CN114685570A - Preparation method of novel green surfactant alkyl glycoside - Google Patents
Preparation method of novel green surfactant alkyl glycoside Download PDFInfo
- Publication number
- CN114685570A CN114685570A CN202210310105.1A CN202210310105A CN114685570A CN 114685570 A CN114685570 A CN 114685570A CN 202210310105 A CN202210310105 A CN 202210310105A CN 114685570 A CN114685570 A CN 114685570A
- Authority
- CN
- China
- Prior art keywords
- alkyl glycoside
- mixed
- starch
- reaction
- high amylose
- 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.)
- Granted
Links
- 229930182470 glycoside Natural products 0.000 title claims abstract description 71
- -1 alkyl glycoside Chemical class 0.000 title claims abstract description 70
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920001685 Amylomaize Polymers 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000003622 immobilized catalyst Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006206 glycosylation reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- 229920000856 Amylose Polymers 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229920002472 Starch Polymers 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 15
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 14
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 229920002261 Corn starch Polymers 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000008120 corn starch Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 240000004922 Vigna radiata Species 0.000 claims description 5
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 5
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 5
- 229940100445 wheat starch Drugs 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- 150000002338 glycosides Chemical class 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
- 239000008103 glucose Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 229930182478 glucoside Natural products 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012029 Fehling's reagent Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000008131 glucosides Chemical class 0.000 description 3
- 230000013595 glycosylation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005858 glycosidation reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B33/00—Preparation of derivatives of amylose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Genetics & Genomics (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a preparation method of a novel green surfactant alkyl glycoside, belonging to the technical field of surfactants. The preparation method comprises the following steps: s1, adding the high amylose starch into the mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid immobilized catalyst into the mixed solution, continuously stirring uniformly, slowly heating to raise the temperature, vacuumizing and placing nitrogen to perform glycosylation reaction; and S2, after the reaction is completed, cooling, adjusting the pH value, and filtering to remove the mixed acid immobilized catalyst and the by-product, thereby obtaining the alkyl glycoside. The preparation method has simple process, the alkyl glycoside is synthesized by taking high amylose starch and mixed fatty alcohol as raw materials and adopting the mixed acid immobilized catalyst, the conversion rate of the glycoside is effectively improved, the side reaction is less, the prepared alkyl glycoside has light color, and the catalyst is easy to separate and recycle and can be recycled.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a preparation method of a novel green surfactant alkyl glycoside.
Background
Alkyl glycoside (APG) is a kind of excellent new nonionic surfactant, and has many advantages of anionic surfactant, such as high surface activity, abundant foam, fine and stable, good detergency, excellent compatibility, good biodegradability, no irritation to skin, good compatibility with human body, etc., so it is widely used in many fields such as washing industry, cosmetics industry, food processing industry and pesticide. The alkyl glycoside is prepared by taking natural renewable resources such as glucose or starch and fatty alcohol as raw materials, and toxicity test experiments show that the toxicity of APG is far lower than that of surfactants such as LAS, AEO and the like, and the alkyl glycoside belongs to a non-toxic product. The Soap and Detergent Association (SDA for short) of the united states of america has experimentally demonstrated that APG has low irritation to the skin and fast and complete biodegradability. Thus, alkyl glycosides are entirely known as green surfactants.
The alkyl glycoside can be synthesized by one step by adopting a direct glycoside method or two steps by adopting a transglycoside method, and the production process is mature. Among them, the direct glycoside method (one-step method) is the most studied method at present, specifically, glucose and fatty alcohol directly react to generate alkyl glycoside under the action of catalyst, compared with transglycoside method, the process of exchanging diol and removing lower alcohol is omitted, so the process is simpler, and the product quality is better. However, because the intersolubility of higher alcohol and glucose is poor, and the reaction speed is slow, the reaction conditions need to be strictly controlled in the reaction process: for example, the water removal rate is ensured to be larger than the water generation rate in the reaction process, otherwise, caramel and glucose agglomeration are easy to generate, and the like. In the method, the kind of the catalyst has great influence on the quality of the alkyl glycoside product, and acidic substances such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, citric acid, inorganic acid and the like are usually adopted as the catalyst. However, for some fatty alcohols with a branched chain at the beta-position, the steric hindrance of the hydroxyl group is large, so that the reaction activity of the fatty alcohols and glucose to generate glucoside is not high, and the reaction conversion rate is low or even not high by using the traditional single acidic catalyst. The contact between the organic acid and the reactant is sufficient, which is beneficial to accelerating the reaction speed and reducing the concentration of the sugar autopolymer, but brings inconvenience to the subsequent separation and purification.
In addition, the alkyl glycoside needs to be prepared under the conditions of high temperature and acid catalysis, and starch or glucose can easily generate side reactions for generating colored impurities such as ether, levulinic acid, furfural or hydroxymethyl furfural and the like in the environment, so that the product is black and dark, the color is darker, the burden of a decoloring step is increased, and the production cost is increased.
Long-carbon-chain alkyl glucoside has the defects of poor water solubility and the like, and currently, fatty alcohol polyoxyethylene ether with low EO addition number is adopted to replace fatty alcohol for glycosylation to prepare an alcohol ether glucoside product, so that the excellent performance of alkyl glucoside can be maintained, and the water solubility of the alkyl glucoside can be improved. But also has the problems of equipment corrosion by liquid acid, complex process, low catalytic activity, impure products and the like.
Therefore, it is necessary to develop a method for preparing alkyl glycoside with simple process, high catalytic activity, high glycoside conversion rate, few side reactions and light color.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of novel green surfactant alkyl glycoside, the preparation method has simple process, the alkyl glycoside is synthesized by taking high amylose starch and mixed fatty alcohol as raw materials and adopting a mixed acid supported catalyst, the conversion rate of the glycoside is effectively improved, the side reactions are less, and the prepared alkyl glycoside has light color.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, adding the high amylose starch into the mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid immobilized catalyst into the mixed solution, continuously stirring uniformly, slowly heating to raise the temperature, vacuumizing and placing nitrogen to perform glycosylation reaction; in the reaction process, a Fehling reagent is adopted to detect or observe the color of the mixture to judge the reaction end point;
and S2, after the reaction is completed, cooling, adjusting the pH value, and filtering to remove the mixed acid immobilized catalyst and the by-product, thereby obtaining the crude product of the alkyl glycoside.
In the above preparation method, the glycosylation reaction of the high amylose starch and the mixed fatty alcohol is as follows:
wherein R1 independently represents a linear or isomeric alkyl group having 2 to 16 carbon atoms; n is the degree of polymerization of glucose, and n is 1 to 10.
In the mixed system prepared by the method, the average polymerization degree of glucose is 1.5-2.6, preferably 1.5-1.8.
In a preferred embodiment of the present invention, the mass ratio of the high amylose starch to the mixed fatty alcohol is 1:3 to 5.
As a preferred embodiment of the invention, the mixed acid supported catalyst is prepared by supporting p-toluenesulfonic acid and citric acid on activated alumina. More preferably, the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1: 3-1: 8, and preferably 1: 6.
In a preferred embodiment of the present invention, the mixed acid supported catalyst is prepared by the following method: roasting activated alumina at 350-450 ℃ for 4-6h, washing with water for 2-3 times, and drying at 100-120 ℃ for 2-4 h; adding the treated activated alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until the water is evaporated to dryness, drying at 125-145 ℃ to constant weight, and calculating the load capacity to obtain the activated alumina carrier.
In a preferred embodiment of the present invention, the amount of the mixed acid supported catalyst added is 0.2 to 3%, preferably 1.5% of the total mass of the high amylose starch and the mixed fatty alcohol.
In a preferred embodiment of the present invention, the mixed fatty alcohol is a mixture of dodecanol and tetradecanol in a mass ratio of 2:1 to 4: 1.
As a preferred embodiment of the present invention, the high amylose starch refers to starch having an amylose content of not less than 50% in the starch granules, preferably having an amylose content of 50%. Further preferably, the high amylose starch is one of corn starch, wheat starch, tapioca starch, potato starch or mung bean starch; preferably corn starch.
In a preferred embodiment of the present invention, the reaction temperature of the glycosylation reaction in step S1 is 90 to 140 ℃, and the reaction is evacuated to a residual pressure of less than 60 mmHg; the reaction time is 130-210 min, preferably 180 min.
In a preferred embodiment of the present invention, in step S2, a NaOH solution or a KOH solution is used to adjust the pH of the mixed solution to be greater than 7, and the pH is preferably 7 to 8. Further preferably, the mass concentration of the NaOH solution or the KOH solution is 30 to 50%, preferably 35 to 40%.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the alkyl glycoside provided by the invention prepares the alkyl glycoside by taking high amylose starch and mixed fatty alcohol as raw materials, adopting a mixed acid immobilized catalyst and adopting a direct glycosidation method (one-step method), and has the following advantages:
1. compared with alkyl glycoside products synthesized by using common starch as a raw material in the prior art, the method has the advantages that the high amylose starch is used as the raw material, side reactions can be avoided, so that the utilization rate of the raw material is higher, the surface tension of the product is low, and the surface activity is higher.
2. The supported solid mixed acid catalyst is adopted for catalytic reaction, so that the catalyst has the advantages of light product color, high catalytic activity, small environmental pollution, no corrosion to a device, easiness in separation, reusability and the like in the synthesis of alkyl glycoside, can alleviate the defects of trouble in subsequent separation, impurity in products, environmental pollution, equipment corrosion and the like caused by the liquid acid serving as the catalyst, and has good economic benefit and environmental benefit.
3. The direct glycosidation method (one-step method) is adopted, the starch and the mixed alcohol directly react to generate the alkyl glycoside under the action of the catalyst, and compared with the transglycosidation method, the process of exchanging the double alcohols and removing the lower alcohol is omitted, so the process is simpler, and the product quality is better.
In conclusion, the preparation method provided by the invention effectively improves the reaction activity of glycosylation of fatty alcohol and high amylose starch, and has the advantages of simple process flow, high glucoside conversion rate, less side reaction, light color and no need of additional decolorization.
Drawings
FIG. 1 is a product diagram of alkyl glycoside synthesized in example 1 of the present invention;
FIG. 2 is a product diagram of alkyl glycoside synthesized in example 2 of the present invention;
FIG. 3 is a product diagram of alkyl glycoside synthesized in example 3 of the present invention;
FIG. 4 is a product diagram of alkyl glycoside synthesized in example 4 of the present invention;
FIG. 5 is a product diagram of alkyl glycoside synthesized in comparative example 1 according to the present invention;
FIG. 6 is a product diagram of alkyl glycoside synthesized in comparative example 2 according to the present invention;
FIG. 7 is a product diagram of alkyl glycoside synthesized in comparative example 3 according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the following detailed description, but the present invention is not limited to the embodiments. The reagents used in the examples are commercially available without specific reference.
A preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, adding high amylose starch into the mixed fatty alcohol according to the mass ratio of the high amylose starch to the mixed fatty alcohol of 1: 3-5, and stirring to uniformly disperse the high amylose starch; adding a mixed acid immobilized catalyst into the mixed solution according to 0.2-3% of the total mass of the high amylose starch and the mixed fatty alcohol, continuously stirring uniformly, slowly heating to 90-140 ℃, vacuumizing until the residual pressure is less than 60mmHg, and placing nitrogen for glycosylation reaction, wherein the reaction time is 130-210 min; judging the reaction end point by adopting a Fehling reagent or observing the color of the mixture in the reaction process; wherein the mixed fatty alcohol is a mixture formed by mixing dodecanol and tetradecanol according to the mass ratio of 2:1-4: 1;
and S2, cooling after the reaction is completed, adjusting the pH to be more than 7 by adopting a NaOH solution or a KOH solution with the mass concentration of 30-50%, and filtering to remove the mixed acid immobilized catalyst and byproducts to obtain the crude product of the alkyl glycoside.
In the method, the mixed acid supported catalyst is prepared by supporting p-toluenesulfonic acid and citric acid on activated alumina. More preferably, the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1: 3-1: 8, and preferably 1: 6. The preparation method of the mixed acid supported catalyst comprises the following steps: roasting activated alumina at 350-450 ℃ for 4-6h, washing with water for 2-3 times, and drying at 100-120 ℃ for 2-4 h; adding the treated activated alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until the water is evaporated to dryness, drying at 125-145 ℃ to constant weight, and calculating the load capacity to obtain the activated alumina carrier.
Example 1
A preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, weighing 32g of high amylose corn starch with amylose content of 50%, adding the high amylose corn starch into a 500ml four-neck flask with a stirrer, a thermometer and a water separation device, which is filled with 160g of mixed fatty alcohol consisting of dodecanol and tetradecanol according to the mass ratio of 2:1, and stirring to uniformly disperse the high amylose corn starch; adding 2.9g of mixed acid immobilized catalyst (the mixing mass ratio of p-toluenesulfonic acid to citric acid is 1:5) into the mixed solution according to 1.5% of the total mass of the high amylose starch and the mixed fatty alcohol, continuously stirring uniformly, installing a condensation reflux pipe, slowly heating to 120 ℃ for glycosylation reaction, reacting for 180min, pumping vacuum by using a diaphragm pump until the residual pressure is less than 60mmHg, and placing nitrogen; taking 1ml of reaction system mixture every 30min in the reaction process, adding 1ml of Fehling reagent, heating in boiling water for 2min, and if only a small amount of brick red precipitate appears on a phase interface or an organic phase, considering that the reaction is at the end point; if a large amount of brick red precipitates appear, a large amount of unreacted high amylose corn starch exists in the system, and the reaction is continued to the end point.
S2, after the reaction is completed, cooling to 70 ℃, adjusting the pH to about 8 by adopting a 35% NaOH solution, filtering to remove the mixed acid immobilized catalyst and other solid byproducts, and obtaining the crude product of the alkyl glycoside with the polymerization degree of 1.6, wherein the appearance of the crude product of the alkyl glycoside is shown in figure 1, and the obtained crude product of the alkyl glycoside is light in color, and the measured residual alcohol content is 0.31%.
Example 2
A preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, weighing 32g of high amylose mung bean starch with 60% amylose content, adding the high amylose mung bean starch into a 500ml four-neck flask with a stirrer, a thermometer and a water diversion device, which is filled with 160g of mixed fatty alcohol consisting of lauryl alcohol and tetradecanol according to the mass ratio of 2:1, and stirring to uniformly disperse the high amylose mung bean starch; adding 2.9g of mixed acid immobilized catalyst (the mixing mass ratio of p-toluenesulfonic acid to citric acid is 1:5) into the mixed solution according to 1.5% of the total mass of the high amylose starch and the mixed fatty alcohol, continuously stirring uniformly, installing a condensation reflux pipe, slowly heating to 130 ℃ for glycosylation reaction, reacting for 120min, vacuumizing to 60mmHg, and placing nitrogen; detecting whether starch is completely hydrolyzed by using a KI-I reagent in the reaction process, taking 1ml of reaction system mixture every 30min, adding 1ml of Fehling reagent, heating in boiling water for 2min, and considering that the reaction is at the end point if only a small amount of brick red precipitate appears on a phase interface or an organic phase; if a large amount of brick red precipitates appear, a large amount of unreacted high amylose corn starch exists in the system, and the reaction is continued to the end point.
S2, after the reaction is completed, cooling to 80 ℃, adjusting the pH to about 8 by adopting a NaOH solution with the mass concentration of 30%, filtering to remove the mixed acid supported catalyst and other solid byproducts, and obtaining the alkyl glycoside crude product with the polymerization degree of 1.4, wherein the appearance of the crude product is shown in figure 2, and the obtained alkyl glycoside crude product is light in color, and the measured residual alcohol content is 0.34%.
Example 3
A preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, weighing 32g of high amylose wheat starch with 50% amylose content, adding the high amylose wheat starch into a 500ml four-neck flask with a stirrer, a thermometer and a water diversion device, which is filled with 160g of mixed fatty alcohol consisting of lauryl alcohol and tetradecanol according to the mass ratio of 2:1, and stirring to uniformly disperse the high amylose wheat starch; adding 2g of mixed acid immobilized catalyst (the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:5) into the mixed solution, continuously stirring uniformly, installing a condensing reflux pipe, slowly heating to 120 ℃ for glycosylation reaction, reacting for 180min, vacuumizing to residual pressure of 30mmHg, and placing nitrogen; when the mixture changed from white milky to translucent paste, the reaction was checked with a kit until the residual starch content was 0.21%.
S2, after the reaction is completed, cooling to 70 ℃, adjusting the pH to 7.5 by using a NaOH solution with the mass concentration of 40%, filtering to remove the mixed acid supported catalyst and other solid byproducts, and obtaining the crude product of the alkyl glycoside with the polymerization degree of 1.3, wherein the appearance of the crude product of the alkyl glycoside is shown in figure 3, and the obtained crude product of the alkyl glycoside has light color, and the measured residual alcohol content is 0.35%.
Example 4
A preparation method of novel green surfactant alkyl glycoside comprises the following steps:
s1, weighing 200kg of high amylose tapioca starch with amylose content of 50% and 830kg of mixed fatty alcohol consisting of lauryl alcohol and tetradecanol according to the mass ratio of 2:1 into a reaction kettle, and stirring to uniformly disperse the fatty alcohol; adding 3.9kg of mixed acid immobilized catalyst (the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:5) into a reaction kettle, continuously stirring uniformly, slowly heating to 125 ℃ for glycosylation reaction, vacuumizing to residual pressure of 30mmHg and nitrogen, wherein the reaction time is 3 h; the reaction is considered to be at the end point when the reaction solution becomes transparent.
S2, after the reaction is completed, cooling to 70 ℃, adjusting the pH to 7.5 by adopting a NaOH solution with the mass concentration of 45%, filtering to remove the mixed acid immobilized catalyst and the byproducts, and obtaining the crude product of the alkyl glycoside with the polymerization degree of 1.5, wherein the appearance of the crude product of the alkyl glycoside is shown in figure 4, and the obtained crude product of the alkyl glycoside is light in color, and the measured residual alcohol content is 0.32%.
Comparative example 1:
weighing 60.7g of high amylose corn starch (with amylose molecular content of 50 percent) and adding the high amylose corn starch into 139.3g of glycol, and uniformly stirring; then adding 1.6g of p-toluenesulfonic acid and 0.4g of phosphoric acid into the mixed solution, and uniformly stirring; heating the mixed solution to 105 ℃, stirring, and reacting for 60min to obtain a clear and transparent solution; keeping the temperature at 105 ℃, and finally adding 69.7g of dodecanol into the clear and transparent solution, and uniformly stirring; the mixed solution was maintained at 105 ℃ and reacted for 180 min. As shown in FIG. 5, the alkyl glycoside product obtained by the above steps has a residual alcohol content of 0.62% and a dark color.
Comparative example 2:
weighing 60.7g of high amylose corn starch (with amylose molecular content of 80 percent) and adding the high amylose corn starch into 139.3g of glycol, and uniformly stirring; then adding 1.6g of p-toluenesulfonic acid and 0.4g of phosphoric acid into the mixed solution, and uniformly stirring; heating the mixed solution to 120 ℃, stirring, and reacting for 60min to obtain a clear and transparent solution; keeping the temperature at 120 ℃, and finally adding 48.7g of octanol into the clear and transparent solution, and uniformly stirring; the mixed solution is maintained at 120 ℃ and reacted for 180 min. The alkyl glycoside product obtained in the above procedure is shown in FIG. 6, and an almost colorless transparent liquid with a residual alcohol content of 0.66% was obtained.
Comparative example 3:
s1, adding 1128kg of fatty alcohol (C18-20) and 198kg of glucose into a reaction kettle, adding 4.5kg of acid catalyst, heating to 110-120 ℃, adjusting the vacuum pressure to 0.09MPa for acetalization reaction, reacting for 8-10 hours, adding potassium hydroxide after the reaction liquid is transparent to adjust the pH value to 6-7, and transferring the reaction liquid into a distillation kettle.
S2, carrying out secondary evaporation in a distillation kettle by using a thin film evaporator to remove excessive C18-20 alcohol, wherein the alkyl glycoside product obtained in the step is shown in figure 7, and the crude alkyl glycoside product with the polymerization degree of 1.4 and the C18-20 alcohol residual quantity of 0.87% is obtained.
As can be seen from FIGS. 1 to 7, the alkyl glycoside products prepared in examples 1 to 4 have light color and residual alcohol content of 0.31 to 0.35%, wherein FIG. 1 has the best color and the lowest residual alcohol content, and thus the product performance of example 1 is the best; the residual alcohol contents in comparative examples 1 to 3 were all high. The preparation method provided by the invention has the advantages that the reaction activity of glycosylation of fatty alcohol and high amylose starch is effectively improved, the process flow is simple, the glucoside conversion rate is high, the side reaction is less, the color is light, and additional decolorization is not needed.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of novel green surfactant alkyl glycoside is characterized in that: the method comprises the following steps:
s1, adding the high amylose starch into the mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid immobilized catalyst into the mixed solution, continuously stirring uniformly, slowly heating to raise the temperature, vacuumizing and placing nitrogen to perform glycosylation reaction;
and S2, cooling to 70-80 ℃ after the reaction is completed, adjusting the pH, and filtering to remove the mixed acid immobilized catalyst and the by-product to obtain the crude product of the alkyl glycoside.
2. The method for producing a novel alkyl glycoside, which is a green surfactant, according to claim 1, wherein: the mass ratio of the high amylose starch to the mixed fatty alcohol is 1: 3-5.
3. The method for producing a novel alkyl glycoside, which is a green surfactant, according to claim 1, wherein: the mixed acid immobilized catalyst is prepared by loading p-toluenesulfonic acid and citric acid on active alumina; the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1: 3-1: 8.
4. The method for producing a novel alkyl glycoside, a green surfactant, according to claim 3, characterized in that: the preparation method of the mixed acid supported catalyst comprises the following steps: roasting activated alumina at 350-450 ℃ for 4-6h, washing with water for 2-3 times, and drying at 100-120 ℃ for 2-4 h; adding the treated activated alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until the water is evaporated to dryness, drying at 125-145 ℃ to constant weight, and calculating the load capacity to obtain the activated alumina carrier.
5. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: the addition amount of the mixed acid immobilized catalyst is 0.2-3% of the total mass of the high amylose starch and the mixed fatty alcohol.
6. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: the mixed fatty alcohol is a mixture formed by mixing dodecanol and tetradecanol according to the mass ratio of 2:1-4: 1.
7. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: the content of amylose in the high amylose starch is more than or equal to 50 percent.
8. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: the high amylose starch is one of corn starch, wheat starch, tapioca starch, potato starch or mung bean starch.
9. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: the reaction temperature of the glycosylation reaction in the step S1 is 90-140 ℃, and the reaction time is 130-210 min.
10. The method for producing a novel green surfactant alkyl glycoside according to any one of claims 1 to 3, wherein: in the step S2, a NaOH solution or a KOH solution with the mass concentration of 30-50% is adopted to adjust the pH value of the mixed solution to be more than 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210310105.1A CN114685570B (en) | 2022-03-28 | 2022-03-28 | Preparation method of green surfactant alkyl glycoside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210310105.1A CN114685570B (en) | 2022-03-28 | 2022-03-28 | Preparation method of green surfactant alkyl glycoside |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114685570A true CN114685570A (en) | 2022-07-01 |
| CN114685570B CN114685570B (en) | 2024-04-02 |
Family
ID=82141784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210310105.1A Active CN114685570B (en) | 2022-03-28 | 2022-03-28 | Preparation method of green surfactant alkyl glycoside |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685570B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794873A (en) * | 2020-12-04 | 2021-05-14 | 华南理工大学 | Sugar ester surfactant and preparation method and application thereof |
| CN115745468A (en) * | 2023-01-06 | 2023-03-07 | 石家庄市长安育才建材有限公司 | Starch-based slump retaining water reducer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058592A (en) * | 2006-04-21 | 2007-10-24 | 蒋和国 | Method of preparing alkyl glycoside from sweet potato starch |
| CN103613620A (en) * | 2013-11-13 | 2014-03-05 | 广州大学 | Method for preparing dodecyl polyglucoside from tapioca starch |
| CN105254686A (en) * | 2015-12-01 | 2016-01-20 | 天津工业大学 | Preparation method of alkyl glycoside |
| CN108358980A (en) * | 2018-01-30 | 2018-08-03 | 广州大学 | A kind of preparation process exempting from decoloration alkyl glycosides |
| CN113512078A (en) * | 2021-07-19 | 2021-10-19 | 上海发凯化工有限公司 | Method for directly preparing alkyl glycoside surfactant by cellulose one-pot method |
-
2022
- 2022-03-28 CN CN202210310105.1A patent/CN114685570B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058592A (en) * | 2006-04-21 | 2007-10-24 | 蒋和国 | Method of preparing alkyl glycoside from sweet potato starch |
| CN103613620A (en) * | 2013-11-13 | 2014-03-05 | 广州大学 | Method for preparing dodecyl polyglucoside from tapioca starch |
| CN105254686A (en) * | 2015-12-01 | 2016-01-20 | 天津工业大学 | Preparation method of alkyl glycoside |
| CN108358980A (en) * | 2018-01-30 | 2018-08-03 | 广州大学 | A kind of preparation process exempting from decoloration alkyl glycosides |
| CN113512078A (en) * | 2021-07-19 | 2021-10-19 | 上海发凯化工有限公司 | Method for directly preparing alkyl glycoside surfactant by cellulose one-pot method |
Non-Patent Citations (1)
| Title |
|---|
| 杨春光，等: "制备浅色烷基糖苷的研究", 《日用化学品科学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794873A (en) * | 2020-12-04 | 2021-05-14 | 华南理工大学 | Sugar ester surfactant and preparation method and application thereof |
| CN112794873B (en) * | 2020-12-04 | 2023-08-22 | 华南理工大学 | Sugar ester surfactant and preparation method and application thereof |
| CN115745468A (en) * | 2023-01-06 | 2023-03-07 | 石家庄市长安育才建材有限公司 | Starch-based slump retaining water reducer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114685570B (en) | 2024-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114685570B (en) | Preparation method of green surfactant alkyl glycoside | |
| US4011389A (en) | Glycoside polyethers | |
| CN101696226B (en) | Synthetic method for preparing colorless transparent alkyl polyglucoside | |
| CN108358980B (en) | Preparation process of decolorization-free alkyl glycoside | |
| US5166337A (en) | Process for the preparation of carbohydrate surfactants | |
| JP3139686B2 (en) | Process for producing alkyl glycoside and alkyl polyglycoside | |
| CN101058592A (en) | Method of preparing alkyl glycoside from sweet potato starch | |
| CN113512078B (en) | Method for directly preparing alkyl glycoside surfactant by cellulose one-pot method | |
| JPH07505403A (en) | Method for producing alkyl glycosides | |
| JP3388739B2 (en) | Preparation of pale alkyl oligoglycoside paste | |
| JPH04264094A (en) | Preparation of alkylglycoside and alkyloligoglycoside | |
| FI83964C (en) | FOERFARANDE FOER FRAMSTAELLNING AV EN FAERGSTABIL GLUKOSIDBLANDNING AV INDUSTRIELL KVALITET INNEHAOLLANDE METYLGLUKOSID. | |
| JP3939094B2 (en) | Method for producing colorless and transparent alkyl glycoside | |
| JP2001515469A (en) | Method for producing alkyl polyglycoside | |
| CA2007514A1 (en) | Process for the production of alkyl glucosides | |
| CN101168761B (en) | Method for synthesizing alkyl polyglycoside catalyzed by amylase | |
| CA2157545A1 (en) | Process for preparing alkyl polyglycosides | |
| CN114437149A (en) | Preparation method of key intermediate calcium salt of pharmaceutic adjuvant salt | |
| CN111620916A (en) | Synthesis method of alkyl amino glucoside | |
| US5955587A (en) | Process for preparing alkyl oligoglucosides with a high degree of oligomerization | |
| CN112778135B (en) | Preparation method of polyglycerol ricinoleate | |
| KR20030093012A (en) | Method for preparing sorbitan fatty acid ester | |
| JPH05155895A (en) | Preparation of light-colored alkyl polyglycoside | |
| CN107868134A (en) | The preparation method of starch from sweet potato APG | |
| US20230167147A1 (en) | Method of producing aliphatic glycoside compound or sugar fatty acid ester compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |