CN106519063A - Preparation method of methyl alginate with high degree of esterification - Google Patents
Preparation method of methyl alginate with high degree of esterification Download PDFInfo
- Publication number
- CN106519063A CN106519063A CN201610871104.9A CN201610871104A CN106519063A CN 106519063 A CN106519063 A CN 106519063A CN 201610871104 A CN201610871104 A CN 201610871104A CN 106519063 A CN106519063 A CN 106519063A
- Authority
- CN
- China
- Prior art keywords
- alginic acid
- esterification
- methyl ester
- preparation
- alginate
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of methyl alginate with high degree of esterification; the preparation method comprises the following steps: in anhydrous methanol, adding alginic acid, starting stirring, adding a dehydrating agent having equal moles to the water content of alginic acid, adding a catalyst, and stirring and heating to reflux; after a reflux temperature is reached, starting to drip the remaining dehydrating agent, and after uniform dripping is completed within 2-4 h, continuing to carry out a reflux reaction for 6-20 h; and finishing the reaction, cooling to room temperature, then adjusting the pH to 6.5-7.0 with an alkali liquor, filtering, washing the filter cake with a methanol aqueous solution with the mass concentration more than 60%, and drying at the temperature of 40 DEG C, to obtain the methyl alginate. With adopting of the preparation method of methyl alginate, the degree of esterification of the prepared methyl alginate is more than 70%, and is obviously more than that of straight-chain alkyl alcohol alginate prepared by the prior art.
Description
Technical field
The present invention relates to a kind of preparation method of alginic acid ester, more particularly to a kind of system of high esterification degree alginic acid methyl ester
Preparation Method.
Background technology
Alginic acid is mainly derived from Brown algae plant and antibacterial, and molecular formula is (C6H7O6Na)n, relative molecular weight is in 32000-
Between 200000, molecule is passed through by beta-D-mannuronic acid and α-L- guluronic acids（1→4）Glycosidic bond links are formed, and are one
Plant linear polyanion water soluble carbohydrates.Alginic acid is white or pale yellow powder insoluble in methanol, ethanol, DMF etc.
Organic solvent.Degradation reaction can all occur under acid, alkalescence and hot conditionss, cause the quick reduction of molecular weight.Therefore exist
Should be placed in the environment of low temperature, drying, ventilation, lucifuge during storage.
The higher alginic acid derivative of degree of commercialization mainly includes sodium alginate and polyetylene glycol alginate at present.As
A kind of biodegradable fully natural green macromolecular material, and there is nontoxic, tasteless, gelation, stability, thickening property, breast
The features such as property changed, suspension and film property, the neck such as food, medicine, weaving, agricultural and wastewater treatment is widely used at present
Domain.
Though alginic acid has certain swellability insoluble in organic solvents such as alcohol, oxirane and expoxy propane to which,
Because intramolecular contains carboxyl, therefore in the presence of acid or base catalyst, can same alkylol, expoxy propane or oxirane etc.
Directly there is esterification and generate alginic acid ester in esterifying reagent.Expoxy propane and reacting ethylene oxide activity are higher, in Tong Hai
Alginic acid does not produce hydrone in there is esterification reaction process, is conducive to balancing response to carry out to positive direction, therefore esterification degree is higher,
For example, esterification is carried out using expoxy propane and alginic acid and prepares propylene glycol alginate（PGA）, esterification degree can reach more than 90%.
However, for the direct-connected alkanol of small molecule, as esterification can generate hydrone, and hydrone is had with small-molecule starting material alcohol
There are the compatibility or the compatibility higher, it is difficult to separated from one another, even if therefore adopting excessive alcohol to promote esterification to positive direction
Carry out, esterification is also difficult to obtain high esterification degree alginic acid ester, and esterification degree is typically smaller than 20%.Such as Broderick
Eilish etc.（Broderick E, Lyons H, Pembroke T, et al. The characterization of a
novel, covalently modified, amphiphilic alginate derivative, which retains
gelling and non-toxic properties[J]. Journal of colloid and interface
science, 2006, 298(1): 154-161.）Sulfur acid as catalyst is used, it is anti-with excessive butanol direct esterification using alginic acid
Sargassum acid butyl ester should be prepared, when esterification reaches balance, esterification degree is less than 20%；For long chain alkanol, due to Sargassum
The compatibility of acid is poor, and reactivity is relatively low, even if therefore being easy to the hydrone separation that same esterification is generated, esterification journey
Degree is relatively low.For the preparation of alginic acid long-chain alcohol ester, generally reacted using Ugi at present（Ugi I. The α‐
Addition of Immonium Ions and Anions to Isonitriles Accompanied by Secondary
Reactions[J]. Angewandte Chemie International Edition in English, 1962, 1(1):
8-21）To prepare, but the esterification degree of the alginic acid ester prepared by the method is also usually less than 20%.Document report is had at present just,
Directly carry out esterification to prepare alginic acid ester using alginic acid and linear alcohols, esterification degree is usually less than 50%.
Trimethyl orthoformate, also known as trimethoxy-methane, are a kind of colourless liquids, inflammable, can be dissolved in methanol, ethanol, second
A kind of important organic synthesis intermediate of the organic solvents such as ether, for the synthesis of various medicine, dyestuff and spice etc..Orthoformic acid
Trimethyl is met water and is decomposed, and generating methanol and methyl formate, therefore can be used as dehydrant in the preparation process of alginic acid ester makes
With.
It is an object of the invention to provide a kind of high esterification degree alginic acid methyl ester and preparation method thereof, is that raw material is easy to get, can
Biodegradable fully natural green macromolecule polysaccharide alginic acid opens up new space.
Compared with existing linear alcohols alginic acid ester technology of preparing, the esterification degree of alginic acid methyl ester prepared by the present invention is reachable
To more than 70%.
The content of the invention
A kind of preparation method of high esterification degree alginic acid methyl ester, it is characterised in that implement as follows：In absolute methanol
In, alginic acid is added, stirring is started, is added and the equimolar dehydrant of alginic acid water content, add catalyst, stirring to be warming up to
Backflow, after reaching reflux temperature, starts Deca residue dehydrant, in 2-4 hours after uniform completion of dropping, continues back flow reaction
6 ~ 20 hours, terminate reaction, after being cooled to room temperature, with lye pH adjustment=6.5 ~ 7.0, filtration, filter cake mass concentration are higher than 60%
Methanol aqueous solution washing, and at 40 DEG C be dried, obtain alginic acid methyl ester；Alginic acid consumption described above and methanol usage
Mass ratio is 1:2~6；Dehydrant described above is trimethyl orthoformate；Deca residue dehydrant described above, is Deca
Remaining trimethyl orthoformate, its dripping quantity are 1 with the mol ratio of alginic acid consumption:0.5-1；Catalyst described above is quality
Concentration is 98% concentrated sulphuric acid, or p-methyl benzenesulfonic acid, mass percent 0.2-3% of its consumption for alginic acid consumption；It is described above
Alkali liquor be sodium carbonate liquor, or sodium hydroxide solution.
Using the preparation method of alginic acid methyl ester of the present invention, the esterification degree of prepared alginic acid methyl ester is higher than 70%, hence it is evident that
The esterification degree of the linear alcohols alginic acid ester prepared higher than prior art.The present invention is further illustrated below by instantiation.
Specific embodiment
Embodiment 1
In 500ml four-hole boiling flasks, 200g absolute methanols, the alginic acid 50g for adding water content to be 6% is added to stir, room
Temperature is lower to add 0.4g concentrated sulphuric acids to make catalyst, is warming up to reflux temperature after stirring, and back flow reaction 12h, reaction terminate cooling
To room temperature, pH to 6.5 ~ 7.0 is adjusted with the aqueous sodium carbonate that mass concentration is 5%, filter, the first of filter cake mass concentration 65%
Alcohol-water solution washing, the drying under the conditions of 40 DEG C, are obtained alginic acid methyl ester sample.Test by GB GB25533-2010, Sargassum
The esterification degree of sour methyl ester is 55.29%；Rotating cylinder viscometer is adopted to distinguish test temperature for 25 DEG C, mass concentration is the sea of 3%, pH=7
Alginic acid and alginic acid methyl ester aqueous solution apparent viscosity, the apparent viscosity for obtaining sodium alginate soln are 156mPa.s；Alginic acid methyl ester
The apparent viscosity of solution is 50mPa.s.
Embodiment 2
In 500ml four-hole boiling flasks, 200g absolute methanols, the alginic acid 50g for adding water content to be 6% is added to stir, room temperature
Lower addition and the trimethyl orthoformate 17.67g of alginic acid water content equimolar amountss, add 0.4g concentrated sulphuric acids and make catalyst, stir
Reflux temperature is warming up to after mixing uniformly, trimethyl orthoformate 15.9g is uniformly added dropwise to again in 2 hours.Continue returning after adding
React 12 hours under stream mode, reaction end is cooled to room temperature, adjusts pH to 6.5 with the aqueous sodium carbonate that mass concentration is 5%
~ 7.0, filtration, the filter cake methanol aqueous solution of mass concentration 65% are washed, are dried under the conditions of 40 DEG C, and alginic acid methyl ester sample is obtained
Product.The esterification degree of Jing test alginic acid methyl ester is 72.21%.Temperature is 25 DEG C, and mass concentration is the alginic acid methyl ester of 3%, pH=7
Aqueous solution apparent viscosity is 71mPa.s.
Embodiment 3
With embodiment 1,0.4g concentrated sulfuric acid catalysts are changed to into 1.40g p-methyl benzenesulfonic acid simply and make catalyst.Obtain alginic acid methyl ester.
The esterification degree of Jing test alginic acid methyl ester is 58.29%.Temperature is 25 DEG C, and mass concentration is that the alginic acid methyl ester of 3%, pH=7 is water-soluble
Liquid apparent viscosity is 77mPa.s.
Embodiment 4
With embodiment 1,0.4g concentrated sulfuric acid catalysts are changed to into 0.6g concentrated sulfuric acid catalysts simply.Obtain alginic acid methyl ester.Jing is tested
The esterification degree of alginic acid methyl ester is 55.85%.Temperature is 25 DEG C, and mass concentration is that the alginic acid methyl ester aqueous solution of 3%, pH=7 is apparent
Viscosity is 48mPa.s.
Embodiment 5
With embodiment 2,0.4g concentrated sulfuric acid catalysts are changed to into 1.4g p-methyl benzenesulfonic acid simply and make catalyst.Obtain alginic acid methyl ester.
The esterification degree of Jing test alginic acid methyl ester is 74.23%.Temperature is 25 DEG C, and mass concentration is that the alginic acid methyl ester of 3%, pH=7 is water-soluble
Liquid apparent viscosity is 81mPa.s.
Embodiment 6
With embodiment 2, simply will be uniformly added dropwise in 2 hours again trimethyl orthoformate 15.9g be changed to it is uniform again in 2 hours
It is added dropwise to trimethyl orthoformate 21.2g.Obtain alginic acid methyl ester.The esterification degree of Jing test alginic acid methyl ester is 72.86%.Temperature is
25 DEG C, it is 74mPa.s that mass concentration is the alginic acid methyl ester aqueous solution apparent viscosity of 3%, pH=7.
Embodiment 7
With embodiment 2,0.4g concentrated sulfuric acid catalysts are changed to into 1.2g p-methyl benzenesulfonic acid simply and make catalyst.Obtain alginic acid methyl ester.
The esterification degree of Jing test alginic acid methyl ester is 72.89%.Temperature is 25 DEG C, and mass concentration is that the alginic acid methyl ester of 3%, pH=7 is water-soluble
Liquid apparent viscosity is 78mPa.s.
As can be seen from the above-described embodiment, under acid catalysiss, by the direct refuxing esterification reaction of alginic acid and methanol, preparation
The esterification degree of alginic acid methyl ester is below 60%, and under identical enzymatic synthesis condition, adds dehydrant trimethyl orthoformate, alginic acid
The esterification degree of methyl ester is improved significantly, and esterification degree is above more than 70%；Catalyst is done relatively using dense sulfur using p-methyl benzenesulfonic acid
Acid as catalyst, the esterification degree of alginic acid methyl ester are improved.The solution viscosity of the alginic acid methyl ester prepared by above-described embodiment
48mPa.s is all higher than, higher than commodity pectin solution viscosity（Low ester：37mPa.s；High ester：18mPa.s）, along with alginic acid first
Ester structure has similarity with the structure of propylene glycol alginate and pectin, therefore alginic acid methyl ester is expected to prepare in milk beverage
In journey, the expensive pectin of fictitious hosts is used.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, the art
Those of ordinary skill, the present invention essential scope in, change, addition or the replacement made, should all belong to the present invention guarantor
Shield scope.
Claims (1)
1. a kind of preparation method of high esterification degree alginic acid methyl ester, it is characterised in that implement as follows：In absolute methanol,
Alginic acid is added, stirring is started, is added and the equimolar dehydrant of alginic acid water content, add catalyst, stirring to be warming up to back
Stream, after reaching reflux temperature, starts Deca residue dehydrant, in the 2-4 hours after uniform completion of dropping, continue back flow reaction 6 ~
20 hours, terminate reaction, after being cooled to room temperature, with lye pH adjustment=6.5 ~ 7.0, filtration, filter cake mass concentration are higher than 60%
Methanol aqueous solution is washed, and is dried at 40 DEG C, obtains alginic acid methyl ester；The matter of alginic acid consumption described above and methanol usage
Amount is than being 1:2~6；Dehydrant described above is trimethyl orthoformate；Deca residue dehydrant described above, is that Deca is remained
Remaining trimethyl orthoformate, its dripping quantity are 1 with the mol ratio of alginic acid consumption:0.5-1；Catalyst described above is that quality is dense
Spend the concentrated sulphuric acid for 98%, or p-methyl benzenesulfonic acid, mass percent 0.2-3% of its consumption for alginic acid consumption；Described above
Alkali liquor is sodium carbonate liquor, or sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610871104.9A CN106519063B (en) | 2016-10-04 | 2016-10-04 | A kind of preparation method of high esterification degree alginic acid methyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610871104.9A CN106519063B (en) | 2016-10-04 | 2016-10-04 | A kind of preparation method of high esterification degree alginic acid methyl esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519063A true CN106519063A (en) | 2017-03-22 |
| CN106519063B CN106519063B (en) | 2019-01-04 |
Family
ID=58331203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610871104.9A Active CN106519063B (en) | 2016-10-04 | 2016-10-04 | A kind of preparation method of high esterification degree alginic acid methyl esters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519063B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539442A (en) * | 2022-04-02 | 2022-05-27 | 青岛海之林生物科技开发有限公司 | Fat-soluble ethyl alginate and preparation method and application thereof |
| CN116396324A (en) * | 2023-03-17 | 2023-07-07 | 南雄志一精细化工有限公司 | Preparation method of light-colored diphenyl phosphite |
-
2016
- 2016-10-04 CN CN201610871104.9A patent/CN106519063B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| DOZ. DR. IVAR UGI: "The α-Addition of Immonium Ions and Anions to Isonitriles Accompanied by Secondary Reactions", 《ANGEW. CHEM. INTERNAT. EDIT.》 * |
| EILISH BRODERICK等: "The characterisation of a novel, covalently modified, amphiphilic alginate derivative, which retains gelling and non-toxic properties", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539442A (en) * | 2022-04-02 | 2022-05-27 | 青岛海之林生物科技开发有限公司 | Fat-soluble ethyl alginate and preparation method and application thereof |
| CN116396324A (en) * | 2023-03-17 | 2023-07-07 | 南雄志一精细化工有限公司 | Preparation method of light-colored diphenyl phosphite |
| CN116396324B (en) * | 2023-03-17 | 2024-01-02 | 南雄志一精细化工有限公司 | Preparation method of light-colored diphenyl phosphite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519063B (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086379B (en) | The synthetic method of the clean intermediate of Da Gelie | |
| KR102549802B1 (en) | Method for producing alkyl cellulose | |
| CN101368074B (en) | Starch adhesive agent and preparation method thereof | |
| CN105413577B (en) | The viscoelastic solution that a kind of abietyl amino acid surfactant is constructed | |
| CN106519062B (en) | A kind of preparation method of high esterification degree seaweed acetoacetic ester | |
| CN107663241B (en) | Cross-linked starch with high resistant starch content and preparation method thereof | |
| MXPA01008023A (en) | Process for preparing alkylhydroxyalkyl cellulose. | |
| CN101768224B (en) | Preparation method of hydroxypropyl starch | |
| CN106519063A (en) | Preparation method of methyl alginate with high degree of esterification | |
| CN101548733A (en) | Preparation method for sodium carboxymethyl cellulose for foodstuff | |
| JP4150186B2 (en) | Method for producing hydroxyalkyl cellulose | |
| CN106519061B (en) | A kind of preparation method of high esterification degree seaweed isopropyl propionate | |
| KR102350759B1 (en) | Method for producing hydroxyalkyl alkyl cellulose | |
| CN106928152A (en) | A kind of preparation method of uracil | |
| KR20010052494A (en) | Method for manufacturing high-cationic starch solutions | |
| CN112646048A (en) | Hydrophobic benzyl modified guar gum thickener and preparation method and application thereof | |
| CN101891841B (en) | Novel method of alkylation for promoting high molecular weight chitosan by microwaves | |
| CN104193836B (en) | Production process for medicinal hydroxypropyl starch | |
| CN106608946B (en) | For drilling fluid tackifier copolymerization associated matter and preparation method thereof | |
| JPH01138201A (en) | Preparation of water-soluble quaternary nitrogen-containing cellulose ether derivative | |
| CN101942033B (en) | High-methoxyl content methyl starch as well as preparation method and application thereof | |
| CN106398236B (en) | A kind of technique of epoxidized linseed oil and citric acid composite elasticizer | |
| CN105566091B (en) | A kind of lead salicylate copper complex preparation method | |
| CN110483650A (en) | One triple composite modified starch of type egg white solution and preparation method thereof | |
| CN1390856A (en) | process for etherifying melon gum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |