CN106496421B - A kind of preparation method and application of graft starch - Google Patents
A kind of preparation method and application of graft starch Download PDFInfo
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- CN106496421B CN106496421B CN201610968612.9A CN201610968612A CN106496421B CN 106496421 B CN106496421 B CN 106496421B CN 201610968612 A CN201610968612 A CN 201610968612A CN 106496421 B CN106496421 B CN 106496421B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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Abstract
The present invention relates to a kind of preparation methods of graft starch, the starch emulsion suspension for first Electro-Fenton process being used to obtain preparation pre-processes, the crystal region for destroying starch, enables the strand of starch molecule to uphold, the exposed reaction site that can be more graft-polymerized；Then grafted monomers are added dropwise into pretreated system, continue logical oxygen and be powered, so that the hydroxyl radical free radical of generation is caused the graft polymerization reaction of starch molecule free radical and grafted monomers as initiator, while avoiding the generation of grafted monomers homopolymer as possible.Grafting processing is carried out to starch using this method, grafting rate is up to 69.2%, and grafting efficiency is up to 87.6%, and homopolymer content is low；The graft starch that this method is prepared has good water imbibition or film forming ability；Meanwhile this method technological operation and post-processing are simple, reaction condition is mild, time-saving and efficiency, and environmental pollution is small, is conducive to expand large-scale production.
Description
Technical field
The invention belongs to biotechnology more particularly to a kind of preparation method and applications of graft starch, more specifically,
Relate to the use of Electro-Fenton process and prepares graft starch.
Background technology
Starch is polymeric carbohydrate, the polysaccharide being made of the sugar unit of single type, can be divided into straight chain shallow lake
Powder and amylopectin.The molecular formula of starch is (C6Hl0O5)n, n is the degree of polymerization, C6Hl0O5For dehydrated glucose unit.
Performance can be influenced by factors such as temperature, mechanical shearing effect, pH value, salts when starch use, therefore different
Use occasion require starch have different characteristics, only adapted to these application requirements, starch can just be used widely.
In order to improve the performance of starch, its application range is widened, it is necessary to be carried out to it structurally-modified.Starch chemical denaturing methods have：
Acidolysis, oxidation, graft copolymerization, etherificate, esterification, crosslinking complex denaturation etc..
The graft copolymer of starch is a kind of novel high molecular material, with hydrophilic, semi-rigid chain starch polymer
It introduces different functional groups with vinyl monomer graft copolymerization for skeleton and adjusts the ratio of Hydrophile-Lipophile segmented structure, can obtain
To the polymer of target product.The graft copolymer of starch is in high polymer coagulant, high-absorbent material, paper industry auxiliary agent, oil
There is excellent performance in the practical application of field chemical material, degradable mulch and plastics etc..
Starch is the high polymer of partially crystallizable, when untreated ative starch is with monomer graft copolymerization, due to tight structure
Internal strand is difficult to uphold, and the active position being graft-polymerized is few, and reaction only occurs in the surface of particle, and main hair
In the amorphous region of starch, graft copolymerization rate is low for life.Therefore, before starch and monomer graft reaction, generally to starch
Pretreatments, the crystal regions for destroying starch such as machinery, gelatinization, oxidation, acidolysis, enzymolysis, heat treatment, radiation is carried out to connect to improve starch
The reaction rate and grafting efficiency of branch copolymerization, improve the performance of graft copolymer.
Starch is placed in by Chinese patent CN101177457B60It in Co irradiation fields, is irradiated under air conditions, irradiates agent
Amount is 4-15kGy, obtains pre-irradiation starch, dicyandiamide-formaldehyde resin solution is sprayed onto on pre-irradiation starch, is uniformly mixed, obtains mixed
Close object；Mixture is placed in60It in Co irradiation fields, is irradiated, irradiation dose 4-15kGy, must be irradiated mixed under air conditions
Object is closed, then irradiation mixture is reacted under the high temperature conditions or under microwave condition, this method is to equipment requirement height, after pretreatment
Starch-grafted rate be 0.95%-1.4%.Chinese patent CN103059225B discloses a kind of life of grafting modified starch sizing agent
Production method uses processor for ultrasonic wave to carry out ultrasonic pretreatment to ative starch breast, acrylic compounds is then added in system first
Mixed grafting monomer is inserted into glow-discharge electrode, carries out glow discharge, and the graft copolymerization in initiation system closes power supply,
It is 35-50 DEG C, polymerisation 2-3h to keep temperature of reaction system, obtains loose graft starch, grafting rate 16.6%-
19.4%.
Li Lin etc. using after dilute hydrochloric acid acid-hydrolyzed maize starch with acrylic graft copolymer, grafting rate 5.14%.It is Chinese special
Sharp CN101735392B is by after cornstarch pre-gelatinized, 100 parts of native cornstarch, 20-25 parts of acrylic acid, dimethyl sulfoxide (DMSO)
0.01-0.02 parts, 1000 parts of tap water stirs evenly in a kettle, and 41-50 parts of butyl methacrylate, potassium peroxydisulfate is added
It 2-8 parts, after stirring, is packed into ceramic reactor, is placed in micro-wave oven field, under 160-180W microwave powers,
Graft copolymerization is carried out, microwave radiation mode is intermittent, after often radiating 3.5-4.0min, ceramic reactor is taken out and is stirred
2-3min is mixed, carries out 4-5 radiation altogether, graft reaction is completed in 3-4 stirring, and after polymer separation to obtain the final product, grafting rate is
17.51%-20.1%, grafting efficiency 52.21%-69.0%.Wang Chengxue etc. is using ammonium persulfate as initiator, with alpha-amylase
For starch degradation agent, the graft copolymerization for having carried out enzymatic starch and Vinyl Acetate Monomer is studied, grafting rate 11.7%-
30.9%, grafting efficiency 19.7%-65.9%.
Method disclosed in the prior art has that grafting rate and grafting efficiency are low, therefore it provides a kind of new shallow lake
Powder method of modifying is meaningful.
Invention content
The object of the present invention is to provide a kind of preparation methods of graft starch, have and are easy to industrialize, grafting rate, grafting effect
Rate is high, the small feature of environmental pollution.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of graft starch, includes the following steps：
(1) starch emulsion suspension of preparation is added in the electrolytic cell equipped with cathode and anode, adjusts the starch emulsion suspension
PH value be acidity, be passed through oxygen to cathode according to the amount of 4.0-8.0L oxygen/L starch emulsion suspensions, and control the electricity of cathode
Current density is 10-15mA/cm2, starch is electrolysed with this condition；
(2) grafted monomers are added dropwise into the reaction system of step (1) and carry out graft reaction, when dropwise addition, adjustment oxygen is passed through
Amount is 2.0-8.0L/L starch emulsion suspensions, cathode-current density 5-10mA/cm2；
(3) after reaction, the reaction solution of filtration step (2) takes filter cake, forms sediment to get grafting after washing, extracting, drying
Powder.
The step (1) of the present invention pre-processes starch using Electro-Fenton process, and the hydroxyl that Electro-Fenton process generates is certainly
By base can fast-attack starch molecule, destroy the crystal region of starch, the strand of starch molecule enable to uphold, it is exposed more
The reaction site that can be graft-polymerized；In step (2), continue to use Fenton condition, the hydroxyl radical free radical of generation main
As initiator initiation grafting polymerisation, that is, in the hydroxyl radical free radical and starch molecule of generation in glycosyl ring on carbon atom
Atomic reaction of hydrogen generates the starch molecule free radical that can be reacted with grafted monomers.Meanwhile the present invention will by way of dropwise addition
Grafted monomers are added in reaction system, and grafted monomers are grafted with the starch molecule free radical of generation rapidly after entering in system
Polymerisation effectively prevents the generation of grafted monomers self-polymerization reaction, can reduce the generation of homopolymer.
Wherein, the starch emulsion suspension is molten for the methanol aqueous solution or ethanol water of 5-30% with percent by volume
Agent." 5-30% " refers to the volumn concentration of methanol or ethyl alcohol in methanol aqueous solution or ethanol water.
Preferably, the mass concentration of the starch emulsion suspension is 10-40%.The study found that the Fenton of the present invention
Law article part there is good graft effect, concentration to be higher than the model starch emulsion suspension within the scope of mass concentration 10%-40%
When enclosing, starch-grafted rate and grafting efficiency are relatively low；When concentration is less than the range, in obtained graft starch homopolymer content compared with
It is high.
Preferably, the pH value of the starch emulsion suspension be 2-4, further preferably 3.
Preferably, electrolyte can also be added in the system of step (1) to promote the progress of cell reaction, the electrolysis of fine quality
It is selected as sodium sulphate and/or sodium chloride, concentration of the electrolyte in system is advisable to reach 0.1-1.0mol/L.
Preferably, in step (1), the time of electrolysis is 30-60min.
Preferably, in step (2), the grafted monomers are selected from acrylonitrile, acrylic acid, acrylates, acrylamide, propylene
Acid esters, methyl methacrylate, butyl methacrylate, vinylacetate, butadiene, styrene, butene dioic acid dimethyl ester, fourth
Enedioic acid dioctyl ester, butene dioic acid diamyl ester, Dimethylaminoethyl Methacrylate, acrylyl oxy-ethyl-trimethyl salmiac,
One or more of 2- acrylamide-2-methylpro panesulfonic acids, dimethyl diallyl ammonium chloride.Wherein, the acrylic acid
Ester refers to butyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, Hexyl 2-propenoate, propylene
Heptyl heptylate, 2-ethyl hexyl acrylate kind it is one or more.
Preferably, it forms grafted monomers solution after grafted monomers being dissolved in solvent to be added dropwise again, the solvent is selected from
It is one or more in methanol, ethyl alcohol, water.The mass percent of the grafted monomers solution is 10-60%.
Preferably, in step (2), the addition of grafted monomers is to prepare the 1-3 of starch weight used in starch emulsion suspension
Times.
Preferably, in step (2), after grafted monomers completion of dropwise addition, the reaction was continued 60-120min with promote reaction fully into
Row.
Preferably, the graft reaction of step (2) carries out under the conditions of 20-40 DEG C.
Preferably, the operation of step (1) and step (2) carries out under agitation, and stirring contributes to starch molecule
It is more fully contacted with hydroxyl radical free radical, additionally it is possible to promote the progress of graft reaction.Mixing speed is preferably 100-600rpm.
Preferably, in step (3), using C3-10Ketones solvent, water or N,N-dimethylformamide are extraction solvent to institute
It obtains graft starch and is stripped processing to remove the homopolymer in thick production.Wherein, the C3-10Ketones solvent is selected from acetone, fourth
At least one of ketone, pentanone.
Preferably, the material of anode of the present invention is iron, and the material of the cathode is graphite.Cathode material is further excellent
It is selected as porous graphite.
In process of production, aerator may be used and blasts oxygen into electrolytic cell.Preferably, using containing at least one
The aerator of a venthole is passed through oxygen to the cathode, depending on the scale of the quantity of venthole according to electrolysis, that is, works as electrolysis
Starch emulsion suspension amount it is big when, multiple ventholes can be used while blasting the mode of oxygen.The air-blowing simultaneously of multiple ventholes has
Help oxygen and be evenly distributed on around cathode sheet uniformly generate hydroxyl radical free radical.It is further preferred that oxygen in each venthole
The speed that is passed through of gas is 0.2-1.0L/min (preferably 0.6-0.8L/min, most preferably 0.7L/min).Those skilled in the art can
To understand, substitutes oxygen with air and above-mentioned purpose equally may be implemented, in specific application, can be used and increase air intake
Means reach purpose identical with pure oxygen tolerance is passed through.
Starch of the present invention is selected from green starch, tapioca, sweet potato starch, potato starch, wheat starch, water chestnut
One kind in starch, Rhizoma Nelumbinis starch, cornstarch, waxy corn starch, rice starch, glutinous rice starch.Wherein, the wheat starch
Specially wheaten starch, barley starch, oat starch, buckwheat starch.
Particularly, method of the present invention has best graft effect to cornstarch.
As the preferable technical solution of the present invention, include the following steps：
(1) starch is added in the methanol aqueous solution or ethanol water that percent by volume is 10-30% and is configured to quality
The starch emulsion suspension of a concentration of 10%-40%, and the pH value for adjusting the starch emulsion suspension is 2-4；
(2) the prepared raw material of step (1) is added in the electrolytic cell equipped with cathode and anode, according to 4.0-8.0L oxygen/L
The amount of starch emulsion suspension is passed through oxygen to cathode, and it is 10-15mA/cm to control cathode-current density2, it is stirred to react 30min-
60min；
(3) grafted monomers are added dropwise into the reaction system of step (2) and carry out graft reaction, when dropwise addition, control oxygen is passed through
Amount is 2.0-8.0L/L starch emulsion suspensions, cathode-current density 5-10mA/cm2, after being added dropwise, the reaction was continued 60min-
120min stops the ventilation that is powered；
(4) filtering reacting liquid, gained filter cake is washed, is extracted, dry after to get the graft starch.
The study found that compared with the graft starch that existing preparation method obtains, the graft starch that the present invention is prepared has
There are more preferably soaking effect or filming performance, therefore, is obtained it is a further object of the present invention to provide any of the above-described preparation method
Application of the graft starch in preparing water-absorbent material or membrane material.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined with each other each preferably to get the present invention
Embodiment.
The present invention has following good effect：The present invention using Electro-Fenton process to starch pre-process and grafting at
Reason, grafting rate is up to 69.2%, and grafting efficiency is up to 87.6%, and homopolymer content is low；Meanwhile this method technological operation is with after
Processing is simple, and time-saving and efficiency, reaction condition is mild, and environmental pollution is small, is conducive to expand large-scale production.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..The raw material or reagent being related to
It is known substance, the operation being related to is this field routine operation unless otherwise specified.
Embodiment 1
A kind of preparation method of Grafted Starch, includes the following steps：
(1) 2kg cornstarch is weighed, being scattered in 18L methanol-water solutions, (volume ratio of methanol and water is 10：90) in, system
At a concentration of 10.19% cornstarch milk suspension, it is fitted into the electrolytic cell that volume is 24L, weighs 255.6g sodium sulphate
(0.1mol/L) is dissolved in cornstarch milk suspension, is 3 with the pH of 1mol/L sulfuric acid adjusting corn starch emulsion suspensions.With
30cm × 30cm wire nettings are anode, and 30cm × 30cm porous graphites are cathode, and distance is 5cm between the two poles of the earth, is passed through 14V direct currents
(cathode-current density 14mA/cm2), be used in combination aerator with the speed of 0.7L/min be passed through oxygen (aerator contain two
Venthole, two ventholes blast oxygen simultaneously), the amount that every liter of cornstarch milk suspension is passed through oxygen is about 4.67L, stirring
Device is stirred with the speed of 250rpm, reacts 60min；
(2) adjustment oxygen intake is 5.06L/L starch emulsion suspensions, cathode-current density 8mA/cm2, other conditions
It is constant, 3kg acrylonitrile (acrylonitrile is dissolved in advance in 6L absolute methanols) is added dropwise into electrolytic cell, controls rate of addition, 30min drops
Add complete, the reaction was continued under room temperature 100min, stopping energization ventilation；
(3) filtering reacting liquid obtains crude product after gained filter cake is washed with water, be that extracting is molten with n,N-Dimethylformamide
Agent is stripped processing to remove homopolymer, to get Grafted Starch sterling after drying to crude product.
Embodiment 2
A kind of preparation method of grafting potato starch, includes the following steps：
(1) 3kg potato starch is weighed, being scattered in 17L ethanol-water solutions, (volume ratio of ethyl alcohol and water is 15：85) in,
A concentration of 15.42% potato starch milk suspension is made, is fitted into the electrolytic cell that volume is 24L, weighs 193.12g sulfuric acid
Sodium (0.08mol/L) is dissolved in potato starch milk suspension, with 1mol/L nitric acid tune pH to 3.With 30cm × 30cm iron wires
Net is anode, and 30cm × 30cm porous graphites are cathode, and distance is 6cm between the two poles of the earth, is passed through the electric (cathode-current density of 12V DC
For 12mA/cm2), being used in combination aerator with the speed of 0.6L/min to be passed through oxygen, (aerator contains three ventholes, and three are logical
Stomata blasts oxygen simultaneously), the amount that every liter of starch solution is passed through oxygen is about 5.29L, and blender is stirred with the speed of 250rpm,
React 50min；
(2) adjustment oxygen intake is 4.24L/L potato starch milk suspensions, cathode-current density 7mA/cm2,
His condition is constant, and 3kg acrylic acid (acrylic acid is dissolved in advance in 6L absolute ethyl alcohols) is added dropwise into electrolytic cell, controls rate of addition,
30min is added dropwise, the reaction was continued under room temperature 90min, stopping energization ventilation；
(3) filtering reacting liquid, after gained filter cake is washed with water, through dry to get potato graft starch sterling.
Embodiment 3
A kind of preparation method of grafting tapioca, includes the following steps：
(1) 4kg tapiocas are weighed, being scattered in 16L methanol-water solutions, (volume ratio of methanol and water is 20：80) in, system
At a concentration of 20.69% tapioca milk suspension, it is fitted into the electrolytic cell that volume is 24L, weighs 272.64g sodium sulphate
(0.12mol/L) is dissolved in tapioca milk suspension, with 1mol/L sulfuric acid tune pH to 3.It is with 30cm × 30cm wire nettings
Anode, 30cm × 30cm porous graphites are cathode, and distance is 5cm between the two poles of the earth, and being passed through 13V direct currents, (cathode-current density is
13mA/cm2) and with aerator with the speed of 0.5L/min be passed through oxygen (aerator contain three ventholes, three ventholes
Blast oxygen simultaneously), the amount that every liter of starch solution is passed through oxygen is about 3.75L, and blender is stirred with the speed of 250rpm, reaction
40min；
(2) adjustment oxygen intake is 4.06L/L tapioca milk suspensions, cathode-current density 8mA/cm2, other
Condition is constant, and 4kg acrylamides (acrylamide is dissolved in advance in 10L deionized waters) are added dropwise, and controls rate of addition, 30min drops
Add complete, the reaction was continued under room temperature 100min, stopping energization ventilation；
(3) filtering reacting liquid, after gained filter cake is washed with water, through dry to get graft starch sterling.
Embodiment 4
A kind of preparation method of grafting potato starch, includes the following steps：
(1) 7kg potato starch is weighed, being scattered in 12L ethanol-water solutions, (volume ratio of ethyl alcohol and water is 30：70) in,
A concentration of 38.38% potato starch milk suspension is made, is fitted into the electrolytic cell that volume is 24L, weighs 102.24g sulfuric acid
Sodium (0.06mol/L) is dissolved in potato starch milk suspension, with 1mol/L nitric acid tune pH to 3, with 30cm × 30cm iron wires
Net is anode, and 30cm × 30cm porous graphites are cathode, and distance is 5cm between the two poles of the earth, is passed through the electric (cathode-current density of 12V DC
For 15mA/cm2), being used in combination aerator with the speed of 0.6L/min to be passed through oxygen, (aerator contains two ventholes, and two are logical
Stomata blasts oxygen simultaneously), the amount that every liter of starch solution is passed through oxygen is about 6L, and blender is stirred with the speed of 250rpm, instead
Answer 60min；
(2) adjustment oxygen intake is 6.5L/L potato starch milk suspensions, cathode-current density 8mA/cm2,
His condition is constant, and 7kg vinylacetates (vinylacetate is dissolved in advance in 10L absolute ethyl alcohols) are added dropwise, and controls rate of addition,
30min is added dropwise, the reaction was continued under room temperature 100min, stopping energization ventilation；
(3) filtering reacting liquid obtains crude product after gained filter cake is washed with water, using acetone as extraction solvent, carried out to crude product
Extracting processing is to remove homopolymer, to get potato graft starch sterling after drying.
Embodiment 5
The embodiment is differed only in embodiment 3：Use binary grafted monomers, the binary grafting single in step (2)
Body is prepared by the following method：2.6kg acrylic acid is dissolved in 6L deionized waters, with 30% sodium hydroxide solution (hydrogen containing 1.2kg
Sodium oxide molybdena) slowly titration, drop is complete, and the ethanol solution (including acrylamide 427g) of 1L acrylamides is added.
Embodiment 6
A kind of preparation method of grafting tapioca, includes the following steps：
(1) 2kg tapiocas are weighed, being scattered in 18L ethanol-water solutions, (ethyl alcohol is 20 with water volume ratio：80) it in, is made
A concentration of 10.4% tapioca milk suspension is fitted into the electrolytic cell that volume is 24L, weighs 255.6g sodium sulphate
(0.1mol/L) is dissolved in tapioca milk suspension, is sun with 30cm × 30cm wire nettings with 1mol/L sulfuric acid tune pH to 3
Pole, 30cm × 30cm porous graphites are cathode, and distance is 6cm between the two poles of the earth, are passed through 12V DC electricity, current density 12mA/cm2,
Being used in combination aerator with the speed of 0.6L/min to be passed through oxygen, (aerator contains three ventholes, and three ventholes blast simultaneously
Oxygen), the amount that every liter of starch solution is passed through oxygen is about 5.0L, and blender is stirred with the speed of 250rpm, reacts 50min；
(2) adjustment oxygen intake is 3.33L/L tapioca milk suspensions, cathode-current density 8mA/cm2, other
Condition is constant, and 3kg grafted monomers solution is added dropwise and (it is anhydrous that 1.6kg methyl methacrylates and 1.4kg vinylacetates are dissolved in 6L
Ethyl alcohol), rate of addition is controlled, 30min is added dropwise, the reaction was continued under room temperature 100min, stopping energization ventilation；
(3) filtering reacting liquid filters to obtain graft starch crude product after gained filter cake is washed with water；It is that extracting is molten with acetone
Agent is stripped processing to remove homopolymer to the graft starch crude product, and drying is to get graft starch sterling.
Comparative example 1
The operation of the comparative example is differed only in embodiment 1：The mass concentration of step (1) cornstarch milk suspension
It is 47.9%.
Comparative example 2
The operation of the comparative example is differed only in embodiment 1：In step (1), with 1mol/L sulfuric acid tune corn starch milks
The pH of suspension is 6.
Comparative example 3
The operation of the comparative example is differed only in embodiment 1：In step (1), every liter of corn starch suspension is passed through oxygen
The amount of gas is the half of embodiment 1, i.e., about 2.33L.
Comparative example 4
2kg cornstarch is weighed, is scattered in 17.63L deionized waters, a concentration of 10.19% corn starch milk is made
Suspension is gelatinized 1h in 65 DEG C, is cooled to room temperature.1.76L ceric ammonium nitrate solutions are added, and (0.1mol/L ceric ammonium nitrate solutions are dissolved in
In 1mol/L salpeter solutions), after stirred under nitrogen atmosphere 30min, 3kg acrylonitrile is added and (acrylonitrile is dissolved in 6L absolute methanols
In), under the conditions of 30 DEG C -33 DEG C, react 3h.Filtering, filters to obtain graft starch crude product after gained graft starch is washed with water；
Using n,N-Dimethylformamide as extraction solvent, the graft starch crude product is stripped and is handled to remove homopolymer, it is dry,
Up to graft starch sterling.
Comparative example 5
3kg potato starch is weighed, is scattered in 17L deionized waters, 1h is gelatinized in 65 DEG C, is cooled to room temperature, is passed through nitrogen
115g/L initiator solution 2L are added in gas, after reacting 30min, are warming up to 70 DEG C, grafted monomers solution is added dropwise, is stirred to react
N, the N of 10g/L is added in 60min ,-methylene-bisacrylamide solution 1.24L, reacts 1h.Filtering, gained graft starch is used
Graft starch crude product is filtered to obtain after water washing, it is dry to get graft starch sterling.
Wherein, the preparation method of grafted monomers solution is：2.6kg acrylic acid is dissolved in 6L deionized waters, with 30% hydrogen
Sodium hydroxide solution (sodium hydroxide containing 1.2kg) slowly titrates, and drop finishes, and the ethanol solution that 1L acrylamides are added (includes acryloyl
Amine 427g).
Initiator solution preparation method：138g potassium peroxydisulfates are weighed respectively, and 92g sodium sulfites are dissolved in 2L deionized waters.
Comparative example 6
2kg tapiocas are weighed, are scattered in 18L deionized waters, 1h is gelatinized in 65 DEG C, is cooled to room temperature, is passed through nitrogen,
30 DEG C are warming up to, the hydrochloric acid solution of 1mol/L adjusts pH to 3, and hydrogen peroxide-monsel solution is added and (includes 629.53g mistakes
Hydrogen oxide, 257.31g ferrous sulfate), after reacting 30min, be added dropwise grafted monomers solution (by 1.6Kg methyl methacrylates and
1.4Kg vinylacetates are dissolved in 6L absolute ethyl alcohols), be stirred to react 3h, be added the quinol solution of 45mL3%, adjust pH to
Graft starch crude product is filtered to obtain in neutrality, filtering after gained graft starch is washed with water, dry to get graft starch sterling.
The grafting result of embodiment 1-6, comparative example 1-6 are listed in table 1-2.
Table 1：The grafting result of embodiment 1-6
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Grafting rate (%) | 69.2 | 62.7 | 61.8 | 57.6 | 58.9 | 67.4 |
| Grafting efficiency (%) | 87.6 | 79.4 | 73.9 | 67.3 | 71.3 | 82.8 |
| Monomer conversion (%) | 50.76 | 74.47 | 74.43 | 76.26 | 90.83 | 51.39 |
| Homopolymer content (%) | 5.79 | 10.00 | 11.89 | 17.76 | 14.9 | 8.36 |
Table 2：The grafting result of comparative example 1-6
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Grafting rate (%) | 41.3 | 19.3 | 52.9 | 47.2 | 38.9 | 24.8 |
| Grafting efficiency (%) | 86.9 | 91.6 | 89.3 | 73.53 | 63.7 | 49.7 |
| Monomer conversion (%) | 90.75 | 6.29 | 37.68 | 40.1 | 45.7 | 27.61 |
| Homopolymer content (%) | 4.48 | 1.48 | 4.15 | 11.54 | 15.96 | 20.11 |
Grafting rate=(grafted branches quality/pure graft starch quality) × 100%
Grafting efficiency=[grafted branches quality/(grafted branches quality+homopolymerization amount of substance)] × 100%
Homopolymer content=(homopolymerization amount of substance/graft polymerization amount of substance) × 100%
Monomer conversion=[(grafted branches quality+homopolymerization amount of substance)/monomer mass] × 100%
From the above it can be seen that：Compared with ammonium ceric nitrate (comparative example 4) causes starch-grafted reaction as initiator,
Method using the present invention have higher grafting rate and grafting efficiency, and the homopolymer generated in process of grafting compared with
It is few.When the hydroxyl radical free radical that reaction system generates is less (comparative example 1-3), products therefrom grafting rate is relatively low, at this time olefines
The less generation of monomer homopolymerization, homopolymer content is relatively low in product, and with starch graft copolymerization occurs for most of olefin monomer
Reaction, grafting efficiency are higher.
Effect experimental examples one：Graft starch water imbibition is tested
Experimental subjects：5 gained graft starch of embodiment 5 and comparative example
Experimental method：0.1g starch dry-eye disease is weighed in 500mL beakers, is separately added into 200mL deionized waters, 0.9%
NaCl solution tap water is filtered with the quasi- sub-sieve of 200 targets after water suction is saturated, the sample after water suction is made to be stood on sieve
Then 10min weighs the quality (g) of sample after sieve and water suction, calculates Water absorption as follows.
Water absorption (g/g)=(quality of quality-standard sub-sieve of the sample after standard sub-sieve and water suction)/starch
The quality of dry-eye disease
Experimental result is listed in table 3：
Table 3：The result data of embodiment 5 and comparative example 5 compares
Water absorption (g/g)=(starch quality-stem grafting branch starch quality is grafted after water suction)/stem grafting branch starch quality
From the above it can be seen that：Compared with potassium peroxydisulfate-sodium sulfite initiation grafting reaction, the present invention is obtained
Graft starch has preferable soaking effect.
Effect experimental examples two：Graft starch film forming is tested
Experimental subjects：6 graft starch of embodiment 6 and comparative example
Experimental method：70g tapiocas, graft starch prepared by embodiment 5 and grafting prepared by comparative example 6 are weighed respectively
100g polyvinyl alcohol is added in starch, and stearic acid 10g is added in high-speed kneading machine, 50 DEG C or less uniform stirring mixing 30min,
Then double screw extruder is added mixture into, extruder temperature of each section is no more than 180 DEG C, squeezes out billot and is cooled down through sink, wind
It is cold, then through pelleter pelletizing, the pellet cut is sent into blown film unit, and control blown film temperature is no more than 180 DEG C, flat to blow, film folding
Diameter 30cm, obtains starch plastics.
According to tensile strength and elongation percentage of the GB1040-79 methods test starch plastics before immersion, then respectively by 3 kinds
Starch plastics impregnate for 24 hours in water, and surface moisture is blotted with filter paper, continue to test starch plastics according to GB1040-79 methods
Tensile strength after immersion and extension rate score.Experimental result is listed in table 4.
Table 4：Starch plastics thin film parameter
From the above it can be seen that：The tensile strength of starch plastics prepared by gained graft starch of the invention is higher than wood
6 starch plastics of sweet potato starch and comparative example, and the hydrophobicity of gained plastic film also improves a lot compared with the two, para arrowroot
Film prepared by powder and 6 gained graft starch of comparative example is after soaking for 24 hours, and film strength and elongation percentage reduction are larger, and this hair
Starch plastics film strength and elongation percentage variation prepared by bright gained graft starch is smaller.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (7)
1. a kind of preparation method of graft starch, which is characterized in that include the following steps：
(1) starch emulsion suspension of preparation is added in the electrolytic cell equipped with cathode and anode, adjusts the pH of the starch emulsion suspension
Value is acidity, is passed through oxygen to cathode according to the amount of 4.0-8.0L oxygen/L starch emulsion suspensions, and the electric current for controlling cathode is close
Degree is 10-15mA/cm2, starch is electrolysed with this condition；
The starch emulsion suspension using percent by volume for 5-30% methanol aqueous solution or ethanol water as solvent, starch milk
The mass concentration of suspension is 10-40%；The pH value of the starch emulsion suspension is 2-4；
Electrolyte, a concentration of 0.1- of the electrolyte in starch emulsion suspension are also added in the starch emulsion suspension
1.0mol/L；
(2) grafted monomers are added dropwise into the reaction system of step (1) and carry out graft reaction, when dropwise addition, adjustment oxygen intake is
2.0-8.0L/L starch emulsion suspensions, control cathode-current density are 5-10mA/cm2；
(3) after reaction, the reaction solution of filtration step (2), gained filter cake is washed, is extracted, dry after to get described
Graft starch.
2. preparation method according to claim 1, it is characterised in that：The grafted monomers are selected from acrylonitrile, acrylic acid, third
Olefin(e) acid salt, acrylamide, methyl methacrylate, butyl methacrylate, vinylacetate, butadiene, styrene, butylene two
Dimethyl phthalate, butene dioic acid dioctyl ester, butene dioic acid diamyl ester, dimethylaminoethyl methacrylate, acrylyl oxy-ethyl three
One or more of ammonio methacrylate, 2- acrylamide-2-methylpro panesulfonic acids, dimethyl diallyl ammonium chloride.
3. preparation method according to claim 2, it is characterised in that：The addition of the grafted monomers is to prepare starch milk
1-3 times of starch weight used in suspension.
4. preparation method according to claim 1, it is characterised in that：In electrolytic cell, the material of anode electrode is iron, cathode
The material of electrode is graphite.
5. according to the preparation method described in any one of claim 1,3 or 4, it is characterised in that：The starch forms sediment selected from mung bean
Powder, tapioca, sweet potato starch, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch, waxy corn form sediment
One kind in powder, rice starch, glutinous rice starch.
6. preparation method according to claim 5, it is characterised in that：The starch is cornstarch.
7. graft starch the answering in preparing water-absorbent material or membrane material that any one of the claim 1-6 preparation methods obtain
With.
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| CN110272579B (en) * | 2019-06-21 | 2022-04-08 | 中国皮革制鞋研究院有限公司 | Preparation method of starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material |
| CN110885380A (en) * | 2019-12-27 | 2020-03-17 | 蚌埠天成包装科技股份有限公司 | Chlorogenic acid grafted modified starch, degradable preservative film and preparation method thereof |
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| CN101824325A (en) * | 2009-03-05 | 2010-09-08 | 北京化工大学 | Oxidized starch grafted acrylic acid acrylamide sand fixing agent and preparation method thereof |
| CN102050925A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Grafted modified starch slurry |
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| CN101824325A (en) * | 2009-03-05 | 2010-09-08 | 北京化工大学 | Oxidized starch grafted acrylic acid acrylamide sand fixing agent and preparation method thereof |
| CN102050925A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Grafted modified starch slurry |
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