of fatty acid, basic catalyst and lower sucrose polyesters to form a mixture of ingredients; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a reaction mixture of the ingredients, reaction products and by-products; and (3) removing from the reaction mixture at least a portion of the by-products comprising glycerin and mono and diglycerides; and (4) further reacting the reaction products and the ingredients of step (3) at a temperature and for a sufficient time to complete the reaction, wherein the molar ratio of the triglyceride fatty acids to the hydroxyl groups of the sucrose It is not less than 1: 1. Preferably at least about 70% by weight of the higher sucrose polyesters are octaesters of sucrose. It has now been found that higher polyesters of sucrose can be produced without using intermediary intermediates of lower alkyl ester or methylcarbitol by transesterification of sucrose with triglyceride. Glycerin, the mono- and / or diglycerides, the byproducts of the reaction, are derived from the triglyceride when at least one ester group of the triglyceride has been transferred to the sucrose. The removal of glycerin, mono and / or diglycerides, drives the reaction towards high degrees of esterification and is formed from penta to octales of polyol. The need to produce lower alkyl esters and fatty acid in a separate step and the need to separate the lower alkyl alcohol are eliminated by these processes, resulting in more economical processes. The elimination of the production of the lower alkyl alcohol also eliminates
• the risk that alcohol will be released into the environment. Surprisingly it has also been found that sucrose polyesters can be produced in a three step process without using basic transesterification catalysts in the second step. The
elimination of the basic transesterification catalyst
• The second step provides superior performance and reduces the undesirable color formation. A reduction in color formation increases the ease of purification of the product. These and other additional objects and advantages will be more apparent in view of the following detailed description.
DETAILED DESCRIPTION OF THE PREFERRED MODALITY The present invention encompasses continuous and batch transesterification processes for synthesizing a polyester fatty acid polyester product, in particular, highly esterified polyol fatty acid polyesters. The highly esterified polyol fatty acid polyesters are polyols wherein at least 50%, preferably at least about 70%, more preferably at least about 75% and most preferably about 95% of the hydroxyl groups are esterified. In one embodiment, the polyol fatty acid polyesters have at least 4 and more preferably an average of about 5 to about 8 fatty acid groups per molecule. In another embodiment, the polyol fatty acid polyesters are linked and esterified alkoxylated glycerines, esterified polyols extended with epoxide and mixtures thereof. A mixture of ingredients comprising a first non-esterified polyol and a second esterified polyol is heated to obtain a transesterification reaction mixture of the ingredients, reaction products and by-products. The products of the transesterification reaction comprise those compounds derived from the first non-esterified polyol after one or more ester groups have been transferred from the second esterified polyol to the initially unesterified first polyol. The byproducts of the transesterification reaction are those compounds derived from the second polyol initially esterified after one or more ester groups have been transferred from the second polyol to the initially unesterified first polyol. The removal of
P1109 the transesterification reaction mixture of the by-products boosts the reaction of the ingredients and the reaction products towards higher grades of
• transesterification. During the synthesis of the polyester of fatty acid and polyol at least a portion of the by-products, preferably all by-products, is removed. Any remaining byproducts can be removed during the refining of the resulting fatty acid polyesters. 10 The products of polyester of fatty acid and
Suitable polyol include sucrose polyesters which on average have at least four, preferably at least about five, ester linkages per sucrose molecule; the fatty acid chains have preference
of about eight to about twenty-four carbon atoms. Other suitable polyol fatty acid polyesters are alkoxylated glycerines linked by esterification, including those comprising polyether glycol linking segments, as described in US Pat.
U.S. Patent No. 5,374,446, incorporated by reference herein and those comprising polycarboxylate linking segments, as described in U.S. Patent Nos. 5,427,815 and
,516,544, incorporated by reference herein; the
that have more reference are those that are described in the
P1109 U.S. Patent No. 5,516,544. Additional suitable polyol fatty acid polyesters are epoxy extended esterified polyols
• of the general formula P (OH) A + c (EPO) N (FE) B, wherein P (OH) is a polyol, A is from 2 to about 8 primary hydroxyl, C is from about 0 to about 8 of total secondary and tertiary hydroxyls, A + C is from about 3 to about 8, EPO is a C3-C6 epoxide, N is a minimum average number of the
epoxylation, FE is an acyl entity of fatty acid and b is
• an average number in a range greater than 2 and not greater than A + C, as described in U.S. Patent No. 4,861,613 and in EP 0324010 Al, incorporated herein by reference. The minimum average number of the index
Epoxylation has a value generally equal to or greater than A and is a sufficient number, so that more than 95% of the primary hydroxyls of the polyol are converted to secondary or tertiary hydroxyls. Preferably, the fatty acid acyl entity has an alkyl chain
C7-C23. Preferred epoxide-extended esterified polyols include esterified propoxylated glycerols, prepared by reacting a propoxylated glycerol having from 2 to 100 oxypropylene units per glycerol, with
fatty acids C? 0-C24 or with fatty acid esters C? 0-C24,
P1109 as described in U.S. Patent Nos. 4,983,329 and 5,175,323, respectively, both incorporated herein by reference. propoxylated glycerols esterified, prepared by reacting an epoxide and a triglyceride with an aliphatic polyalcohol are also preferred, as described in patent US No. 5,304,665, incorporated herein by reference or with an alkali metal or alkaline an aliphatic alcohol, as described in U.S. Patent No. 5,399,728, incorporated herein by reference. The most preferred are the adiados glycerols extended with propylene oxide having an index greater propoxylation about 2, preferably in the range from about 2 to about 8, more preferably about 5 or above, wherein the groups acyl are C8-C24 compounds, preferably C? 4-C? 8, as described in U.S. Patent Nos. 5,603,978 and 5,641,534, both incorporated herein by reference. Particularly preferred are propoxylated glycerols esterified with fatty acid which have a defined lower melting point of about 92 ° F (33 ° C) and which have a fat fat dilaomeric index at 92 ° F.
(33 ° C) less than about 30, as described in WO 97/2260 or having a solid fat dilaomeric index
P1109 of at least about 50 to 70 ° F (21 ° C) and at least about 10 to 98.6 ° F (37 ° C), as described in U.S. Patent Nos. 5,589,217 and 5,597,605, both incorporated here as a reference. Other esterified polyols extended with suitable epoxide include esterified alkoxylated polysaccharides. The esterified alkoxylated polysaccharides are esterified alkoxylated polysaccharides preferred containing anhydromonosaccharide units, more preferred are esterified propoxylated polysaccharides containing anhydromonosaccharide units, as described in Patent No. 5,273,772 United States, incorporated herein by reference. As used herein, all proportions are molar proportions, unless otherwise specified and all percentages are by weight, unless otherwise specified.
Step 1. Formation of the ingredient mixture In the first step of the present process, the ingredients comprising the first unesterified polyol, the second polyol esterified with fatty acids, the basic catalyst and the emulsifying agent are mixed to form a mixture of ingredients . The second esterified polyol and the first non-esterified polyol are
P1109 mix in a proportion that produces a molar ratio of the fatty acid chains of the second esterified polyol to the hydroxyl groups of the first polyol not
• esterified greater than 0.5: 1, preferably greater than 1: 1, 5 more preferably greater than about 1.5: 1 and most preferably greater than about 2.25: 1. . As used herein, the term "first unesterified polyol" is intended to include any aliphatic or aromatic compound containing at least two free hydroxyl groups. During the practice of
• the processes disclosed herein, the selection of a suitable non-esterified polyol is simply a matter of choice. For example, suitable non-esterified polyols can be selected from the following classes:
aliphatic straight and branched chain saturated and unsaturated; saturated and unsaturated cyclic compounds, including heterocyclic, or mononuclear or polynuclear aromatic compounds, including heterocyclic aromatic compounds. Carbohydrates and
non-toxic glycols are the preferred non-esterified polyols. Monosaccharides suitable for use herein include, for example, mannose, galactose, glucose, arabinose, xylose, ribose, apiose, rhamnose, sicosa, fructose, sorbose, tagatose, ribulose, xylulose and
erythrulose. The right oligosaccharides to use them
P1109 in the present include, for example, maltose, kojibiosa, nigerosa, cellobiose, lactose, melibiose, gentiobiose, turanosa, rutinose, trehalose, sucrose and raffinose. Polysaccharides suitable for use herein include, for example, amylose, glycogen, cellulose, chitin, inulin, agarose, zylanes, mannan and galactans. Although sugar alcohols are not carbohydrates in a strict sense, naturally occurring sugar alcohols are so closely related to carbohydrates that they are also preferred for use in the present. The natural sugar alcohols which are suitable for use herein are sorbitol, mannitol and galactitol. Particularly preferred kinds of materials suitable for use herein include monosaccharides, disaccharides and sugar alcohols. Preferred non-esterified polyols include glucose, fructose, glycerol, polyglycerols, sucrose, zilotol, alkoxylated sorbitols and alkoxylated sorbitans, alkoxylated polyglycerols and sugar ethers; particularly preferred is sucrose. Preferred non-esterified alkoxylated polyols include alkoxylated glycerol, alkoxylated polyglycerols, alkoxylated sorbitols and alkoxylated sorbitans, alkoxylated polysaccharides and linked alkoxylated polyols, such as alkoxylated glycerines
P1109 linked. The polyols may be alkoxylated with C3-C6 epoxides, such as propylene oxide, butylene oxide, isobutylene oxide and pentene oxide, to produce epoxide-extended polyols having a minimum epoxylation rate of at least about 2, preferably in the range from about 2 to about 8, as described in U.S. Patent No. 4,816,613, incorporated herein by reference. The polyols can also be alkoxylated with an epoxide, preferably a 1,2-C3-C?? Alkylene oxide, in the presence of a ring-opening polymerization catalyst, as described in U.S. Patent No. 5,399,729 and No. 5,512,313, incorporated by reference herein. Suitable alkoxylated polyols are described in U.S. Patent Nos. 4,983,329; No. 5,175,323; No. 5,288,884; No. 5,298,637; No. 5,362,894; No. 5,387,429; No. 5,446,843; No. 5,589,217; No. 5,597,605; No. 5,603,978 and No. 5,641,534, all incorporated by reference herein. Suitable alkoxylated polyols include alkoxylated sugar alcohols, alkoxylated monosaccharides, alkoxylated disaccharides, alkoxylated polysaccharides, C2-C? Alkoxylated aliphatic diols, and C3-C? 2 alkoxylated aliphatic triols. Preferred C3-C? 2 alkoxylated tri-alkoxylates are
P1109 alkoxylated glycerols, propoxylated glycerols are most preferred, and propoxylated glycerols having from about 3 to about 21 moles of propylene oxide per mole of glycerol are particularly preferred. Preferred alkoxylated polysaccharides are alkoxylated polysaccharides containing anhydromonosaccharide units, the most preferred being propoxylated polysaccharides containing anhydromonosaccharide units, as described in U.S. Patent No. 5,273,772, incorporated herein by reference. Preferred bonded alkoxylated glycerines include those comprising polyether glycol linking segments, as described in U.S. Patent No. 5,374,446, incorporated by reference herein and those comprising polycarboxylate linking segments, as described in US Pat. U.S. Patent Nos. 5,427,815 and 5,516,544, incorporated by reference herein; most preferred are those described in U.S. Patent No. 5,516,544. As used herein, the term "second polyol" is intended to include fatty acid esters and polyols, in which the hydroxyl groups were replaced with fatty acid esters. The polyol component of the second esterified polyol can be the same
P1109 polyol than the first unesterified polyol although it will generally be different. Suitable fatty acids, used to esterify the second polyol may be derived from either saturated or unsaturated fatty acids. Suitable preferred fatty acids include, for example, capric, lauric, palmitic, stearic, behenic, isomiristic, isomargaric, myristic, caprylic and anteisoarachidic acids. Preferred and suitable unsaturated fatty acids include, for example, maleic, linoleic, lycanic, oleic, eladic, linolenic and erythrogenic acids. Lower fatty acids having 2 to 8 carbons can also be used herein. In a preferred embodiment of the invention, the fatty acid chains of the esterified polyols have at least 8 carbon atoms; in a more preferred embodiment, the fatty acid chains have from about eight to about twenty-four carbon atoms. The esterified polyols can be obtained from hydrogenated and non-hydrogenated oils of natural occurrence; preferred are soybean oil, palm kernel oil, palm oil, coconut oil, sunflower oil, safflower oil, corn oil, cottonseed oil, peanut oil, canola oil, high rapeseed oil erucic acid and rapeseed oil
P1109 Hydrogenated erucic acid. The naturally occurring oils can contain free fatty acids together with the esterified polyols, these fatty acids can be removed before using the esterified polyols. A preferred esterified polyol is a triglyceride; particularly preferred is a triglyceride wherein the fatty acid chains have from about eight to about twenty-four carbon atoms. The triglyceride will result in the formation of glycerin and / or mono and diglycerides as by-products. The second polyol is preferably compatible with food grade polyols, the second suitable polyols include, for example, triglycerides. The second polyol is preferably free of esters that have potentially toxic effects, such as, for example, methylcarbitol. Suitable basic catalysts include alkali metals, such as sodium, lithium and potassium, alloys of two or more alkali metals, such as sodium-lithium and sodium-potassium alloys; alkali metal hydrides, such as sodium, lithium and potassium hydride; lower alkyl (Cx-C) alkali metal such as butyllithium; and alkali metal alkoxides of lower alcohols (C? -C4), such as lithium methoxide, potassium t-butoxide, potassium methoxide and / or methoxide of
P1109 sodium. Potassium methoxide and sodium methoxide are the preferred catalysts. Other suitable basic compounds include carbonates and bicarbonates of alkali metals and alkaline earth metals. A preferred class of basic catalysts includes potassium carbonate, sodium carbonate, barium carbonate or mixtures of these compounds having particle sizes that are less than about 100 microns, preferably less than about 50 microns. These preferred catalysts can be used in a mixture with the more conventional basic catalysts described above. The use of these catalysts is further disclosed in U.S. Pat. No.
4,517,360 (Volpenhein), the disclosure of said catalyst is incorporated herein by reference. As used herein, the term "emulsifying agent" is intended to include substances that have the ability to emulsify and / or solubilize the mixture of the unesterified polyol and esterified polyol, such as soaps, partially esterified polyols and solvents. Suitable soaps include soaps of alkali metal fatty acids. As used herein, the term "alkali metal fatty acid soaps" is intended to include metal salts
P1109 alkalines of saturated or unsaturated fatty acids having from about eight to about twenty-four carbon atoms, preferably from about eight to about eighteen carbon atoms. Accordingly, suitable alkali metal fatty acid soaps include, for example, lithium, sodium, potassium, rubidium and cesium salts of the fatty acids described herein. Mixtures of fatty acids derived from soybean oil, sunflower oil, safflower oil, cottonseed oil and corn oil are preferred. Accordingly, the preferred alkali metal fatty acid soaps include, for example, potassium soap prepared from fatty acids of soybean oil. The soap emulsifier does not. it is essential after the first polyol has been partially esterified and sufficient partially esterified polyol exists to maintain the homogeneity of the reaction mixture. Removal of the soap can be achieved by known techniques, for example, by filtration, centrifugation, etc., since the soap is relatively insoluble in the reaction mixture at higher degrees of esterification. As used herein, the term "partially esterified polyol" is those esters of the polyol, wherein it has been esterified to approximately
P1109 50% of the hydroxyl groups of the polyol. Preferred emulsifiers include lower sucrose polyesters, i.e., sucrose polyesters having on average less than about 4 fatty acid groups per molecule of sucrose. Suitable solvents include dimethylformamide (DMF), formamide, dimethyl sulfoxide or pyridine. The solvent can be removed from the reaction mixture of Step 1, by distillation before or after the removal of the by-products of the reaction. If the polyol polyester will be an edible product, a system without solvents is preferred; A system without soap is also preferred. An especially preferred system is a solvent free system of sucrose, lower polyesters of sucrose and triglyceride; When lower polyesters of sucrose are used as the emulsifying agent, there is no need to remove the emulsifying agent after the end of the second step.
Step 2. React the mixture of the ingredients In the second step of the present processes, the mixture of ingredients is reacted at a temperature sufficient to obtain a reaction mixture by transesterification of the ingredients, the reaction products and the by-products . A sufficient temperature
P1109 is that temperature which exceeds the activation energy of the transesterification reaction and which causes transesterification to occur. The activation energy will depend partially on the amount and type of catalyst used and on the type of the first and second polyols. In general, it is not necessary to heat the ingredient mixture to a temperature greater than 350 ° C (662 ° F). Step 2 is performed at a temperature of up to about 350 ° C (662 ° F), preferably from about 15 ° C (59 ° F) to about 350 ° C
(662 ° F), more preferably about 50 ° C
(122 ° F) at about 350 ° C (662 ° F), with an even greater preference of about 50 ° C (122 ° F) to about 200 ° C (392 ° F). Particularly preferred temperatures from 70 ° C (158 ° F) to 150 ° C
(302 ° F). When sucrose is used as the first non-esterified polyol, temperatures of less than about 150 ° C (302 ° F) are preferred, since sucrose tends to caramelize at a temperature greater than about 150 ° C (302 ° F). The preferred temperature depends, in part, on the type of emulsifier used.
Generally when solvents are used as the emulsifier, such as DMF, the temperature may be from about 15 ° C (59 ° F) to about 200 ° C (392 ° F), preferably from about 50 ° C (122 ° F) to
P1109 approximately 140 ° C (284 ° F). When partially esterified polyols or a soap as an emulsifier are used, the temperature can be from about 50 ° C (122 ° F) to about 350 ° C (662 ° F), preferably from about 50 ° C (122 ° F) to about 200 ° C (392 ° F) and more preferably from about 70 ° C (158 ° F) to about 150 ° C (302 ° F). Step 2 is generally performed at a pressure from about 1 x 10"8 m [sic] Hg to about 3 m [sic] Hg. In one embodiment, a time interval for Step 2 is from about 5 minutes to about 2 hours, preferably from about 10 minutes to about 60 minutes, although the reaction time may vary depending on the rest of the process conditions.In general, the second step is terminated when the transesterification reaction rate decreases and in general they are esterified less than about 50% of the hydroxyl groups of the first polyol After the completion of Step 2, it is preferably removed to the basic catalyst Removal of the catalyst can be achieved by filtration and / or centrifugation.
Step 3 Removing By-products In Step 3 the by-products are removed, by
Example P1109, glycerin and / or mono and diglycerides when the second esterified polyol is triglyceride, thereby promoting the further transesterification of the reaction products. The driving force of the reaction is provided by any process or means sufficient to remove or remove these by-products in a form that allows the reaction to continue, such as by distillation, liquid-liquid extraction, supercritical fluid extraction and gas extraction. inert. The distillation can be carried out at reduced pressure. A preferred embodiment uses short path distillation. Sufficient reduced pressure is used to remove or remove the byproducts, based on the molecular weights of the by-products and the concentrations of the liquid phase. The pressure is preferably from about 10"s mm Hg to about 100 mm Hg, more preferably from about 10.4 mm Hg to about 1 mm Hg, more preferably about 10" mm Hg about 10"1 mm Hg and with the maximum preference is approximately 10"3 mm Hg to approximately 10" 2 mm Hg. Distillation can be carried out at the boiling point of the by-products.The exact temperature used depends on the molecular weight of the by-products
P1109 that will be eliminated and the system pressure. A preferred distillation temperature for Step 3 is from about 100 ° C (212 ° F) to about 350 ° C (662 ° F), more preferably from about 140 ° C (284 ° F) to about 250 ° C ( 482 ° F). When sucrose is used as the first non-esterified polyol, the temperature of Step 2 is preferably less than about 150 ° C (302 ° F) in order to avoid caramelization of the non-esterified sucrose. However, the partially esterified sucrose formed in Step 2 can be heated to higher temperatures in Step 3 (from about 100 ° C to 350 ° C) without caramelization. Bubbling with nitrogen can be used to promote agitation and by-product removal.
Step 4 Further Reaction of the Mixture of the Reaction Products and the Ingredients In Step 4, the products of the transesterification and the ingredients are further reacted at a temperature for a sufficient time to esterify at least about 50%, preferably at less about 70% and more preferably at least about 75% of the hydroxyl groups of the first polyol. Most preferably, step 4 proceeds for a time to terminate the reaction, that is,
P1109 when at least about 95% of the hydroxyl of the first polyol was esterified. When the first polyol is sucrose, the reaction is completed when about 70% by weight of the sucrose polyesters are octaesters. Anyone of ordinary skill in the art will appreciate that the exact time depends on the temperature and the pressure of the system. The basic catalysts can be omitted, in particular when a sufficient reaction temperature is provided in step 4. In a preferred embodiment, the mixture of the reaction products and the ingredients of Step 4 is practically free of the basic catalyst; as used herein, it is intended that "substantially free of basic catalyst" means less than 0.05% by weight of the mixture. More preferably, the mixture of the products of the transesterification reaction and the ingredients contains less than
0. 01% by weight of the catalyst, with an even greater preference, the mixture of ingredients does not contain catalyst. The removal of the byproducts from step 3 will generally occur simultaneously with step 4.
It is also possible to sequentially remove the by-products and further react the reaction products and the ingredients. The process can alternate between step 3 and step 4 in a series of cycles.
P1109 The resultant polyol fatty acid polyester product can be centrifuged, washed with water and bleached, for example, with silica gel for refining. The centrifugation can be done with a disk stack centrifuge. Washing with water can be done in a stirred tank; the water level is from about 5% to about 18% by weight of the unrefined polyester, the mixing time is from about 10 to about 30 minutes. Preferred mixing vessels for washing with water are multistage columns with agitation. Multistage columns suitable for use with the present invention include, but are not limited to, rotating disk compactors, extractors, Oldshue-Rushton, Scheibel extraction towers, Kuhni towers and the like. These columns are analyzed by Perry, et al., Chemical Engineers Handbook, 6th Edition, 1984, pages 21-77 to 21-79, incorporated herein by reference. The columns in Perry et al. Are shown schematically with countercurrent flow. From the top of a vertical column a heavy liquid is fed and removed from the bottom with a light liquid fed near the bottom and extracted near the top. The two streams of the present invention can be fed countercurrently,
P1109 that is, currents flow through the column in opposite directions or concurrently, that is, both streams flow through the column in the same direction. When the two streams are fed at or near the same end of the column, they are usually removed at the opposite end of the column or close to it. Baffles within the column may be provided between the stages, wherein the size and shape of the opening in the baffle are designed to provide the desired residence time within each stage as well as other process conditions. Likewise, a propeller can be supplied within each stage and, normally, the propellers are connected to a single arrow that runs through the column. In this way, an arrow can drive all the propellers, keeping the agitation speed relatively constant within the different stages. However, as can be appreciated, propellers with independent motors and / or drive gears can be provided in individual stages or between stages, so that the respective speeds of the propellers vary from one stage to the next. The speed of agitation within the column and within the individual stages, the shape and size of the deflector openings that separate the stages and
P1109 the number of stages, are all design criteria that can be varied to achieve the desired purification. Multistage columns may be provided with quiet or "calm" zones at one or both ends of the column. If a calm zone is provided, two phases can be separated by the use of two extraction ports, that is, a first port for the extraction of the first phase and a second port for the extraction of the second phase. In another embodiment, the water phase can be separated by centrifugation, such as for example with a disk stack centrifuge. Alternatively, the water phase can be separated by gravity sedimentation. The polyol polyester can then be dried to a moisture content of less than about 0.1% in a vacuum dryer. Bleaching can be performed with silica gel by contacting dry silica with the polyol polyester in a stirred tank for 30 minutes. The silica level is preferably about 1% by weight of the polyol polyester. The silica gel can be separated from the polyol polyester with a filter press. The following examples are intended to further clarify the invention and should not be construed as limiting. All proportions are proportions
P1109 molars, unless otherwise specified, percentages are by weight unless otherwise specified.
Supercritical Fluid Chromatography The composition of the polyol polyester can be determined by supercritical fluid chromatography. First a sample of polyglycerol ester is silylated to derive any hydroxyl groups that did not react. The silylated sample is then injected into a supercritical fluid chromatograph (SFC for its acronym in English). The esters are separated by the degree of esterification in a capillary column DB1 and detected by a flame ionization detector. The distribution of the esters is calculated by the peak area of the chromatogram.
Equipment and Conditions SFC: Supercritical fluid chromatograph Lee scientific series 6000 or equivalent; SFC conditions: A) DB1 capillary column, film of 0.2 u, 50 u ID, 10 m. J &W Scientific. B) Oven temperatures - 90 ° C Detector - 400 ° C
P1109 C) Pressure Program 125-375 atmospheres at 10 atmospheres per minute with a final retention time of 10 minutes. D) C02 Grade SFC, Scott Specialty Gases E) Hydrogen Approximately 30 mL / minute F) Air Approximately 300-350 mL / minute 10 G) Auxiliary Gas (nitrogen) Approximately 25 mL / minute H) Syringe for injection to SFC ^ F 50ul Hamilton I) Vials 15 Kimble Glass Fischer Scientific # 03-340-lC of 2 or 4 drachmas. J) Heating plate 90 ° C K) Filter 20 0.45 u from Alltech Associates # 2092 L) Disposable syringe 3.0 mL from Fisher Scientific # 14-823-39
Reagents 25 BSTFA (bis (trimethylsilyl) -trifluoroacetamide) Supelco, Inc., # 3-3027; TMSI (trimethylsilylimidazole) Supelco, Inc. # 3- 3068; ACS grade pyridine, MCB # PX2020-01.
P1109 Sample Analysis The sample was completely melted and mixed thoroughly. A disposable pipette was used to weigh
• 80-100 mg of sample in a four-drach vial. The weight of the sample was recorded. To the vial was added 1 mL of pyridine and 1 mL of TMSI / BSTFA solution (mixed at 5: 1). The vial was capped and heated on the heating plate at 90 ° C for 15 minutes. The sample was allowed to cool. A filter of 0.45 was placed
microns at the end of a 3 cc disposable syringe. He
• Derived standard was emptied into the disposable syringe and filtered into a GC vial vial. The sample was injected into the Supercritical Fluid Chromatograph.
Example 1 Step (1): Sucrose (50 g) and 412 g of C8 triglycerides which can be obtained in commercial form, were mixed in a molar ratio of about 6: 1 and solubilized in 750 ml of dimethylformamide (DMF). HE
added potassium carbonate (4 g). Step (2): The mixture was reacted for approximately 20 minutes at 120 ° C (248 ° F) and at atmospheric pressure; the DMF was then removed by distillation. The reaction products are sucrose esters that
have an average of approximately 3.7 acid groups
P1109 fatty per molecule of sucrose. The reaction by-products are glycerol esters that have an average of
2. 3 fatty acid groups per glycerol molecule. At the end of Step (2), the mixture comprises: Monoglycerides 5.5% Diglycerides 33.1% Triglycerides 36% Sucrose 0.1% Sucrose monoester (SEl) 0.6% Sucrose diaster (SE2) 2.5% Sucrose sucrose (SE3) 6.2% Tetraster Sucrose (SE4) 8.4% Sucrose pentaester (SE5) 4.2% Sucrose sucrose (SE6) 3.1% Sucrose sucrose (SE7) 0.4% Sucrose octaester (SE8) 0%
Steps (3) and (4): Sodium methoxide (0.3 g) was added to 300 g of the material produced in Step (2). The mixture was further reacted for approximately 42 hours at approximately 140-160 ° C (284-320 ° F) and approximately 0.015 mm Hg pressure. The fluid was recirculated through a thin film evaporator. The glycerin and the mono and diglycerides were removed simultaneously. The remainder of the reaction mixture comprises, by weight, about 76.4% sucrose esters, about 23% triglycerides and about 0.67% diglycerides. The process results
P1109 in the formation of highly esterified sucrose esters (approximately 78%, by weight, of the sucrose ester products were octaesters).
Example 2 Step (1): Sucrose (35 g) and 543 g of high oleic sunflower oil triglyceride were mixed in a molar ratio of about 6: 1 and solubilized in 525 ml of dimethylformamide (DMF). Carbonate added
potassium (3 g). • Step (2): The mixture was reacted for approximately 65 minutes at 120 ° C (248 ° F) at atmospheric pressure; the DMF was then removed by distillation. At the end of Step (2), the mixture comprises
Approximately 15: Monoglycerides 3.7% Diglycerides 31% Triglycerides 41% Sucrose 0.1% • 20 SE 1 0.4% SE 2 2.4% SE 3 5.1% SE 4 7.2% SE 5 6.3% 25 SE 6 2.9% SE 7 0.4%
P1109 Steps (3) and (4): Sodium methoxide (0.3 g) was added to 300 g of the material produced in Step (2). The mixture was further reacted for approximately 76 hours at 150 to 230 ° C (302-446 ° F) and 60 x 10"3 mm Hg at 20 x 10" 3 mm Hg. The fluid was recirculated through a thin film evaporator. The glycerin and the mono and diglycerides were removed simultaneously. The process results in the formation of highly esterified sucrose esters (approximately 70% of the sucrose polyesters were octaesters). The remainder of the reaction mixture comprises approximately: Diglycerides 1.8% Triglycerides 62% SE 6 2.2% SE 7 8.6% SE 8 25.3% The mixture does not comprise monoglycerides or lower sucrose esters.
Example 3 Steps (1) and (2): The sucrose ester feed material was produced by the transesterification of soybean methyl esters with sucrose. The crude material was washed, dried under vacuum, bleached with silica gel and filtered. The excess of
P1109 methyl esters were removed in a film evaporator. The composition of the sucrose ester feedstock is approximately: SE 1 0.2% SE 2 0.4% SE 3 2.4% SE 4 6.8% SE 5 14.5% SE 6 23.8% SE 7 28.8% SE 8 20.9%
Steps (3) and (4): The sucrose ester feed material (6580 g) and 4770 g of triglycerides from a mixture of corn / canola oils were mixed. The catalyst was added, 55 g of 25% sodium methoxide in methanol. . The mixture was reacted at a temperature of about 225 ° C (437 ° F) and a pressure of about 2 x 10"3 mm Hg to about 4 x 10" 3 mm Hg. The mixture was passed 41 times through a molecular distiller. The total residence time of the passes was approximately 6 minutes. Short path distillation was used to remove the byproducts of the transesterification reaction. A carved film evaporator with an internal condenser was used.
P1109 The process results in the formation of highly esterified sucrose esters (approximately 75% of the sucrose polyesters were octaesters). The rest of the
• Reaction mixture comprises approximately: Diglycerides 0.81% Triglycerides 82.8% SE 6 0.81% SE 7 2.95% SE 8 11.48% The mixture does not comprise monoglycerides or lower sucrose esters. The preceding examples were set forth to illustrate specific embodiments of the invention and are not intended to limit the scope of the methods
of the present invention. Additional embodiments and modifications within the scope of the claimed invention will be apparent to those of ordinary skill in the art. In accordance with the foregoing, the scope of the present invention should be considered in terms of the
following claims and it will be understood that it is not constrained or limited to the details of the methods described in the specification.
P1109
Claims (15)
- CLAIMS: 1. A process for synthesizing polyesters of fatty acid and polyol, comprising the steps of: (1) mixing the following ingredients: (a) a first non-esterified polyol having hydroxyl groups, (b) a second polyol esterified with fatty acids, (c) a basic catalyst and (d) an emulsifying agent to form a mixture of ingredient-s; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a transesterification reaction mixture comprising ingredients, products of the transesterification reaction and by-products, wherein the mixture of ingredients is reacted preferably at a temperature from about 15 ° C to about 350 ° C; (3) removing from the transesterification reaction mixture at least a portion of the by-products; and (4) further reacting the products of the transesterification reaction and the ingredients of step (3) at a temperature and for a time sufficient to esterify at least about 50% of the hydroxyl groups of the first polyol; wherein the first non-esterified polyol is P1109 preferably selects from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, sugar alcohols, sugar esters, polyglycerols and polyalkoxylated glycerols; and wherein the second polyol is preferably derived from hydrogenated and non-hydrogenated oils, of natural origin, selected from the group consisting of: soybean oil, cottonseed oil, palm kernel oil, palm oil, coconut oil, sunflower oil, safflower oil, corn oil, cottonseed oil, peanut oil, canola oil, high erucic acid rapeseed oil, high-erucic hydrogenated rapeseed oil and mixtures thereof; and wherein the basic catalyst is preferably selected from the group consisting of: alkali metals, alkali metal alloys, alkali metal hydrides, alkali metal alkoxides, alkali metal carbonates, alkali metal bicarbonates and mixtures thereof.
- 2. A process according to claim 1, wherein step (3) and step (4) occur simultaneously 3.
- A process according to claim 1, wherein step (3) and step (4) occur at minus one cycle of step (3) followed by step (4) 4.
- A process according to claims 1, 2, P1109 3 or 4, which comprises the step of removing the basic catalyst or the emulsifying agent after the end of step (2).
- A process according to claims 1, 2, 3 or 4, comprising the step of heating a mixture of the reaction products and the ingredients of step (3), wherein the mixture is practically free of the basic catalyst.
- 6. A process according to claims 1, 2, 3, 4 or 5, wherein the first non-esterified polyol is sucrose and the emulsifying agent are lower sucrose polyesters.
- 7. A process according to claims 1, 2, 3, 4, 5 or 6, wherein the second polyol is a triglyceride.
- 8. A process according to claims 1, 2, 3, 4, 5, 6 or 7, wherein the mixture of ingredients has a molar ratio of fatty acids of the second polyol to hydroxyl groups of the first unesterified polyol greater than about 1: 1.
- 9. A process according to claims 1, 2, 3, 4, 5, 6, 7 or 8, wherein the reaction of step (4) is for a time sufficient to esterify at least about 70%, more preferably at least about 95% of the hydroxyl groups of the first polyol. P1109
- 10. A process according to claims 1, 2, 3, 4, 5, 6, 7, 8 or 9, comprising the step of removing the by-products of the reaction mixture of step (3) by distillation under reduced pressure, wherein the step of the distillation comprises, preferably, distilling at a pressure of between about 10"5 mm Hg and 100 mm Hg and wherein the step of the distillation comprises, more preferably, distill at a temperature between about 100 ° C and 350 ° C and at a pressure between about 10 ~ 4 mm Hg and 1 mm Hg.
- 11. A process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the process is a batch process.
- 12. A process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the process is a continuous process.
- 13. A process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein the polyol fatty acid polyesters comprise polyol fatty acid polyesters selected from the group which consists of: linked and esterified alkoxylated glycerines, esterified polyols extended with epoxide and mixtures thereof.
- 14. A process for synthesizing polyesters of fatty acid and polyol, comprising the steps of: P1109 (1) mixing the following ingredients: (a) a first non-esterified polyol having hydroxyl groups and selected from a group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, sugar alcohols, sugar ethers, polyglycerols and glycerols polyalkoxylates, (b) a second polyol esterified with fatty acids, (c) a basic catalyst and (d) a solvent to form a mixture of ingredients, wherein the solvent is preferably selected from the group consisting of: dimethylformamide, formamide, dimethylsulfoxide and pyridine; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a transesterification reaction mixture, comprising ingredients, transesterification reaction products and by-products; (3) remove the solvent by distillation; and (4) removing by-products from the transesterification reaction mixture; and (5) further reacting the products of the transesterification reaction and the ingredients of step (3) at a temperature and for a time sufficient to esterify at least about 50% of the hydroxyl groups of the first P1109 polyol.
- 15. A process for synthesizing higher sucrose polyesters, comprising the steps of: (1) mixing the following ingredients: sucrose, fatty acid triglyceride, basic catalyst and lower sucrose polyesters, to form a mixture of ingredients; (2) reacting the mixture of ingredients at a temperature sufficient to obtain a transesterification reaction mixture; the reaction mixture comprises ingredients, reaction products and by-products comprising glycerin and mono and diglycerides; (3) removing from the transesterification reaction mixture the by-products comprising glycerin and mono and diglycerides, and (4) further reacting the reaction products and ingredients from step (3) at a temperature and for a sufficient time to complete the reaction; wherein the molar ratio of the triglyceride fatty acids to the hydroxyl groups of the sucrose is not less than 1: 1 and wherein, preferably, at least about 70% by weight of the higher sucrose polyester are sucrose octaesters. P1109
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US60/079,089 | 1998-03-23 |
Publications (1)
Publication Number | Publication Date |
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MXPA00009330A true MXPA00009330A (en) | 2001-07-09 |
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