CN1962700A - Nitrogenous polysaccharid derivative and its preparing process - Google Patents
Nitrogenous polysaccharid derivative and its preparing process Download PDFInfo
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Abstract
The invention discloses a nitrogen polysaccharide derivant and preparing method, which comprises the following structures: 2-3 kinds of sulfate group, phosphate group or carboxy group, 1-3 kind of carbamate group, thiocarbamate group, carbamido, ghiourea group or melamine group, wherein the polysaccharide is selected from starch, cellulose, hemicellulose, chitin, guar gum, chitose, xylan, glucomannan, barley beta-gluglucosan, beta-1, 3-gluglucosan, glycogen, cyclodextrin and normal random one polysaccharide through acidolyzing, oxidizing or crosslinking method.
Description
Technical field
The present invention relates to macromole high-efficiency adsorbent of a kind of nitrogenous polysaccharid derivative and preparation method thereof.
Background technology
Along with ballooning oil prices, the energy are deficient day by day, for the research of the renewable resources ever more important that seems.Natural glycan such as chitosan, starch in occupation of critical role, their wide material sources, is easy to modification in renewable resources.And utilize nitrogenous reagents such as cationic reagent, urea, acrylamide, and by solid state reaction glycan is carried out modification, can prepare nitrogenous polysaccharid derivative.The introducing of nitrogen element makes this kind polysaccharid derivative have special nature, be applied in a lot of fields, as be used as wet toughener, Surface Size, coating adhesive, waste water conditioner etc. in paper industry, textile industry is as the fiber sizing agent, be used as the treatment of dyeing wastewater agent in the printing and dyeing industry, metal etch industry is as heavy metal chelant, petroleum industry is used as the hydrate inhibitor of oil field fluid loss agent, emulsion splitter, clay and shale etc., sewage disposal and coal mining industries are as flocculation agent, and the flotation of ores aspect is used as ore dressing sinking agent etc.
Siemion utilizes carbamylhydrazine hydrochloride and starch through solid state reaction, obtains cationic starch, and product nitrogen content reaches 20.3% (Carbohydrate Polymers 62 (2005) 182-186).GB875542 adopts dialdehyde starch and urea reaction, obtains urea groups starch, and product can be used as tackiness agent.People such as Khalil utilize starch and single nitrogen hydroxymethyl urea, single nitrogen methylol thiocarbamide and single nitrogen melamine methylol, under magnesium chloride catalysis, obtain containing urea groups, thioureido or melamine-based starch derivative, product nitrogen content reaches (Carbohydrate Research 324 (2000) 189-199) more than 5%.Khalil (Carbohydrate Research 48 (2002) 255-261) and Heinze people such as (Starch/St rke 55 (2003) 55-60) also utilize starch, phosphoric acid, urea to synthesize phosphorylated amino starch formats ester for raw material, phosphate-based introducing has improved the water-soluble of treated starch.USP6703496,3539553,3843377 and JP62116602 also reported the preparation of phosphorylated amino starch formats ester.Persons such as Tu Mei are starting material with chitose, on its main chain, introduce carboxyl and two kinds of groups of sulfonic group and be prepared into the heparitin compound, product have good blood compatibility (Ji'nan University's journal, 1999,20 (5), 78-83).USP3484287, JP61174244, GB823073 utilize starch and thionamic acid, urea reaction, obtain urea starch.
Nitrogenous polysaccharid derivative is the important polysaccharid derivative of a class, the extensive concern that the exploitation of glycan biolobic material resource derivative and application are subjected to the various countries scholar, and at present not about 2～3 kinds in containing sulfuric ester, phosphoric acid ester or carboxyl in the polysaccharid derivative structure, also contain the research of carbamate, thiocarbamate or urea groups, relevant knowledge is preparation and the application about urea glycan, thiocarbamide glycan, phosphorylated amino formic acid glycan ester.
Therefore, the objective of the invention is to develop a kind of new nitrogenous polysaccharid derivative, promptly by solid state reaction except on the glycan molecular chain, introducing 2～3 kinds in sulfuric ester, phosphoric acid ester or the carboxyl, also introduce nitrogenous carbamate, thiocarbamate, urea groups, thioureido or melamine-based in 1～3 kind of group.Sulfuric ester, phosphoric acid ester or carboxylic acid group's introducing has increased the electronegativity of polysaccharid derivative, strengthened the adsorptive power of its absorption cationic charge such as metal ion, cationic dyestuff, and utilize carbamate, thiocarbamate, urea groups, thioureido or melamine-based introducing amino, can improve its sequestering power to metal ion, reduce the injury of heavy metal ion to human body, therefore nitrogenous polysaccharid derivative provided by the invention is a kind of high-efficiency adsorbent with universality owing to have anionic electronegativity concurrently and amino strong sequestering power.
Summary of the invention
The nitrogenous polysaccharid derivative of the present invention is phosphate cpd, sulfamic acid compound, anhydride compound and the nitrogenous compound modified product to glycan, and it has following general structure:
[A(B)
x(C)
y(D)
z(E)
m]
n (1)
(1) in the formula: A is the glycan unit, be selected from starch, Mierocrystalline cellulose, hemicellulose, chitin, melon glue, chitosan, xylan, konjac glucomanna, barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin and any with in the glycan of conventional acidolysis, oxidation or cross-linking method preparation thereof; B be nitrogenous carbamate groups, thiocarbamate base, urea groups, thioureido or melamine-based in 1～3 kind, be the reacted product of glycan polymer and nitrogenous compound, nitrogenous compound is selected from 1～3 kind in urea, thiocarbamide, single nitrogen hydroxymethyl urea, single nitrogen methylol thiocarbamide, single nitrogen melamine methylol, dinitrogen hydroxymethyl urea, dinitrogen methylol thiocarbamide or the dinitrogen melamine methylol; C is phosphate-based, be the reacted product of glycan polymer and phosphate cpd, phosphate cpd is selected from 1～3 kind in phosphoric acid, potassiumphosphate, ammonium phosphate, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, trisodium phosphate or the ammonium pyrophosphate; D is a sulfate group, is the reacted product of glycan polymer and sulfamic acid compound, and sulfamic acid compound is selected from 1～3 kind in thionamic acid, Ammonium sulfamate, nitrogen base sodium sulfonate, thionamic acid potassium, thionamic acid magnesium or the thionamic acid calcium; E is a carboxylic acid ester groups, be the reacted product of glycan polymer and anhydride compound, anhydride compound is selected from 1～3 kind in Succinic anhydried, Pyroglutaric acid, quinolinic anhydride, maleic anhydride, Tetra hydro Phthalic anhydride, 4-bromobenzene acid anhydride, tetrachlorophthalic anhydride, PHT4, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic dianhydride; X, y, z, m are substitution value, 0＜x＜3,0≤y＜3,0≤z＜3,0≤m＜3,0＜x+y+z+m≤3 wherein, any two among y, z, the m can not be zero simultaneously; N is sugared cyclopolymerization degree, is 10～1000000 integer.
Preparation method: will all account for 2～3 kinds in the thionamic acid of glycan dry weight 2～50% or its salt, phosphoric acid or its salt, the acid anhydrides and 1～40% the water that accounts for the nitrogenous compound of glycan dry weight 2～50% and account for the glycan dry weight mixes, to the glycan that wherein adds glycan or acidolysis routinely, oxidation, cross-linking method preparation, restir mixes then; The reactant transfer that mixes is arrived solid phase reactor, react 0.1～10hr down at 100～200 ℃; Reaction finishes, with obtaining nitrogenous glycan or acidolysis, oxidation, crosslinked polysaccharid derivative product after anhydrous methanol or deionized water wash, drying, the pulverizing.
Characteristics of the present invention are to have developed a kind of new nitrogenous polysaccharid derivative, 2～3 kinds in its structure in containing sulfuric ester, phosphoric acid ester or carboxyl, also contain carbamate, thiocarbamate, urea groups, thioureido or melamine-based in 1～3 kind of group.Owing to have anionic electronegativity and amino strong sequestering power concurrently, be a kind of high-efficiency adsorbent with universality, and product low toxicity even nontoxic, biodegradable, help environment protection.
Embodiment
Embodiment 1
100g chitosan, 50～250mL water, 0.5～5g sodium-chlor, 1～20937% formalin, 2～20mL epoxy chloropropane are added and have in the churned mechanically there-necked flask, be warmed up to 20～60 ℃, reaction 1～5hr utilizes 10% potassium hydroxide solution to keep the pH value of system between 7～12 in the reaction process.React finish after-filtration, washing, drying, obtain the water-insoluble cross-linked chitosan.Above-mentioned cross-linked chitosan 20g, urea 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, water 0.1～2g are mixed, place vacuum drying oven, react 1～6hr down at 100～200 ℃.Reaction finishes, and the deionized water repetitive scrubbing obtains water-insoluble amido-containing acid ester base, sulfate group, phosphate-based chitosan absorbent after the drying.
Embodiment 2
100g starch, 50～250mL water, 0.5～5g sodium-chlor, 1～20g, 37% formalin, 2～20mL epoxy chloropropane are added and have in the churned mechanically there-necked flask, be warmed up to 20～60 ℃, reaction 1～5hr.Utilize 10% potassium hydroxide solution to keep the pH value of system between 7～12 in the reaction process.React finish after-filtration, washing, drying, obtain the water-insoluble cross-linking starch.Above-mentioned cross-linking starch 20g, urea 2～10g, thionamic acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the deionized water repetitive scrubbing obtains the starch sorbent material of water-insoluble amido-containing acid ester base, sulfate group, carboxyl after the drying.
Embodiment 3
100g chitin, 50～250mL water, 0.5～5g sodium-chlor, 1～20937% formalin, 2～20mL epoxy chloropropane are added and have in the churned mechanically there-necked flask, be warmed up to 20～60 ℃, reaction 1～5hr.Utilize 10% potassium hydroxide solution to keep the pH value of system between 7～12 in the reaction process.React finish after-filtration, washing, drying, obtain the water-insoluble cross-linking starch.Above-mentioned cross-linking starch 20g, urea 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the deionized water repetitive scrubbing obtains the chitin sorbent material of water-insoluble amido-containing acid ester base, sulfate group, phosphate-based and carboxyl after the drying.
Embodiment 4～12
Method is with embodiment 3, promptly utilize Mierocrystalline cellulose, hemicellulose, melon glue, xylan, konjac glucomanna, the barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin replaces chitin, with the formaldehyde among the embodiment 3, epichlorohydrin reaction, obtain crosslinked Mierocrystalline cellulose, hemicellulose, melon glue, xylan, konjac glucomanna, the barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin, then with urea, thionamic acid, phosphoric acid, phthalic anhydride obtains water-insoluble amido-containing acid ester base, sulfate group, the polysaccharid derivative of phosphate-based and carboxyl.
Embodiment 13～18
Method is with embodiment 1, promptly utilize wantonly 1～3 kind in potassiumphosphate, ammonium phosphate, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, trisodium phosphate or the ammonium pyrophosphate to replace phosphoric acid, with cross-linked chitosan among the embodiment 1, urea, thionamic acid reaction, obtain water-insoluble amido-containing acid ester base, sulfate group, phosphate-based cross-linked chitosan derivative.
Embodiment 19～20
Method is with embodiment 2, promptly utilize 1～3 kind in Ammonium sulfamate, thionamic acid sodium, thionamic acid potassium, thionamic acid magnesium or the thionamic acid calcium to replace thionamic acid, with cross-linking starch, urea, the phthalic anhydride among the embodiment 2, obtain the cross-linking starch derivative of water-insoluble amido-containing acid ester base, sulfate group, carboxyl.
Embodiment 21
Synthetic cross-linking starch 20g, thiocarbamide 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g among the embodiment 2 are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and filters, the deionized water repetitive scrubbing, obtains the water-insoluble starch derivative that contains sulfo-carbamate groups, sulfate group, phosphate-based, carboxyl after the drying.
Embodiment 22～32
Method is with embodiment 21, promptly utilize crosslinked chitosan, Mierocrystalline cellulose, hemicellulose, chitin, melon glue, xylan, konjac glucomanna, barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin replace cross-linking starch, with thiocarbamide, thionamic acid, phosphoric acid, the phthalic anhydride among the embodiment 21, obtain the water-insoluble polysaccharid derivative that contains sulfo-carbamate groups, sulfate group, phosphate-based, carboxyl.
Embodiment 33
Cross-linking starch 20g, single nitrogen hydroxymethyl urea 2～10g, thionamic acid 2～10g, ammonium phosphate 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g among the embodiment 2 are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the deionized water repetitive scrubbing obtains the water-insoluble starch derivative that contains urea groups, sulfate group, phosphate-based, carboxylic acid ester groups.
Embodiment 34～38
Method is with embodiment 33, utilize the single nitrogen hydroxymethyl urea among single nitrogen methylol thiocarbamide, single nitrogen melamine methylol, dinitrogen hydroxymethyl urea, dinitrogen methylol thiocarbamide or the dinitrogen melamine methylol replacement embodiment 33, with cross-linking starch, thionamic acid, phosphoric acid, the phthalic anhydride among the embodiment 33, obtain the water-insoluble starch derivative that contains urea groups or melamine-based, sulfate group, phosphate-based, carboxyl.
Embodiment 39～41
Method is with embodiment 33, utilize 1～3 kind of Tetra hydro Phthalic anhydride that replaces among the embodiment 33 in Succinic anhydried, Pyroglutaric acid, quinolinic anhydride, maleic anhydride, 4-bromobenzene acid anhydride, tetrachlorophthalic anhydride, PHT4, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic dianhydride, with the cross-linking starch among the embodiment 33, single nitrogen hydroxymethyl urea, thionamic acid, phosphatase reaction, obtain the water-insoluble starch derivative that contains urea groups, sulfate group, phosphate-based, carboxyl.
Embodiment 42
Chitosan 20g, urea 2～10g, thionamic acid 2～10g, phosphoric acid 2～10, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and obtains water miscible amido-containing acid ester base, sulfate group, phosphate-based chitosan derivatives after utilizing methyl alcohol repetitive scrubbing, drying.
Embodiment 43
Starch 20g, urea 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and obtains water miscible amido-containing acid ester base, phosphate-based, carboxyl starch derivative after utilizing methyl alcohol repetitive scrubbing, drying.
Embodiment 44
Chitin 20g, urea 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and utilizes the chitin derivativ that obtains water miscible amido-containing acid ester base, sulfate group, phosphate-based, carboxyl after methyl alcohol repetitive scrubbing, the drying.
Embodiment 45～51
Method is with embodiment 44, promptly utilize melon glue, xylan, konjac glucomanna, barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin replace chitin, with urea, thionamic acid, phosphoric acid, the phthalic anhydride among the embodiment 44, obtain the polysaccharid derivative of water miscible amido-containing acid ester base, sulfate group, phosphate-based, carboxyl.
Embodiment 52
Starch 20g, thiocarbamide 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the methyl alcohol repetitive scrubbing obtains the water miscible starch derivative that contains sulfo-carbamate groups, sulfate group, phosphate-based, carboxyl after the drying.
Embodiment 53～61
Method is with embodiment 52, promptly utilize chitosan, chitin, melon glue, xylan, konjac glucomanna, barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin replace starch, with thiocarbamide, thionamic acid, phosphoric acid, the phthalic anhydride among the embodiment 52, obtain the water miscible polysaccharid derivative that contains sulfo-carbamate groups, sulfate group, phosphate-based, carboxyl.
Embodiment 62
Starch 20g, single nitrogen hydroxymethyl urea 2～10g, thionamic acid 2～10g, ammonium phosphate 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum to react 1～6hr down at 100～200 ℃ in dry case.Reaction finishes, and the methyl alcohol repetitive scrubbing obtains the water miscible starch derivative that contains urea groups, sulfate group, phosphate-based, carboxyl.
Embodiment 63～67
Method is with embodiment 62, utilize the single nitrogen hydroxymethyl urea among single nitrogen methylol thiocarbamide, single nitrogen melamine methylol, dinitrogen hydroxymethyl urea, dinitrogen methylol thiocarbamide or the dinitrogen melamine methylol replacement embodiment 62, with starch, thionamic acid, phosphoric acid, the phthalic anhydride among the embodiment 62, obtain the water miscible starch derivative that contains urea groups or melamine-based, sulfate group, phosphate-based, carboxyl.
Embodiment 68
10～100g starch, 100～1000ml water, 1～10% concentrated hydrochloric acid (based on the starch butt) are added in the there-necked flask, and normal temperature is warmed up to 20～100 ℃ after stirring 2～20min down, reaction 0.5～6hr.After reaction finishes methanol wash, drying are separated out, utilized to reaction solution in methyl alcohol, get hydrolyzed starch.Hydrolyzed starch 20g, urea 2～10g, thionamic acid 2～10g, ammonium phosphate 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the methyl alcohol repetitive scrubbing obtains the hydrolyzed starch derivative of water miscible amido-containing acid ester base, sulfate group, phosphate-based, carboxyl.
Embodiment 69
10～100g chitosan, 100～1000ml water, 1～10% concentrated hydrochloric acid (based on the chitosan butt) are added in the there-necked flask, and normal temperature is warmed up to 20～100 ℃ after stirring 2～20min down, reaction 0.5～6hr.After reaction finishes methanol wash, drying are separated out, utilized to reaction solution in methyl alcohol, get hydrolyzing chitosan.Hydrolyzing chitosan 20g, urea 2～10g, thionamic acid 2～10g, ammonium phosphate 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the methyl alcohol repetitive scrubbing obtains the hydrolyzing chitosan derivative of water miscible amido-containing acid ester base, sulfate group, phosphate-based, carboxyl
Embodiment 70
10～100g starch, 100～1000ml water, 1～10% clorox (based on the starch butt) are added in the there-necked flask, and normal temperature is warmed up to 20～100 ℃ after stirring 2～20min down, reaction 0.5～6hr.After reaction finishes methanol wash, drying are separated out, utilized to reaction solution in methyl alcohol, get Sumstar 190.Sumstar 190 20g, urea 2～10g, thionamic acid 2～10g, phosphoric acid 2～10g, Tetra hydro Phthalic anhydride 2～10g, water 0.1～2g are mixed, place vacuum drying oven to react 1～6hr down at 100～200 ℃.Reaction finishes, and the methyl alcohol repetitive scrubbing obtains the Sumstar 190 derivative of water miscible amido-containing acid ester base, sulfate group, phosphate-based, carboxyl.
Claims (2)
1, a kind of nitrogenous polysaccharid derivative, it is characterized in that in the nitrogenous polysaccharid derivative structure 2～3 kinds in containing sulfate group, phosphate-based or carboxyl, also contain carbamate groups, thiocarbamate base, urea groups, thioureido or melamine-based in any 1～3 kind, it has following general structure:
[A(B)
x(C)
y(D)
z(E)
m]
n (1)
(1) in the formula: A is the glycan unit, be selected from starch, Mierocrystalline cellulose, hemicellulose, chitin, melon glue, chitosan, xylan, konjac glucomanna, barley beta-glucan, β-1,3 dextran, glycogen, cyclodextrin and any with in the glycan of conventional acidolysis, oxidation or cross-linking method preparation thereof;
B be nitrogenous carbamate groups, thiocarbamate base, urea groups, thioureido or melamine-based in 1～3 kind, be the reacted product of glycan polymer and nitrogenous compound, nitrogenous compound is selected from 1～3 kind in urea, thiocarbamide, single nitrogen hydroxymethyl urea, single nitrogen methylol thiocarbamide, single nitrogen melamine methylol, dinitrogen hydroxymethyl urea, dinitrogen methylol thiocarbamide or the dinitrogen melamine methylol;
C is phosphate-based, be the reacted product of glycan polymer and phosphate cpd, phosphate cpd is selected from 1～3 kind in phosphoric acid, potassiumphosphate, ammonium phosphate, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, trisodium phosphate or the ammonium pyrophosphate;
D is a sulfate group, is the reacted product of glycan polymer and sulfamic acid compound, and sulfamic acid compound is selected from 1～3 kind in thionamic acid, Ammonium sulfamate, thionamic acid sodium, thionamic acid potassium, thionamic acid magnesium or the thionamic acid calcium;
E is a carboxylic acid ester groups, be the reacted product of glycan polymer and anhydride compound, anhydride compound is selected from 1～3 kind in Succinic anhydried, Pyroglutaric acid, quinolinic anhydride, maleic anhydride, Tetra hydro Phthalic anhydride, 4-bromobenzene acid anhydride, tetrachlorophthalic anhydride, PHT4, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic dianhydride;
X, y, z, m are substitution value, 0＜x＜3,0≤y＜3,0≤z＜3,0≤m＜3,0＜x+y+z+m≤3 wherein, any two among y, z, the m can not be zero simultaneously;
N is sugared cyclopolymerization degree, is 10～1000000 integer.
2, according to the preparation method of the described nitrogenous polysaccharid derivative of claim 1, it is characterized in that this method at first will all account for 2～3 kinds in the thionamic acid of glycan dry weight 2～50% or its salt, phosphoric acid or its salt, the acid anhydrides and 1～40% the water that accounts for the nitrogenous compound of glycan dry weight 2～50% and account for the glycan dry weight mixes, to the glycan that wherein adds glycan or acidolysis routinely, oxidation, cross-linking method preparation, restir mixes then; The reactant transfer that mixes is arrived solid phase reactor, react 0.1～10hr down at 100～200 ℃; Reaction finishes, with obtaining nitrogenous glycan or acidolysis, oxidation, crosslinked polysaccharid derivative product after anhydrous methanol or deionized water wash, drying, the pulverizing.
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| CN100509861C (en) * | 2007-07-27 | 2009-07-08 | 中国科学院海洋研究所 | Chitosan thiosemicarbazone derivatives and preparation method thereof |
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| CN104017093B (en) * | 2014-04-18 | 2016-08-24 | 大连理工大学 | The preparation method of a kind of hydrophobized starch sulfuric ester and the application in cement water reducing agent thereof |
| CN104017093A (en) * | 2014-04-18 | 2014-09-03 | 大连理工大学 | Preparation method and application of hydrophobic starch sulfate ester in cement water-reducing agent |
| CN104558244A (en) * | 2014-12-19 | 2015-04-29 | 华南理工大学 | O-pyridine acid ester chitosan as well as preparation method and application thereof |
| CN106983149A (en) * | 2017-04-10 | 2017-07-28 | 青海大学 | A kind of microcapsules |
| WO2019004950A1 (en) * | 2017-06-30 | 2019-01-03 | Scg Packaging Public Company Limited | High-strength sheet material |
| CN110743509A (en) * | 2019-12-10 | 2020-02-04 | 齐鲁工业大学 | Starch-based carbon composite material and application thereof in selective and efficient adsorption of mercury ions and methylene blue |
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