CN117487037B - Method for preparing multiposition substituted carboxymethyl dextran and its product - Google Patents
Method for preparing multiposition substituted carboxymethyl dextran and its product Download PDFInfo
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- CN117487037B CN117487037B CN202311839664.2A CN202311839664A CN117487037B CN 117487037 B CN117487037 B CN 117487037B CN 202311839664 A CN202311839664 A CN 202311839664A CN 117487037 B CN117487037 B CN 117487037B
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- 229920002307 Dextran Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229920001503 Glucan Polymers 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000006467 substitution reaction Methods 0.000 claims abstract description 21
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 claims abstract description 3
- 230000003113 alkalizing effect Effects 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 9
- KUBWXQUHENSKGC-UHFFFAOYSA-N 2-chloroacetic acid;ethanol Chemical compound CCO.OC(=O)CCl KUBWXQUHENSKGC-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000047 product Chemical class 0.000 abstract description 15
- WQZGKKKJIJFFOK-UHFFFAOYSA-N hexopyranose Chemical compound OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000725 suspension Substances 0.000 description 12
- 239000008186 active pharmaceutical agent Substances 0.000 description 11
- 238000004061 bleaching Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000010561 standard procedure Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229920002498 Beta-glucan Polymers 0.000 description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 4
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
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- 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
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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- 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 relates to a preparation method of carboxymethyl dextran, in particular to a method for preparing multi-position substituted carboxymethyl dextran and a product thereof. The method comprises the following steps: dispersing beta- (1, 3) -D-glucan in ethanol, stirring and swelling at the temperature of 30-80 ℃, and adding alkali liquor for alkalizing; after alkalization, adopting a seed initiation mode, and dropwise adding chloroacetic acid solution into the solution to form a microenvironment; simultaneously dropwise adding alkali liquor and chloroacetic acid solution for reaction; then dripping alkali liquor for reaction; purifying and drying to obtain the final product. The method can prepare the carboxymethyl glucan with substitution positions of C-6, C-4 and C-2 and substitution degree of 0.6-1.
Description
Technical Field
The invention relates to a preparation method of carboxymethyl dextran, in particular to a method for preparing multi-position substituted carboxymethyl dextran and a product thereof.
Background
The carboxymethyl beta-glucan sodium is carboxymethyl derivative of beta-glucan, which is obtained by connecting a proper amount of carboxymethyl groups to partial sugar hydroxyl groups in beta-glucan through reaction so as to achieve the aim of improving the water solubility of the beta-glucan, and generally exists in a sodium salt form. At present, the production of carboxymethyl dextran is scaled, but the purity of the finished product prepared by the existing production process is lower, most of the finished product is substituted on the C-6 position, and the space structure is seriously damaged.
Researches show that the substitution degree DS is 0.75 when the carboxymethylation beta-1, 3-glucan has the highest activity, and the optimal DS is 0.6-0.8; when the degree of substitution DS is less than 0.5, the carboxymethylated beta-1, 3-glucan is insoluble or slightly soluble in water; when the degree of substitution DS is more than 1.0, the catalyst is inactive.
There is a need for a new process capable of preparing multiposition substituted carboxymethyl dextran.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing multi-site substituted carboxymethyl dextran and a product thereof. The method can prepare the carboxymethyl glucan with substitution positions of C-6, C-4 and C-2 and substitution degree of 0.6-1.
In order to achieve the above purpose, the invention adopts the following technical means:
the invention provides a method for preparing multi-site substituted carboxymethyl dextran, which comprises the following steps:
(1) Dispersing beta- (1, 3) -D-glucan in ethanol, stirring and swelling at the temperature of 30-80 ℃, and adding alkali liquor for alkalizing;
(2) After alkalization, adopting a seed initiation mode, and dropwise adding chloroacetic acid solution into the solution to form a microenvironment;
(3) Simultaneously dropwise adding alkali liquor and chloroacetic acid solution for reaction;
(4) Then dripping alkali liquor for reaction;
(5) Purifying and drying to obtain the final product.
Preferably, in the step (1), the mass ratio of the beta- (1, 3) -D-glucan to the ethanol is 1:3-1:10, and stirring and swelling are carried out at the temperature of 50-60 ℃.
Preferably, in the step (1), the mass ratio of alkali in the alkali liquor to beta- (1, 3) -D-glucan is 0.5-1.5:1, and the alkalization time is 1-5 h.
Preferably, in the step (3), the mass ratio of the alkali in the alkali liquor to the beta- (1, 3) -D-glucan is 1-10:1.
Preferably, the mass ratio of alkali in the alkali liquor to beta- (1, 3) -D-glucan in the step (4) is 0.1-5:1, and the reaction time is 1-5 h.
Preferably, in the step (2), the mass ratio of chloroacetic acid to beta- (1, 3) -D-glucan is 0.5-2:1, and the reaction is carried out for 1-5 hours.
Preferably, in the step (3), the mass ratio of chloroacetic acid to beta- (1, 3) -D-glucan is 1-10:1, and the dropwise adding time of the chloroacetic acid solution is 20-50 min.
Preferably, the purification in step (5) is carried out by the following steps: filtering the solution obtained after the reaction in the step (4), washing filter residues obtained after the filtering by ethanol, and adjusting the pH value to be neutral; repeating suction filtration and washing for at least two times; adding hydrogen peroxide into the ethanol washing liquid, and performing suction filtration and ethanol washing to obtain the product.
Preferably, the lye is sodium hydroxide or potassium hydroxide solution.
Preferably, the chloroacetic acid solution is chloroacetic acid ethanol solution.
Preferably, the hydrogen peroxide is used in an amount of 1-3% by mass of beta- (1, 3) -D-glucan, and the concentration of the hydrogen peroxide is 5-10% by weight.
Preferably, the conductivity of the multi-position substituted carboxymethyl dextran obtained after purification is less than or equal to 600us/cm.
The invention also provides the multi-position substituted carboxymethyl glucan prepared by the method, wherein the multi-position substituted carboxymethyl glucan is simultaneously substituted at the C-6 position, the C-4 position and the C-2 position.
Preferably, the substitution degree of the multi-site substituted carboxymethyl dextran is 0.6-1.0.
Compared with the prior art, the invention has the following technical advantages:
the invention provides a novel carboxymethyl dextran preparation method and a product prepared by the same.
The method is characterized in that the multi-position substituted carboxymethyl glucan is prepared through the steps of micro seed initiation, a two-section chloroacetic acid adding method, a three-section alkali liquor adding method and the like by technological improvement. The polysubstituted carboxymethyl dextran prepared by the method has substitution at not only the C-6 position but also the C-4 position and the C-2 position, the substitution degree can be controlled between 0.6 and 1, and the polysubstituted carboxymethyl dextran has higher activity.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the multi-site substituted carboxymethyl dextran prepared in example 2.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular forms also are intended to include the plural forms unless the context clearly indicates otherwise, and furthermore, it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) 120g of raw material beta- (1, 3) -D-glucan is added into ethanol according to the mass ratio of 1:5 to prepare suspension, and the suspension is stirred and swelled for 1h at the constant temperature of 51 ℃; 448g of 40% strength by weight NaOH solution are added dropwise with stirring and alkalified for 1h.
(2) 400g of an ethanol solution of chloroacetic acid with a concentration of 46wt% was added dropwise as a seed to initiate a reaction for 1h.
(3) Simultaneously, 700g of NaOH solution with the concentration of 40wt% and 1000g of ethanol solution with the concentration of 46wt% of chloroacetic acid are added dropwise for reaction for 2 hours, wherein the dropwise adding time of the chloroacetic acid solution is 20min.
(4) After the chloroacetic acid is added dropwise, 252g of 40wt% NaOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 6wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 2%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.65 according to the national standard method of GB 1886.232-2016.
Example 2
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) 120g of raw material beta- (1, 3) -D-glucan is added into ethanol according to the mass ratio of 1:5 to prepare suspension, and the suspension is stirred and swelled for 1h at the constant temperature of 53 ℃; 420g of 40wt% NaOH solution are added dropwise with stirring for alkalization for 1h.
(2) 300g of 46wt% chloroacetic acid ethanol solution was added dropwise as a seed to initiate a reaction for 1h.
(3) Simultaneously, 700g of NaOH solution with the concentration of 40wt% and 1100g of ethanol solution with the concentration of 46wt% of chloroacetic acid are added dropwise for reaction for 2 hours, wherein the dropwise addition time of the chloroacetic acid solution is 20min.
(4) After the chloroacetic acid is added dropwise, 280g of 40wt% NaOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 6wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 2%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.78 according to the national standard method of GB 1886.232-2016.
Example 3
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) 120g of raw material beta- (1, 3) -D-glucan is added into ethanol according to the mass ratio of 1:5 to prepare suspension, and the suspension is stirred and swelled for 1h at the constant temperature of 51 ℃; 390g of NaOH solution with a concentration of 40% by weight are added dropwise with stirring for alkalization for 1h.
(2) 400g of 46wt% chloroacetic acid ethanol solution was added dropwise as a seed to initiate a reaction for 1h.
(3) Simultaneously, 700g of 40wt% NaOH solution and 1000g of ethanol solution of 46wt% chloroacetic acid are added dropwise for reaction for 2 hours, wherein the dropwise addition time of the chloroacetic acid solution is 30min.
(4) After the chloroacetic acid is added dropwise, 300g of 40wt% NaOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 6wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 2%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.82 according to the national standard method of GB 1886.232-2016.
Example 4
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) 120g of raw material beta- (1, 3) -D-glucan is added into ethanol according to the mass ratio of 1:5 to prepare suspension, and the suspension is stirred and swelled for 1h at the constant temperature of 53 ℃; 450g of 40% strength by weight NaOH solution are added dropwise with stirring and alkalified for 1h.
(2) 300g of 46wt% chloroacetic acid ethanol solution was added dropwise as a seed to initiate a reaction for 1h.
(3) Simultaneously, 700g of NaOH solution with the concentration of 40wt% and 1100g of ethanol solution with the concentration of 46wt% of chloroacetic acid are added dropwise for reaction for 2 hours, wherein the dropwise adding time of the chloroacetic acid solution is 40min.
(4) After the chloroacetic acid is added dropwise, 252g of 40wt% NaOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 6wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 2%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The detection is carried out according to the national standard method of GB1886.232-2016, and the substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.9.
Example 5
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) 120g of raw material beta- (1, 3) -D-glucan is added into ethanol according to the mass ratio of 1:5 to prepare suspension, and the suspension is stirred and swelled for 1h at the constant temperature of 55 ℃; 420g of 40wt% KOH solution are added dropwise with stirring and alkalified for 1h.
(2) 300g of 46wt% chloroacetic acid ethanol solution was added dropwise as a seed to initiate a reaction for 1h.
(3) Simultaneously, 700g of 40wt% KOH solution and 1000g of ethanol solution of 46wt% chloroacetic acid are added dropwise for reaction for 2 hours, wherein the dropwise addition time of the chloroacetic acid solution is 50min.
(4) 280g of 40wt% KOH solution was added after the chloroacetic acid dropwise addition was completed, and the reaction was continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 6wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 2%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.94 according to the national standard method of GB 1886.232-2016.
Example 6
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) Adding 100g of raw material beta- (1, 3) -D-glucan into ethanol according to a mass ratio of 1:3 to prepare suspension, and stirring and swelling for 1h at a constant temperature of 60 ℃; 100g of 50% strength by weight KOH solution are added dropwise with stirring and alkalified for 1h.
(2) 200g of a 25wt% ethanol chloroacetate solution was added dropwise as a seed to initiate a reaction for 1h.
(3) 200g of 50wt% KOH solution and 400g of 25wt% chloroacetic acid in ethanol were simultaneously added dropwise and reacted for 2 hours, wherein the chloroacetic acid solution was added dropwise for 50 minutes.
(4) After the chloroacetic acid is added dropwise, 20g of 50wt% KOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding 5wt% concentration hydrogen peroxide for bleaching after ethanol is redispersed, wherein the mass ratio of the hydrogen peroxide to the dextran is 3%, and obtaining white-like carboxymethyl dextran; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
Example 7
A method of preparing a multi-position substituted carboxymethyl dextran, the method comprising the steps of:
(1) Adding 100g of raw material beta- (1, 3) -D-glucan into ethanol according to a mass ratio of 1:10 to prepare suspension, and stirring and swelling for 1h at a constant temperature of 80 ℃; 300g of 50% strength by weight KOH solution are added dropwise with stirring and alkalified for 5h.
(2) 800g of a 25wt% chloroacetic acid ethanol solution was added dropwise as a seed to initiate a reaction for 5 hours.
(3) 2000g of 50wt% KOH solution and 4000g of 25wt% chloroacetic acid in ethanol were simultaneously added dropwise and reacted for 2 hours, wherein the chloroacetic acid solution was added dropwise for 50 minutes.
(4) After the chloroacetic acid is added dropwise, 1000g of 50wt% KOH solution is added, and the reaction is continued for 3 hours.
(5) Dispersing the product obtained in the step (4) by suction filtration and then ethanol, adding hydrochloric acid/acetic acid to adjust the pH to be neutral, and performing suction filtration and ethanol washing for more than or equal to two times; stirring and adding hydrogen peroxide with the concentration of 10wt% for bleaching after redispersing the ethanol, wherein the mass ratio of the hydrogen peroxide to the glucan is 1%, so as to obtain white-like carboxymethyl glucan; suction filtering and ethanol washing are carried out for more than or equal to two times, so as to obtain purified multiposition substituted carboxymethyl dextran, wherein the conductivity of the multiposition substituted carboxymethyl dextran is less than or equal to 600us/cm; vacuum drying, pulverizing, and making into multi-substituted carboxymethyl dextran.
The detection is carried out according to the GB1886.232-2016 national standard method, and the substitution degree DS values of the multi-bit substituted carboxymethyl dextran obtained in the example 6 and the example 7 are all within the range of 0.6-1.0.
Comparative example 1
The process differs from example 5 in that the chloroacetic acid solution is fed for 8min, all other times as in example 5.
The substitution degree DS value of the obtained multiposition substituted carboxymethyl dextran is tested to be 0.45 according to the national standard method of GB 1886.232-2016.
The nuclear magnetic resonance of the multi-site substituted carboxymethyl dextran obtained in examples 1-7 was detected, the signal peak of carboxymethyl C=O was observed at 177.96ppm, the characteristic signal peak of the carbon spectrum resonance signal of the sugar rings C-1 to C-6 was also observed, the signal peak of C-6 was significantly shifted from 61.5ppm to 70.9ppm, more than C-6 was substituted, a new stronger carbon signal was present in the 60-110 ppm region, both the signal peaks of C-4 and C-2 were shifted, indicating that the dextran samples were more highly substituted at C-4 and C-2, and the molecular weights were medium and low, the shift of the substitutions at C-6, C-4, and C-2 was relatively large, indicating that the ratio of substitutions at C-6, C-4, and C-2 was relatively balanced, and about 1:1. Wherein, the nuclear magnetic spectrum of the multi-position substituted carboxymethyl dextran obtained in the example 2 is shown in figure 1.
The parts not described in the above modes can be realized by adopting or referring to the prior art. The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A method of preparing a multiposition substituted carboxymethyl dextran, said method comprising the steps of:
(1) Dispersing beta- (1, 3) -D-glucan in ethanol, stirring and swelling at the temperature of 30-80 ℃, and adding alkali liquor for alkalizing;
(2) After alkalization, adopting a seed initiation mode, and dropwise adding chloroacetic acid solution into the solution to form a microenvironment;
(3) Simultaneously dropwise adding alkali liquor and chloroacetic acid solution for reaction;
(4) Then dripping alkali liquor for reaction;
(5) Purifying and drying to obtain the product;
in the step (1), the mass ratio of the beta- (1, 3) -D-glucan to the ethanol is 1:3-1:10, and stirring and swelling are carried out at the temperature of 50-60 ℃; the mass ratio of alkali in the alkali liquor to the beta- (1, 3) -D-glucan is 0.5-1.5:1, and the alkalization time is 1-5 h;
in the step (3), the mass ratio of alkali in the alkali liquor to the beta- (1, 3) -D-glucan is 1-10:1;
in the step (4), the mass ratio of alkali in the alkali liquor to the beta- (1, 3) -D-glucan is 0.1-5:1, and the reaction time is 1-5 h;
in the step (2), the mass ratio of chloroacetic acid to beta- (1, 3) -D-glucan is 0.5-2:1, and the reaction is carried out for 1-5 h;
in the step (3), the mass ratio of chloroacetic acid to beta- (1, 3) -D-glucan is 1-10:1, and the dropwise adding time of the chloroacetic acid solution is 20-50 min;
the purification method in the step (5) comprises the following steps: filtering the solution obtained after the reaction in the step (4), washing filter residues obtained after the filtering by ethanol, and adjusting the pH value to be neutral; repeating suction filtration and washing for at least two times; adding hydrogen peroxide into the ethanol washing liquid, and performing suction filtration and ethanol washing to obtain the product.
2. The method of preparing a multiposition substituted carboxymethyl dextran according to claim 1, wherein the lye is sodium hydroxide or potassium hydroxide solution; the chloroacetic acid solution is chloroacetic acid ethanol solution.
3. The method for preparing multi-position substituted carboxymethyl dextran according to claim 1, wherein the hydrogen peroxide is used in an amount of 1-3% of the mass of beta- (1, 3) -D-dextran, and the concentration of the hydrogen peroxide used is 5-10 wt%.
4. The method of preparing a multi-position substituted carboxymethyl dextran according to claim 1, wherein the multi-position substituted carboxymethyl dextran has a conductivity of less than or equal to 600us/cm after purification.
5. The multi-position substituted carboxymethyl dextran prepared by the method of claim 1, wherein the C-6 position, the C-4 position and the C-2 position are simultaneously substituted.
6. The multi-position substituted carboxymethyl dextran according to claim 5, wherein the degree of substitution is 0.6 to 1.0.
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