US2756242A - Preparation of epoxidized acids - Google Patents
Preparation of epoxidized acids Download PDFInfo
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- US2756242A US2756242A US2756242DA US2756242A US 2756242 A US2756242 A US 2756242A US 2756242D A US2756242D A US 2756242DA US 2756242 A US2756242 A US 2756242A
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- United States
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- acids
- esters
- acid
- nitriles
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- 239000002253 acid Substances 0.000 title claims description 62
- 150000007513 acids Chemical class 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title description 16
- 150000002825 nitriles Chemical class 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- 150000002148 esters Chemical class 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 238000000034 method Methods 0.000 description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- -1 saturated aliphatic nitrile Chemical class 0.000 description 26
- 239000003921 oil Substances 0.000 description 22
- 235000019198 oils Nutrition 0.000 description 22
- 239000002585 base Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 125000001475 halogen functional group Chemical group 0.000 description 16
- 125000003700 epoxy group Chemical group 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 125000004432 carbon atoms Chemical group C* 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 125000004423 acyloxy group Chemical group 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000003549 soybean oil Substances 0.000 description 8
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-Phenylethanol Natural products OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000008158 vegetable oil Substances 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 4
- VAWIMRJUUNGWMM-UHFFFAOYSA-N 8-(3-octyloxiran-2-yl)octanenitrile Chemical compound CCCCCCCCC1OC1CCCCCCCC#N VAWIMRJUUNGWMM-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- JTLQPGPCEJUJCM-UHFFFAOYSA-M ClC(=O)OC(C(=O)[O-])CCCCCCCCCCCCCCCC Chemical compound ClC(=O)OC(C(=O)[O-])CCCCCCCCCCCCCCCC JTLQPGPCEJUJCM-UHFFFAOYSA-M 0.000 description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N Erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- 240000007842 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- ZMPWEPBNNLNZEX-UHFFFAOYSA-N O1C(CCCCCCCCCCCC(=O)OCCCCCC)C1CCCCCCCC Chemical compound O1C(CCCCCCCCCCCC(=O)OCCCCCC)C1CCCCCCCC ZMPWEPBNNLNZEX-UHFFFAOYSA-N 0.000 description 2
- 229940049964 Oleate Drugs 0.000 description 2
- 241001125046 Sardina pilchardus Species 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N Trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N butylene glycol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000012343 cottonseed oil Nutrition 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
- 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
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000004426 flaxseed Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000004679 hydroxides 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peracetic acid Chemical class CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 235000019512 sardine Nutrition 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 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
- 238000003756 stirring Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
Definitions
- This invention relates to a process of preparing epoxidized acids, esters and nitriles. It relates to the preparation of epoxy acids containing 16 to 22 carbon atoms and to esters and nitriles of these epoxy acids. It has as its main object the preparation of epoxidized acids, esters and nitriles without the use of peracids, such as performic and peracetic acids, which are usually employed in the preparation of epoxides.
- the process of this invention comprises reactingpreferably in the presence of an organic solvent at a relatively low temperature a strong base, such as an alkali metal hydroxide, with a saturated aliphatic nitrile which contains 16 to 22 carbon atoms and which also contains vicinal halogen and acyloxy groups, or with a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains vicinal halogen and acyloxy groups, or with an ester of such an acid.
- a strong base such as an alkali metal hydroxide
- acyloxy-halo nitriles, acids and esters which are thus reacted, are themselves prepared by reacting an olefinically unsaturated acid containing 16 to 22 carbon atoms or an ester or nitrile of such an acid with a tertiaryalkyl hypohalite in the presence of an organic acid, preferably formic or acetic acid, according to the process of U. S. Patent 2,054,814.
- Such acyloxy-halo compounds are the subject of another of my applications for Letters Patent, Serial No. 423,846, filed April 27, 1954.
- These compounds all contain 16 to 22 carbons in the acid or nitrile chain and in the acid chain or acid moiety of the ester, and they also contain at least one grouping having the configuration 2 (IJCOR -CHCH in which the portion is a part of the acid chain, and in which X is a chlorine or bromine atom, and in which R represents a hydrogen atom or a lower alkyl group, preferably a methyl group.
- the acids, esters and nitriles can contain as many as three such groupings in their acid moieties by virtue of 7 having been made from acids containing as many as three double bonds.
- the acids and nitriles which give rise to acyloxy-halo compounds and hence to the epoxy acids and nitriles by the process of this invention include oleic, erucic, eleostearic, linoleic, linolenic, clupadonic, palmitoleic and palmitolenic acids and the corresponding nitriles.
- esters of (a) the above described acids, and (b) monohydric or polyhydric alcohols.
- esters which are embraced are those of (a) the acyloxy-halo-substituted acids described above, and (b) alcohols which are typified by the following: ethyl, isopropyl, n-butyl,
- glycols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, 2-ethylhexandiol-1,3,dodecandiol-1,12; polyalkylene glycos such as diethylene glycol and trithylene glycol; gycerol; pentaerythritol; and the isomers and homologues of the above.
- This process also applies to the production of epoxidized animal and vegetable oilsparticularly those listed aboveby the conversion of the derivatives of the oils which contain a plurality of acyloxy-halo groupings on the acid moieties of the oils.
- an acid or ester or nitrile containing at least one such acyloxy-halo grouping is dissolved in a solventpreferably an alcohol such as methanol, ethanol or butanol and is reacted with a strong base.
- Strong bases constitute a recognized class of compounds which ionize almost completely in water to provide hydroxyl ions.
- the most common of the strong bases are the hydroxides of the alkali metals such as sodium hydroxide and potassium hydroxide.
- Strong organic bases include quaternary ammonium hydroxides such as trirnethylbenzylammonium hydroxide.
- Strong bases also include anion-exchange resins which contain quaternary ammonium hydroxide groups and which, although they are insoluble, provide hydroxyl groups.
- anion-exchange resins which contain quaternary ammonium hydroxide groups and which, although they are insoluble, provide hydroxyl groups.
- Such resins are well known and are available commercially. They are described, for example, in U. S. Patents 2,540,985; 2,591,573; and 2,614,099.
- Two hydroxyl groups of the strongly basic compound are required to convert one acyloxy-halo grouping to one epoxide group. Ordinarily, however, an excess of the base over the stoichiometrical amount is used. Since the acyloxy groups and the halogen groups per se are split ofi during the reaction as salts of the strongly basic compound there does not appear to be any point in using any but the cheaper formoxy-chloro or acetoxy-chloro derivatives even though the compounds containing bromine groups and higher acyloxy groups are easily converted to the corresponding epoxy compounds.
- the epoxy products of this invention are used in the preparation and modification of a wide variety of resinous materials where advantage is taken of the reactivity of the epoxy groups.
- the esters and nitriles in particular are employed as plasticizers and stabilizers for those plastics which are degraded by light and heat and which include vinyl halide resins, vinylidene halide resins, chlorinated rubber and the like.
- Heavy metal salts of the epoxidized acids, particularly the cadmium and lead salts, are also used as stabilizers in vinyl resin compositions.
- Epoxidized soybean oil was prepared by the procedure of Example I. Thus a solution of 67 grams (0.25 mole) of formoxychloro-soybean oil in 100 ml. of ethanol was stirred and maintained at 0 to 5 C., by means of an ice-bath, while to the solution was added, over a period of an hour, a solution of 56.1 grams (1.0 mole) of potassium hydroxide in 944 grams of ethanol. The reaction mixture was allowed to warm to room temperature and stirring was continued overnight. The product, epoxidized soybean oil, was isolated in the manner described. It was completely compatible with polyvinyl chloride and exerted a definite plasticizing effect.
- a process for preparing epoxidized acids, nitriles and esters which comprises reacting a strong base with a member of the class consisting of saturated aliphatic nitriles containing 16 to 22 carbon atoms, saturated aliphatic acids containing 16 to 22 carbon atoms and esters of said acids, said member also containing groupings having the structure in which X is an atom of a halogen from the class consisting of chlorine and bromine, and R is a member of the class consisting of a hydrogen atom and a methyl group.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
Description
United States Patent PREPARATION OF EPOXIDIZED A'CIDS, ESTERS AND NITRILES Edward F. Riener, Haddonfield, N. J., assignor to Rollin & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application October 12, 1954, Serial No. 461,915
8 Claims. (Cl. 260348.6)
This invention relates to a process of preparing epoxidized acids, esters and nitriles. It relates to the preparation of epoxy acids containing 16 to 22 carbon atoms and to esters and nitriles of these epoxy acids. It has as its main object the preparation of epoxidized acids, esters and nitriles without the use of peracids, such as performic and peracetic acids, which are usually employed in the preparation of epoxides.
The process of this invention comprises reactingpreferably in the presence of an organic solvent at a relatively low temperaturea strong base, such as an alkali metal hydroxide, with a saturated aliphatic nitrile which contains 16 to 22 carbon atoms and which also contains vicinal halogen and acyloxy groups, or with a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains vicinal halogen and acyloxy groups, or with an ester of such an acid.
The acyloxy-halo nitriles, acids and esters, which are thus reacted, are themselves prepared by reacting an olefinically unsaturated acid containing 16 to 22 carbon atoms or an ester or nitrile of such an acid with a tertiaryalkyl hypohalite in the presence of an organic acid, preferably formic or acetic acid, according to the process of U. S. Patent 2,054,814. Such acyloxy-halo compounds are the subject of another of my applications for Letters Patent, Serial No. 423,846, filed April 27, 1954. These compounds all contain 16 to 22 carbons in the acid or nitrile chain and in the acid chain or acid moiety of the ester, and they also contain at least one grouping having the configuration 2 (IJCOR -CHCH in which the portion is a part of the acid chain, and in which X is a chlorine or bromine atom, and in which R represents a hydrogen atom or a lower alkyl group, preferably a methyl group.
The acids, esters and nitriles can contain as many as three such groupings in their acid moieties by virtue of 7 having been made from acids containing as many as three double bonds. The acids and nitriles which give rise to acyloxy-halo compounds and hence to the epoxy acids and nitriles by the process of this invention include oleic, erucic, eleostearic, linoleic, linolenic, clupadonic, palmitoleic and palmitolenic acids and the corresponding nitriles. All of these acids occur in animal or vegetable oils and fats, such as soybean, cottonseed, rapeseed, safllower, linseed, and sardine oils and tallow; and they are readily obtained by saponification of the oils or fats. The instant process is also applicable to the acyloxy-halo esters of (a) the above described acids, and (b) monohydric or polyhydric alcohols. Thus, the esters which are embraced are those of (a) the acyloxy-halo-substituted acids described above, and (b) alcohols which are typified by the following: ethyl, isopropyl, n-butyl,
sec-butyl, tert-butyl, tert-amyl, n-octyl, Z-ethylhexyl, 2- ethyl-butyl, lauryl, octadecyl, cyclohexyl, benzyl and phenethyl alcohols; glycols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, 2-ethylhexandiol-1,3,dodecandiol-1,12; polyalkylene glycos such as diethylene glycol and trithylene glycol; gycerol; pentaerythritol; and the isomers and homologues of the above. This process also applies to the production of epoxidized animal and vegetable oilsparticularly those listed aboveby the conversion of the derivatives of the oils which contain a plurality of acyloxy-halo groupings on the acid moieties of the oils.
In the preferred embodiment of the instant process, an acid or ester or nitrile containing at least one such acyloxy-halo grouping is dissolved in a solventpreferably an alcohol such as methanol, ethanol or butanol and is reacted with a strong base. Strong bases constitute a recognized class of compounds which ionize almost completely in water to provide hydroxyl ions. The most common of the strong bases are the hydroxides of the alkali metals such as sodium hydroxide and potassium hydroxide. Strong organic bases include quaternary ammonium hydroxides such as trirnethylbenzylammonium hydroxide. Strong bases also include anion-exchange resins which contain quaternary ammonium hydroxide groups and which, although they are insoluble, provide hydroxyl groups. Such resins are well known and are available commercially. They are described, for example, in U. S. Patents 2,540,985; 2,591,573; and 2,614,099.
The reaction whereby acyloxy-halo groupings are converted to epoxy groups has been carried out as low as -10 C. and as high as 150 C. A very satisfactory procedure is to hold the reaction mixture including a solvent at its refluxing temperature. Since at high temperatures the esters tend to hydrolyze, it is preferred, in the case of esters, to employ a solvent which boils below about 100 C. and to operate within the range of about 40 C. to about 85 C.
Two hydroxyl groups of the strongly basic compound are required to convert one acyloxy-halo grouping to one epoxide group. Ordinarily, however, an excess of the base over the stoichiometrical amount is used. Since the acyloxy groups and the halogen groups per se are split ofi during the reaction as salts of the strongly basic compound there does not appear to be any point in using any but the cheaper formoxy-chloro or acetoxy-chloro derivatives even though the compounds containing bromine groups and higher acyloxy groups are easily converted to the corresponding epoxy compounds.
The epoxy products of this invention are used in the preparation and modification of a wide variety of resinous materials where advantage is taken of the reactivity of the epoxy groups. The esters and nitriles in particular are employed as plasticizers and stabilizers for those plastics which are degraded by light and heat and which include vinyl halide resins, vinylidene halide resins, chlorinated rubber and the like. Heavy metal salts of the epoxidized acids, particularly the cadmium and lead salts, are also used as stabilizers in vinyl resin compositions.
The following examples serve to further illustrate the process of this invention:
EXAMPLE I A. Preparation of n-hexyl 9,10(10,9)-
formoxychlorosteare A mixture of 183.3 g. (0.5 mole) of n-hexyl oleate, 400 ml. of 98% formic acid, and 1 g. of p-toluenesulfonic acid was stirred and held at 10 to 15 C. while 60 g. (0.55 mole) of t-butylhypochlorite was added over a period of one hour. The mixture was stirred at 10 to 15 for one-half hour longer. The cooling bath was then removed and the white reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was then added to one liter of water. with one liter of benzene. The extract was washed with water until free of acid, and the benzene solution was concentrated on a steam bath under vacuum. The residual clear pale oil weighed 220g. (theory: 223 g.). A small amount of NaCl present in the oil was removed by filtration. The oil was placed under high vacuum (0.3 mm.) for one-half hour, during which time its loss in weight was found to be negligible. It was a mixture of the n-hexyl esters of 9,10- and 10,9-chloroform'oxystearic acid as confirmed by analysis. (Chlorine: theory=7.95 analysis: 8 .2 Acid number: theory=; analysis=0.3).
B. Conversion of n-hexyl 9,10(10,9)-f0rm0xychl0r0- stearate to n-hexyl 9,10-ep0xylstearate A solution of 16.8 g. (0.3 mole) of potassium hydroxide in 600 ml. of anhydrous ethanol was added at room temperature to 44.7 g. (0.1 mole) of the mixture of chloroformoxy esters prepared above. The solution was stirred for four hours. A crystalline solid formed. The reaction mixture was then poured into 500 ml. of water and extracted with 500 ml. of benzene. The oil was washed twice with water and was then dried over anhydrous MgSO4 and was finally filtered. The filtrate was concentrated on a steam bath, under vacuum. The residual pale oil had an oxirane oxygen-content of 3.80%. It was compatible with polyvinyl chloride and not only served as a plasticizer but also as a stabilizer.
EXAMPLE II A solution of 59 grams (0.12 mole) of n-hexyl 13,14- (14,13)-formoxychlorobehenate (prepared from n-hexyl erucate) in 75 grams of ethanol was stirred and cooled by means of an ice-bath to 0 to '5 C. A solution of 19.8 grams (0.35 mole) of potassium hydroxide in 334 grams of ethanol was added over a period of 30 minutes, after which the mixture was stirred at 0 to 5 C. for an additional hour. The reaction mixture was then poured into water, extracted with benzene and the product was isolated by the procedure described in Example I. A yield of 49.5 grams of an oil was obtained. Analysis proved it to be n-hexyl 13,14-epoxybehenate.
EXAMPLE III The general procedure described above was followed in the preparation of 9,10-epoxystearonitrile. Thus, a solution of 46 grams (0.13 mole) of 9,10(10,9)-formoxychlorostearonitrile in 60 grams of ethanol was stirred and cooled to 0 to 5 C. To the stirred solution was added over a period of 50 minutes a solution of 22.4 grams (0.4 mole) of potassium hydroxide in 377.6 grams of ethanol. The reaction mixture was then stirred at 0 to 5 C. for an additional 50 minutes. The product was isolated in the manner described in Example I and a yield of 37 grams of 9,10-epoxystearonitrile was obtained. Its composition was confirmed by analysis.
EXAMPLE IV Epoxidized soybean oil was prepared by the procedure of Example I. Thus a solution of 67 grams (0.25 mole) of formoxychloro-soybean oil in 100 ml. of ethanol was stirred and maintained at 0 to 5 C., by means of an ice-bath, while to the solution was added, over a period of an hour, a solution of 56.1 grams (1.0 mole) of potassium hydroxide in 944 grams of ethanol. The reaction mixture was allowed to warm to room temperature and stirring was continued overnight. The product, epoxidized soybean oil, was isolated in the manner described. It was completely compatible with polyvinyl chloride and exerted a definite plasticizing effect.
EXAMPLE V The conversion of acyloxy-halo compounds to the cor- This was extracted I responding epoxy-derivatives by means of strongly basic, quaternary ammonium, anion-exchange resins is somewhat slower than when. a caustic alkali is employed. However, the use of such resins provides a safe and practical method which can be employed to advantage when large masses of reactants are involved or when an acyloxy-halo compound is particularly reactive.
The rate of conversion of Z-ethylbutyl 9,l0(l0,9)- chloroformoxystearate to 2-ethylbutyl epoxystearate by means of such a strongly basic anion-exchange resin was studied. The progress was followed by measurements of the amount of oxirane oxygen which developed as the formoxy-chloro groupings were converted to epoxide groups. Solutions of the chloroformoxystearate in methanol at a concentration of were treated with a pulverized commercially available, strongly basic anionexchange resin known to have been made by reacting trimethylamine with a chloromethylated copolymer of styrene and divinylbenzene by the process of U. S. Patent No. 2,591,573. The resin was used in the ratio of 250 grams per hundred grams of the ester; and in all cases all of the resin was added at the outset to the methanol solution at room temperature.
It was found that approximately 40% of the chloroforrnoxy ester was converted to the corresponding epoxy ester in one hour at 40. C. or in 15 minutes at the refluxing temperature. In 2 hours at 40 C. the conversion was approximately 50% while in 18 hours at room temperature (20 to 25 C.) the conversion was approximately 65%.
I claim:
1. A process for preparing epoxidized acids, nitriles and esters which comprises reacting a strong base with a member of the class consisting of saturated aliphatic nitriles containing 16 to 22 carbon atoms, saturated aliphatic acids containing 16 to 22 carbon atoms and esters of said acids, said member also containing groupings having the structure in which X is an atom of a halogen from the class consisting of chlorine and bromine, and R is a member of the class consisting of a hydrogen atom and a methyl group.
2. The process of claim 1 in which the'strong base is .an hydroxide of an alkali metal.
7. The process of claim 6 in which the vegetable oil is soybean oil.
8. The process of claim 6 in which the vegetable oil is safilower oil.
References Cited in the file of this patent UNITED STATES PATENTS 2,458,484 Terry Jan. 4, 1949 2,485,160 Niederhauser Oct. 18, 1949 2,556,145 Niederhauser June 5, 1951- 2,569,502 Swern Oct. 2, 1951
Claims (1)
1. A PROCESS FOR PREPARING EPOXIDIZED ACIDS, NITRILES AND ESTERS WHICH COMPRISES REACTING A STRONG BASE WITH A MEMBER OF THE CLASS CONSISTING OF SATURATED ALIPHATIC NITRILES CONTAINING 16 TO 22 CARBON ATOMS, SATURATED ALIPHATIC ACIDS CONTAINING 16 TO 22 CARBON ATOMS AND ESTERS OF SAID ACIDS, SAID MEMBER ALSO CONTAINING GROUPINGS HAVING THE STRUCTURE
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US2756242D Expired - Lifetime US2756242A (en) | Preparation of epoxidized acids |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3022259A (en) * | 1955-05-06 | 1962-02-20 | John W Pearce | Process for purifying acid-containing compositions |
US3119846A (en) * | 1960-02-29 | 1964-01-28 | Archer Daniels Midland Co | Method of preparing epoxy fatty amines |
US3261819A (en) * | 1962-08-22 | 1966-07-19 | Exxon Research Engineering Co | Preparation and polymerization of 1,2-divinyl ethylene oxide |
US3335156A (en) * | 1965-01-29 | 1967-08-08 | Dow Chemical Co | Process for the preparation of glycidyl esters |
US4568759A (en) * | 1984-03-08 | 1986-02-04 | The Dow Chemical Company | Preparation of epoxides |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2458484A (en) * | 1946-06-17 | 1949-01-04 | Gen Mills Inc | Process of preparing epoxy derivatives from unsaturated aliphatic compounds |
US2485160A (en) * | 1948-10-23 | 1949-10-18 | Rohm & Haas | Process for the epoxidation of esters of oleic and linoleic acids |
US2556145A (en) * | 1948-11-23 | 1951-06-05 | Rohm & Haas | Chlorinated rubber and epoxidized oils |
US2569502A (en) * | 1945-02-07 | 1951-10-02 | Swern Daniel | Epoxidized oils |
-
0
- US US2756242D patent/US2756242A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2569502A (en) * | 1945-02-07 | 1951-10-02 | Swern Daniel | Epoxidized oils |
US2458484A (en) * | 1946-06-17 | 1949-01-04 | Gen Mills Inc | Process of preparing epoxy derivatives from unsaturated aliphatic compounds |
US2485160A (en) * | 1948-10-23 | 1949-10-18 | Rohm & Haas | Process for the epoxidation of esters of oleic and linoleic acids |
US2556145A (en) * | 1948-11-23 | 1951-06-05 | Rohm & Haas | Chlorinated rubber and epoxidized oils |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3022259A (en) * | 1955-05-06 | 1962-02-20 | John W Pearce | Process for purifying acid-containing compositions |
US3119846A (en) * | 1960-02-29 | 1964-01-28 | Archer Daniels Midland Co | Method of preparing epoxy fatty amines |
US3261819A (en) * | 1962-08-22 | 1966-07-19 | Exxon Research Engineering Co | Preparation and polymerization of 1,2-divinyl ethylene oxide |
US3335156A (en) * | 1965-01-29 | 1967-08-08 | Dow Chemical Co | Process for the preparation of glycidyl esters |
US4568759A (en) * | 1984-03-08 | 1986-02-04 | The Dow Chemical Company | Preparation of epoxides |
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