US2992237A - Process for the production of com- - Google Patents
Process for the production of com- Download PDFInfo
- Publication number
- US2992237A US2992237A US2992237DA US2992237A US 2992237 A US2992237 A US 2992237A US 2992237D A US2992237D A US 2992237DA US 2992237 A US2992237 A US 2992237A
- Authority
- US
- United States
- Prior art keywords
- acid
- molecular weight
- esters
- oil
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000002253 acid Substances 0.000 claims description 86
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 84
- 150000001875 compounds Chemical class 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 56
- -1 ALIPHATIC HYDROCARBON ALCOHOLS Chemical class 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- 239000012190 activator Substances 0.000 claims description 34
- 150000002118 epoxides Chemical group 0.000 claims description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 32
- 239000000194 fatty acid Substances 0.000 claims description 32
- 150000004665 fatty acids Chemical class 0.000 claims description 28
- 150000001298 alcohols Chemical class 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 150000004676 glycans Polymers 0.000 claims description 22
- 229920001282 polysaccharide Polymers 0.000 claims description 22
- 239000005017 polysaccharide Substances 0.000 claims description 22
- 150000004804 polysaccharides Polymers 0.000 claims description 22
- 239000003549 soybean oil Substances 0.000 claims description 18
- 235000012424 soybean oil Nutrition 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 16
- 235000019198 oils Nutrition 0.000 claims description 16
- 229920005862 polyol Polymers 0.000 claims description 16
- 235000000346 sugar Nutrition 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 235000012343 cottonseed oil Nutrition 0.000 claims description 14
- 239000002385 cottonseed oil Substances 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N Perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 239000010775 animal oil Substances 0.000 claims description 8
- 235000021388 linseed oil Nutrition 0.000 claims description 8
- 239000000944 linseed oil Substances 0.000 claims description 8
- 229920000856 Amylose Polymers 0.000 claims description 6
- 229920001202 Inulin Polymers 0.000 claims description 6
- JYJIGFIDKWBXDU-MNNPPOADSA-N Inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 6
- 229940029339 Inulin Drugs 0.000 claims description 6
- 229920000615 alginic acid Polymers 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 238000005755 formation reaction Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229920001277 pectin Polymers 0.000 claims description 6
- 239000001814 pectin Substances 0.000 claims description 6
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 6
- 229920000945 Amylopectin Polymers 0.000 claims description 4
- WMGFVAGNIYUEEP-WUYNJSITSA-N Amylopectin 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](OC[C@@H]2[C@H]([C@H](O)[C@@H](O)[C@@H](O[C@@H]3[C@H](O[C@H](O)[C@H](O)[C@H]3O)CO)O2)O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H]1O WMGFVAGNIYUEEP-WUYNJSITSA-N 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M Sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 229940023913 cation exchange resins Drugs 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- YVWBQGFBSVLPIK-UHFFFAOYSA-N cyclohex-2-ene-1-carboxylic acid Chemical class OC(=O)C1CCCC=C1 YVWBQGFBSVLPIK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002605 large molecules Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- 150000004965 peroxy acids Chemical class 0.000 claims description 4
- 150000003460 sulfonic acids Chemical group 0.000 claims 2
- MVJKXJPDBTXECY-UHFFFAOYSA-N trifluoroborane;hydrate Chemical class O.FB(F)F MVJKXJPDBTXECY-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 description 26
- 239000011630 iodine Substances 0.000 description 20
- 229910052740 iodine Inorganic materials 0.000 description 20
- 239000007858 starting material Substances 0.000 description 20
- 238000006735 epoxidation reaction Methods 0.000 description 18
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 16
- 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 description 14
- 229960004793 Sucrose Drugs 0.000 description 14
- 150000001735 carboxylic acids Chemical class 0.000 description 12
- 230000001264 neutralization Effects 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 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 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 125000004432 carbon atoms Chemical group C* 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 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 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 240000007170 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- YTBSYETUWUMLBZ-IUYQGCFVSA-N Erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- 229920002527 Glycogen Polymers 0.000 description 4
- 229940093915 Gynecological Organic acids Drugs 0.000 description 4
- 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 4
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 4
- YYGNTYWPHWGJRM-RUSDCZJESA-N Squalene Natural products C(=C\CC/C(=C\CC/C=C(\CC/C=C(\CC/C=C(\C)/C)/C)/C)/C)(\CC/C=C(\C)/C)/C YYGNTYWPHWGJRM-RUSDCZJESA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000004164 Wax ester Substances 0.000 description 4
- 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 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 229940093476 ethylene glycol Drugs 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 235000021313 oleic acid Nutrition 0.000 description 4
- 150000002889 oleic acids Chemical class 0.000 description 4
- 239000004006 olive oil Substances 0.000 description 4
- 235000008390 olive oil Nutrition 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000010987 pectin Nutrition 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
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- 235000019386 wax ester Nutrition 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (Z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-Dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 2
- 241000209134 Arundinaria Species 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N Benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 240000008213 Brosimum alicastrum Species 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N Cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose 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)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 2
- 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 2
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- DLRVVLDZNNYCBX-LIZSDCNHSA-N Gentiobiose 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-LIZSDCNHSA-N 0.000 description 2
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- 239000002841 Lewis acid Substances 0.000 description 2
- 241001237731 Microtia elva Species 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N Octadecene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N Oleyl alcohol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229940031439 Squalene Drugs 0.000 description 2
- 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 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Vitamin C Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229960003487 Xylose Drugs 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229940053200 antiepileptics Fatty acid derivatives Drugs 0.000 description 2
- 150000001479 arabinose derivatives Chemical class 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical class OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 235000019425 dextrin Nutrition 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecan-1-amine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 229950006191 gluconic acid Drugs 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 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 2
- 239000008101 lactose Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N methyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000010697 neat foot oil Substances 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000005828 ramon Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical compound CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000013311 vegetables Nutrition 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
Definitions
- epoxide compounds can be obtained when olefinically-unsaturated compounds, preferably high-molecular weight olefin'ically-unsaturated compounds containing aliphatic hydrocar- .bon lipophilic radicals, are admixed with organic polyhydroxy compounds, such as monoor poly-saccharides or aliphatic hydrocarbon polyols, in the presence of acid activators, the mixture thus formed is treated with hydrogen peroxide and the epoxide-oxygen containing compounds formed thereby are isolated.
- organic polyhydroxy compounds such as monoor poly-saccharides or aliphatic hydrocarbon polyols
- Suitable olefinically-unsaturated starting compounds are: aliphatic olefinic hydrocarbons, such as pentene, octene, dodecene, octadecene, squalene, etc., del rivatives of olefinically-unsaturated high-molecular weight hydrocarbon alcohols, such as the esters of alcohols obtained by reduction of naturally occurring vegetable or animal olefinically-unsaturated fatty acids under reaction conditions whereby the double bond is preserved,
- esters of olefinically-unsaturated fatty alcohols which are obtained by saponifying natural wax esters, such as the esters of olefinically-unsaturated fatty 2,992,237 Patented July 11, 196 1 2 unsaturated fatty acids, may be used as starting materials, such as the amidation products of unsaturated'fatty acids or fatty acid mixtures with ammonia, dimethylamin'e, dodecylamine, oleylamine, ethylene diamine, cyclohexylamine, benzylamine, etc. Also nitriles such as tetradecenyl nitrile',,hexadecenyl nitrile or mixtures of alkylene-nitriles with 14 to 18 carbon atoms may be used.
- the process is inherently applicable also to epoxidizable compounds of a non-aliphatic character, especially to unsaturated cycloaliphaticor heterocyclic compounds.
- suitable starting materials of this type are tetrahydrobenzoic acid derivatives and tetrahydrophthalic acid derivatives, or condensation products formedfby diene components with atleast two conjugated double bonds and philodiene components with at least one nosaturated bond.
- the above-mentioned starting materials are treated with an epoxidation mixture containing an organic polyhydroxy compound such as monoor poly-saccharides or aliphatic hydrocarbon polyols.
- organic polyhydroxy compound such as monoor poly-saccharides or aliphatic hydrocarbon polyols.
- monoor polysaccharides which may be used for this purpose are threose, erythrose, arabinose, ribose, xylose, glucose, mannose, fructose, galactose, gluconic acid, mannonic acid, mucic acid, ascorbic acid and other sugar acids.
- sugar-like polysacchrides are sucrose, gentiobiose, maltose, cello biose, tr'ehalose, lactose, and the like.
- polysaccharides not related to sugar may be used in degrad-af tion form, if desired, such as amylose, amylopectiri, dextn'ns, glycogens, inulin, pectins, alginates, celluloses, etc.
- aliphatic hydrocarbon polyols as glycerine, hexanetn'ols, pentites, hexites, heptites, pentaerythrite, dipentaerythn'te, and the like.
- olefinically-unsaturated high-molecular weight fatty acids such as their esters, amides or nitriles.
- glycerides, -'moiety of which may be monoor poly-unsaturated such as the-semi-drying oils, primarily soybean oil, cottonseed oil and linseed oil.
- olive oil such as olive oil,
- esterifying components for the olefinically-unsaturated high-molecular weight fatty acids are the following alcohols; ethyl, isopropyl, n-bntyl', sec- .Ondary butyl, tertiary butyl, tertiary amyl,,n-octyl, .2- "ethylhexyl, dodecyl, octadecyl, octadecenyl, cyclohexyl, methylcyclohexyl, naphthenyl, benzyl and the like; polyhydroxy alcohols, such as' ethyleneglycol, 1,2-propylene glycol, 2-ethyl-hexanedi0l-1,3, butanediol-LB, butanediol-1,4, dodecanediol-l,l2, glycerine, pentaerythrite and polyalky
- esters formedby the olefinically-unsaturated carboxylic acids and alooholrnixtures may be used as starting materials, as well as mixed esters formed by polyhydroxy alcohols and different olefinically-unsaturated fatty acids, such as the mixed esters formedby ethylene glycol with oleic acid and linseed oil fatty acid.
- the esters in which both the acid moiety as well as the alcohol moiety contain a high-molecular weight aliphatic monoor poly-unsaturated hydrocarbon radical may also be used.
- the amides of olefinicallythe fatty acid ble to use mixtures of monoand poly-saccharidcs and polyols for the epoxidation.
- customary, inorganic or organic acids or acid halides are used as activators, for example, mineral acids, such as phosphoric acid, nitric acid, sulfuric, acid or per chloric acid, boron 'trifluon'de or boron trifludride-water adducts; organic acids, such as acid phosphoric acid esters, p-toluenesulfonic acid; and high-molecularweight synthetic resins containing sulfonic acid groups, such as those used as base exchangers, and the like.
- mineral acids such as phosphoric acid, nitric acid, sulfuric, acid or per chloric acid, boron 'trifluon'de or boron trifludride-water adducts
- organic acids such as acid phosphoric acid esters, p-toluenesulfonic acid
- high-molecularweight synthetic resins containing sulfonic acid groups such as those used as base exchangers, and the like.
- the epoxid-ation probably proceeds by a reaction between the monoor poly-saccharides or polyols and the hydrogen peroxide,forming organic, complex, acid oxidation mixtures which effect the transfer of active oxygen to the doublefbond of the high-molecular weight olefinically-unsaturated compounds.
- Y t The quantitative ratios in which the reaction components according to the invention are employed, de-
- the concentration of activeoxygen should as a rule be between 1.1 and 2 mols per molar equivalent of double bonds present in the starting material.
- the hydrogen peroxide may also 'be used in excess of this amount.
- the required maximum amount of monoor poly-saccharides or polyols and their activator should together be about 2.5 to 15% by weight of the unsaturated starting'material and should .not normally exceed these quantities. However, when a-base exchange resin containing sulfonic acid groups is used as the activator larger quantities of activator are sometimes recommended.
- the reaction temperatures to be employed are between 0 and 100 C. and preferably between 50 and C. I
- the process is performed according to customary epoxidation procedures. For example, a mixture-of the olefinically-unsaturated fatty substance and the organic polyhydroxy compound is formed and then the calculated amount of hydrogen peroxide together with the acid activator is added to the mixture, accompanied by vigorous stirring.
- the process may also be carried out bysimultaneously adding the. organic polyhydroxy com pound and the mixture of hydrogen peroxide and acid activator, both while stirring.
- the addition of the hydrogen peroxide is, as a rule, carried'out over. a period of several hours. At least a 30% "solution of hydrogen peroxide, and preferably a 50-60% solution, is used.
- the acid components which sometimes also contain small amounts of hydrogen peroxide, may be separated in accordance with known methods and may be re-admixed as a starting material with an volefinic substrate in a preliminary step or preliminary reaction or in accordance with the well-known counter-current flow principle.
- the present process as in most known epoxidation processes, if the reaction is extended over longer periods of time, dihydroxy compounds are obtained in large amount from the epoxidized compounds due to bydrolysis of the epoxy-group. Accordingly, the present process alsoprovides a means for the production of such dihydroxy compounds.
- the process according to my invention has a number of advantages over other known epoxidation processes. (1) It obviates the use of expensive low-molecular weight carboxylic acids. (2) The organic oxidation mixtures formed from the organic polyhydroxy compounds are far less explosive than performic acid or peracetic acid formed in the known epoxidation processes. (3) In contrast to known processes, in which the total required amount of hydrogen peroxide is added to the reaction mixture in the beginning, the present process, where thehydrogen peroxide is added gradually, has the advantage that the epoxidation process can be more easily controlled by control .of the exothermic course of reaction.
- plasticizers and stabilizers for polyvinyl chloride and its copolymers are useful as plasticizers and stabilizers for polyvinyl chloride and its copolymers and are thus important auxiliary agents in the production of synthetics.
- plasticizers and stabilizers for polyvinyl chloride and its copolymers are thus important auxiliary agents in the production of synthetics.
- they are useful as lubricants, lubricating oil additives or textile oils.
- Example 1 200 parts by weight of a soybean oil (acid number 0.1; saponification number 187; iodine number 120) and 20 parts 'by weight of technical grade cane sugar were placed into a VA-steel vessel provided with a. stirring me ns. acoilheater and cooling means. Thereafter, the
- Example 2 1000 parts by weight of a cotton seed oil fatty acidmethylcyclohexyl ester .(produced from the liquid components of a cottonseed oil fatty acid and methylcyclohexanol; saponification number 149.8; iodine number 94.9; acid number 0.95) were admixed with parts by weight of cane sugar and the mixture was raised to a temperature of 65 C. Thereafter 400 parts by weight of a 60% by volume hydrogen peroxide solution, to which 13.3 parts by weight of concentrated phosphoric acid and 6.66 parts by weight of concentrated sulfuric acid has been previously added, were stirred into the mixture over a. period of 3-4 hours, taking care that the temperature of 65 C. was accurately maintained. The reaction mixture was then stirred for about six additional hours.
- Example 1 When the procedure of Example 1 was altered by using in place of cane sugar an equal weight of glucose in the reaction, while operating under otherwise identical conditions, a soybean oil epoxide having an epoxide oxygen content of 5.33% was obtained after 15 hours.
- Example 4 750.0 parts by weight of soybean oil having the charactcristic values:
- reaction 0.28 7 18-89 temperature is maintained at about 60 C.
- the mixture 7Y5 is vigorously stirred for 15-23 hours and after that'th 7 aqueous parts are drawn elf and the reaction product is worked up in a usual manner.
- carboxylic acid esters of lower alkoxy substituted aliphatic hydrocarbon alcohols low molecular weight monohydroxy alcohol esters of fatty acids, dihydroxy alcohol esters of fatty acids, and unsubstituted amides of fatty acids
- low molecular weight monohydroxy alcohol esters of tetrahydrobenzene :canboxylic acids which comprises the steps of (1) mixing said olefinically unsaturated compounds with (a) an organic polyhydroxy compound selected from the group consisting of aliphatic hydrocarbon polyols containing from 3 to 10 carbon atoms, monosaccharides, monosaccharidic acids, sugar polysaccharides, amylose, amylopectin, dextrins, glycogens, inulin, pectins, alginates, and acid degraded cellulose, and (b) an acid activator capable of accelerating peracid formation selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, sodium acid sulf
- high-molecular weight fatty acid derivatives such as the fatty acid amides and fatty acid nitriles and the esteiified high-molecular weight fatty alcohols can also be epoxidized by my invention.
- a process for the introduction of epoxide groups into olefinically unsaturated compounds selected from the group consisting of (a) high molecular weight olefinically unsaturated compounds containing aliphatic hydrocarbon lipophilic radicals selected from the group consisting of linseed oil, soybean oil, cottonseed oil, olive oil, neatshydroxy compound and said acid activator are added in an amount in combination of from 7 to 15% by weight of said olefinically-unsaturated compound.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Compounds (AREA)
Description
United States Patent This invention relates to an improved process of producing epoxidized organic compounds and to the epoxideoxygen containing compounds so prepared.
I have found that technically valuable epoxide compounds can be obtained when olefinically-unsaturated compounds, preferably high-molecular weight olefin'ically-unsaturated compounds containing aliphatic hydrocar- .bon lipophilic radicals, are admixed with organic polyhydroxy compounds, such as monoor poly-saccharides or aliphatic hydrocarbon polyols, in the presence of acid activators, the mixture thus formed is treated with hydrogen peroxide and the epoxide-oxygen containing compounds formed thereby are isolated.
Examples of suitable olefinically-unsaturated starting compounds are: aliphatic olefinic hydrocarbons, such as pentene, octene, dodecene, octadecene, squalene, etc., del rivatives of olefinically-unsaturated high-molecular weight hydrocarbon alcohols, such as the esters of alcohols obtained by reduction of naturally occurring vegetable or animal olefinically-unsaturated fatty acids under reaction conditions whereby the double bond is preserved,
hereinafter sometimes referred to as olefinically-unsaturated fatty alcohols, or esters of olefinically-unsaturated al'coholswhich are obtained by saponifying natural wax esters, such as the esters of olefinically-unsaturated fatty 2,992,237 Patented July 11, 196 1 2 unsaturated fatty acids, may be used as starting materials, such as the amidation products of unsaturated'fatty acids or fatty acid mixtures with ammonia, dimethylamin'e, dodecylamine, oleylamine, ethylene diamine, cyclohexylamine, benzylamine, etc. Also nitriles such as tetradecenyl nitrile',,hexadecenyl nitrile or mixtures of alkylene-nitriles with 14 to 18 carbon atoms may be used.
The process is inherently applicable also to epoxidizable compounds of a non-aliphatic character, especially to unsaturated cycloaliphaticor heterocyclic compounds. Examples of suitable starting materials of this type are tetrahydrobenzoic acid derivatives and tetrahydrophthalic acid derivatives, or condensation products formedfby diene components with atleast two conjugated double bonds and philodiene components with at least one nosaturated bond. Q'-
In accordance with the invention, the above-mentioned starting materials are treated with an epoxidation mixture containing an organic polyhydroxy compound such as monoor poly-saccharides or aliphatic hydrocarbon polyols. Examples of monoor polysaccharides which may be used for this purpose are threose, erythrose, arabinose, ribose, xylose, glucose, mannose, fructose, galactose, gluconic acid, mannonic acid, mucic acid, ascorbic acid and other sugar acids. Examples of sugar-like polysacchrides are sucrose, gentiobiose, maltose, cello biose, tr'ehalose, lactose, and the like. In addition, polysaccharides not related to sugar may be used in degrad-af tion form, if desired, such as amylose, amylopectiri, dextn'ns, glycogens, inulin, pectins, alginates, celluloses, etc. Further suitable are aliphatic hydrocarbon polyols as glycerine, hexanetn'ols, pentites, hexites, heptites, pentaerythrite, dipentaerythn'te, and the like. It is also possialcohols with 14 to 18 carbon atoms, especially of oleyl alcohol, and other monoor polyolefinically-unsaturated alcohols formed with any desired lowor high-molecular weight carboxylic acids. Also suitable are the corresponding ethers of the above-mentioned unsaturated alcohols formed preferably with low-molecular weight alcohols.
Further suitable as starting materials are derivativesof olefinically-unsaturated high-molecular weight fatty acids, such as their esters, amides or nitriles. Especially suitable are naturally-occurring, glycerides, -'moiety of which may be monoor poly-unsaturated, such as the-semi-drying oils, primarily soybean oil, cottonseed oil and linseed oil. Further suitable are olive oil,
' neats-foot oil, sperm oil and other marine animal oils.
Examples of other esterifying components for the olefinically-unsaturated high-molecular weight fatty acids are the following alcohols; ethyl, isopropyl, n-bntyl', sec- .Ondary butyl, tertiary butyl, tertiary amyl,,n-octyl, .2- "ethylhexyl, dodecyl, octadecyl, octadecenyl, cyclohexyl, methylcyclohexyl, naphthenyl, benzyl and the like; polyhydroxy alcohols, such as' ethyleneglycol, 1,2-propylene glycol, 2-ethyl-hexanedi0l-1,3, butanediol-LB, butanediol-1,4, dodecanediol-l,l2, glycerine, pentaerythrite and polyalkyleneglycols, such diethylene glycol, and the like. Similarly, esters formedby the olefinically-unsaturated carboxylic acids and alooholrnixtures may be used as starting materials, as well as mixed esters formed by polyhydroxy alcohols and different olefinically-unsaturated fatty acids, such as the mixed esters formedby ethylene glycol with oleic acid and linseed oil fatty acid. Finally, the esters in which both the acid moiety as well as the alcohol moiety contain a high-molecular weight aliphatic monoor poly-unsaturated hydrocarbon radical may also be used.
In addition to the esters, the amides of olefinicallythe fatty acid ble to use mixtures of monoand poly-saccharidcs and polyols for the epoxidation.
, customary, inorganic or organic acids or acid halides are used as activators, for example, mineral acids, such as phosphoric acid, nitric acid, sulfuric, acid or per chloric acid, boron 'trifluon'de or boron trifludride-water adducts; organic acids, such as acid phosphoric acid esters, p-toluenesulfonic acid; and high-molecularweight synthetic resins containing sulfonic acid groups, such as those used as base exchangers, and the like. Some of these activators are commonly known as Lewis acids. The epoxid-ation probably proceeds by a reaction between the monoor poly-saccharides or polyols and the hydrogen peroxide,forming organic, complex, acid oxidation mixtures which effect the transfer of active oxygen to the doublefbond of the high-molecular weight olefinically-unsaturated compounds. Y t The quantitative ratios in which the reaction components according to the invention are employed, de-
pend'primarily on the number of double bonds in the starting materials which are to' be transformed into epoxide groups. The concentration of activeoxygen, that is, the content of hydrogen peroxide, should as a rule be between 1.1 and 2 mols per molar equivalent of double bonds present in the starting material. The hydrogen peroxide, however, may also 'be used in excess of this amount. The required maximum amount of monoor poly-saccharides or polyols and their activator should together be about 2.5 to 15% by weight of the unsaturated starting'material and should .not normally exceed these quantities. However, when a-base exchange resin containing sulfonic acid groups is used as the activator larger quantities of activator are sometimes recommended. The reaction temperatures to be employed are between 0 and 100 C. and preferably between 50 and C. I
The process is performed according to customary epoxidation procedures. For example, a mixture-of the olefinically-unsaturated fatty substance and the organic polyhydroxy compound is formed and then the calculated amount of hydrogen peroxide together with the acid activator is added to the mixture, accompanied by vigorous stirring. The process may also be carried out bysimultaneously adding the. organic polyhydroxy com pound and the mixture of hydrogen peroxide and acid activator, both while stirring. Finally, it is also possible, whenpolysaccharides unrelated to sugars are used, to first produce a mixture of the polysaccharides with the-acid activators and thereby bring about a partial degradation or hydrolysis ofthe poly-saccharides, and add this mixture, together with the hydrogen peroxide to the olefinic fatty compound in the reaction mixture.
The addition of the hydrogen peroxide is, as a rule, carried'out over. a period of several hours. At least a 30% "solution of hydrogen peroxide, and preferably a 50-60% solution, is used.
At the end of the reaction the acid components, which sometimes also contain small amounts of hydrogen peroxide, may be separated in accordance with known methods and may be re-admixed as a starting material with an volefinic substrate in a preliminary step or preliminary reaction or in accordance with the well-known counter-current flow principle.
In the present process, as in most known epoxidation processes, if the reaction is extended over longer periods of time, dihydroxy compounds are obtained in large amount from the epoxidized compounds due to bydrolysis of the epoxy-group. Accordingly, the present process alsoprovides a means for the production of such dihydroxy compounds.
The process according to my invention has a number of advantages over other known epoxidation processes. (1) It obviates the use of expensive low-molecular weight carboxylic acids. (2) The organic oxidation mixtures formed from the organic polyhydroxy compounds are far less explosive than performic acid or peracetic acid formed in the known epoxidation processes. (3) In contrast to known processes, in which the total required amount of hydrogen peroxide is added to the reaction mixture in the beginning, the present process, where thehydrogen peroxide is added gradually, has the advantage that the epoxidation process can be more easily controlled by control .of the exothermic course of reaction. (4) Because of the delayed course of reaction, the danger of formation of undesirable dihydroxy or acyloxy compounds due to cleavage of the epoxide ring is reduced. (5) In those cases where synthetic resins containing sul-fonic acid groups are used as acid activators, there is a further advantage in that these resins do not cause a cleavage of the epoxidegroups formed by the reaction even when present in amounts above 0.5 mol per molar equivalent of double bonds. The high-molecular weight epoxide compounds obtainable by the method of the invention are of versatile technical interest. For example, because of their compatibility and resistance to migration, they are useful as such, or in the form of their derivatives, as plasticizers and stabilizers for polyvinyl chloride and its copolymers and are thus important auxiliary agents in the production of synthetics. Furthermore, they are useful as lubricants, lubricating oil additives or textile oils.
The following examples will further illustrate the present invention and enable others skilled in the art to understand it more completely. .It will be understood,
however, that the invention is not limited to these particular examples. Example 1 200 parts by weight of a soybean oil (acid number 0.1; saponification number 187; iodine number 120) and 20 parts 'by weight of technical grade cane sugar were placed into a VA-steel vessel provided with a. stirring me ns. acoilheater and cooling means. Thereafter, the
temperature of the contents of the vessel was raised to 65 C. In the course of 3-4 hours parts by weight of a 50% by weight hydrogen peroxide solution containing 4 parts by weight of concentrated phosphoric acid were added to the contents of the vessel While stirring and-maintaining the temperature at 65 C. by cooling. The reaction product was stirred for another two hours at this temperature and was then washed with water until neutral. In order to remove small amounts of residual acid components, the reaction product was refined by washing with a dilute sodium hydroxide solution and again washed until neutral. By heating the product to 70-90 C. under reduced pressure to dehydrate, a dry soybean oil epoxide was obtained having an epoxide oxygen content of 5.1% (iodine number 31.5; acid number 0.)
Example 2 1000 parts by weight of a cotton seed oil fatty acidmethylcyclohexyl ester .(produced from the liquid components of a cottonseed oil fatty acid and methylcyclohexanol; saponification number 149.8; iodine number 94.9; acid number 0.95) were admixed with parts by weight of cane sugar and the mixture was raised to a temperature of 65 C. Thereafter 400 parts by weight of a 60% by volume hydrogen peroxide solution, to which 13.3 parts by weight of concentrated phosphoric acid and 6.66 parts by weight of concentrated sulfuric acid has been previously added, were stirred into the mixture over a. period of 3-4 hours, taking care that the temperature of 65 C. was accurately maintained. The reaction mixture was then stirred for about six additional hours. After cooling, the contents of the vessel were washed twice with a volume of distilled water corresponding to the reaction mixture, and the reaction product was de-acidified in a refining vessel. The epoxide ester was washed until neutral and subsequently freed from water under reduced pressure, The epoxide thus obtained has the following characteristic values:
When the procedure of Example 1 was altered by using in place of cane sugar an equal weight of glucose in the reaction, while operating under otherwise identical conditions, a soybean oil epoxide having an epoxide oxygen content of 5.33% was obtained after 15 hours.
Per ent Reaction Period Acid No. Iodine No. epoxide oxygen After 5.!ihours 0.17 80. 5 2. 67 After 9.5 hours 0.28 50. 6 4. 23 After 15.0 hours; 0. 23 27. 7 5. 33
Example 4 750.0 parts by weight of soybean oil having the charactcristic values:
Acid number 0.2 saponification No. 186.5 Hydroxyl No. 2
Iodine No. 122
were placed into a VA-steel vessel provided with a stirrer, together with 37.5 parts by weight of cane sugar and 10.0 parts by weight of a base exchanger of the type Lewatit S100 (ion exchanger of Farbenfabriken B yer AG based on sulfonated styrene resin) which had previously been treated with acid and then thoroughly washed until neutral. 400 parts by weight of a 50% by weight hydrogen peroxide solution was then added to the reaction mixture over a period of two to three hours at atemperature of 65 C; The heat of reaction formed thereby was withdrawn from the mixture sotha-t the temperature of the contents of the vessel did not rise above 65 C. The reaction was accompanied by thorough mechanical agitation. At the end of the exothermic reaction, the reaction mixture was maintained at a temperature of-65 C. with the aid of a heater for a total reaction period of 22 to 25 hours. The solid components of the base exchanger may be reused after filtration and regeneration.
The filtration was washed with water and the raw epoxide, which was obtained by allowing the mixture to Example 6 A black marine animal oil of mediocre quality and unpleasant oder was bleached in accordance with the previously described process using the following reaction mixture:
settle, was refined by a wash with dilute sodium hydroxide, I
washed until neutral and dried.
106.9; saponifica-tion No. 105.8; hydroxyl No. 21.9 parts by weight cane sugar 150 parts by weight of a 50% hydrogen peroxide solution 10 parts by weight concentrated phosphoric acid Reaction temperature 65 C. a Reaction period 7 hours After purification a light yellow fish oil having the follow- Acid number h t 'sti a1 w obtained:
Iodine number 27.9 (after 16 hours) mg c arac en 0 v as Epoxide oxygen 5.1% (after 16 hours) Add Ep oxygen -8% e 16 u Iodine No. 70.7
h I I i Id Example 5 20 Epoxr e oxygen percen I g If in :place of the reaction mixture of the preceding Example 7 example the Ramon camed out When other monoor polysaccharides are substituted, the previously described process yielded fatty epoxides 1500 parts by welght soybean 011 (same l u with the following epoxide content values; in each case parts byweight sugar 15 parts by weight base exchanger (Lewatit S100), aciditied and washed until neutral and 700 parts by weight of a 5 0% hydrogen peroxide solution 750 parts by weight soybean oil (acid No. 0.2; saponification No. 186.5; iodine No. 122) were used. The reaction temperature was 65 C. and the reaction period. 15.17 hours. i
l Pretreated with theactlvator in dilute phase.
the peroxide being added over a periodof one and the temperature held at 65 C.; a fatty epoxide having Example 8 g V I The following results were obtained with the indicated starting materials "having the indicated characteristic values! p vSapon, Gm. Gm. Reae Reac- Epox- H I Substance Acid ifica- Iodine amount Gm. activator Gm H202 tion tion ide Acid Iodine No. tion 'gNo. used sugar temp. period oxygen 'No." -No;".':
No. in O. in hrs. percent Agcotfontsxeed oil-methylcyclo- 0.45 149.7 94.0 750 s Lewatlt $100..-- 20 s20 is 3.37 0. 0' "17.5
e es 1'.
A 0. 45 149. 7 94. 9 750 8 Lcwatit 5100..-; 40 350 65 22 4. 01 0. 6 8. 77 0.42 152 88.3 750 NaHS04. 16 350 65 12 3.70 0.6 12.4 0.2 186.5 122 750 400 65 35 5.60 0.4 12.3
the following characterstic values was obtained afterthe Example 9 indicated period of reaction.
1018 parts by weight of anaryloxy-alkyl carboxylic I 65 acid ester or an aryl carboxylic acid ester or an alkyl I Percent carboxylic acid ester respectively as described in the fol? Reaction Perm mime 9 2 3; lowing table are placed into an epoxidation apparatus according to Example 1. 70 parts by weight of cane Af 15 o M 4 50 v sugar are added and the mixture is heated up'to 70 C. After '70 During three hours a solution of 700 parts by weight igg 32 233;; 8:59 3' 2 23 of hydrogen peroxide, 50% by weight and 50 parts by 3.; 53.? Egg weight of concentrated phosphoric acid are gradually added. The heat of reaction is removed and the reaction 0.28 7 18-89 temperature is maintained at about 60 C. The mixture 7Y5 is vigorously stirred for 15-23 hours and after that'th 7 aqueous parts are drawn elf and the reaction product is worked up in a usual manner.
foot oil, marine animal oil, aliphatic hydrocarbons, low molecular weight carboxylic acid esters of aliphatic hydro- Oharacteristic numbers of the parent Characteristic numbers of the material epoxides Reaction Reaction Substance erlod temp. in
Saponl- Hydroxyl Iodine Iodine Percent hrs. 0. Acid No. ficlartion No. No. Acid No. No. epoxide Example 10 carbon alcohols, natural wax esters, low molecular weight Oleic acid esters are prepared from oleic acids by esterification under pressure with methyl alcohol, raflination and distillation. In such manner the following esters are obtained:
(a) Fluid parts of a C coconut oil fatty acid methyl ester (once pressed at 17 C.), (b) Fluid parts of a C coconut ester (twice pressed at 17 C.), (c) Fluid parts of a cotton seed oil fatty acid methyl ester, (d) Fluid parts of a tallow fatty acid methyl ester, (e) Sperm oil fatty acid methyl ester (C -C oil fatty acid methyl These esters were epoxidized according to the process described in Example 9, using the following charges:
After working up the epoxidized mixtures methyl ester epoxides are obtained having the following characteristic numbers:
carboxylic acid esters of lower alkoxy substituted aliphatic hydrocarbon alcohols, low molecular weight monohydroxy alcohol esters of fatty acids, dihydroxy alcohol esters of fatty acids, and unsubstituted amides of fatty acids, and (b) low molecular weight monohydroxy alcohol esters of tetrahydrobenzene :canboxylic acids which comprises the steps of (1) mixing said olefinically unsaturated compounds with (a) an organic polyhydroxy compound selected from the group consisting of aliphatic hydrocarbon polyols containing from 3 to 10 carbon atoms, monosaccharides, monosaccharidic acids, sugar polysaccharides, amylose, amylopectin, dextrins, glycogens, inulin, pectins, alginates, and acid degraded cellulose, and (b) an acid activator capable of accelerating peracid formation selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, sodium acid sulfate, perchloric acid, boron trifluoride, boron trifiuoride-water adducts, acid phosphoric acid alkyl esters, p-toluenesulfonic acid and high molecular weight synthetic cation exchange resins containing sulfonic acid groups, (2) adding from 1.1 to 2.0 moles per molar equivalent of the olefinic bonds of said high molecular weight compound of an aqueous hydrogen peroxide solution containing from about 30 to by weight of hydrogen peroxide during a period of from about 1 to 4 hours to said mixture while stirring vigorously and maintaining the reaction temperature between 0 C. and 100 (3., and (3) isolating the epoxidized olefinically-unsaturated compounds.
2. The process of claim 1 where said organic poly- Parent material Ep xi e Epoxlde Epoxlde Fromoxygen Saponl- Iodine Iodine percent Acid No. fic a tiou No. Acid No. No.
Methyl e o stearate Coconut 0ll- 0. 95 193. 9 70.7 0 3.9 3. Dix-9" do 0. 9 190. 2 75. 0 0 4. 0 3. 84 Do Cottonseed oil. 0.3 193. 2 114 0 11.2 5-23 Do Tallow 0. 4 191. 0 s4 0 4- 8 4.35 Methyl epoxystearate 18/22. Sperm oil 0. 9 184. 2 81. 1 0 2- 8 4.26
In like manner other high-molecular weight fatty acid derivatives such as the fatty acid amides and fatty acid nitriles and the esteiified high-molecular weight fatty alcohols can also be epoxidized by my invention.
While I have disclosed various specific embodiments of my invention, it will be apparent to persons skilled in the art that the present invention is not limited to these specific embodiments and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.
I claim:
1. A process for the introduction of epoxide groups into olefinically unsaturated compounds selected from the group consisting of (a) high molecular weight olefinically unsaturated compounds containing aliphatic hydrocarbon lipophilic radicals selected from the group consisting of linseed oil, soybean oil, cottonseed oil, olive oil, neatshydroxy compound and said acid activator are added in an amount in combination of from 7 to 15% by weight of said olefinically-unsaturated compound.
3. The process of claim 1 wherein said acid activator is sulfuric acid.
4. The process of claim lwherein said acid activator is phosphoric acid.
5. The process of claim 1 wherein said acid activator is a high molecular weight synthetic ion-exchange resin containing free sulfonic acid groups.
6. The process of claim 1 wherein said compound is technical cane sugar.
7. The process of claim 1 wherein said polyhydroxy compound is glucose.
8. The process of claim 1 wherein said olefinically-nus saturated compound is soybean oil.
polyhydroxy (References on following page) References Cited in the file of this patent UNITED STATES PATENTS Terry et al. Jan. 4, 1949 Niederhauser et al. Oct. 18, 1949 6 Swern et al. Oct. 2, 1951 Greenspan et al. Dec. 18, 1956 Payne et al. Jan. 1, 1957 10 Phillips et al. Jan. 29, 1957 Greenspan et a1 July 30, 1957 Greenspan et al. Oct. 22, 1957 Wallace May 6, 1958 FOREIGN PATENTS Canada Oct. 2, 1956 UNITED STATES PATENT. OFFICE CERTIFICATE OF CORRECTION Patent No. 2392 237 July 11 1961 Gerhard Dii ckelmann It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 5 line 19 for "(after 16 hours)" read we (after 25 hours) column 7, line 38 for concphosphoric acid" read con. phosphoric acid Signed and sealed this 30th day of January 1962.,
(SEAL) Attest:
ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents
Claims (1)
1. A PROCESS FOR THE INTRODUCTION OF EPOXIDE GROUPS INTO OLEFINICALLY UNSATURATED COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF (A) HIGH MOLECULAR WEIGHT OLEFINICALLY UNSATURATED COMPOUNDS CONTAINING ALIPHATIC HYDROCARBON LIPOPHILIC RADICALS SELECTED FROM THE GROUP CONSISTING OF LINSEED OIL, SOYBEAN OIL, COTTONSEED OIL, OLIVE OIL, NEAT''SFOOT OIL, MARINE ANIMAL OIL, ALIPHATIC HYDROCARBONS, LOW MOLECULAR WEIGHT CARBOXYLIC ACID ESTERS OF ALIPHATIC HYDROCARBON ALCOHOLS, NATURAL WAX ESTERS, LOW MOLECULAR WEIGHT CARBOXYLIC ACID ESTERS OF LOWER ALKOXY SUBSTITUTED ALIPHATIC HYDROCARBON ALCOHOLS, LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL ESTERS OF FATTY ACIDS, DIHYDROXY ALCOHOL ESTERS OF FATTY ACIDS, AND UNSUBSTITUTED AMIDES OF FATTY ACIDS, AND (B) LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL ESTERS OF TETRAHYDROBENZENE CARBOXYLIC ACIDS WHICH COMPRISES THE STEPS OF (1) MIXING SAID OLEFINICALLY UNSATURATED COMPOUNDS WITH (A) AN ORGANIC POLYHYDROXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBON POLYOLS CONTAINING FROM 3 TO 10 CARBON ATOMS, MONOSACCHARIDES, MONOSACCHARIDIC ACIDS, SUGAR POLYSACCHARIDES, AMYLOSE, AMYLOPECTIN, DEXTRINS, GLYCOGENS, INULIN, PECTINS, ALGINATES, AND ACID DEGRADED CELLULOSE, AND (B) AN ACID ACTIVATOR CAPABLE OF ACCELERATING PERACID FORMATION SELECTED FROM THE GROUP CONSISTING OF PHOSPHORIC ACID, NITRIC ACID, SULFURIC ACID, SODIUM ACID SULFATE, PERCHLORIC ACID, BORON TRIFLUORIDE, BORON TRIFLUORIDE-WATER ADDUCTS, ACID PHOSPHORIC ACID ALKYL ESTERS, P-TOLUENESULFONIC ACID AND HIGH MOLECULAR WEIGHT SYNTHETIC CATION EXCHANGE RESINS CONTAINING SULFONIC ACID GROUPS, (2) ADDING FROM 1.1 TO 2.0 MOLES PER MOLAR EQUIVALENT OF THE OLEFINIC BONDS OF SAID HIGH MOLECULAR WEIGHT COMPOUND OF AN AQUEOUS HYDROGEN PEROXIDE SOLUTION CONTAINING FROM ABOUT 30 TO 60% BY WEIGHT OF HYDROGEN PEROXIDE DURING A PERIOD OF FROM ABOUT 1 TO 4 HOURS TO SAID MIXTURE WHILE STIRRING VIGOROUSLY AND MAINTAINING THE REACTION TEMPERATURE BETWEEN 0*C. AND 100*C., AND (3) ISOLATING THE EPOXIDIZED OLEFINICALLY-UNSATURATED COMPOUNDS.
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Cited By (4)
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US3248404A (en) * | 1962-08-11 | 1966-04-26 | Dehydag Deutsche Hydriewerke G | Novel epoxidation process |
US4244829A (en) * | 1978-03-07 | 1981-01-13 | Exxon Research & Engineering Co. | Hydrocarbon-soluble epoxidized fatty acid esters as lubricity modifiers for lubricating oils |
US5274140A (en) * | 1979-07-19 | 1993-12-28 | Instituto Guido Donegani, S.P.A. | Process for catalytically epoxidizing olefin with hydrogen peroxide |
US20030119042A1 (en) * | 2001-03-12 | 2003-06-26 | Biotools Biotechnological & Medical Laboratories, S.A. | Process for preparing stabilized reaction mixtures which are totally or partially dried, comprising at least one enzyme, reaction mixtures and kits containing said mixtures |
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US2779771A (en) * | 1954-03-25 | 1957-01-29 | Union Carbide & Carbon Corp | Higher fatty ester diepoxides and process of producing the same |
US2801253A (en) * | 1957-07-30 | In situ epoxidation of organic esters | ||
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CA531112A (en) * | 1956-10-02 | E.I. Du Pont De Nemours And Company | Method of oxidizing olefinically unsaturated compounds | |
US2801253A (en) * | 1957-07-30 | In situ epoxidation of organic esters | ||
US2810732A (en) * | 1957-10-22 | In situ epoxidation of fatty acids | ||
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US2485160A (en) * | 1948-10-23 | 1949-10-18 | Rohm & Haas | Process for the epoxidation of esters of oleic and linoleic acids |
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US2779771A (en) * | 1954-03-25 | 1957-01-29 | Union Carbide & Carbon Corp | Higher fatty ester diepoxides and process of producing the same |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3248404A (en) * | 1962-08-11 | 1966-04-26 | Dehydag Deutsche Hydriewerke G | Novel epoxidation process |
US4244829A (en) * | 1978-03-07 | 1981-01-13 | Exxon Research & Engineering Co. | Hydrocarbon-soluble epoxidized fatty acid esters as lubricity modifiers for lubricating oils |
US5274140A (en) * | 1979-07-19 | 1993-12-28 | Instituto Guido Donegani, S.P.A. | Process for catalytically epoxidizing olefin with hydrogen peroxide |
US20030119042A1 (en) * | 2001-03-12 | 2003-06-26 | Biotools Biotechnological & Medical Laboratories, S.A. | Process for preparing stabilized reaction mixtures which are totally or partially dried, comprising at least one enzyme, reaction mixtures and kits containing said mixtures |
US7919294B2 (en) * | 2001-03-12 | 2011-04-05 | Biotools Biotechnological & Medical Laboratories, S.A. | Process for preparing stabilized reaction mixtures which are partially dried, comprising at least one enzyme, reaction mixtures and kits containing said mixtures |
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