US2729660A - Phosphite esters as esterification catalysts - Google Patents

Phosphite esters as esterification catalysts Download PDF

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Publication number
US2729660A
US2729660A US332555A US33255553A US2729660A US 2729660 A US2729660 A US 2729660A US 332555 A US332555 A US 332555A US 33255553 A US33255553 A US 33255553A US 2729660 A US2729660 A US 2729660A
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Prior art keywords
esterification
acid
acids
rosin
esters
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US332555A
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Stuart A Harrison
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General Mills Inc
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General Mills Inc
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
    • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04—Chemical modification, e.g. esterification
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol

Definitions

  • the present invention relates to a process of esterification in which esters of phosphorous acid are employed as esterification catalysts.
  • the invention is applicable to the esterification of fatty acids or rosin acids with aliphatic alcohols, either monohydric or polyhydric.
  • These catalysts can be used without causing appreciable color formation during the esterification, which is particularly troublesome with conventional catalysts, especially when unsaturated higher fatty acids are esterified.
  • Common esterification catalysts such as strong acids cause darkening of the product during esterification.
  • acid catalysts are difficult to remove.
  • the phosphorous esters of the present invention are volatile, and can be removed easily by vacuum distillation at the end of the reaction.
  • the esters which are obtained according to the present invention may have a very low free hydroxyl content, depending upon the extent to which it is desired to carry the esterification.
  • the invention is applicable to the esterification of 1 higher fatty acids or rosin acids, or mixtures thereof.
  • higher fatty acids as used herein, it is meant acids containing from 8-22 carbon atoms. These may be single isolated fatty acids or may be the whole mixed acids of a fat or oil, or any selected fraction thereof, either saturated or unsaturated.
  • the rosin acids which may be employed in the present invention may be any of a wide variety of rosin acids which are available naturally or which have been made available by the modification of naturally occurring rosin acids.
  • rosin hydrogenated rosin, dehydrogenated rosin, polymerized rosin, tall oil, the isolated rosin acid fraction of tall oil, and many others.
  • the application is applicable to mixtures of fatty acids and rosin acids, as in the case of tall oil or in the case of the rosin acid fraction of tall oil, which fraction may contain approximately 30% fatty acids and approximately 70% rosin acids, with a minor amount of unsaponifiable material.
  • aliphatic alcohols may be employed including the monohydric alcohols, methyl, ethyl, propyl, butyl alcohol and the like, and also the polyhydric alcohols, such as the glycols, ethyleneglycol, diethyleneglycol, glycerol, pentaeryt'nritol, 2,2,6,6-tetramethylolcyclohexanol and others.
  • the catalysts employed in the present invention are ei her aliph tic or ar matic esters of phosphorous acid.
  • the phosphorous acid may be completely or only partially esterified.
  • Typical of the phosphorous acid esters which may be'employed are triphenylphosphite, tn'paracresyb phosphite, tri-(Z-ethylhexyl)phosphite and di-.(2-ethyl. hexyDphosphite.
  • the esterification is effected by introducing the alcohol, the esterifying acid and the catalyst into a reaction vessel, preferably together with an azeotrope such as xylene or toluene.
  • the quantity of catalyst which may be ernployed may vary from %5% based on the Weight of the cid being employed for esterifieat on. Usually, howe r, from 12% is found to be a pref rr d rang
  • the temperatures employed during the esterification may vary quite widely, depending upon the nature of the materials being esterified. For example, with low molecular weight monohydric aliphatic alcohols which are quite volatile, it is preferred to operate at fairly low temperatures.
  • the reaction is preferably carried out at a much more elevated temperature.
  • temperatures of from l50-250 C. are suitable.
  • any temperature up to the decomposition temperature of the materials employed may be used.
  • the time period for esterification likewise, varies with the nature of the materials, and with the extent to which esterification is desired. It has been found, however, that the employment of the phosphorous esters appreciably reduces the time required, as compared with the same process in which no catalyst is employed.
  • Example 1 The following materials were placed in a three-necked round bottom flask: glycerine, 33 g., soybean oil acids, 280 g., triphenyl phosphite, 2 g., and xylene cc.
  • the flask was equipped with a mechanical stirrer, a Stark and Dean tube with condenser and a thermometer.
  • the reaction was heated by a mantle heater.
  • the mixture was heated rapidly to a pot temperature of 180 C., thenv gradually raised to a final temperature of 197-199 C.
  • the Water was removed azeotropically.
  • the following data show the comparative speed of the above esterification and a control in which the triphenyl phosphite was left out.

Description

United States Patent PHDSPHITE ESTERS AS ESTERKFICATK DN CATALYSTS No Dra ing. Application January 21, 1e53,
' Seria Pin-3 2, 55
. 4 Claims. c1. 2e0-.-41s.6)
The present invention relates to a process of esterification in which esters of phosphorous acid are employed as esterification catalysts.
The invention is applicable to the esterification of fatty acids or rosin acids with aliphatic alcohols, either monohydric or polyhydric. These catalysts can be used without causing appreciable color formation during the esterification, which is particularly troublesome with conventional catalysts, especially when unsaturated higher fatty acids are esterified. Common esterification catalysts such as strong acids cause darkening of the product during esterification. Moreover, such acid catalysts are difficult to remove. In contrast, the phosphorous esters of the present invention are volatile, and can be removed easily by vacuum distillation at the end of the reaction. Moreover, the esters which are obtained according to the present invention may have a very low free hydroxyl content, depending upon the extent to which it is desired to carry the esterification.
It is, therefore, an object of the present invention to provide a novel esterification process involving the use of phosphorous esters as esterification catalysts.
The invention is applicable to the esterification of 1 higher fatty acids or rosin acids, or mixtures thereof. The
invention may be applied to the esterification of saturated higher fatty acids, but is particularly adapted to the esterification of unsaturated higher fatty acids, since it is with these unsaturated higher fatty acids that the greatest advantages are obtained. By higher fatty acids as used herein, it is meant acids containing from 8-22 carbon atoms. These may be single isolated fatty acids or may be the whole mixed acids of a fat or oil, or any selected fraction thereof, either saturated or unsaturated. The rosin acids which may be employed in the present invention may be any of a wide variety of rosin acids which are available naturally or which have been made available by the modification of naturally occurring rosin acids. These include rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, tall oil, the isolated rosin acid fraction of tall oil, and many others. Moreover, the application is applicable to mixtures of fatty acids and rosin acids, as in the case of tall oil or in the case of the rosin acid fraction of tall oil, which fraction may contain approximately 30% fatty acids and approximately 70% rosin acids, with a minor amount of unsaponifiable material.
A wide variety of aliphatic alcohols may be employed including the monohydric alcohols, methyl, ethyl, propyl, butyl alcohol and the like, and also the polyhydric alcohols, such as the glycols, ethyleneglycol, diethyleneglycol, glycerol, pentaeryt'nritol, 2,2,6,6-tetramethylolcyclohexanol and others.
The catalysts employed in the present invention are ei her aliph tic or ar matic esters of phosphorous acid. The phosphorous acid may be completely or only partially esterified. Typical of the phosphorous acid esters which may be'employed are triphenylphosphite, tn'paracresyb phosphite, tri-(Z-ethylhexyl)phosphite and di-.(2-ethyl. hexyDphosphite.
The esterification is effected by introducing the alcohol, the esterifying acid and the catalyst into a reaction vessel, preferably together with an azeotrope such as xylene or toluene. The quantity of catalyst which may be ernployed may vary from %5% based on the Weight of the cid being employed for esterifieat on. Usually, howe r, from 12% is found to be a pref rr d rang The temperatures employed during the esterification may vary quite widely, depending upon the nature of the materials being esterified. For example, with low molecular weight monohydric aliphatic alcohols which are quite volatile, it is preferred to operate at fairly low temperatures. Where, however, the alcohol is not appreciably volatile, as for example is the case with the glycerine, the reaction is preferably carried out at a much more elevated temperature. In preparing esters of these acids with the usual polyhydric alcohols, such as the glycols and glycerol, temperatures of from l50-250 C. are suitable. However, any temperature up to the decomposition temperature of the materials employed may be used. The time period for esterification, likewise, varies with the nature of the materials, and with the extent to which esterification is desired. It has been found, however, that the employment of the phosphorous esters appreciably reduces the time required, as compared with the same process in which no catalyst is employed.
Example 1 The following materials were placed in a three-necked round bottom flask: glycerine, 33 g., soybean oil acids, 280 g., triphenyl phosphite, 2 g., and xylene cc. The flask was equipped with a mechanical stirrer, a Stark and Dean tube with condenser and a thermometer. The reaction was heated by a mantle heater. The mixture was heated rapidly to a pot temperature of 180 C., thenv gradually raised to a final temperature of 197-199 C. The Water was removed azeotropically. The following data show the comparative speed of the above esterification and a control in which the triphenyl phosphite was left out.
Percent Esteritication Esterifieation Time in hours Trlphenyl phosphite catalyzed y Example 2 The following materials were refluxed in a stirred l-liter, 3-necked flask equipped with thermometer and Stark and Dean tube with condenser: Wood rosin, 340 g. (1 mole rosin acid), pentaerythritol (pentek), 36 g. (1 equivalent of hydroxyl), 6.8 g. di(2-ethylhexyl)phosphite (catalyst), and 60 cc. xylene (azeotrope). A similar run was made with one exception that no di(2-ethylhexyl) phosphite was used. The water which was produced was separated and measured in the Stark and Dean tube. The data obtained were as follows:
Percent Esterifica- Esterification Time Water Eliminated tion on Basis of Water r- Catalyst, No Cata- No Gate- Hours 31m. cc lyst Catalyst lyst I claim as my invention: 1. Process of esterifying an acid selected from the group'consisting of higher fatty acids and rosin acids with an aliphatic alcohol which comprises heating the alcohol and the acid in the presence of a phosphite ester, said ester being selected from the group consisting of aliphatic and aromatic esters.
2. Process of esterifying a higher unsaturated fatty acid with an aliphatic alcohol comprising heating the alcohol and the acid in the presence of a phosphite ester selected from the group consisting of aliphatic and aromatic esters.
3. Process of esterifying an unsaturated higher fatty acid with a polyhydric aliphatic alcohol which comprises heating the alcohol and the acid in the presence of an aromatic phosphite ester.
4. Process of esterifying an unsaturated higher fatty acid with a polyhydric aliphatic alcohol which comprises heating the alcohol and the acid in the presence of phos phite aliphatic ester.
References Cited in the file of this patent UNITED STATES PATENTS 1,796,231 Bannister Nov. 10, 1931

Claims (1)

1. PROCESS OF ESTERIFYING AN ACID SELECTED FROM THE GROUP CONSISTING OF HIGHER FATTY ACIDS AND ROSIN ACIDS WITH AN ALIPHATIC ALCOHOL WHICH COMPRISES HEATING THE ALCOHOL AND THE ACID IN THE PRESENCE OF A PHOSPHITE ESTER, SAID ESTER BEING SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND AROMATIC ESTERS.
US332555A 1953-01-21 1953-01-21 Phosphite esters as esterification catalysts Expired - Lifetime US2729660A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4409148A (en) * 1981-12-09 1983-10-11 Uop Inc. Process for the reduction of unsaturated carboxylic acids
US4548746A (en) * 1984-05-14 1985-10-22 Westvaco Corporation Rosin pentaerythritol ester preparation improvement
US4643848A (en) * 1986-02-21 1987-02-17 Westvaco Corporation Modified rosin ester preparation
US4690783A (en) * 1986-08-29 1987-09-01 Union Camp Corporation Method of preparing rosin ester from polyol with phosphorous acid catalyst
US4693847A (en) * 1986-11-14 1987-09-15 Union Camp Corporation Method of preparing hot-melt stable rosin ester with organic ester of hypophosphorous acid catalyst
EP0270773A1 (en) * 1986-11-14 1988-06-15 Union Camp Corporation Method of preparing rosin esters of improved thermal stability
US4758379A (en) * 1986-11-14 1988-07-19 Union Camp Corporation Process of preparing polyol esters of rosin with excess rosin
EP0459760A2 (en) * 1990-05-30 1991-12-04 Union Camp Corporation Method for the preparation of light-colored rosin esters
US5543110A (en) * 1993-03-16 1996-08-06 Westvaco Corporation Tall oil deodorization process
US5830992A (en) * 1996-12-12 1998-11-03 Union Camp Corporation Light color, color stable rosin esters and methods for preparing same
US20070104923A1 (en) * 2005-11-04 2007-05-10 Whitaker Robert H Novel mineral composition
US20080173212A1 (en) * 2005-11-04 2008-07-24 Whitaker Robert H Novel mineral composition
US20110213120A1 (en) * 2010-03-01 2011-09-01 Arizona Chemical Company Rosin esters for non-woven applications, methods of making and using and products therefrom
WO2015048426A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Methods of making rosin esters
WO2015048415A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Rosin esters and compositions thereof
WO2015048421A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Rosin esters and compositions thereof
WO2016154456A1 (en) 2015-03-26 2016-09-29 Arizona Chemical Company, Llc Compositions containing rosin ester and ethylene polymers
WO2017117576A1 (en) 2015-12-31 2017-07-06 Arizona Chemical Company, Llc Oligoesters and compositions thereof
WO2018058005A1 (en) 2016-09-23 2018-03-29 Kraton Chemical, Llc Oligoesters compositions and methods of making and using same
US9951254B2 (en) 2013-09-27 2018-04-24 Arizona Chemical Company, Llc Compositions containing ethylene polymers

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1796231A (en) * 1930-05-16 1931-03-10 Commercial Solvents Corp Oleic acid ester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1796231A (en) * 1930-05-16 1931-03-10 Commercial Solvents Corp Oleic acid ester

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4409148A (en) * 1981-12-09 1983-10-11 Uop Inc. Process for the reduction of unsaturated carboxylic acids
US4548746A (en) * 1984-05-14 1985-10-22 Westvaco Corporation Rosin pentaerythritol ester preparation improvement
DE3516776A1 (en) * 1984-05-14 1985-11-14 Westvaco Corp., New York, N.Y. METHOD FOR PRODUCING COLOPHONIUM PENTAERYTHRITESTER
FR2564101A1 (en) * 1984-05-14 1985-11-15 Westvaco Corp IMPROVED PROCESS FOR ESTERIFYING POTATORY THERAPY WITH PENTAERYTHRITOL
NL8501335A (en) * 1984-05-14 1985-12-02 Westvaco Corp METHOD FOR EESTIFYING NATURAL RESIN WITH PENTAERYTRITOL AND THE PRODUCT OBTAINED BY THIS METHOD
US4643848A (en) * 1986-02-21 1987-02-17 Westvaco Corporation Modified rosin ester preparation
US4690783A (en) * 1986-08-29 1987-09-01 Union Camp Corporation Method of preparing rosin ester from polyol with phosphorous acid catalyst
US4693847A (en) * 1986-11-14 1987-09-15 Union Camp Corporation Method of preparing hot-melt stable rosin ester with organic ester of hypophosphorous acid catalyst
EP0270773A1 (en) * 1986-11-14 1988-06-15 Union Camp Corporation Method of preparing rosin esters of improved thermal stability
US4758379A (en) * 1986-11-14 1988-07-19 Union Camp Corporation Process of preparing polyol esters of rosin with excess rosin
EP0459760A2 (en) * 1990-05-30 1991-12-04 Union Camp Corporation Method for the preparation of light-colored rosin esters
EP0459760A3 (en) * 1990-05-30 1993-03-24 Union Camp Corporation Method for the preparation of light-colored rosin esters
US5543110A (en) * 1993-03-16 1996-08-06 Westvaco Corporation Tall oil deodorization process
US5830992A (en) * 1996-12-12 1998-11-03 Union Camp Corporation Light color, color stable rosin esters and methods for preparing same
US20070104923A1 (en) * 2005-11-04 2007-05-10 Whitaker Robert H Novel mineral composition
US20080173212A1 (en) * 2005-11-04 2008-07-24 Whitaker Robert H Novel mineral composition
US7651559B2 (en) 2005-11-04 2010-01-26 Franklin Industrial Minerals Mineral composition
US20110213120A1 (en) * 2010-03-01 2011-09-01 Arizona Chemical Company Rosin esters for non-woven applications, methods of making and using and products therefrom
US9940852B2 (en) 2013-09-27 2018-04-10 Kranton Chemical, LLC Rosin esters and compositions thereof
WO2015048415A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Rosin esters and compositions thereof
WO2015048421A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Rosin esters and compositions thereof
WO2015048426A2 (en) 2013-09-27 2015-04-02 Arizona Chemical Company, Llc Methods of making rosin esters
US9951254B2 (en) 2013-09-27 2018-04-24 Arizona Chemical Company, Llc Compositions containing ethylene polymers
US10011740B2 (en) 2013-09-27 2018-07-03 Kraton Chemical, Llc Rosin esters and compositions thereof
US10336922B2 (en) 2013-09-27 2019-07-02 Kraton Chemical, Llc Compositions containing ethylene polymers
WO2016154456A1 (en) 2015-03-26 2016-09-29 Arizona Chemical Company, Llc Compositions containing rosin ester and ethylene polymers
WO2017117576A1 (en) 2015-12-31 2017-07-06 Arizona Chemical Company, Llc Oligoesters and compositions thereof
US10435586B2 (en) 2015-12-31 2019-10-08 Kraton Chemical, Llc Oligoesters and compositions thereof
WO2018058005A1 (en) 2016-09-23 2018-03-29 Kraton Chemical, Llc Oligoesters compositions and methods of making and using same
US10407593B2 (en) 2016-09-23 2019-09-10 Kraton Chemical, Llc Oligoesters compositions and methods of making and using same

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