CN102212201A - Surface cross-linking modification method for starch nanocrystals - Google Patents
Surface cross-linking modification method for starch nanocrystals Download PDFInfo
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Abstract
The invention relates to a surface cross-linking modification method for starch nanocrystals, and belongs to the technical field of solid material modification methods. The technical scheme is that the method comprises the following steps of: dispersing the starch nanocrystals into an aqueous medium by using ultrasonic waves, adding an auxiliary reagent and a multi-functional group reaction reagent (a cross-linking agent), heating the system (the temperature is lower than the gelatinization temperature of starch) to ensure that a reaction of the cross-linking agent and extended hydroxyl radicals on the surfaces of the nanocrystals is performed so as to connect adjacent hydroxyl radicals on the surfaces of crystal grains, and performing centrifugal washing and drying to obtain starch nanocrystals of which the surfaces are subjected to cross-linking modification. Through surface cross-linking modification treatment, the agglomeration phenomenon among the starch nanocrystals caused by the action of hydrogen bonds can be effectively inhibited, and the starch nanocrystals can be uniformly and steadily dispersed in the aqueous medium; the starch nanocrystals modified by certain cross-linking agents can also be dispersed in an organic solvent medium; moreover, crystal structures of the starch nanocrystals are not damaged basically. The method has the characteristic of low cost and is easy to operate.
Description
Technical field
The present invention is a kind of surface-crosslinked method of modifying to nanometer starch crystal, relates to polyfunctional group reaction reagent (linking agent) the close hydroxyl in nanometer starch crystal surface is coupled together, and belongs to solid material method of modifying technical field.
Background technology
Native starch particles generally is made up of amylose starch and amylopectin, has the hypocrystalline structure.Amylose starch is the main component of amorphous domain, and crystal region is then mainly formed by amylopectin.Starch granules is after acid or enzyme mild hydrolysis, and pars amorpha wherein is removed, thereby obtains the higher nanoscale particle of degree of crystallinity, i.e. nanometer starch crystal.
Nanometer starch crystal is as a kind of function modified starch, not only have renewable, degradable, advantage such as density is little, production energy consumption is low, and compact structure, rigidity are big, rate of perviousness is low and have a small thin slices shape, it is the desirable toughener of preparation high molecule nano composite material, particularly thermoplastic starch powder nano-composite material.Nanometer starch crystal strengthen the thermoplastic starch powder nano-composite material not only mechanical property significantly improve, hinder moist also be improved significantly.
The surface has the polar nanometer starch crystal reunites in water easily, needs to help to disperse by ultrasonic wave; And in non-polar solvent, the dispersiveness of nanometer starch crystal is poorer.This makes nanometer starch crystal can only be added in the nano composite material for preparing by the aqueous solution, has limited its application in the high molecule nano composite material that needs the organic solvent preparation.In addition, hydrophilic nanometer starch crystal and hydrophobic polymer or non-polar resin consistency are poor, if nanometer starch crystal is prepared nano composite material as wild phase, not only nanocrystalline being difficult in matrix disperses, and because combining between nanometer starch crystal and the matrix is not strong, the limited in one's ability of stress transmitted at the interface, causes the function of its wild phase to descend significantly.Therefore, nanometer starch crystal is carried out modification, reduce the wetting ability and the polarity of nanometer starch crystal or give nanometer starch crystal certain hydrophobic function, become the important means of expanding the nanometer starch crystal range of application.
At present, the method for modifying of the nanometer starch crystal of reporting in the document is divided into two classes substantially, and a class is the hydroxyl reaction with reaction reagent and starch nano crystal grain surface; Another kind of is to starch nano crystal grain surface with some polymer grafts.The reaction reagent that uses comprises isocyanic ester, phenylcarbimide, acid anhydrides and lipid acid etc., and being used for polymers grafted has polytetrahydrofuran, polycaprolactone and polystyrene etc.It is pointed out that the method for modifying of these nanometer starch crystals, the overwhelming majority carries out in the bigger organic solvent of toxicity such as toluene, tetrahydrofuran (THF), severe reaction conditions, and the reaction scheme complexity, industrializing implementation cost height and difficulty are big.Therefore, starch nano crystal grain parent/hydrophobic reaction reagent can be effectively regulated and be controlled in searching, and the processing method that is easy to industrializing implementation, has important use and is worth.
The great amount of hydroxy group that the nanometer starch crystal surface is contained is its hydrophilic root, also provides convenience for its surface modification and possibility.Use for reference the production principle and the method for crosslinking modified starch, in aqueous media, react by the overhanging hydroxyl that contains multi-functional linking agent and nanometer starch crystal surface, the close hydroxyl in starch nano crystal grain surface is coupled together, can under the prerequisite that keeps nanometer starch crystal burl crystal structure, reduce the wetting ability of nanometer starch crystal.In addition, by selection, can give nanometer starch crystal certain hydrophobicity reducing on the hydrophilic basis of nanometer starch crystal, thereby regulate the polarity of nanometer starch crystal the contained functional group of linking agent.The surface-crosslinked modification of nanometer starch crystal in aqueous media, not only technology is simple, and has avoided with an organic solvent, is a kind of eco-friendly green method.
Summary of the invention
The object of the present invention is to provide the surface-crosslinked method of modifying of a kind of nanometer starch crystal.The reaction reagent of selecting for use and the processing method of employing are prerequisite with the industrializing implementation that is easy to the surface-crosslinked modification of nanometer starch crystal.This method can be regulated the surface polarity or the parent/hydrophobicity of nanometer starch crystal, so as nanometer starch crystal to disperse in the solvent of opposed polarity or with the compound preparation nano composite material of the macromolecular material of opposed polarity.The present invention as reaction medium, reduces the use of organic solvent with water, have pollution-free, cost is low and advantage such as energy-conservation.
Because the present invention only carries out crosslinking Treatment to the overhanging hydroxyl on nanometer starch crystal surface, and the temperature of reaction in aqueous media is lower than the gelatinization point of starch, so can not change substantially under the condition of nanometer starch crystal burl crystal structure, realizing reducing nanometer starch crystal surface polarity and hydrophilic purpose.In addition, by the selection of the contained functional group of linking agent, can also give nanometer starch crystal certain hydrophobic function.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of surface-crosslinked method of modifying to nanometer starch crystal, in aqueous media by containing the reaction that multi-functional reaction reagent is the overhanging hydroxyl in linking agent and nanometer starch crystal surface, the close hydroxyl in starch nano crystal grain surface is coupled together, regulate the surface polarity of starch nano crystal grain, this method may further comprise the steps:
(1) nanometer starch crystal suspension liquid of aqueous phase preparation: nanometer starch crystal and water press the mixing of 1/25-1/200 mass ratio, 30-50 ℃ of water-bath ultra-sonic oscillation and stirred 20-60 minute, obtain the nanometer starch crystal aqeous suspension;
(2) the pH value is regulated: according to used linking agent difference, with the pH value that acid solution or alkaline solution are regulated the nanometer starch crystal suspension liquid of aqueous phase, scope is between 1.0-12.0;
(3) crosslinking reaction: in the nanometer starch crystal suspension liquid of aqueous phase of regulating the pH value, add the linking agent that accounts for nanometer starch crystal weight 0.1%-150%, under 20-60 ℃ temperature condition, reacted 30 minutes-10 hours, finish the surface-crosslinked modification of nanometer starch crystal;
(4) washing is dry: add neutralization reagent in the nanometer starch crystal suspension liquid of aqueous phase after crosslinking reaction is finished, regulating the pH value is 6-8, centrifugal then washing, and 40 ℃ of dryings obtain the nanometer starch crystal of surface-crosslinked modification.
Described acid solution is the hydrochloric acid or the vitriolic aqueous solution, and alkaline solution is the aqueous solution of sodium hydroxide or yellow soda ash, and the mole number of acid solution and alkaline solution is between 0.05-2.0mol/L.
Described linking agent is a water-soluble cross-linker, comprise borax, boric acid, Trisodium trimetaphosphate, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, phosphorus oxychloride, formaldehyde, oxalic dialdehyde, one or more any mixed thing in the glutaraldehyde, citric acid.
In crosslinking reaction, decompose in order to prevent linking agent, improve its penetration coefficient, add and comprise that sodium-chlor and/or sodium sulfate neutral salt, add-on are 0.5-2 times of nanometer starch crystal weight.
Nanometer starch crystal after the surface-crosslinked modification can be dispersed in the water uniformly and stably, has suppressed the agglomeration that nanometer starch crystal takes place because of hydrogen bond action effectively; Nanometer starch crystal through some linking agent modification can also disperse in organic solvent, as N, and dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Described neutralization reagent is sodium hydroxide, yellow soda ash or aqueous hydrochloric acid.
Described nanometer starch crystal is obtained by the sulphuric acid hydrolysis waxy corn starch: waxy corn starch is scattered in the 3.16mol/L aqueous sulfuric acid, the quality of waxy corn starch is 10% (w/v) of sulphuric acid soln volume content, stirred 6 days down at 40 ℃, stirring velocity is 200rpm, centrifugal water is washed till the pH value for 6-8 then, and drying obtains nanometer starch crystal.
Effect of the present invention
Nanometer starch crystal after the surface-crosslinked modification can be dispersed in the water uniformly and stably, has suppressed the agglomeration that nanometer starch crystal takes place because of hydrogen bond action effectively; Nanometer starch crystal through some linking agent modification can also disperse in organic solvent, as N, and dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.The present invention has simple, the outer characteristics such as other solvent, cost are low that need not that dewater of technology, is a kind of very green and economic nanometer starch crystal surface modifying method.
Embodiment
Nanometer starch crystal and water are mixed by required quality, make the nanometer starch crystal suspension liquid of aqueous phase with ultra-sonic oscillation and stirring at a certain temperature; Regulate required pH of suspension value with acid solution or alkaline solution, the linking agent that adds different varieties/various dose, react certain hour at a certain temperature, make the overhanging hydroxyl reaction on linking agent and nanometer starch crystal surface, washing and the dry nanometer starch crystal that obtains surface-crosslinked modification.The linking agent difference, the pH value difference that the nanometer starch crystal suspension liquid of aqueous phase is required.
Embodiment 1:
Waxy corn starch is scattered in the 3.16mol/L aqueous sulfuric acid, the quality of waxy corn starch is 10% (w/v) of sulphuric acid soln volume content, stirs 6 days down at 40 ℃, and stirring velocity is 200rpm, centrifugal water is washed till the pH value for 6-8 then, and drying obtains nanometer starch crystal.
Mix making nanometer starch crystal and water mass ratio, obtained the nanometer starch crystal suspension liquid of aqueous phase in 60 minutes in 30 ℃ of water-bath ultra-sonic oscillation, stirring by 1/100; Regulating the pH of suspension value with the sodium hydroxide solution of 1mol/L is 11.0, add the sodium sulfate of 0.5 times of nanometer starch crystal quality and the phosphorus oxychloride of nanometer starch crystal quality 20%, 20 ℃ were reacted 2 hours, regulating the pH value with the hydrochloric acid soln of 0.1mol/L is 6, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 2:
With embodiment 1, difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 2mol/L be 12.0, add the sodium-chlor of 1 times of nanometer starch crystal quality and the phosphorus oxychloride of nanometer starch crystal quality 30%, 30 ℃ were reacted 5 hours, regulating the pH value with the hydrochloric acid soln of 0.2mol/L is 6, washing is also dry, obtains being dispersed in uniformly and stably in the water also can being scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 3:
With embodiment 1, difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 0.05mol/L be 10.0, the Trisodium trimetaphosphate that adds nanometer starch crystal quality 15%, 50 ℃ were reacted 8 hours, regulating the pH value with the hydrochloric acid soln of 0.05mol/L is 6, washing is also dry, obtains being dispersed in uniformly and stably in the water also can being scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 4:
With embodiment 1 difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 0.1mol/L be 11.0, add the sodium-chlor of 1 times of nanometer starch crystal quality and the Sodium hexametaphosphate 99 of nanometer starch crystal quality 150%, 50 ℃ were reacted 3 hours, regulating the pH value with the hydrochloric acid soln of 0.05mol/L is 7, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 5:
With embodiment 1, difference is to add the sodium sulfate of 1 times of nanometer starch crystal quality and the tripoly phosphate sodium STPP of nanometer starch crystal quality 90%, 35 ℃ were reacted 6 hours, regulating the pH value with the hydrochloric acid soln of 0.1mol/L is 7, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 6
With embodiment 1, difference is to add the sodium sulfate of 1 times of nanometer starch crystal quality and the Trisodium trimetaphosphate and tripoly phosphate sodium STPP (mass ratio is 1: the 2) mixture of nanometer starch crystal quality 60%, 40 ℃ were reacted 6 hours, regulating the pH value with the hydrochloric acid soln of 0.05mol/L is 7, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 7:
With embodiment 6, difference is Trisodium trimetaphosphate and tripoly phosphate sodium STPP (mass ratio is 1: the 1) mixture that adds nanometer starch crystal quality 80%, 50 ℃ were reacted 4 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 8:
With embodiment 6, difference is to add the sodium sulfate of 2 times of nanometer starch crystal quality and the Trisodium trimetaphosphate and Sodium hexametaphosphate 99 (mass ratio is 2: the 1) mixture of nanometer starch crystal quality 60%, 35 ℃ were reacted 6 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 9:
Waxy corn starch is scattered in the 3.16mol/L aqueous sulfuric acid, the quality of waxy corn starch is 10% (w/v) of sulphuric acid soln volume content, stirs 6 days down at 40 ℃, and stirring velocity is 200rpm, centrifugal water is washed till the pH value for 6-8 then, and drying obtains nanometer starch crystal.
Mix making nanometer starch crystal and water mass ratio, obtained the nanometer starch crystal suspension liquid of aqueous phase in 20 minutes in 50 ℃ of water-bath ultra-sonic oscillation, stirring by 1/200; Regulating the pH of suspension value with the sodium hydroxide solution of 1mol/L is 12.0, add the sodium-chlor of 2 times of nanometer starch crystal quality and Trisodium trimetaphosphate, Sodium hexametaphosphate 99 and tripoly phosphate sodium STPP (mass ratio is 1: 1: the 1) mixture of nanometer starch crystal quality 90%, 45 ℃ were reacted 10 hours, regulating the pH value with the hydrochloric acid soln of 1mol/L is 7, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal in dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), the butanols.
Embodiment 10:
With embodiment 9, difference is that to regulate the pH of suspension value with the sulphuric acid soln of 0.1mol/L be 1.0, the formaldehyde that adds nanometer starch crystal quality 6%, 40 ℃ were reacted 4 hours, regulating the pH value with the sodium hydroxide solution of 0.1mol/L is 8, washing is also dry, obtains being scattered in N the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 11:
With embodiment 9, difference is that to regulate the pH of suspension value with the hydrochloric acid soln of 0.1mol/L be 2.0, the oxalic dialdehyde that adds nanometer starch crystal quality 0.1%, 38 ℃ were reacted 3 hours, regulating the pH value with the sodium hydroxide solution of 0.1mol/L is 8, washing is also dry, obtains being scattered in N the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 12:
With embodiment 11, difference is that nanometer starch crystal and water are mixed by 1/50 mass ratio, obtained the nanometer starch crystal suspension liquid of aqueous phase in 40 minutes in 40 ℃ of water-bath ultra-sonic oscillation, stirring, the glutaraldehyde that adds nanometer starch crystal quality 25%, 45 ℃ were reacted 6 hours, washing is also dry, obtains being scattered in N the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 13:
With embodiment 12, difference is oxalic dialdehyde and glutaraldehyde (mass ratio is 1: the 20) mixture that adds nanometer starch crystal quality 20%, 40 ℃ were reacted 5 hours, regulating the pH value with the sodium hydroxide solution of 0.05mol/L is 7, washing is also dry, obtain to be scattered in N the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 14:
With embodiment 12, difference is that to regulate the pH of suspension value with the hydrochloric acid soln of 0.2mol/L be 1.6, formaldehyde, oxalic dialdehyde and glutaraldehyde (mass ratio is 5: 1: the 20) mixture that adds nanometer starch crystal quality 10%, 40 ℃ were reacted 5 hours, regulating the pH value with the sodium hydroxide solution of 0.05mol/L is 7, washing is also dry, obtains being scattered in N the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 15:
Waxy corn starch is scattered in the 3.16mol/L aqueous sulfuric acid, the quality of waxy corn starch is 10% (w/v) of sulphuric acid soln volume content, stirs 6 days down at 40 ℃, and stirring velocity is 200rpm, centrifugal water is washed till the pH value for 6-8 then, and drying obtains nanometer starch crystal.
Mix making nanometer starch crystal and water mass ratio, obtained the nanometer starch crystal suspension liquid of aqueous phase in 50 minutes in 35 ℃ of water-bath ultra-sonic oscillation, stirring by 1/25; Regulating the pH of suspension value with the sodium carbonate solution of 0.1mol/L is 8.0, the citric acid that adds nanometer starch crystal quality 50%, 25 ℃ were reacted 30 minutes, regulating the pH value with the hydrochloric acid soln of 0.1mol/L is 6, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 16:
With embodiment 15, different is, and to regulate the pH of suspension value with the sodium carbonate solution of 0.1mol/L be 10.0, the citric acid that adds nanometer starch crystal quality 30%, 30 ℃ were reacted 1 hour, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 17:
With embodiment 15, different is, and to regulate the pH of suspension value with the sodium carbonate solution of 1mol/L be 11.0, add the sodium-chlor of 1 times of nanometer starch crystal quality and the phosphorus oxychloride and citric acid (mass ratio 1: the 1) mixture of nanometer starch crystal quality 40%, 30 ℃ were reacted 2 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 18:
Waxy corn starch is scattered in the 3.16mol/L aqueous sulfuric acid, the quality of waxy corn starch is 10% (w/v) of sulphuric acid soln volume content, stirs 6 days down at 40 ℃, and stirring velocity is 200rpm, centrifugal water is washed till the pH value for 6-8 then, and drying obtains nanometer starch crystal.
Mix making nanometer starch crystal and water mass ratio, obtained the nanometer starch crystal suspension liquid of aqueous phase in 30 minutes in 45 ℃ of water-bath ultra-sonic oscillation, stirring by 1/150; Regulating the pH of suspension value with the sodium carbonate solution of 0.05mol/L is 8.0, the boric acid that adds nanometer starch crystal quality 15%, 60 ℃ were reacted 2 hours, regulating the pH value with the hydrochloric acid soln of 0.05mol/L is 6, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols.
Embodiment 19:
With embodiment 18, difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 0.1mol/L be 9.0, the borax that adds nanometer starch crystal quality 90%, 55 ℃ were reacted 3 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols.
Embodiment 20:
With embodiment 18, difference is boric acid and borax (mass ratio 2: the 1) mixture that adds nanometer starch crystal quality 10%, 60 ℃ were reacted 8 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols.
Embodiment 21:
With embodiment 18, difference is that to regulate the pH of suspension value with the sodium carbonate solution of 2mol/L be 10.0, add the sodium-chlor of 0.5 times of nanometer starch crystal quality and the Sodium hexametaphosphate 99 and borax (mass ratio 1: the 1) mixture of nanometer starch crystal quality 80%, 50 ℃ were reacted 10 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols.
Embodiment 22:
With embodiment 18, difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 0.5mol/L be 9.0, add the sodium-chlor of 1 times of nanometer starch crystal quality and the Trisodium trimetaphosphate and citric acid (mass ratio 1: the 1) mixture of nanometer starch crystal quality 50%, 50 ℃ were reacted 7 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 23:
With embodiment 18, difference is that to regulate the pH of suspension value with the sodium hydroxide solution of 0.5mol/L be 10.0, the boric acid and citric acid (mass ratio 1: the 3) mixture that add nanometer starch crystal quality 20%, 40 ℃ were reacted 10 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 24:
With embodiment 22, difference is Sodium hexametaphosphate 99 and citric acid (mass ratio 1: the 3) mixture that adds nanometer starch crystal quality 50%, 55 ℃ were reacted 8 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 25:
With embodiment 22, difference is tripoly phosphate sodium STPP and citric acid (mass ratio 1: the 2) mixture that adds nanometer starch crystal quality 50%, 50 ℃ were reacted 6 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Embodiment 26:
With embodiment 23, the borax and citric acid (mass ratio 1: the 3) mixture that add nanometer starch crystal quality 15%, 40 ℃ were reacted 6 hours, washing is also dry, obtain to be dispersed in uniformly and stably in the water and also can be scattered in N, the nanometer starch crystal of dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), butanols, ethylene dichloride, methylene dichloride.
Claims (5)
1. surface-crosslinked method of modifying to nanometer starch crystal, it is characterized in that, in aqueous media by containing the reaction that multi-functional reaction reagent is the overhanging hydroxyl in linking agent and nanometer starch crystal surface, the close hydroxyl in starch nano crystal grain surface is coupled together, regulate the surface polarity of starch nano crystal grain, this method may further comprise the steps:
(1) nanometer starch crystal suspension liquid of aqueous phase preparation: nanometer starch crystal and water press the 1/25-1/200 mass ratio mix,, obtain the nanometer starch crystal suspension liquid of aqueous phase 30-50 ℃ of water-bath ultra-sonic oscillation and with 50-400 rev/min speed stirring 20-60 minute;
(2) the pH value is regulated: according to used linking agent difference, with the pH value that acid solution or alkaline solution are regulated the nanometer starch crystal suspension liquid of aqueous phase, scope is between 1.0-12.0;
(3) crosslinking reaction: in the nanometer starch crystal suspension liquid of aqueous phase of regulating the pH value, add the linking agent that accounts for nanometer starch crystal weight 0.1%-150%, under 20-60 ℃ temperature condition, reacted 30 minutes-10 hours, finish the surface-crosslinked modification of nanometer starch crystal;
(4) washing is dry: add neutralization reagent in the nanometer starch crystal suspension liquid of aqueous phase after crosslinking reaction is finished, regulating the pH value is 6-8, centrifugal then washing, and 40 ℃ of dryings obtain the nanometer starch crystal of surface-crosslinked modification.
2. a kind of surface-crosslinked method of modifying according to claim 1 to nanometer starch crystal, it is characterized in that, described acid solution is the hydrochloric acid or the vitriolic aqueous solution, and alkaline solution is the aqueous solution of sodium hydroxide or yellow soda ash, and the mole number of acid solution and alkaline solution is between 0.05-2.0mol/L.
3. a kind of surface-crosslinked method of modifying according to claim 1 to nanometer starch crystal, it is characterized in that, described linking agent is a water-soluble cross-linker, comprise borax, boric acid, Trisodium trimetaphosphate, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, phosphorus oxychloride, formaldehyde, oxalic dialdehyde, one or more any mixed thing in the glutaraldehyde, citric acid.
4. a kind of surface-crosslinked method of modifying to nanometer starch crystal according to claim 1 is characterized in that, in crosslinking reaction, in order to prevent that linking agent from decomposing, improve its penetration coefficient, add and comprise that neutral salt such as sodium-chlor and/or sodium sulfate, add-on are 0.5-2 times of nanometer starch crystal weight.
5. a kind of surface-crosslinked method of modifying to nanometer starch crystal according to claim 1 is characterized in that described neutralization reagent is sodium hydroxide, yellow soda ash or aqueous hydrochloric acid.
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| CN114848888A (en) * | 2022-05-12 | 2022-08-05 | 上海威高医疗技术发展有限公司 | Absorbable starch hemostatic material and preparation method thereof |
| CN117004152A (en) * | 2023-09-28 | 2023-11-07 | 苏州翠屏塑胶有限公司 | CPVC (chlorinated polyvinyl chloride) mixed material for pipe fittings and injection molding parts and preparation method thereof |
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| CN103193890A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院化学研究所 | Functionalized starch nano-crystals and preparation method thereof |
| CN103193890B (en) * | 2012-01-05 | 2016-01-06 | 中国科学院化学研究所 | Functionalization nanometer starch crystal and preparation method thereof |
| CN102633890A (en) * | 2012-04-22 | 2012-08-15 | 吉林大学 | Surface cross-linking esterification compound modification method of starch nanocrystal |
| CN104844718A (en) * | 2015-05-18 | 2015-08-19 | 吉林大学 | Preparation method with high yield and short complexing time for starch nanocrystal |
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| CN105601757A (en) * | 2016-03-22 | 2016-05-25 | 中南林业科技大学 | Preparation method of drug carrier crosslinking-modified rice starch nanocrystals |
| CN107446059A (en) * | 2016-05-31 | 2017-12-08 | 齐鲁工业大学 | A kind of short tube shape nanometer starch crystal and preparation method thereof |
| CN107446059B (en) * | 2016-05-31 | 2019-10-11 | 齐鲁工业大学 | A kind of short tube shape nanometer starch crystal and preparation method thereof |
| CN110292166A (en) * | 2019-05-23 | 2019-10-01 | 江苏大学 | A method of resistant starch is prepared based on frequency sweep ultrasonic wave technology |
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| CN111196889A (en) * | 2019-09-20 | 2020-05-26 | 九江智达环能科技有限公司 | Multi-arm cross-linking agent and starch nanocrystal modification-based furan resin material and preparation method and application thereof |
| CN111196889B (en) * | 2019-09-20 | 2022-10-18 | 汉中聚智达远环能科技有限公司 | Multi-arm cross-linking agent and starch nanocrystal modification-based furan resin material and preparation method and application thereof |
| CN110790984A (en) * | 2019-12-03 | 2020-02-14 | 陕西科技大学 | Cellulose nanocrystal/borax composite film and preparation method thereof |
| CN114848888A (en) * | 2022-05-12 | 2022-08-05 | 上海威高医疗技术发展有限公司 | Absorbable starch hemostatic material and preparation method thereof |
| CN117004152A (en) * | 2023-09-28 | 2023-11-07 | 苏州翠屏塑胶有限公司 | CPVC (chlorinated polyvinyl chloride) mixed material for pipe fittings and injection molding parts and preparation method thereof |
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