US3281477A - Production of alkyl ethers of polyalkylene glycols - Google Patents

Production of alkyl ethers of polyalkylene glycols Download PDF

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Publication number
US3281477A
US3281477A US379361A US37936164A US3281477A US 3281477 A US3281477 A US 3281477A US 379361 A US379361 A US 379361A US 37936164 A US37936164 A US 37936164A US 3281477 A US3281477 A US 3281477A
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US
United States
Prior art keywords
borate
glycol
alkyl
ether
dodecyl
Prior art date
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Expired - Lifetime
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US379361A
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English (en)
Inventor
Robert P Nielsen
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Shell USA Inc
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Shell Oil Co
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Filing date
Publication date
Priority to GB1053196D priority Critical patent/GB1053196A/en
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US379361A priority patent/US3281477A/en
Priority to BE666048D priority patent/BE666048A/xx
Priority to FR22500A priority patent/FR1439517A/fr
Priority to NL6508311A priority patent/NL6508311A/xx
Application granted granted Critical
Publication of US3281477A publication Critical patent/US3281477A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/135—Saturated ethers containing hydroxy or O-metal groups having more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/166—Organic compounds containing borium

Definitions

  • This invention relates to a process for the preparation of monoalkylethers of alkylene glycols, especially of polyalkylene glycols. More particularly, the invention relates to the conversion of aliphatic hydrocarbons to hydrocarbyloxy alkanols and hydrocarbyloxy polyalkyleneoxy alkanols and to borate esters thereof.
  • borate esters can be hydrolyzed to yield corresponding secondary alcohols.
  • the ethoxylation of higher aliphatic secondary alcohols in the presence of Friedel- Crafts type catalysts, e.g., boron trifluoride is known; see Carter, U.S. 2,870,220, issued January 20, 1959.
  • borate esters of glycol monoethers have been prepared by reaction of the glycol monoethers with boric acid; see Young, U.S. 3,080,412, issued March 5, 1963. It would be advantageous to alkoxylate borate esters directly to borate esters of glycol (including polyglycol) monoethers which can be hydrolyzed directly to corresponding glycol monoethers.
  • a principle object of the present invention to provide a process for oxidizing and alkoxylating aliphatic hydrocarbons to hydrocarbyl polyoxyalkylene alkyanol.
  • a further object of the invention is to provide a process for alkoxylating hydrocarbyl borate esters to corresponding hydrocarbyloxy alkanols and hydrocarbyloxy alkyleneoxy alkanols.
  • borate esters particularly secondary alkyl borates produced by controlled oxidation of higher nparafiins in the presence of boric oxide/acid
  • borate esters can be alkoxylated by alkylene oxides, especially lower vicinal alkylene oxides of 2-4 carbon atoms, in the presence of a suitable catalyst, as described hereinafter, to insert one or more oxyalkylene groups in the borate ester to form borate esters of glycol monoethers.
  • a suitable catalyst as described hereinafter
  • R-H denotes a saturated aliphatic hydrocarbon of from 1 to 20 carbon atoms which can be normal or branched acyclic or cyclic but preferably essentially free of tertiary hydrogen atoms. Satisfactory results are obtained especially where R is an aliphatic hydrocarbyl of 3 to 20 carbons and preferably of 4 to 16 carbons, especially an alkyl of to 16 carbons.
  • Suitable hydrocarbons include propane, iso-butane, npentane, cyclopentane, n-hexane, cyclohexane, n-octane, cyclooctane, ndodecane, n-tetradecane and n-eicosane.
  • n is meant any number of oxyalkalene groups of from 1 to 12, more advantageously 2 to 10, and preferably 3 to 8.
  • 19%6 oxides are those wherein there are at least three R'-hydrogens, e.g.,
  • R being defined as above, and more specifically, ethylene oxide.
  • Other preferred oxides are propylene oxide and l,2-butene oxide.
  • B 0 Boron-containing compounds which are suitable as starting materials, in addition to boron oxide (B 0 include, for example, other boron compounds which are boron acids or give rise to boron acids, such as orthoboric acid and metaboric acid and lower alkyl boric acid esters, e.g., methyl borate and the like.
  • the borate esters may be prepared by any of the known prior art methods. For example, at atmospheric pressure and at temperature of -170 C., slowly passing a gas containing 33.5% 0 into a reactor containing boric acid and a parafiin hydrocarbon feed in about a 1:3 mole ratio will result in oxidation of the paraffin to secondary alcohol and its esterification to corresponding borate ester. Preferred results can be obtained when partially dehydrated boric acid is used. Further advantages are obtained where the parafiin feed contains less than 0.5% aromatics.
  • the hydrocarbyloxy(poly)alkyleneoxy alkanols (monoalkyl ethers of polyalkylene glycols) produced by the process of this invention include those containing from 7 to 40 carbons, more advantageously from 9 to 30 and preferably about 12-24 carbons, and more specifically, mono-dodecyl ether of tetraethylene glycol.
  • the desired hydrocarbyloxy polyalkyleneoxy alkanols include lower alkoxy polyalkyleneoxyalkanols, preferably where the polyalkyleneoxyalkanol is polyethyleneoxyethanol or polypropyleneoxy propanol.
  • monoether products of this invention include propyl ether of diethylene glycol, propyl ether of triethylene glycol, nbutyl ether of triethylene glycol, n-hexyl ether of dipropylene glycol, n-dodecyl ether of triethylene glycol, ndodecyl ether of tetraethylene glycol, n-dodecyl ether of dipropylene glycol, n-dodecyl ether of tripropylene glycol, n-dodecyl ether of tetrapropylene glycol and the like.
  • halides particularly middle halides, and alkoxides, especially lower alkoxides, of metals of Groups II-B, III-B and lV-B and having an atomic number from 12 to 50 are useful catalysts for the alkoxylation of the borate esters with alkylene oxides and of these catalysts, those of zinc, cadmium, aluminum and titanium are preferred; zinc halides, aluminum alkoxides and titanium alkoxides and mixtures thereof are especially useful.
  • Exemplary effective catalysts are: zinc chloride, zinc bromide, zinc methoxide, zinc isopropoxide, aluminum isopropoxide, aluminum methoxide, aluminum chloride, aluminum bromide, titanium tetra-ethoxide, titanium dimethoxide d-ibutoxide and titanium dipropoxide dichloride. Mixtures of the alkoxides of the more acidic metal oxides and the halides of the less acidic metal oxides, e.g., mixtures of aluminum and/or titanium alkoxides and zinc chloride are particularly effective.
  • the reaction of the borate esters with the alkylene oxides may be advantageously performed in a closed container under pressure from an inert gas, such as nitrogen.
  • the reaction should be performed in the substantial absence of water as the catalyst is inactivated by Water.
  • the pressure can be varied over a wide range, generally Within the range of p.s.i.g. to 1000 p.s.i.g., with 80 p.s.i.g. to 500 p.s.i.g. being preferred.
  • the pressure will vary with the temperature at which reaction is performed.
  • a solvent such as a hydrocarbon, especially a normally liquid saturated aliphatic hydrocarbon alicyclic or cyclic, such as isopentane or cyclohexane.
  • the solvent is not indispensable as the alkoxylation can be carried out in the absence of added solvent.
  • the reaction period for the alkoxylation is not critical but depends on various variable factors which determine the rate of the reaction, including the particular alkylene oxide and borate ester involved, their concentrations in the reaction mixture, the catalyst employed and the temperature. Forty minutes to four hours is usually suitable while about 1 to 2 hours is preferred.
  • the temperature employed may vary considerably over a broad range depending on the type of reactants involved, it being generally desirable to maintain a temperature in the range of 80 C. to 150 C., with the preferred range being from 100 C. to 130 C.
  • the alkoxylation catalyst as described supra, and various mixtures thereof is added to the reaction mixture in catalytic amounts which may vary from, e.g., 0.001% to by weight of the borate ester, with 1.0% to 5.0% being preferred.
  • Example I 90 mole percent of isobutyl borate, 5 mol percent of aluminum isopropoxide and 5 mole percent of zinc chloride were placed in a closed vessel and ethylene oxide in a mole ratio of 9:1 to the isobutyl borate was introduced into the vessel.
  • the reactor was heated slowly to 150 C. over a period of 1 hour.
  • the reactants were maintained at 150 C. and a pressure of 90 p.s.i.g. for an additional hour. Thereafter, the reaction mixture was separated by distillation, with recovery of 63% of the isobutyl borate as a mixture of isobutyl ethoxylated borates containing an average of 4 ethyleneoxy units per isobutyl radical.
  • Example II When 1 mole of tri-(sec-dodecyl)borate is reacted with about 9 moles of propylene oxide, in the presence of aluminum isopropoxide and zinc chloride and the intermediate product hydrolyzed, sec-dodecyl ether of tripropylene glycol is obtained.
  • Example 111 850 grams of n-dodecane was placed in a closed container. To this vessel was added 29.75 grams of boric anhydride. 21.25 cubic centimeters of a gas containing 3.5% by weight of oxygen was introduced into the vessel. The mixture was heated at 180 C. and 1 atmosphere pressure for about 1 hour. About 20% of the n-dodecane was converted to the corresponding secondary alkyl borate. Subsequent hydrolysis of the sec-dodecyl borate gave an 80% yield of secondary dodecyl alcohol.
  • each R represents hydrogen or alkyl of 1 to 5 carbon atoms under anhydrous conditions in the presence of 0.001 to 10% weight, based on said alkyl borate, of a catalyst of the group consisting of the middle halides and alkoxides of metals of Groups IIB, IIIB, and IVB having atomic numbers from 12 to 50, and hydrolyzing the alkoxylated borate ester thereby producing the corresponding alkyl ether of polyalkylene glycol.
  • alkyl borate ester having alkyl of 10 to 16 carbon atoms is reacted with ethylene oxide using about 2 to 10 moles of ethylene oxide per alkyl radical of said ester.
  • alkyl ether of 7 to 40 carbon atoms is made by alkoxylating the alkyl borate product of oxidizing a hydrocarbon of from 3 to 20 carbon atoms per molecule in presence of a compound of the group consisting of boric oxide and boric acid.
  • a process in accordance with claim 3 wherein the alkylene oxide is propylene oxide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US379361A 1964-06-30 1964-06-30 Production of alkyl ethers of polyalkylene glycols Expired - Lifetime US3281477A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB1053196D GB1053196A (fr) 1964-06-30
US379361A US3281477A (en) 1964-06-30 1964-06-30 Production of alkyl ethers of polyalkylene glycols
BE666048D BE666048A (fr) 1964-06-30 1965-06-28
FR22500A FR1439517A (fr) 1964-06-30 1965-06-28 Procédé de préparation d'esters borates et d'hydrocarbyl-éthers de monoalcoylène et polyalcoylène-glycols
NL6508311A NL6508311A (fr) 1964-06-30 1965-06-29

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US379361A US3281477A (en) 1964-06-30 1964-06-30 Production of alkyl ethers of polyalkylene glycols

Publications (1)

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US3281477A true US3281477A (en) 1966-10-25

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BE (1) BE666048A (fr)
GB (1) GB1053196A (fr)
NL (1) NL6508311A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932531A (en) * 1972-07-14 1976-01-13 Nippon Shokubai Kaguku Kogyo Co., Ltd. Method of manufacturing alkylene oxide adducts of an aliphatic alcohol
US3959389A (en) * 1972-07-14 1976-05-25 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method of manufacturing alkylene oxide adducts of an aliphatic alcohol
US4052493A (en) * 1971-10-26 1977-10-04 Imperial Chemical Industries Limited Process for producing conductive fiber
US4091022A (en) * 1972-11-08 1978-05-23 Imperial Chemical Industries Limited Polyamide fiber

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4403146A1 (de) * 1994-02-02 1995-08-03 Henkel Kgaa Wasch- und Reinigungsmittelgemische für den Einsatz im neutralen bis alkalischen Bereich

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052493A (en) * 1971-10-26 1977-10-04 Imperial Chemical Industries Limited Process for producing conductive fiber
US3932531A (en) * 1972-07-14 1976-01-13 Nippon Shokubai Kaguku Kogyo Co., Ltd. Method of manufacturing alkylene oxide adducts of an aliphatic alcohol
US3959389A (en) * 1972-07-14 1976-05-25 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method of manufacturing alkylene oxide adducts of an aliphatic alcohol
US4091022A (en) * 1972-11-08 1978-05-23 Imperial Chemical Industries Limited Polyamide fiber

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Publication number Publication date
NL6508311A (fr) 1965-12-31
GB1053196A (fr)
BE666048A (fr) 1965-12-28

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