CN1062734A - The direct synthesis technique of alkyl glucoside - Google Patents
The direct synthesis technique of alkyl glucoside Download PDFInfo
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- CN1062734A CN1062734A CN 91111414 CN91111414A CN1062734A CN 1062734 A CN1062734 A CN 1062734A CN 91111414 CN91111414 CN 91111414 CN 91111414 A CN91111414 A CN 91111414A CN 1062734 A CN1062734 A CN 1062734A
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Abstract
The invention provides a kind of with the method for acidic substance as catalyzer one-step synthesis of alkyl glucoside.Product does not need fractionation refining, can be directly in industrial use.It has adopted binary or the ternary combination of acidic catalyzer that contains ethylenediamine tetraacetic acid (EDTA); Use NaBH
4With mineral alkali and or organic bases as compound neutralizing agent; Use boiling point be the alcohols of 70-160 ℃ of scopes as the activation solvent, suitable carbohydrate is the aldose and the ketose of various single, double and polysaccharide forms.
Description
The invention belongs to the category on the Sauerstoffatom that is directly connected on the saccharide radical.
The synthetic Fisher synthesis method of tracking and coming out of alkyl glycoside to 1909.This method is made of following step: a. glucose and anhydride reaction generate glucose penta acetic ester; B. change glucose penta acetic ester into bromo glucose tetraacetate with hydrogen bromide; C. in the presence of silver suboxide or zinc chloride, generate the alkyl glucoside tetraacetate with the Fatty Alcohol(C12-C14 and C12-C18) reaction; D. obtain alkyl glucoside after the hydrolysis.This method is very loaded down with trivial details and produce special resultant, is difficult to suitability for industrialized production.
Nineteen sixty-five, USP 3,170, described a technology that is prepared ethers by glucose and Fatty Alcohol(C12-C14 and C12-C18) in 915(Monsanto).Sugar forms the soda derivative with the sodium formiate reaction in the presence of methyl-sulphoxide, generates alkyl glycoside with the reaction of halo paraffin again.This technology is complicated, and product need be made with extra care, and cost is very high.
Nineteen sixty-five, USP 3,219,656(Rohm ﹠amp; The technology for preparing alkyl glucoside by the etherificate shift reaction between glucose and the higher alcohols of methylating has been described Haas Co.).The proposition glucose that methylates is stablized than glucose in heating with during oligomerization.Methylate in this technology between glucose and butanols the etherificate shift reaction and further carry out simultaneously with the transfer etherification reaction of Fatty Alcohol(C12-C14 and C12-C18).Will separate two kinds of low-carbon alcohol excessive separation Fatty Alcohol(C12-C14 and C12-C18) more continuously, multistep operation and solvent loss make cost too high.In addition at USP 3,037, several Zeo-karbs as catalysts have been described in 052.
Propose among the USP 3,547,828 of promulgation in 1970 in the presence of an acidic catalyst, low-carbon alcohol reactions such as carbohydrate elder generation and propyl carbinol generate the low-carbon alkyl glucoside, and then react with higher carbon alcohol.This is two step synthesis techniques that form the higher carbon alkyl glucoside by the transfer acetylization reaction.An acidic catalyst of enumerating is: mineral acid and organic acids such as tosic acid, methylsulphonic acid such as sulfuric acid, nitric acid.And point out that Lawis acid all can be used as catalyzer generally speaking, and best with the sulfuric acid effect.
1971, USP 3,598, described sugar and higher carbon alcohol in 865 and reacted in the presence of an acidic catalyst, prepared the technology of higher carbon alkyl glucoside as " inert solvent " with low-carbon alcohol.Point out that Fatty Alcohol(C12-C14 and C12-C18) should be fully excessive.Product fractionation again is refining.
1974, USP 3,839,318(Rohm ﹠amp; Haas Co.) described in the presence of an acidic catalyst, used excessive C
6-C
18Alcohol and glucose direct reaction prepare the method for alkyl glucoside and alkyl oligomerization glucoside mixture.Higher alcohols carry out glycosyl shift reaction difficulty with higher carbon alcohol with sugared direct reaction again than preparing the low-carbon alkyl glucoside earlier.This patent has only provided the example of preparation octyl glucoside.
The EP 0077,167 of nineteen eighty-three promulgation has described in the presence of the composite catalyst of an acidic catalyst and condensing agent composition, with the technology of monose and Fatty Alcohol(C12-C14 and C12-C18) prepared in reaction alkyl oligomerization glucoside.Think that suitable condensing agent is phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid, nitric acid and nitrous acid.Fatty Alcohol(C12-C14 and C12-C18) is 1.25～4: 1 with the mol ratio of sugar during reaction.Reaction product needs vacuum distilling, molecular distillation or rotating thin film distillation to remove excess fat alcohol.Provided product the highest alkyl carbon number and be 10 preparation example.
The EP 0132,043 of promulgation in 1985 proposes the improved technology of a preparation alkyl glucoside.Suggestion uses anion surfactant alkylsurfuric acid, alkyl benzene sulphonate (ABS) and alkylsulphonic acid etc. as catalyzer, thinks and can reduce sugared autohemagglutination like this.The centrifugal insolubles that shifts out of thick product after the neutralization, alcohol excess is removed in fractionation again.
0132,046 couple of the EP of promulgation in 1985 proposes improvement project with the neutralization method that acid catalysis prepares alkyl glucoside technology, and (RO) used in suggestion
nThe organic bases of M form neutralizes an acidic catalyst as neutralizing agent when reaction finishes.Think the generation that helps when alcohol excess is put forward in steaming to reduce the by product that adds lustre to like this.
JP 89,283 in 1989, and 294 propositions are the Preparation of Catalyst alkyl glucoside with the heteropolyacid.But the raw material that uses is five acetyl glucoses, with excess fat alcohol direct reaction.Provided the example of preparation octyl group tetrem acidylate glucoside.Product also needs fractionation refining.Limitation is all arranged on raw material and kind.
Above-mentioned various synthesis technique all uses excess fat alcohol and sugar or sugared derivatives reaction.Have a large amount of unreacting alcohols in the product, need fractionation more refining, energy consumption and material consumption are quite high, and product cost is increased.The fractionation treating process can exert an adverse impact to quality product.Though proposed some protect quality product in fractionation process scheme; as Ger.Offen 3 in 1981; 001,064(BASF A.G.) adding ethylene glycol prevents the method that product color deepens when proposing the fractionation alcohol excess, but this makes technology complicated accordingly again.In addition, be subjected to the restriction of higher alcohols boiling point and alkyl glycoside coking temperature, any technology of putting forward alcohol excess of need steaming will prepare the alkyl carbon number and is higher than 12 product and is actually difficulty.
Our task is that a kind of technology of development is simple, the one-step synthesis of less investment, productive rate height, the alkyl glucoside that just can directly use without fractionation.
The present invention is a kind of with the method for acidic substance as catalyzer synthesis of alkyl glucoside, it is characterized in that being suitable for chemical general formula
Wherein: n=0-10
G ' represents monose group identical or inequality with G
R represents to have straight chain or branched, the saturated or unsaturated alkyl or the aralkyl chain of 6～32 carbon atoms
The one-step synthesis of alkyl glucoside, do not need fractionation refining, can be directly in industrial use.
A) used the combination of acidic catalyzer;
B) adopted NaBH
4With mineral alkali and or the compound neutralizing agent of organic bases;
C) used boiling point be 70～160 ℃ of scopes alcohols as the activation solvent;
D) carbohydrate of Shi Yonging is the aldose and the ketose of various single, double and polysaccharide forms.
The present invention puts forward on the basis of having studied the alkyl glucoside synthetic method.Although synthetic method has multiple, improve response behaviour and product color, it is quite difficult particularly reducing in industrialized production or avoiding the interference of trace metal ion.For this reason, our ad hoc proposal has been used binary or the ternary combination of acidic catalyzer that ethylenediamine tetraacetic acid (EDTA) and common acid are formed; NaBH
4With mineral alkali and or organic bases form compound neutralizing agent; Use boiling point at the low-carbon (LC) alcohols of 70～160 ℃ of scopes as the activation solvent; The carbohydrate that is suitable for is that various single, double and aldose and ketoses the polysaccharide form constitute main body of the present invention.The product that reaction obtains, without separation, the content of alkyl oligomerization glucoside can reach more than 90%, and the unreacted Fatty Alcohol(C12-C14 and C12-C18) is generally 5～10%.Product Status is light yellow or yellowish translucent thickness lotion, can directly apply to makeup, medicine, food, washing composition, printing and dyeing, printing and other industry.
The present invention is in the presence of an acidic catalyst, uses C
6-C
32The monohydroxy alcohols and maybe can be degraded to the various saccharidess reaction of monose together with monose than low-carbon alcohol, one-step synthesis goes out higher degree, can be without the refining and light alkyl glucoside that directly use of fractionation in most of application scenarios.This synthetic method also comprises the composite catalyst that can improve response behaviour and product color, contain ethylenediamine tetraacetic acid (EDTA), and can significantly improve product color, contains NaBH
4The use of compound neutralizing agent.
The monohydroxy alcohols that is applicable to this synthetic method is straight chain and branched, saturated or unsaturated primary, secondary alkyl alcohols and the aralkyl alcohols with 6～32 carbon atoms.The carbohydrate that is suitable for is the aldose and the ketose of various single, double and polysaccharide forms.Comprise single saccharidess such as glucose, fructose, sorbose, seminose, pectinose, semi-lactosi, ribose, wood sugar, can be degraded to the disaccharide or the polysaccharide of monose with sucrose, maltose, lactose, raffinose and other, and the hydrolysis and saccharification thing of poly-polysaccharide such as starch, Mierocrystalline cellulose.
Suitable is that boiling point is the low-carbon (LC) alcohols of 70～160 ℃ of scopes as what activate the solvent use, comprises n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, Pentyl alcohol, primary isoamyl alcohol, sec.-amyl alcohol, tertiary amyl alcohol, 3-amylalcohol, cyclopentanol, n-hexyl alcohol, 2-hexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.These low-carbon alcohol that propose play the activation solvent in reaction, make under the comparatively gentle condition of being reflected at of Fatty Alcohol(C12-C14 and C12-C18) and single saccharides and more easily finish.Though the reaction rate constant of low-carbon alcohol and saccharides is much larger than the reaction rate constant of high-carbon fatty alcohol and saccharides, and cause and have a plurality of competing reactions and chemical equilibrium in the reaction system simultaneously, but reaction is carried out very even in the method, make the higher carbon alkyl glucoside generation (comprise higher alcohols directly and the reaction of saccharides and glycosyl be transferred to reaction on the higher alcohols by low-carbon alcohol) under relatively mild condition, with comparatively faster speed, equably, controlledly carry out.This response behaviour is very accurate, must strictly control moving of each chemical equilibrium.Present method also makes easy coking component be protected in reaction process under the inexcessive situation of Fatty Alcohol(C12-C14 and C12-C18).
This synthetic method can make reactant Fatty Alcohol(C12-C14 and C12-C18) and sugared ratio, is improved to pure sugared equivalent or sugared excessive by the pure excessive of past, thereby makes one-step synthesis higher degree alkyl glucoside become possibility.Be applicable to that the Fatty Alcohol(C12-C14 and C12-C18) of present method and the mol ratio of saccharides can be 1: 1～1: 10.For the product that obtains higher degree and make it good surfactivity and water-soluble, the sugared mol ratio of optimum alcohol is 1: 1～1: 3.As the low-carbon alcohol of strong solvent and the molar ratio range of saccharides is 1: 1～20: 1.
General Lawis acid, as sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, methylsulphonic acid, tosic acid, alkylsulphonic acid and acidic ion exchange resin, and other known valid catalyst for etherification all are applicable to this synthetic method.But the present invention proposes to use composite binary of ethylenediamine tetraacetic acid (EDTA) and an acidic catalyst and condensing agent or ternary complex catalyst especially.Suitable condensing agent is phosphoric acid or phosphorous acid.The composite catalyst that is proposed can improve response behaviour and product color, particularly can reduce or avoid the detrimentally affect of metal ion in suitability for industrialized production.The weight percent of ethylenediamine tetraacetic acid (EDTA) in composite catalyst is 1～40.In the composite catalyst that contains an acidic catalyst and the condensing agent that has katalysis concurrently, the ratio of the former with the latter can be 2: 8～9: 1.
Neutralizing agent commonly used is a mineral alkali or (RO)
nThe organic bases of M form.M can be basic metal, alkaline-earth metal or amine in the formula.The present invention proposes to use NaBH especially
4With mineral alkali and or organic bases composite as neutralizing agent.NaBH
4Aldose can be changed into corresponding alcohol sugar, improve product color effectively.NaBH in compound neutralizing agent
4With mineral alkali and or the weight ratio of organic bases be 9: 1～1: 9.
Reaction can be carried out in having agitation as appropriate device and the glass flask that is connected with vacuum system or other various reactors.The C that will meet the aforementioned ratio scope during reaction
6-C
32The monohydroxy alcohols is the low-carbon alcohol of 70-160 ℃ of scope as the boiling point that activates solvent, and single saccharides or suitable carbohydrate and an acidic catalyst add in the lump.Wherein part material such as higher alcohols, low-carbon alcohol and catalyzer also can add by a graded in batches, perhaps add a kind of raw material or more than one mixing raw material continuously, carry out with semicontinuous reactive mode.Chemical equilibrium in the reaction process between the reaction of necessary accurately control purpose, intermediary's reaction and the side reaction and mobile.In the ratio of strict control activation solvent of each stage of reaction in reaction system.Reaction can be carried out under 80-130 ℃ of temperature, and optimal reaction temperature is 105-120 ℃.After room temperature is warming up to temperature of reaction gently, reacted about 1.5～3 hours.Reaction should be carried out under the inert gas flow protection.The vacuum tightness of reactive system should be controlled between 0.005～0.50MPa.Be cooled to 90 ℃ after reacting completely and add neutralizing agent, neutralize the catalyzer stopped reaction.Neutralization back system pH is about 6.5～7.0.
Add the aqueous solution contain a small amount of discoloring agent at last and further decolour, and make reaction product become 70～80%(weight) the aqueous solution.Product is light yellow or little yellow, translucent thickness lotion, and colourity is APHA 100～150 usually.Alkyl glucoside content in total solid matters is 90%(weight) more than, in all no longer refining and directly uses of fractionation of most of occasions.So not only reduced the material consumption energy consumption but also avoided the detrimentally affect of distillation quality product.In addition, the excessive method of aforementioned various Fatty Alcohol(C12-C14 and C12-C18) when the fractionation alcohol excess, is subjected to the restriction of alkyl glucoside variable color and coking temperature, makes in fact will to prepare the alkyl carbon number to be higher than 12 product be difficult.This synthetic method is higher than 12 product owing to there is not the excessive problem of Fatty Alcohol(C12-C14 and C12-C18) and can easily prepare the alkyl carbon number.
Further specify for example below.
Embodiment one.
In having the reaction flask of stirring, add lauryl alcohol 93g(0.5mol), dextrose anhydrous 180g(1.0mol), propyl carbinol 555g(7.5mol) and, the three-way catalyst 0.65g that is proposed.Be warming up to 110 ℃ of reactions 2 hours, stir and distillate water and propyl carbinol that reaction generates simultaneously.Be cooled to 90 ℃ then and add NaBH
4The neutralization of-NaOH solution, neutralization back system PH ≈ 6.5.Contain dodecyl glucoside 93.40%(W/W in the not separated reactant), the average glucosides polymerization degree is 2.35; Unreacted lauryl alcohol 5.86%, free sugar 0.77%.Decolouring after product form and aspect are APHA 100.This mix thick product after measured the surface tension of the aqueous solution be 29.5mNS/m, critical micelle concentration (cmc) is 2.3 * 10
-4Mol/L(25 ± 1 ℃).
Embodiment two.
It is identical with embodiment one with schedule of operation to feed intake.When reaction finishes, add NaBH
4-NaOCH
3Compound neutralizing agent neutralization.Alkyl glucoside accounts for 94.36%(W/W in the last thick product), the average glucosides polymerization degree is 2.27; Unreacting alcohol 4.71%, free sugar 0.93%.Decolouring back product form and aspect APHA 100.
Embodiment three.
It is identical with embodiment one with schedule of operation to feed intake.When reaction finishes, add NaBH
4-NaOH-NaOCH
3Compound neutralizing agent neutralization and decolouring.Product form and aspect APHA 100.
Embodiment four.
Reactant is that molecular-weight average is 198.6 coconut oleyl alcohol 85g(0.43mol), dextrose anhydrous 180g(1.0mol), sec.-amyl alcohol 443g(5.0mol) and, the three-way catalyst 0.70g that is proposed.Wherein about 2/5 solvent and part catalyzer add in reaction process continuously.Be warming up to 115 ℃ of reactions 2 hours.When finishing, reaction presses the neutralization of embodiment one method.Contain alkyl glucoside 92.5%(W/W in the unsegregated reactant), the average glucosides polymerization degree is 2.89; Unreacted coconut oleyl alcohol 7.08%, free sugar 0.87%.Decolouring after product form and aspect APHA 100.
Embodiment five.
In reaction flask, add molecular-weight average and be 198.6 coconut oleyl alcohol 50g(0.25mol), dextrose anhydrous 90g(0.5mol), propyl carbinol 149g(2.0mol) and the three-way catalyst 0.30g that proposed.Be warming up to 115 ℃ of reactions 2 hours.Add NaBH
4Neutralization of-NaOH neutralizing agent and decolouring.Not separated product contains alkyl glucoside 90.85%(w/w), the average glucosides polymerization degree is 2.62; Unreacted coconut oleyl alcohol 8.59%, free sugar 0.56%.Product form and aspect APHA 100.
Embodiment six.
According to embodiment one same schedule of operation, add hexadecanol 97.0g(0.4mol), dextrose anhydrous 158.5g(0.88mol), propyl carbinol 491g(6.6mol) and the three-way catalyst 0.50g that proposed.React and be cooled to 90 ℃ after 2.5 hours, use NaBH
4Neutralization of-NaOH solution and decolouring.Contain hexadecyl glucoside 88.67% in the reaction product, the average glucosides polymerization degree 2.93; Unreacted hexadecanol 10.34%, free sugar 0.87%.Product form and aspect APHA 150.
Embodiment seven.
According to embodiment one same schedule of operation, add n-Octanol 65g(0.5mol), dextrose anhydrous 135g(0.75mol), isopropylcarbinol 112g(1.5mol) and, three-way catalyst 0.35g.React and be cooled to 90 ℃ after 1.5 hours, use NaBH
4Neutralization of-NaOH solution and decolouring.Octyl glucoside is 93.17%(W/W in the reaction product), the average glucosides polymerization degree 1.81; Unreacted n-Octanol 6.22%, free sugar 0.61%.Product form and aspect APHA 150.
Embodiment eight.
According to embodiment three same schedule of operation, reactant is tetradecyl alcohol 85.8g(0.40mol), dextrose anhydrous 129.7g(0.72mol), sec.-amyl alcohol 319g(3.6mol).Three-way catalyst 0.45g.When finishing, reaction uses NaBH
4Neutralization of-NaOH solution and decolouring.The tetradecyl glucoside is 88.84%(W/W in the unsegregated product), the average glucosides polymerization degree 2.34; Unreacted tetradecyl alcohol 10.29%, free sugar 0.87%.Product form and aspect APHA 100.
Embodiment nine.
According to embodiment three same schedule of operation, reactant is oleyl alcohol 107.4g(0.40mol), dextrose anhydrous 158.5g(0.88mol), sec.-amyl alcohol 310g(3.5mol).The three-way catalyst 0.40g that proposes.When finishing, reaction uses NaBH
4Neutralization of-NaOH solution and decolouring.Alkyl glucoside is 90.13%(W/W in the unsegregated product), average glucosides aggregate number is 2.71; Unreacted oleyl alcohol 8.72%, free sugar 1.15%.Product form and aspect APHA 150.
Embodiment ten.
According to embodiment three schedule of operation, reactant is lauryl alcohol 116g(0.625mol), β-pectinose 150g(1.0mol); Isopropylcarbinol 297g(4mol), wherein 1/3 interpolation continuously in reaction.The three-way catalyst 0.45g that is proposed.When finishing, reaction uses NaBH
4Neutralization of-NaOH solution and decolouring.Plantacare APG 1200G is 93.08%(W/W in the unsegregated product), average glucosides aggregate number is 1.79; Unreacted lauryl alcohol 5.85%, free sugar 1.07%.Product form and aspect APHA 150.
Embodiment 11.
According to embodiment three schedule of operation, reactant is lauryl alcohol 103.5g(0.56mol), L-sorbose 180g(1.0mol), primary isoamyl alcohol 398g(4.5mol) and, the three-way catalyst 0.50g that is proposed.When finishing, reaction uses NaBH
4Neutralization of-NaOH solution and decolouring.Contain Plantacare APG 1200G 92.80%(W/W in the unsegregated product), average glucosides aggregate number is 2.08; Unreacted lauryl alcohol 5.93%, free sugar 1.27%.Product form and aspect APHA 150.
Embodiment 12.
In the 100 liter reactors that link to each other with vacuum system, add lauryl alcohol 11.18kg(60mol), dextrose anhydrous 16.21kg(90mol), propyl carbinol 26.65kg(360mol) and, the three-way catalyst 49g that is proposed.Be warming up to 110 ℃ of reactions 2 hours, stir and distillate water and solvent, n-butanol that reaction generates simultaneously.After finishing, reaction adds NaBH
4The neutralization of-NaOH solution.Neutralization back system pH is about 6.5.Contain dodecyl glucoside 90.66%(w/w in the unsegregated reaction product), the average glucosides polymerization degree is 1.74; Unreacted lauryl alcohol 7.17%, free sugar 2.17%.Product is diluted to 70% aqueous solution and decolouring back form and aspect are APHA 100.
Embodiment 13.
Device adds industrial coconut oleyl alcohol 11.92kg(60mol with embodiment 11), dextrose anhydrous 19.45kg(108mol), the three-way catalyst 68g that is proposed.Propyl carbinol 40.02kg(540mol), wherein 30% adding continuously in reaction.The same example of all the other working method.Contain alkyl glucoside 91.82%(w/w in the reaction product), the average glucosides polymerization degree is 2.06; Unreacted coconut oleyl alcohol 6.25%, free sugar 1.93%.Product is diluted to 70% the aqueous solution and the back form and aspect of decolouring are APHA 150.
Reference example A.
In the reaction flask of stirring is housed, add lauryl alcohol 93g(0.5mol), dextrose anhydrous 180g(1.0mol), propyl carbinol 555g(7.5mol).Catalyzer is a 0.65g sulfuric acid.Be warming up to 110 ℃ of reactions 2 hours, stir and distillate water and propyl carbinol that reaction generates simultaneously.Be cooled to 90 ℃ and add NaOH solution catalyst neutralisation stopped reaction, neutralization back system PH ≈ 6.5.Contain dodecyl glucoside 89.37%(W/W in the not separated reactant), the average glucosides polymerization degree is 2.65.Unreacted lauryl alcohol 9.38%, free sugar 1.25%.Decolouring after product form and aspect are APHA 250.
Reference example B.
Feed intake and operate according to reference example A, but NaBH is used in reaction when finishing
4Compound neutralizing agent neutralization of-NaOH and decolouring.The product form and aspect are APHA 200.
Reference example C.
Feed intake and operate according to embodiment one, but do neutralizing agent neutralization and decolouring with NaOH.The product form and aspect are APHA 150.
Reference example D.
Charging capacity and schedule of operation according to embodiment three are reacted, and do not contain NaBH but do not add when reaction finishes
4Neutralizing agent and add NaOH solution neutralization.Decolouring back product form and aspect APHA 150.
Reference example E.
According to the technological operation of EP 96,917, the raw material add-on is lauryl alcohol 186g(1.0mol), butyl glucoside-butanol solution 363g(amounts to single from glucose 72g, 0.4mol).Alkyl glucoside content is 39.46%(w/w in the reaction product), mean polymerisation degree 1.50; Unreacted lauryl alcohol 56.73%, free sugar 3.81%.Need fractionate out the unreacted lauryl alcohol.
Reference example F.
Charging capacity and schedule of operation according to embodiment three are reacted, and add sodium methylate neutralization and decolouring when reaction finishes.The product form and aspect are APHA 150.
By the narration and the example of front, be not difficult to find out that this synthetic method can make the pure sugared ratio of reaction be improved to pure sugared equivalent or sugared excessive by Fatty Alcohol(C12-C14 and C12-C18) is excessive, thereby make the highly purified alkyl glucoside of one-step synthesis become possibility.Also can save the fractionation refining step.Not only improve response behaviour and product color, and reduced material consumption and energy consumption significantly, be suitable for suitability for industrialized production.We claim at this, and present method is a kind of with the Perfected process of acidic substance as catalyzer one-step synthesis of alkyl glucoside.
Claims (3)
1, a kind of with the method for acidic substance as catalyzer synthesis of alkyl glucoside, it is characterized in that being suitable for chemical general formula
R-O-(G′)n-G
Wherein: n=0-10
G ' and G represent identical or different monose group
R represents to have straight chain or branched, the saturated or unsaturated alkyl or the aralkyl chain of 6-32 carbon atom
The one-step synthesis of alkyl glucoside, need not divide gold-plating refining, can be directly in industrial use.
A) used the combination of acidic catalyzer:
The binary combination of acidic catalyzer that ethylenediamine tetraacetic acid (EDTA) and sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, nitric acid, nitrous acid, methylsulphonic acid, tosic acid, alkylsulphonic acid, acidic ion exchange resin are formed perhaps adds the ternary combination of acidic catalyzer that etherificate condensing agent commonly used such as phosphoric acid, phosphorous acid are formed again;
B) adopted NaBH
4With mineral alkali and or the compound neutralizing agent formed of organic bases;
C) used boiling point as the alcohols of 70-160 ℃ of scope as the activation solvent, as n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, Pentyl alcohol, primary isoamyl alcohol, sec.-amyl alcohol, cyclopentanol, n-hexyl alcohol, 2-hexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether;
D) carbohydrate of Shi Yonging is the aldose and the ketose of various single, double and polysaccharide forms, as single saccharidess such as glucose, fructose, sorbose, seminose, pectinose, semi-lactosi, ribose, wood sugars, can be degraded into the disaccharide or the polysaccharide of monose with sucrose, maltose, lactose, raffinose etc., and the hydrolysis and saccharification thing of starch, the poly-polysaccharide of Mierocrystalline cellulose.
2, according to the method for the alleged acidic substance of claim 1, it is characterized in that as catalyzer synthesis of alkyl glucoside
A) mol ratio of Fatty Alcohol(C12-C14 and C12-C18) and sugar is 1: 1～1: 10;
B) the activation solvent is 1: 1～20: 1 with the mol ratio of sugar;
C) catalyst levels is 0.001～0.01(weight of sugar).
3, according to the method for an acidic catalyst synthesis of alkyl glucoside of claim 1 and 2, it is characterized in that in laboratory that has whipping appts, vacuum system and well heater and full scale plant, carrying out
A) temperature of reaction: 80～130 ℃, optimal reaction temperature is 105～120 ℃;
B) vacuum tightness: 0.005～0.5MPa;
C) reaction times: can finish the synthetic of alkyl glucoside in 1.5～3 hours.
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|---|---|---|---|
| CN 91111414 CN1031573C (en) | 1991-12-06 | 1991-12-06 | Directly synthetic method of glucoside alkyl |
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|---|---|---|---|
| CN 91111414 CN1031573C (en) | 1991-12-06 | 1991-12-06 | Directly synthetic method of glucoside alkyl |
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| CN1031573C CN1031573C (en) | 1996-04-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786555A (en) * | 2011-05-19 | 2012-11-21 | 扬州晨化科技集团有限公司 | Preparation method of hexadecyl glucopyranoside |
| CN102786559A (en) * | 2011-05-19 | 2012-11-21 | 扬州晨化科技集团有限公司 | Preparation method of octyl glucopyranoside |
| CN103159804A (en) * | 2013-03-15 | 2013-06-19 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of octyl-beta-D-glucopyranoside |
-
1991
- 1991-12-06 CN CN 91111414 patent/CN1031573C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786555A (en) * | 2011-05-19 | 2012-11-21 | 扬州晨化科技集团有限公司 | Preparation method of hexadecyl glucopyranoside |
| CN102786559A (en) * | 2011-05-19 | 2012-11-21 | 扬州晨化科技集团有限公司 | Preparation method of octyl glucopyranoside |
| CN102786555B (en) * | 2011-05-19 | 2014-12-10 | 扬州晨化新材料股份有限公司 | Preparation method of hexadecyl glucopyranoside |
| CN103159804A (en) * | 2013-03-15 | 2013-06-19 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of octyl-beta-D-glucopyranoside |
| CN103159804B (en) * | 2013-03-15 | 2015-06-17 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of octyl-beta-D-glucopyranoside |
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| CN1031573C (en) | 1996-04-17 |
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