CA1045130A - Production of surface active material - Google Patents
Production of surface active materialInfo
- Publication number
- CA1045130A CA1045130A CA237,872A CA237872A CA1045130A CA 1045130 A CA1045130 A CA 1045130A CA 237872 A CA237872 A CA 237872A CA 1045130 A CA1045130 A CA 1045130A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- fatty acid
- sucrose
- ester
- solvent
- 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
Links
- 239000011149 active material Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229930006000 Sucrose Natural products 0.000 claims abstract description 62
- 239000005720 sucrose Substances 0.000 claims abstract description 62
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 claims abstract description 31
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 14
- 239000000344 soap Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000002198 insoluble material Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract 3
- 150000002576 ketones Chemical class 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 75
- 239000004094 surface-active agent Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- -1 fatty acid ester Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000005690 diesters Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000003626 triacylglycerols Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 239000002798 polar solvent Substances 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 159000000007 calcium salts Chemical group 0.000 claims 1
- 239000003759 ester based solvent Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000005453 ketone based solvent Substances 0.000 claims 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000003599 detergent Substances 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000003814 drug Substances 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
- 238000005187 foaming Methods 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XJRIDJAGAYGJCK-UHFFFAOYSA-N (1-acetyl-5-bromoindol-3-yl) acetate Chemical compound C1=C(Br)C=C2C(OC(=O)C)=CN(C(C)=O)C2=C1 XJRIDJAGAYGJCK-UHFFFAOYSA-N 0.000 description 1
- 235000009581 Balanites aegyptiaca Nutrition 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 150000002943 palmitic acids Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000004760 silicates Chemical group 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
- C07H13/06—Fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/002—Sources of fatty acids, e.g. natural glycerides, characterised by the nature, the quantities or the distribution of said acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/02—Organic and inorganic agents containing, except water
Abstract
ABSTRACT OF THE DISCLOSURE
A surface active material is prepared by reacting solid particulate sucrose with at least one alkyl ester of a fatty acid in the presence of a basic trans-esterification catalyst, at a temperature from 110 to 140°C, at atmospheric pressure and in the absence of any solvent. The reaction product may be purified by conversion of fatty acids and salts thereof into soaps, extracting -the water-insoluble material with a ketone or ester solvent and extracting the residue with a alcohol.
A surface active material is prepared by reacting solid particulate sucrose with at least one alkyl ester of a fatty acid in the presence of a basic trans-esterification catalyst, at a temperature from 110 to 140°C, at atmospheric pressure and in the absence of any solvent. The reaction product may be purified by conversion of fatty acids and salts thereof into soaps, extracting -the water-insoluble material with a ketone or ester solvent and extracting the residue with a alcohol.
Description
:
.3~
~his invention relates to the production of a surface active material comprising or consis-ting o~ one or more ~at-ty acia es-ters of sucrose.
~sters of sucrose with fatty acids, particularly the 5 sucrose mono-esters and di-esters, are potentially very $~ valuable as s~factants and ha~e a number of uni~ue aavantages j~ in this role~ ~hus, the~ are non-toxic, odourless and I ~ .
¦ tasteless; they are non-irrita-tlng to the skin; and, when ingested, the~ hydrolyse to form normal food products. Unlike ~ 10 mos-t surfactants, the~ are biodegradable under both aerobic and -: f anaerobic conditions; and~ unlike most.other non-ionic i ~! surfactants, the~ are solid and thus readily usable in powdered ~ or spray-dried products ~he~ are ver~ good emulsi~iers; and ` ' the~ perform well as detergents, either alone or in combination . ~ . . . . .
j 15 with anionic surfactants, and can be formulated either as high-: ...foaming or low-foaming detergents Accordingly, they ca~ be used generally as domestic or industrial deter~ents, and also in : .
. ~ ; . . . ..
~ 1: specialized uses such as additi~es for foodstu~fs, animal feeds~
i ~ i : ~ ~cosmetics, pharmaceuticals and agricultural chemicals. ~owever~ .
.' 20 : in spite of possessing these advantages? sucrose ester surfactants i ha~e never been exploited to their full potential, because of difficulties arising in their production. Man~ processes ha~e ~ been proposed for the preparation of sucrose ester surfactants`~ - W , due to technical and economic disadvantages, it is still25 ~ : difficult to achieve large-scale industrial production at a price ::~~: ~ competiti~e with other sur.~actantsO
. ...
. . . .. . .
`. . . , . ., .~
:'': ,. : ` ' . ' .
~0451a30 ~ucrose esters cannot ~e prepared by the direct esterification of sucrose with a fatty acid, but three other methods are possible: reaction with a fatty acid chloride;
reaction with a fatty acid anhydride~ and trans esterification with a fatty acid ester. r~he reaction with acid chlorides~ which ; - is per~ormed in the presence of pyridine, is uneconomical and will not gi~e good yields of sucrose mono-esters or di-esters.
i-t can be used to prepare sucrose octa-esters, but these are unsatisfactory as surfactants. Acid anhydrides of the hlgher fatty acids are not a~ailable commercially, and their preparation is complicated and expensi~e. Consequently, attempts at finding a commercial process for the preparation of sucrose ester surfactants have concentrated on the tràns-esteri~icatio reaction, generallg usi~g methyl or glyceryl esters o~ ~atty acids.
. .
Most of the known trans-esterification processes are~
c OEried out~in a solvent ~he most commonly used sol~ent lS
dimethylformamide. ~he~reaction is usually performed at- about goa, in;the~presence o~an alkaline catalyst (e.gO potassium 20 ~ carbonate), using the methyl ester of the fatty acid. ~t is neoessary to~remove all traces of water~ by heating the system under reduced pressure~as each component is added; ana the methanol, or other alkanol, ~y-prodllct of the trans-esterification must~also be removed by prolonged heating of the reactlon mix*ure 5~ under reduced pressure, so as to drive -the reaction e~uilibrium ~ . . ., ... , ~
~045~30 in the desired direction. ~he critical need for anhydrous conditions, the prolonged heating~ under reduced pressure and, above all, the use o~ a solvent such as dimethylformamide are all serious disad~antages of this process: not only must the dimethylformamide ~e recovered ~or economic operation, ~ut its residual presence can render the product toxic and smelly. It - is generally necessary to employ a substantial excess of svcrose in the reaction, and this also has to be removed from the product.
.. .. . . .... ..
In a modified form of the so:Lvent trans-esterification process, sucrose is reacted with a methyl ester, such as methyl -tallowate,~in a solvent such as propylene glycol which dissolves the sucrose but not the fatty component. An emulsifying agent is used, and the reaction is ~erformed in a so-called "micro-` 15 emulsion". Although this process a~oids the disadva~tages ; arising from the use of a toxio solvent such as dimethylformamide, it still employs an exæensive solvent which has to ~e recovered, and it still has to ~e performed under reduced pressure and in the absence of any water.
. . ;
~ A more recent modification of the solvent trans-esterificatioh process, described in British Patent pecification ~o. lt332,190, uses water as the solvent. ~he .
sucrose is completelyaissolved in water, in the presence of a fatty acid soap, a fatty acid ester and a trans-esterification - . .
25 ~ ~ ~
:` ', ~ ' ' ~ : ' ' . .
~, . . .
.. ..
~, ,.. ., " ~ , ......... ... . . .
~09L~i~130 catalyst are added, and the mixture is dehydra-ted under reduced pressure and at elevated temperature so as to produce a homogeneous melt ~he melt is then main-tained at elevated temperature, for the trans-esteri~ica-tion recction to take place. Although this process a~oids the problems which ari.se - when using an organic solvent such as dimethylformamide or propylene glycol, it is a multi-stage process which still requires heating under reduced pressure, and the pressure must be c~refully controlled in relation to the temperature when producing the dehydrated melt, in order to avoid hydrolysis of the fatty acid ester. ~he process is, therefore, undesirably complicated for use on an industrial scale.
:
~ solvent-free trans-esterification process has also been proposed recently [vide J. Amer. Oil Chem Soc 1970, ~, (2), 56-60; and U.S. Pa-tent Specification ~o. 3,71~ ~]. In .. . .
accordance with this process~ it is stated that the solvent-free trans-esterification must ~e carried out with the sucrose in the molten state; and the process is, therefore, performed a~t a tem~era-ture of from 170 to 190a. After a short time, the 20 ~ ~ molten sucrose begins to degrade to a black tarry mass, and the ; reaction with the fatty acid ester must necessaril~ be performed very ~uickly: the reaction is generally stopped within 20 minutes1 and sometimes after only 2 minutes As in the sol~ent processes, the reaction~is~performed under reduced pressure, to distil off the alcoholic ~y-pxoduct. ~rthermore, the reaction must be performed in the presence of an alkali-free anhydrcus soap~ which serves to solubilize the fatty acid ester in the - ~ .
,, , !j, . : . ' ~' ' ' ' ' ' ; ~
~;
:
~045~il30 molten sucrose and to catalyse the trans-esterifica-tion: -alkoxiaes, free alkalis and ordinary soaps are entirely unsatis~actory as catal~sts in this process, a~d -their presence results in very rapid decomposition of the sucrose and darkening of the reaction mixture. ~hus, although this process avoids some of the disad~antages arising ~rom the use of a sol~ent such as dimethylformamide, it has disadvantages of its own ~-tending to make it unsatisfac-tory as a commerical-scale preparation for sucrose ester surfactants. Specifically, it is di~icult, to control, because the reaction must be completed very quickly to avoid degrading the sucrose, it must ~- ~ still be performed under reduced pressure, and it requires the use of expensive speclal catalysts . ~ A process which u-tilises no solvent and ~eeps the eucrose ~ in the solid phase is described in ~.S. Patent Specification No. 3,558,597. In this prooess, the trans-esterifica-tion of ~ ` sucrose ~ith a fatty acid al~l ester is conducted in the presence ;~ of a basic trans-esteri~ication catalyst under conditions close to istil off the alcohol by-product. ~hese conditions~are a i 20 temperature of from 100 to 170C and a pressure of 0~1 to 500 mm Hg, i e. a pressure considerably below atmospheric ~1 pressure ana typically about 15 mm Hg. ~hus even in this process ; ~ low pressure conditions are re,~uirea.
~! ~
`' ~:'' ~ ~' , i:
~ ~ ~ S~.30 In our ~ritish Pa-tent Specification No. 1,3995053~ we have already described how, contrary to all previous proposals, it was surprisi:ngly discovered that sucrose ester surfactants - can be prepared by the trans-esterification of sucrose with . triglycerides, without using a sol~ent for any of the reacta~ts~
without performing the reaction in molten sucrose, without having to complete the reaction in a short time, without performing the reaction under reduced pressure, and without the use of a special t~pe of catalyst, thus providing a simple and cheap process for the preparation of sucroae ester surfactants which does not require the use of special solvents or reagents or operation under difficult conditions such as a partial vacuum, which overcomes the mo~t serious technical : and economic disadvantage of previous processes, ana which is consequently eminently suitable for use on an industrial scale.
: In~accordance with the process of our said Patent, a surfactant is prepared by reacting solid particulate sucrose with at : ~ least one trlglyceride in the presence of a basic trans-~ esterification catalyst~ at:a temperature in the range of~from .
20~ - ~ 110 to l40~, at atmospheric pressure and in the absence of any sol~ent.
~ : :
.
We ha~e now further discovered that the process of o~r ~æaid Patent can be modified by using one or more fatty acid alkyl esters in place of the triglyceride~ in the trans-:
.
: ~
... .. . . .
: , . ' , :
~ 0~5i~3(~esterification with sucrose, with the advantage -tha-t tke yield of especially valua~le sucrose mono--ester in the product ca-n be increased thereby .
Accordingly, the invention provides a process for the preparatio~ of a surface active material comprising reaction of solid particulate sucrose with at least one al~yl ester of a - ~at-ty acid ha~ing 1 to 6 carbon atoms in the alkyl moiety and -~- at least 8 carbon atoms in the fa-tty acid moiety, in ~he presence ~ of a basic trans-esterification catalyst, at a -temperature -~ 10 from 110 to 140C, at atmospheric pressure and in the absence - . .
~ of~any solvent ,, : . .
., It will be appreciated that the process of the present invention, like that of our said Patent, is completel~ different ~`1 from the previous ones, in that it uses a heterogeneous reaction ; ~ 15~ mixture~whereln the solid particulate sucrose is suspended in the fatty acid ester at atmospheric pressure, whereas~the previoùs processes mostly~aimed at achieving a homogeneous system by either dissolving~or me;lting the sucrosa, and always utilised a reduced;pressure.~ In view~of the methods used in~the prior '~ ~; 20 ~; ~ art processes, it is very~surprising to find that a~l effecti~e surfaotant material, oontaining a substantial proportion of the desirable sucrose mo~o-ester, can be obtained without the use of a solvent and without mel~ing the sucrose, at atmospherio pressure, under the conditions of the present in~ention.
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One or more lower alkyl esters of fatt~ acids having at least 8 carbon atoms, preferably from 10 to 2~ and most preferably ~rom 16 to 18 carbon atoms, may be used in the process of the in~ention. Preferably, methyl esters are used. It is normally convenient to use lower alkyl esters deri~ed from naturally occurring mixturss o~ -triglycerides, for example methyl tallowate ~hich contains methyl esters of stearic~ palmitic and oleic acids; but lower alkyl esters derived from other triglyceride fats and oils can be used, for example from lard, palm oil, cottonseed oil, soybean oil~
olive oil, groundnu-t oil, coconut oil, castor oil and linseed oil. Xowever~ it is generally less desirable to use lower alk~yl esters of highly unsaturated fa-tty acids, ~or example derived from the so-called "drying oils" such as linseed oil, because they tend to oxidize and become discoloured duri~g the process of ~ the invention, and the product has relatively inferior .... . ..- ,..~-.--surfaotant propertieso in general, lt is preferred to use lower aIkyl esters of acids containing not more than one double bond.
~he presence of hydroxyl groups in the acid chain can also be detrimental to the surfactant properties of the product. ~able 1 shows the composition of some examples of triglyceride fats ~nd oils, in terms of the fatty acids from which they are derived and .
the number of carbon atoms in the acid chains, of which the corresponding Iowar alkyl esters are suitable for use in the ~ prooess~of the invention. While me-thyl esters are preferred, ~ ethyl, propyl or butyl esters may, for example, also be used.
LS~L3~
~ he lower alXyl ester and sucrose are suitably used in substa~tially equimolar amounts, although the proportions are - not critical, In the case of an alkyl tallowa-te, such as methyl tallowate, for example, the amou~t can be calcula-ted o~ the basis of the a~h~yl s-tearate, -: .
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~he catalyst used in the process of the in~en-tion ma~- be any o$ the basic compounds co~entionally used as trans-esterification catalysts, but alkali metal carbonates and alkoxides, e.g. po-tassium carbonate and sodium methoxide, are found to gi~re par-ticularly good results. Other basic compounds, such as tertiary or quaternary organic bases, silicates and borates may also be used If desired, a mixture of such compounds may be employed. ~he catalyst concentration is not cri~ical, but it is generally desirable to use at least 2% of catalyst in order to attain a satisfactory rate of reaction and thus produce a surfactant material within a reasona~ly short time. ~he reaction can be accelerated by using higher concentrations of 5 to 12%, preferabl~ a~out l~/o. In general, i no additional benefit is derived by $urther raising the catalyst , concentration, and levels of above 20% are not likely -to be used in practice~ (All these percentage concentrations are by weight, on the basis of the weight o$ the reaction mixture).
-In carr~ing out the process of the in~e~tion~ the sucrose and the basic catalyst can be added to t-he alkyl es-ter and the ; 20~ resulting suspension heated with stirring, to bring about the trans-est-erification reaction~ Alternati~ely, the aIk~l ester oan first be heated with the catalyst alone, so that it is partly saponified, and the sucrose then added to the reac-tion :
mixture for the trans-esterification to ta~e place. Howe~er, ~ this preliminar~ saponificatio~ step is generally unnecessar~
when using a surfactant, i~ accord~nce w~-th the preferred Z~
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i ~ ~ ~ S ~ 3 - embodiment of the invention described hereina~ter~
Although no solvent is used in the process of the in~ention~ the reac-tion is performed at a temperature well below the mel-ting point of sucrose, in the range of ~rom 110 to 140C ~he preferred temperature range is f'rom 120 to 130C, and -the reaction is most prefera~l~ performed at about 125C.
(All these values refer to the internal temperature of the - reaction mixture). Subs-tantially no reaction takes place at temperatures below 110O, while at temperatures above 140G
charring occurs and the product does not have satisfactory surfactant properties. ~he reaction mi~ture can be maintained .
at the desired temperature by any con~entional means allowing ade~uate heat transfer and temperature control, ~or example by~
' providing the reaction vessel wlth an ex*ernal jacket through which steam is passed.- In some cases, especi'all~ if violent ' ~agitation is applied to the reaction mixture, it may be necessar~ to cool the mi~ture during the course o'f the reaction so as to malntain the~re~uired temperature, for example by passing water through the external jacket. ~he process i8 ~ carried out at atmospheric pressure: for example, it can ~e carried~out in a~simple open reaction vessel provided with suitable heating and stlrring means. ~ conve~tional type~
of motor-driven stirrer ma;~ be used; but i~ order to provide ;adequate mixing and ~eep the temperature constant throughout 25 ~ ~ ~the~reaotion mixture, espeoiall~ in a large ~essel7 i-t is ~: : ~ : , .,-. .
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1045~3~.
sometimes desirable to use a hig~h-shear mixer driven at - several thousand re~olutions per minute~
, ~o special conditions are chosen to dis-til off the alcohol by-product. When the alcohol by-proauct is particularl~ low-boiling; for example methanol (b.p. 65C~i) and ethanol (b.p. 78C),some may distil out under the reaction conditions~ ~he extremely viscous nature of the reaction ~i mixture does, however, prevent ~ree distilla-tion a~d in order to . . - ~i . .
remove subs-tantially all the alcohol it has been considered necessary i~ the prior art processes, to use considerably reduced pressure. ~hus the use o~ a-tmospheric pressure might be thought to - result in a significant proportion of the alcohol by-prod~ct re~aining 3~ situo ~ur~r~singly, h~w~er, the yield of sucrose ester, . . , . . . ~ . . ~ . . -. ~$pecial~y the mono este~, is not reduced and may actually be ..
~i~creased. ~ , 15 ~ We ha~e ~ound that a surprising advantage o~ using .
- atmospheric pressure, apart from the si~pler apparatus invol~ed~
is~the fact that the sucrose is very much more easil~ maintained in suspension in the ester. At reduced pressures phase separation ocours~ and,since the reaction can only occur at the interface,the rate of reaction is decreased. At atmospheric .
pressure, howeYer, the sucrose can ~e kept in ~inely distributed ;suspension in the reaction mix*ure and the rate of reaction and the yield are enhanced even lf the alcohol by-product is not oompletely removed. ~ . ;
:- ~
104S~30 ~he sucrose used in the process of the invention is no.rmally in the ~orm of particulate refined sugar, such as ' granulated sugar. ~he sucrose par-ticle size is not critical, but particles which'are too large can be di~ficult to disperse adequately in the reac-tion mixture~ and it is there~ore general~y preferred to use sucrose o~ a particle size small.er than 250 microns. ~he sucrose can be ground and sie~ed before use, so as to obtain the desired particle size9 but thi.s is unnecessar~ if a high-shear mixer is being used to agitate the ~ 10 reaction mixture~ since such a mixer will immediate'Ly comminute : ~ the sucrose partioles ~ : I
. Unlike~the trans-esteri~ication processes using an organic' æol~ent, the process o~ the present in~ention does'~not reguire ~ ~
~ dehydratlon of the reaotants, a~d the traces of wa~er normally ~ ~' : ~' 15 present in the starting materials are not detrimental. On the~
other~hand, the process of the in~ention does not use water as;
a reaction solvent, and its presence at le~els in excess of 'about 1% by weight tends to~be:~detrimental, because the reaction slows ~ ' do ~ ,~the~suorose tends to ~orm large lumps, and soap formation ~ :
20~ rapldl~occurs he 'auration~o~ the reaction.depends upon the nature o~ the alkyl ester, the amount and type o~ catalyst,~the efficiency of mixIng,~ and~the reaction temperature used ~he m~ture becomes ' more:viscous as:the reaction proceeds, and the reaction i~
~`
. ' ~(~45 ~30 ; -terminated when the mixture becomes too viscous for adequate stirring. ~he reaction can be finished in as little as 6 hours, but is sometimes conti~ued for l~ to 16 hours~ or even longer, in order to o~tain optimum yields of surfacta~t. ~he progress of the reaction can be followed, forlexample, by subjecting sampIes of the reaction mixture to chromatography at appropriate time intervals.
It is highly preferred -to per~orm the process of the - invention in the presence of a surfactant. ~he most ef~ective ~ur~actant so ~ar discovered is the surfactant product of the present process or of the corresponding process starting ~r~m the triglyceride, and this is suitably added at a concentration of , 5 to l~/o by weight, based on the total weight o~ the reaction mixture. Other effecti~e sur~acta~ts~ which may be added in similar ~uantities, are diglycerides and monoglycerides, -the ~ .. . . . .
former being more e~fective than the latter. ~oaps such as sodium stearate are found to be less e~fective for this purpose.
.~ 1 , , is theorized that these additi~es act as physical catalysts in the heterogeneous solid/liquid reaction system used in the process of the in~ention.~ ~he use o~ a sur~actant in this way is particularly ad~antageous when the ~asic trans-~sT~ ;c~lon catalyst is used in low ooncentratlonsO If a small proportion~ ~~
o~ the surfaotan-t ~ ~;
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produc-t, or of a diglyceride or monoglyceride, is added to the reaction mixture, the reaction time is considerabl~ shor-tened.
~he product of the process contains the sucrose mono-ester of the fa-t-ty acid together with v~rious unreacted sta~ting materials and by-products.~ ~his product has nota~le surfacta-Qt properties and can be used in àn unrefined s-tate as a biodegradable, non-to~ic sur~actant for many cleansing pu~poses.
A large proportion of the product is made up of the sucrose - mono-e~ters which are particularly valuable as surfactants~ this proportion gene~ally being higher than in a product of the corresponding process starting from trigl~cerides instead o~
lower alkyl esters. ~he produc-t of the reaction solidi~ies when it cools and it can then ~e formulated into various compositions: for example, it can ~e formulated with the oon~entional ex*enders and adjuvants, to produce detergent powder compositions~ Compositions for other purposes, such as oosmetics, foodstuffs-and agricul-tural chemicals, can be fo~mulated in the conventional manner. ~ince no solve~t is :
~used in the process of the in~ention, the costly and complicat~d ~ steps o~ solvent reco~ery and product purification are completely~avoided~
here is a need however for the preparation of relatively :: , : :
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~ 04S~30 pure mono-esters for use as surfactan-ts, emulsifiers etc.
in such ~ields as foodstuffs, fine toiletries, pharmaceuticals, rubber and plas-tics, paints and brewing Various purification te.chni~ues have been p.roposea ~o~ :
sucrose mono-esters, depending on the reaction medium ; used to prepare them ~hese techniques ha~e largely relied .
on partition between solven-ts, a technique ~hich is complicated by the efficiency of the desired product as an emulsifier.
~ ,.
' We have now ~ound that the trans~esterification process can be followed by a simple three-stage purification procedure to yield a sucrose mono-ester product of at least 80% purit~.
' ; According to a further feature of the present in~ention, therefore, there is provided a process for preparing a surfactant ~hich comprises reacting solid particulate sucrose as defined ~ above; and then (a) treating the crude reaction product.with an a~eous salt of a metal capable of forming an insolu~le salt : (soap) with a fatty acid, and separating the insoluble materlal;
: ~ (b) extracting the separate~ insoluble material with an organic ~ sol~ent in which lower.alkyl esters of fatty acids are soluble ; . 20 ~: but sucrose mono~ and di-esters are substantiall~ in.soluble;
:~ and (c) ex*racting the insoluble residue from (b) with a polar ~: sol~ent ~or sucrose mono- and di-esters, but in which fatty ~- acid soaps are substantiall~ insoluble .
104513~
~he treatment in stage (a) is conveni.ently with a Group 2 metal salt and serves to convert any free fat-t~ acid and/or soaps thereof into water-solu.ble Group 2 metal soapsO ~he a~ueous salt solution must th.us contain su~icient Group 2 metal salts for complete conversion. ~ypical Group 2 metals include calcium, magnesium and barium in Group 2a and zinc in Group 2~, calcium being particularly preferred.
lhe solid residue ~rom stage (a) can be filtered off, conveniently on a rotary drum ~ilter. ~he separation of the insoluble residue i.s improved if the slurry obtained in step (a) is gen-tly stirxed at a modera~ely elevated temperature (e.g.
about 35C) ~his treatment helps to coagulate the solid material so that it can ~e more easil~ filtered. `~
' ~ ' ; ' .
~he cake obtained from the filtration is then submitted to stage (b) o~ the purification namely solvent extrac-tion, . preferably a~ter being drled Any con~enient sol~ent ma~ bs used whioh is a good solvent for lower alk~l esters of ~atty acids and sucrose higher es-ters (i.e sucrose esteri~ied with more~than two fatty acid moieties)~ Ketonic soIvents such - ~ 20~ as acetone and methyl ethyl ketone are suitable in this : ~ ~ ex*raotion, but more pre~eràbly a les~ polar water-immlscible , ~6~45~3~
solven-t is used, fox example an ester such as ethyl aceta-t~
~his extraction removes fatt~ acid lower alkyl esters~ where present in the reaction migture, and also the higher esters o~
sucrose. An~ of these esters can be recovered as b~-products from the solvent extract , ~he residue from this extraction contains mainly -~
the desired sucrose mono~ester and di-ester and the Group 2 metal soaps, together with a small quantity of sucro~e. E~traction~-of this residue i~ stage (c) is preferably effec-ted using a lower alcohol containing 1 to 4 carbon atoms. ~he ; extraction eliminates the soaps as an insoluble residue and . ; :
provides an alcoholic ex~ract containing a purified material - ; -comprising at least 8~/o of the desired sucrose mono-ester.
Any con~enient lower alcohol can be used, ~ut it is preferred to use ethanol or isopropanol. Removal of the alcohol from the ~` ; obtained extract yields a purified product.
~- . , ~ he invention is illustrated b~ the followîng Examplesu , ~ . , .
Example 1 A mixture o~ 40 g of~methyl tallowate, 17 g of sucrose9 20~ ~ 5 g of potassium carbonate and 2.5 g of surfactant ~prepared from sucrose and tallow by the process of our said Patent No.
, `
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1,399,053) was stirred for ll hours at 125~o ~he tnick, waxy material produced hardened to a bri-ttle solid on cool~ng.
Yield ~ g. ~he product had good sur~actant properties and contained appro~imately 30% ~y weight of sucrose mono-esters, with some di-esters and higher esters.
~xamples 2 ~ 1~
Similar reactions were effected ~ith -the .reac-tan-ts and results detailed ~elow, .
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.3~
~his invention relates to the production of a surface active material comprising or consis-ting o~ one or more ~at-ty acia es-ters of sucrose.
~sters of sucrose with fatty acids, particularly the 5 sucrose mono-esters and di-esters, are potentially very $~ valuable as s~factants and ha~e a number of uni~ue aavantages j~ in this role~ ~hus, the~ are non-toxic, odourless and I ~ .
¦ tasteless; they are non-irrita-tlng to the skin; and, when ingested, the~ hydrolyse to form normal food products. Unlike ~ 10 mos-t surfactants, the~ are biodegradable under both aerobic and -: f anaerobic conditions; and~ unlike most.other non-ionic i ~! surfactants, the~ are solid and thus readily usable in powdered ~ or spray-dried products ~he~ are ver~ good emulsi~iers; and ` ' the~ perform well as detergents, either alone or in combination . ~ . . . . .
j 15 with anionic surfactants, and can be formulated either as high-: ...foaming or low-foaming detergents Accordingly, they ca~ be used generally as domestic or industrial deter~ents, and also in : .
. ~ ; . . . ..
~ 1: specialized uses such as additi~es for foodstu~fs, animal feeds~
i ~ i : ~ ~cosmetics, pharmaceuticals and agricultural chemicals. ~owever~ .
.' 20 : in spite of possessing these advantages? sucrose ester surfactants i ha~e never been exploited to their full potential, because of difficulties arising in their production. Man~ processes ha~e ~ been proposed for the preparation of sucrose ester surfactants`~ - W , due to technical and economic disadvantages, it is still25 ~ : difficult to achieve large-scale industrial production at a price ::~~: ~ competiti~e with other sur.~actantsO
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~0451a30 ~ucrose esters cannot ~e prepared by the direct esterification of sucrose with a fatty acid, but three other methods are possible: reaction with a fatty acid chloride;
reaction with a fatty acid anhydride~ and trans esterification with a fatty acid ester. r~he reaction with acid chlorides~ which ; - is per~ormed in the presence of pyridine, is uneconomical and will not gi~e good yields of sucrose mono-esters or di-esters.
i-t can be used to prepare sucrose octa-esters, but these are unsatisfactory as surfactants. Acid anhydrides of the hlgher fatty acids are not a~ailable commercially, and their preparation is complicated and expensi~e. Consequently, attempts at finding a commercial process for the preparation of sucrose ester surfactants have concentrated on the tràns-esteri~icatio reaction, generallg usi~g methyl or glyceryl esters o~ ~atty acids.
. .
Most of the known trans-esterification processes are~
c OEried out~in a solvent ~he most commonly used sol~ent lS
dimethylformamide. ~he~reaction is usually performed at- about goa, in;the~presence o~an alkaline catalyst (e.gO potassium 20 ~ carbonate), using the methyl ester of the fatty acid. ~t is neoessary to~remove all traces of water~ by heating the system under reduced pressure~as each component is added; ana the methanol, or other alkanol, ~y-prodllct of the trans-esterification must~also be removed by prolonged heating of the reactlon mix*ure 5~ under reduced pressure, so as to drive -the reaction e~uilibrium ~ . . ., ... , ~
~045~30 in the desired direction. ~he critical need for anhydrous conditions, the prolonged heating~ under reduced pressure and, above all, the use o~ a solvent such as dimethylformamide are all serious disad~antages of this process: not only must the dimethylformamide ~e recovered ~or economic operation, ~ut its residual presence can render the product toxic and smelly. It - is generally necessary to employ a substantial excess of svcrose in the reaction, and this also has to be removed from the product.
.. .. . . .... ..
In a modified form of the so:Lvent trans-esterification process, sucrose is reacted with a methyl ester, such as methyl -tallowate,~in a solvent such as propylene glycol which dissolves the sucrose but not the fatty component. An emulsifying agent is used, and the reaction is ~erformed in a so-called "micro-` 15 emulsion". Although this process a~oids the disadva~tages ; arising from the use of a toxio solvent such as dimethylformamide, it still employs an exæensive solvent which has to ~e recovered, and it still has to ~e performed under reduced pressure and in the absence of any water.
. . ;
~ A more recent modification of the solvent trans-esterificatioh process, described in British Patent pecification ~o. lt332,190, uses water as the solvent. ~he .
sucrose is completelyaissolved in water, in the presence of a fatty acid soap, a fatty acid ester and a trans-esterification - . .
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~09L~i~130 catalyst are added, and the mixture is dehydra-ted under reduced pressure and at elevated temperature so as to produce a homogeneous melt ~he melt is then main-tained at elevated temperature, for the trans-esteri~ica-tion recction to take place. Although this process a~oids the problems which ari.se - when using an organic solvent such as dimethylformamide or propylene glycol, it is a multi-stage process which still requires heating under reduced pressure, and the pressure must be c~refully controlled in relation to the temperature when producing the dehydrated melt, in order to avoid hydrolysis of the fatty acid ester. ~he process is, therefore, undesirably complicated for use on an industrial scale.
:
~ solvent-free trans-esterification process has also been proposed recently [vide J. Amer. Oil Chem Soc 1970, ~, (2), 56-60; and U.S. Pa-tent Specification ~o. 3,71~ ~]. In .. . .
accordance with this process~ it is stated that the solvent-free trans-esterification must ~e carried out with the sucrose in the molten state; and the process is, therefore, performed a~t a tem~era-ture of from 170 to 190a. After a short time, the 20 ~ ~ molten sucrose begins to degrade to a black tarry mass, and the ; reaction with the fatty acid ester must necessaril~ be performed very ~uickly: the reaction is generally stopped within 20 minutes1 and sometimes after only 2 minutes As in the sol~ent processes, the reaction~is~performed under reduced pressure, to distil off the alcoholic ~y-pxoduct. ~rthermore, the reaction must be performed in the presence of an alkali-free anhydrcus soap~ which serves to solubilize the fatty acid ester in the - ~ .
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~045~il30 molten sucrose and to catalyse the trans-esterifica-tion: -alkoxiaes, free alkalis and ordinary soaps are entirely unsatis~actory as catal~sts in this process, a~d -their presence results in very rapid decomposition of the sucrose and darkening of the reaction mixture. ~hus, although this process avoids some of the disad~antages arising ~rom the use of a sol~ent such as dimethylformamide, it has disadvantages of its own ~-tending to make it unsatisfac-tory as a commerical-scale preparation for sucrose ester surfactants. Specifically, it is di~icult, to control, because the reaction must be completed very quickly to avoid degrading the sucrose, it must ~- ~ still be performed under reduced pressure, and it requires the use of expensive speclal catalysts . ~ A process which u-tilises no solvent and ~eeps the eucrose ~ in the solid phase is described in ~.S. Patent Specification No. 3,558,597. In this prooess, the trans-esterifica-tion of ~ ` sucrose ~ith a fatty acid al~l ester is conducted in the presence ;~ of a basic trans-esteri~ication catalyst under conditions close to istil off the alcohol by-product. ~hese conditions~are a i 20 temperature of from 100 to 170C and a pressure of 0~1 to 500 mm Hg, i e. a pressure considerably below atmospheric ~1 pressure ana typically about 15 mm Hg. ~hus even in this process ; ~ low pressure conditions are re,~uirea.
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~ ~ ~ S~.30 In our ~ritish Pa-tent Specification No. 1,3995053~ we have already described how, contrary to all previous proposals, it was surprisi:ngly discovered that sucrose ester surfactants - can be prepared by the trans-esterification of sucrose with . triglycerides, without using a sol~ent for any of the reacta~ts~
without performing the reaction in molten sucrose, without having to complete the reaction in a short time, without performing the reaction under reduced pressure, and without the use of a special t~pe of catalyst, thus providing a simple and cheap process for the preparation of sucroae ester surfactants which does not require the use of special solvents or reagents or operation under difficult conditions such as a partial vacuum, which overcomes the mo~t serious technical : and economic disadvantage of previous processes, ana which is consequently eminently suitable for use on an industrial scale.
: In~accordance with the process of our said Patent, a surfactant is prepared by reacting solid particulate sucrose with at : ~ least one trlglyceride in the presence of a basic trans-~ esterification catalyst~ at:a temperature in the range of~from .
20~ - ~ 110 to l40~, at atmospheric pressure and in the absence of any sol~ent.
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.
We ha~e now further discovered that the process of o~r ~æaid Patent can be modified by using one or more fatty acid alkyl esters in place of the triglyceride~ in the trans-:
.
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~ 0~5i~3(~esterification with sucrose, with the advantage -tha-t tke yield of especially valua~le sucrose mono--ester in the product ca-n be increased thereby .
Accordingly, the invention provides a process for the preparatio~ of a surface active material comprising reaction of solid particulate sucrose with at least one al~yl ester of a - ~at-ty acid ha~ing 1 to 6 carbon atoms in the alkyl moiety and -~- at least 8 carbon atoms in the fa-tty acid moiety, in ~he presence ~ of a basic trans-esterification catalyst, at a -temperature -~ 10 from 110 to 140C, at atmospheric pressure and in the absence - . .
~ of~any solvent ,, : . .
., It will be appreciated that the process of the present invention, like that of our said Patent, is completel~ different ~`1 from the previous ones, in that it uses a heterogeneous reaction ; ~ 15~ mixture~whereln the solid particulate sucrose is suspended in the fatty acid ester at atmospheric pressure, whereas~the previoùs processes mostly~aimed at achieving a homogeneous system by either dissolving~or me;lting the sucrosa, and always utilised a reduced;pressure.~ In view~of the methods used in~the prior '~ ~; 20 ~; ~ art processes, it is very~surprising to find that a~l effecti~e surfaotant material, oontaining a substantial proportion of the desirable sucrose mo~o-ester, can be obtained without the use of a solvent and without mel~ing the sucrose, at atmospherio pressure, under the conditions of the present in~ention.
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One or more lower alkyl esters of fatt~ acids having at least 8 carbon atoms, preferably from 10 to 2~ and most preferably ~rom 16 to 18 carbon atoms, may be used in the process of the in~ention. Preferably, methyl esters are used. It is normally convenient to use lower alkyl esters deri~ed from naturally occurring mixturss o~ -triglycerides, for example methyl tallowate ~hich contains methyl esters of stearic~ palmitic and oleic acids; but lower alkyl esters derived from other triglyceride fats and oils can be used, for example from lard, palm oil, cottonseed oil, soybean oil~
olive oil, groundnu-t oil, coconut oil, castor oil and linseed oil. Xowever~ it is generally less desirable to use lower alk~yl esters of highly unsaturated fa-tty acids, ~or example derived from the so-called "drying oils" such as linseed oil, because they tend to oxidize and become discoloured duri~g the process of ~ the invention, and the product has relatively inferior .... . ..- ,..~-.--surfaotant propertieso in general, lt is preferred to use lower aIkyl esters of acids containing not more than one double bond.
~he presence of hydroxyl groups in the acid chain can also be detrimental to the surfactant properties of the product. ~able 1 shows the composition of some examples of triglyceride fats ~nd oils, in terms of the fatty acids from which they are derived and .
the number of carbon atoms in the acid chains, of which the corresponding Iowar alkyl esters are suitable for use in the ~ prooess~of the invention. While me-thyl esters are preferred, ~ ethyl, propyl or butyl esters may, for example, also be used.
LS~L3~
~ he lower alXyl ester and sucrose are suitably used in substa~tially equimolar amounts, although the proportions are - not critical, In the case of an alkyl tallowa-te, such as methyl tallowate, for example, the amou~t can be calcula-ted o~ the basis of the a~h~yl s-tearate, -: .
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~he catalyst used in the process of the in~en-tion ma~- be any o$ the basic compounds co~entionally used as trans-esterification catalysts, but alkali metal carbonates and alkoxides, e.g. po-tassium carbonate and sodium methoxide, are found to gi~re par-ticularly good results. Other basic compounds, such as tertiary or quaternary organic bases, silicates and borates may also be used If desired, a mixture of such compounds may be employed. ~he catalyst concentration is not cri~ical, but it is generally desirable to use at least 2% of catalyst in order to attain a satisfactory rate of reaction and thus produce a surfactant material within a reasona~ly short time. ~he reaction can be accelerated by using higher concentrations of 5 to 12%, preferabl~ a~out l~/o. In general, i no additional benefit is derived by $urther raising the catalyst , concentration, and levels of above 20% are not likely -to be used in practice~ (All these percentage concentrations are by weight, on the basis of the weight o$ the reaction mixture).
-In carr~ing out the process of the in~e~tion~ the sucrose and the basic catalyst can be added to t-he alkyl es-ter and the ; 20~ resulting suspension heated with stirring, to bring about the trans-est-erification reaction~ Alternati~ely, the aIk~l ester oan first be heated with the catalyst alone, so that it is partly saponified, and the sucrose then added to the reac-tion :
mixture for the trans-esterification to ta~e place. Howe~er, ~ this preliminar~ saponificatio~ step is generally unnecessar~
when using a surfactant, i~ accord~nce w~-th the preferred Z~
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i ~ ~ ~ S ~ 3 - embodiment of the invention described hereina~ter~
Although no solvent is used in the process of the in~ention~ the reac-tion is performed at a temperature well below the mel-ting point of sucrose, in the range of ~rom 110 to 140C ~he preferred temperature range is f'rom 120 to 130C, and -the reaction is most prefera~l~ performed at about 125C.
(All these values refer to the internal temperature of the - reaction mixture). Subs-tantially no reaction takes place at temperatures below 110O, while at temperatures above 140G
charring occurs and the product does not have satisfactory surfactant properties. ~he reaction mi~ture can be maintained .
at the desired temperature by any con~entional means allowing ade~uate heat transfer and temperature control, ~or example by~
' providing the reaction vessel wlth an ex*ernal jacket through which steam is passed.- In some cases, especi'all~ if violent ' ~agitation is applied to the reaction mixture, it may be necessar~ to cool the mi~ture during the course o'f the reaction so as to malntain the~re~uired temperature, for example by passing water through the external jacket. ~he process i8 ~ carried out at atmospheric pressure: for example, it can ~e carried~out in a~simple open reaction vessel provided with suitable heating and stlrring means. ~ conve~tional type~
of motor-driven stirrer ma;~ be used; but i~ order to provide ;adequate mixing and ~eep the temperature constant throughout 25 ~ ~ ~the~reaotion mixture, espeoiall~ in a large ~essel7 i-t is ~: : ~ : , .,-. .
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1045~3~.
sometimes desirable to use a hig~h-shear mixer driven at - several thousand re~olutions per minute~
, ~o special conditions are chosen to dis-til off the alcohol by-product. When the alcohol by-proauct is particularl~ low-boiling; for example methanol (b.p. 65C~i) and ethanol (b.p. 78C),some may distil out under the reaction conditions~ ~he extremely viscous nature of the reaction ~i mixture does, however, prevent ~ree distilla-tion a~d in order to . . - ~i . .
remove subs-tantially all the alcohol it has been considered necessary i~ the prior art processes, to use considerably reduced pressure. ~hus the use o~ a-tmospheric pressure might be thought to - result in a significant proportion of the alcohol by-prod~ct re~aining 3~ situo ~ur~r~singly, h~w~er, the yield of sucrose ester, . . , . . . ~ . . ~ . . -. ~$pecial~y the mono este~, is not reduced and may actually be ..
~i~creased. ~ , 15 ~ We ha~e ~ound that a surprising advantage o~ using .
- atmospheric pressure, apart from the si~pler apparatus invol~ed~
is~the fact that the sucrose is very much more easil~ maintained in suspension in the ester. At reduced pressures phase separation ocours~ and,since the reaction can only occur at the interface,the rate of reaction is decreased. At atmospheric .
pressure, howeYer, the sucrose can ~e kept in ~inely distributed ;suspension in the reaction mix*ure and the rate of reaction and the yield are enhanced even lf the alcohol by-product is not oompletely removed. ~ . ;
:- ~
104S~30 ~he sucrose used in the process of the invention is no.rmally in the ~orm of particulate refined sugar, such as ' granulated sugar. ~he sucrose par-ticle size is not critical, but particles which'are too large can be di~ficult to disperse adequately in the reac-tion mixture~ and it is there~ore general~y preferred to use sucrose o~ a particle size small.er than 250 microns. ~he sucrose can be ground and sie~ed before use, so as to obtain the desired particle size9 but thi.s is unnecessar~ if a high-shear mixer is being used to agitate the ~ 10 reaction mixture~ since such a mixer will immediate'Ly comminute : ~ the sucrose partioles ~ : I
. Unlike~the trans-esteri~ication processes using an organic' æol~ent, the process o~ the present in~ention does'~not reguire ~ ~
~ dehydratlon of the reaotants, a~d the traces of wa~er normally ~ ~' : ~' 15 present in the starting materials are not detrimental. On the~
other~hand, the process of the in~ention does not use water as;
a reaction solvent, and its presence at le~els in excess of 'about 1% by weight tends to~be:~detrimental, because the reaction slows ~ ' do ~ ,~the~suorose tends to ~orm large lumps, and soap formation ~ :
20~ rapldl~occurs he 'auration~o~ the reaction.depends upon the nature o~ the alkyl ester, the amount and type o~ catalyst,~the efficiency of mixIng,~ and~the reaction temperature used ~he m~ture becomes ' more:viscous as:the reaction proceeds, and the reaction i~
~`
. ' ~(~45 ~30 ; -terminated when the mixture becomes too viscous for adequate stirring. ~he reaction can be finished in as little as 6 hours, but is sometimes conti~ued for l~ to 16 hours~ or even longer, in order to o~tain optimum yields of surfacta~t. ~he progress of the reaction can be followed, forlexample, by subjecting sampIes of the reaction mixture to chromatography at appropriate time intervals.
It is highly preferred -to per~orm the process of the - invention in the presence of a surfactant. ~he most ef~ective ~ur~actant so ~ar discovered is the surfactant product of the present process or of the corresponding process starting ~r~m the triglyceride, and this is suitably added at a concentration of , 5 to l~/o by weight, based on the total weight o~ the reaction mixture. Other effecti~e sur~acta~ts~ which may be added in similar ~uantities, are diglycerides and monoglycerides, -the ~ .. . . . .
former being more e~fective than the latter. ~oaps such as sodium stearate are found to be less e~fective for this purpose.
.~ 1 , , is theorized that these additi~es act as physical catalysts in the heterogeneous solid/liquid reaction system used in the process of the in~ention.~ ~he use o~ a sur~actant in this way is particularly ad~antageous when the ~asic trans-~sT~ ;c~lon catalyst is used in low ooncentratlonsO If a small proportion~ ~~
o~ the surfaotan-t ~ ~;
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produc-t, or of a diglyceride or monoglyceride, is added to the reaction mixture, the reaction time is considerabl~ shor-tened.
~he product of the process contains the sucrose mono-ester of the fa-t-ty acid together with v~rious unreacted sta~ting materials and by-products.~ ~his product has nota~le surfacta-Qt properties and can be used in àn unrefined s-tate as a biodegradable, non-to~ic sur~actant for many cleansing pu~poses.
A large proportion of the product is made up of the sucrose - mono-e~ters which are particularly valuable as surfactants~ this proportion gene~ally being higher than in a product of the corresponding process starting from trigl~cerides instead o~
lower alkyl esters. ~he produc-t of the reaction solidi~ies when it cools and it can then ~e formulated into various compositions: for example, it can ~e formulated with the oon~entional ex*enders and adjuvants, to produce detergent powder compositions~ Compositions for other purposes, such as oosmetics, foodstuffs-and agricul-tural chemicals, can be fo~mulated in the conventional manner. ~ince no solve~t is :
~used in the process of the in~ention, the costly and complicat~d ~ steps o~ solvent reco~ery and product purification are completely~avoided~
here is a need however for the preparation of relatively :: , : :
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~ 04S~30 pure mono-esters for use as surfactan-ts, emulsifiers etc.
in such ~ields as foodstuffs, fine toiletries, pharmaceuticals, rubber and plas-tics, paints and brewing Various purification te.chni~ues have been p.roposea ~o~ :
sucrose mono-esters, depending on the reaction medium ; used to prepare them ~hese techniques ha~e largely relied .
on partition between solven-ts, a technique ~hich is complicated by the efficiency of the desired product as an emulsifier.
~ ,.
' We have now ~ound that the trans~esterification process can be followed by a simple three-stage purification procedure to yield a sucrose mono-ester product of at least 80% purit~.
' ; According to a further feature of the present in~ention, therefore, there is provided a process for preparing a surfactant ~hich comprises reacting solid particulate sucrose as defined ~ above; and then (a) treating the crude reaction product.with an a~eous salt of a metal capable of forming an insolu~le salt : (soap) with a fatty acid, and separating the insoluble materlal;
: ~ (b) extracting the separate~ insoluble material with an organic ~ sol~ent in which lower.alkyl esters of fatty acids are soluble ; . 20 ~: but sucrose mono~ and di-esters are substantiall~ in.soluble;
:~ and (c) ex*racting the insoluble residue from (b) with a polar ~: sol~ent ~or sucrose mono- and di-esters, but in which fatty ~- acid soaps are substantiall~ insoluble .
104513~
~he treatment in stage (a) is conveni.ently with a Group 2 metal salt and serves to convert any free fat-t~ acid and/or soaps thereof into water-solu.ble Group 2 metal soapsO ~he a~ueous salt solution must th.us contain su~icient Group 2 metal salts for complete conversion. ~ypical Group 2 metals include calcium, magnesium and barium in Group 2a and zinc in Group 2~, calcium being particularly preferred.
lhe solid residue ~rom stage (a) can be filtered off, conveniently on a rotary drum ~ilter. ~he separation of the insoluble residue i.s improved if the slurry obtained in step (a) is gen-tly stirxed at a modera~ely elevated temperature (e.g.
about 35C) ~his treatment helps to coagulate the solid material so that it can ~e more easil~ filtered. `~
' ~ ' ; ' .
~he cake obtained from the filtration is then submitted to stage (b) o~ the purification namely solvent extrac-tion, . preferably a~ter being drled Any con~enient sol~ent ma~ bs used whioh is a good solvent for lower alk~l esters of ~atty acids and sucrose higher es-ters (i.e sucrose esteri~ied with more~than two fatty acid moieties)~ Ketonic soIvents such - ~ 20~ as acetone and methyl ethyl ketone are suitable in this : ~ ~ ex*raotion, but more pre~eràbly a les~ polar water-immlscible , ~6~45~3~
solven-t is used, fox example an ester such as ethyl aceta-t~
~his extraction removes fatt~ acid lower alkyl esters~ where present in the reaction migture, and also the higher esters o~
sucrose. An~ of these esters can be recovered as b~-products from the solvent extract , ~he residue from this extraction contains mainly -~
the desired sucrose mono~ester and di-ester and the Group 2 metal soaps, together with a small quantity of sucro~e. E~traction~-of this residue i~ stage (c) is preferably effec-ted using a lower alcohol containing 1 to 4 carbon atoms. ~he ; extraction eliminates the soaps as an insoluble residue and . ; :
provides an alcoholic ex~ract containing a purified material - ; -comprising at least 8~/o of the desired sucrose mono-ester.
Any con~enient lower alcohol can be used, ~ut it is preferred to use ethanol or isopropanol. Removal of the alcohol from the ~` ; obtained extract yields a purified product.
~- . , ~ he invention is illustrated b~ the followîng Examplesu , ~ . , .
Example 1 A mixture o~ 40 g of~methyl tallowate, 17 g of sucrose9 20~ ~ 5 g of potassium carbonate and 2.5 g of surfactant ~prepared from sucrose and tallow by the process of our said Patent No.
, `
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1,399,053) was stirred for ll hours at 125~o ~he tnick, waxy material produced hardened to a bri-ttle solid on cool~ng.
Yield ~ g. ~he product had good sur~actant properties and contained appro~imately 30% ~y weight of sucrose mono-esters, with some di-esters and higher esters.
~xamples 2 ~ 1~
Similar reactions were effected ~ith -the .reac-tan-ts and results detailed ~elow, .
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a) . h--~ ~ N t~t ~ ) o . I ~ ~ _ .~.-.. _ _ ~ 3 I ~ ~l 4Lt bLt h ., to ~d b~q ~c> o '`. .
F3 1:~ ~ 0~ N ~
- o ~ ~ ~ ~ ~ . - C ~ . . .d O cq h O O . O tq m Lr~
. ~ _ __~ h : :
0~ ~ ~ct ~ . ~ . ~ .
c~l . O . O O `O ~ ~d ~ __ ~ ,~ .,~ .
h ~ ~ . . h ~ :'* ~1~ ~ ~ ~ ~. o~
cn __ _---.
ho `~~ a) , tJ) ..c>
t3~r-l Ir~r~ r-l ~ ~ tl . ~ t ~ tq ~r l r~ ~ 1--1 - : a)~3 ~ O ~ tD ~d ~ ~~D
_ ~ ~ ~ ~D ~ ~ __
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a surface active material comprising reacting solid particulate sucrose with at least one alkyl ester of a fatty acid having 1 to 6 carbon atoms in the alkyl moiety and at least 8 carbon atoms in the fatty acid moiety, in the presence of a basic trans-esterification catalyst, at a temperature from 110 to 140°C, at atmospheric pressure and in the absence of any solvent.
2. A process according to claim 1 in which the fatty acid ester has a fatty acid moiety with 10 to 22 carbon atoms.
3. A process according to claim 1 in which the fatty acid ester has a fatty acid moiety with 16 to 18 carbon atoms.
4. A process according to claim 1 in which the alkyl fatty acid ester is a mixed ester derived from a naturally occurring mixture of triglycerides.
5. A process according to claim 1 in which the alkyl moiety of the ester is a methyl group.
6. A process according to claim 1 in which the basic catalyst is selected from the group consisting of alkali metal carbonates and alkoxides and is present as at least 2% of the reaction mixture.
7. A process according to claim 6 in which the catalyst is used at a concentration of 5 to 12%.
8. A process according to claim 7 effected at a temperature of 120 to 130°C.
9. A process according to claim 9 effected at about 125°C.
10. A process according to claim 1 effected with high-shear mixing.
11. A process according to claim 1 in which the sucrose is of a particle size less than 250 microns.
12. A process according to claim 1 effected in the presence of a surfactant.
13. A process according to claim 12 in which the surfactant is selected from the group consisting of (a) the product of the process or the corresponding process using a triglyceride;
(b) a diglyceride; and (c) a monoglyceride.
(b) a diglyceride; and (c) a monoglyceride.
14. A process according to claim 13 in which the surfactant is present at a concentration of 5 to 10% by weight.
15. A process for the purification of the reaction product obtained after reacting solid particulate sucrose with at least one alkyl ester of a fatty acid having 1 to 6 carbon atoms in the alkyl moiety and at least 8 carbon atoms in the fatty acid moiety, in the presence of a basic trans-esterification catalyst, at a temperature from 110 to 140°C, at atmospheric pressure and in the absence of any solvent, comprising (a) treating the crude reaction product with an aqueous salt of a metal capable of forming an insoluble salt (soap) with a fatty acid, and separating the insoluble material; (b) extracting the separated insoluble material with an organic solvent in which lower alkyl esters of fatty acids are soluble but sucrose mono- and di-esters are substantially insoluble; and (c) extracting the insoluble residue from (b). with a polar solvent for sucrose mono- di-esters, but in which fatty acid soaps are substantially insoluble
16. A process according to claim 15 in which the aqueous salt used is a salt of a Group 2 metal.
17 A process according to claim 16 in which the salt is a calcium salt.
18. A process according to claim 15 in which the slurry obtained in step (a) is gently stirred at a moderately elevated temperature before separation.
19. A process according to claim 15 in which the solvent in step (b) is a ketone or an ester and the solvent in step (c) is a lower alcohol with 1 to 4 carbon atoms.
20. A process according to claim 19 in which the solvent is step (b) is selected from the group consisting of acetone, methyl ethyl ketone and ethyl acetate and in step (c) is selected from the group consisting of ethanol and isopropanol.
21. A process for the preparation of a surface active material comprising reacting solid particulate sucrose with at least one alkyl ester of a fatty acid having 1 to 6 carbon atoms in the alkyl moiety and 16 to 18 carbon atoms in the fatty acid moiety, in the presence of a basic trans-esterification process at a temperature of about 120 to about 130°C at atmospheric pressure and in the absence of any solvent;
the reaction being effected in the presence of a surfactant selected from (a) the product of the process or of the corresponding process using a triglyceride; (b) a diglyceride,: or (c) a monoglyceride; and then purifying the reaction product by (a) treating the crude reaction product with an aqueous salt of a Group 2 metal selected from the group consisting of calcium, magnesium, barim and zinc and separating the insoluble material from the slurry so formed;
(b) extracting the separated insoluble material with an organic solvent selected from the group consisting of ketone and ester solvents to remove lower alkyl esters of fatty acids and leave an insoluble residue; and (c) extracting the insoluble residue from step (b) with a polar solvent selected from the group consisting of lower alcohols with 1 to 4 carbon atoms and evaporating the extract to dryness
the reaction being effected in the presence of a surfactant selected from (a) the product of the process or of the corresponding process using a triglyceride; (b) a diglyceride,: or (c) a monoglyceride; and then purifying the reaction product by (a) treating the crude reaction product with an aqueous salt of a Group 2 metal selected from the group consisting of calcium, magnesium, barim and zinc and separating the insoluble material from the slurry so formed;
(b) extracting the separated insoluble material with an organic solvent selected from the group consisting of ketone and ester solvents to remove lower alkyl esters of fatty acids and leave an insoluble residue; and (c) extracting the insoluble residue from step (b) with a polar solvent selected from the group consisting of lower alcohols with 1 to 4 carbon atoms and evaporating the extract to dryness
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB45122/74A GB1499989A (en) | 1974-10-17 | 1974-10-17 | Production of a surface active material containing sucrose esters |
GB1622275 | 1975-04-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1045130A true CA1045130A (en) | 1978-12-26 |
Family
ID=26251906
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA237,872A Expired CA1045130A (en) | 1974-10-17 | 1975-10-17 | Production of surface active material |
Country Status (21)
Country | Link |
---|---|
US (1) | US4032702A (en) |
JP (1) | JPS5165704A (en) |
AR (1) | AR212161A1 (en) |
AT (1) | AT347410B (en) |
BR (1) | BR7506830A (en) |
CA (1) | CA1045130A (en) |
CH (1) | CH606074A5 (en) |
CU (1) | CU34398A (en) |
DE (1) | DE2546716C3 (en) |
DK (1) | DK142148B (en) |
ES (1) | ES441908A2 (en) |
FR (1) | FR2288143A2 (en) |
GB (1) | GB1499989A (en) |
IE (1) | IE42171B1 (en) |
IT (1) | IT1048249B (en) |
NL (1) | NL172761B (en) |
NO (1) | NO140983C (en) |
SE (1) | SE430339B (en) |
SU (1) | SU906383A3 (en) |
TR (1) | TR18880A (en) |
ZA (1) | ZA756573B (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1593856A (en) * | 1976-11-17 | 1981-07-22 | Gist Brocades Nv | Process for the treatment of fruit and vegetables |
JPS6037085B2 (en) * | 1978-09-22 | 1985-08-24 | 花王株式会社 | bar-shaped cosmetics |
JPS5547610A (en) * | 1978-09-29 | 1980-04-04 | Kao Corp | Hair cosmetic |
JPS6026368B2 (en) * | 1978-09-29 | 1985-06-24 | 花王株式会社 | Powder compressed cosmetics |
JPS6037086B2 (en) * | 1978-09-26 | 1985-08-24 | 花王株式会社 | cosmetics |
JPS6037087B2 (en) * | 1978-09-28 | 1985-08-24 | 花王株式会社 | cosmetics |
DE2965461D1 (en) * | 1978-11-06 | 1983-07-07 | Tate & Lyle Plc | Gramophone record composition and gramophone records produced therefrom |
EP0011419A1 (en) * | 1978-11-09 | 1980-05-28 | TATE & LYLE PUBLIC LIMITED COMPANY | P.V.C. compositions for extrusion moulding |
IE50028B1 (en) * | 1979-12-19 | 1986-02-05 | Tate & Lyle Plc | Process for the production of a surfactant containing sucrose esters |
US4517360A (en) * | 1983-06-23 | 1985-05-14 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters using carbonate catalysts |
US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
JPS6115893A (en) * | 1984-06-29 | 1986-01-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Purification of sucrose fatty acid ester |
NL8601904A (en) * | 1986-07-23 | 1988-02-16 | Unilever Nv | PROCESS FOR THE PREPARATION OF POLYOL FATTY ACID POLYESTERS. |
JPS63179884A (en) * | 1987-01-17 | 1988-07-23 | Mitsubishi Kasei Corp | Production of sucrose ester with fatty acid |
DE69028759T2 (en) * | 1989-12-21 | 1997-02-20 | Unilever Nv | Process for refining soap-containing crude product from a polyol fatty acid esterification mixture |
ATE146182T1 (en) | 1990-09-11 | 1996-12-15 | Procter & Gamble | METHOD FOR PRODUCING POLYOL POLYESTERS |
KR100249601B1 (en) * | 1991-04-12 | 2000-03-15 | 데이비드 엠 모이어 | Process for improving oxidative stability of polyol fatty acid polyesters |
US5945529A (en) * | 1996-07-19 | 1999-08-31 | The Procter & Gamble Company | Synthesis of polyol fatty acid polyesters using column with inert gas stripping |
US5767257A (en) * | 1996-07-19 | 1998-06-16 | The Procter & Gamble Company | Methods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure |
AU3736897A (en) * | 1996-08-08 | 1998-03-06 | Procter & Gamble Company, The | Polyol polyester synthesis |
US6121440A (en) * | 1998-01-29 | 2000-09-19 | The Procter & Gamble Company | Process for synthesis of polyol fatty acid polyesters |
WO2000072953A2 (en) * | 1999-06-01 | 2000-12-07 | Astion Development Aps | A method of producing organic emulsifiers and organic surfactants, products produced by said method, and the use of such products |
GB0608512D0 (en) | 2006-04-28 | 2006-06-07 | Vincent Processes Ltd | Process for the production of esters of sugars and sugar derivatives |
EP3031443A1 (en) | 2014-12-12 | 2016-06-15 | Basf Se | Composition comprising carbohydrate partial ester |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1200276B (en) * | 1959-10-08 | 1965-09-09 | Bayer Ag | Process for the preparation of carboxylic acid esters of non-reducing sugars |
DE1643795A1 (en) * | 1967-08-04 | 1971-07-01 | Cassella Farbwerke Mainkur Ag | Process for the production of sugar esters |
US3597417A (en) * | 1968-07-23 | 1971-08-03 | Procter & Gamble | Process for the preparation of fatty acid esters of sugar glycosides |
DE2004899C2 (en) * | 1969-02-05 | 1984-07-26 | Dai-Ichi Kogyo Seiyaku Co.,Ltd., Kyoto | Process for the separation of impurities from sucrose fatty acid ester raw products |
US3714144A (en) * | 1969-05-29 | 1973-01-30 | Us Agriculture | Process for the production of sucrose esters of fatty acids |
GB1399053A (en) * | 1973-03-16 | 1975-06-25 | Tate & Lyle Ltd | Process for the production of surface active agents comprising sucrose esters |
-
1974
- 1974-10-17 GB GB45122/74A patent/GB1499989A/en not_active Expired
-
1975
- 1975-04-18 TR TR18880A patent/TR18880A/en unknown
- 1975-10-15 US US05/622,495 patent/US4032702A/en not_active Expired - Lifetime
- 1975-10-15 AR AR260811A patent/AR212161A1/en active
- 1975-10-16 DK DK465675AA patent/DK142148B/en not_active IP Right Cessation
- 1975-10-16 IT IT69587/75A patent/IT1048249B/en active
- 1975-10-16 SE SE7511612A patent/SE430339B/en unknown
- 1975-10-16 NO NO753492A patent/NO140983C/en unknown
- 1975-10-17 JP JP50124459A patent/JPS5165704A/ja active Pending
- 1975-10-17 FR FR7531806A patent/FR2288143A2/en active Granted
- 1975-10-17 CA CA237,872A patent/CA1045130A/en not_active Expired
- 1975-10-17 ES ES441908A patent/ES441908A2/en not_active Expired
- 1975-10-17 AT AT793375A patent/AT347410B/en not_active IP Right Cessation
- 1975-10-17 ZA ZA00756573A patent/ZA756573B/en unknown
- 1975-10-17 IE IE2270/75A patent/IE42171B1/en unknown
- 1975-10-17 NL NLAANVRAGE7512252,A patent/NL172761B/en not_active IP Right Cessation
- 1975-10-17 DE DE2546716A patent/DE2546716C3/en not_active Expired
- 1975-10-17 BR BR7506830A patent/BR7506830A/en unknown
- 1975-10-17 CH CH1354075A patent/CH606074A5/xx not_active IP Right Cessation
- 1975-10-17 SU SU752184053A patent/SU906383A3/en active
- 1975-11-12 CU CU34398A patent/CU34398A/es unknown
Also Published As
Publication number | Publication date |
---|---|
IE42171B1 (en) | 1980-06-18 |
AR212161A1 (en) | 1978-05-31 |
SE7511612L (en) | 1976-04-20 |
DK142148B (en) | 1980-09-08 |
NO753492L (en) | 1976-04-21 |
CH606074A5 (en) | 1978-10-13 |
FR2288143B2 (en) | 1979-02-02 |
DE2546716A1 (en) | 1976-04-29 |
NL7512252A (en) | 1976-04-21 |
SU906383A3 (en) | 1982-02-15 |
NO140983B (en) | 1979-09-10 |
ZA756573B (en) | 1976-09-29 |
DE2546716B2 (en) | 1981-04-09 |
GB1499989A (en) | 1978-02-01 |
ES441908A2 (en) | 1977-07-01 |
JPS5165704A (en) | 1976-06-07 |
SE430339B (en) | 1983-11-07 |
BR7506830A (en) | 1976-08-31 |
IE42171L (en) | 1976-04-17 |
US4032702A (en) | 1977-06-28 |
CU34398A (en) | 1977-06-08 |
AU8582875A (en) | 1977-04-21 |
DE2546716C3 (en) | 1983-11-17 |
AT347410B (en) | 1978-12-27 |
DK142148C (en) | 1981-02-02 |
DK465675A (en) | 1976-04-18 |
NO140983C (en) | 1979-12-19 |
ATA793375A (en) | 1978-05-15 |
NL172761B (en) | 1983-05-16 |
FR2288143A2 (en) | 1976-05-14 |
IT1048249B (en) | 1980-11-20 |
TR18880A (en) | 1977-10-13 |
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